Chemistry and Technology of Rubber PDF

“Chemistry and Technology of Rubbers”
Chemistry and Technology of Rubbers

1. Overview on Rubbers, Definitions, Market, Properties, Production and Applications
2.1. Natural Rubber

2.2. Synthetic Polyisoprene
3. Overview on Emulsion Rubbers

3.1. Emulsion-Styrene/Butadiene-Rubber
3.2. Polychloroprene
3.3. Nitrile Rubber
4. Overview on Solution Rubbers

4.1. Overview on Polybutadiene
4.2. Li-Polybutadiene and Solution-Styrene/Butadiene-Rubber with an Emphasis on
Integral Rubber
4.3. Chemistry and Production Technology of High cis-1,4-BR with a Special Emphasis on
Nd-BR
4.4. Ethylene/Propene-Co- und Terpolymers
4.5. Butyl- and Halobutyl Rubber
5. High Performance Rubbers

5.1. Fluoro Rubber
5.2. Silicon Rubber
5.3. Hydrogenated Nitrile Rubber
5.4. Ethylene/Vinylacetate-Copolymers
6. Thermoplastic Elastomers
7. Test Questions
1. Overview on Rubbers, Definitions, Market, Properties,
Production, and Applications
• Definition of the Terms “Rubber“, “Elastomer“ and “Thermoplastic

Elastomer“
• Nomenclature
• Market
• Important Rubbers and Property Profiles
• Rubber Producers
• Production Technologies
• Producers of Synthetic Rubber and Production Capacities
• Available Vulcanization Methods and Network Properties
Standard Terminology Relating to Rubber

(ASTM D 1566 - 98 )
rubber, n-a material that is capable of 30

recovering from large deformations 1 min
quickly and forcibly, and can be, or 25
already is modified to a state in which
it is essentially insoluble (but can 20
swell) in boiling solvent, such as
Stress [MPa]
benzene, methyl ethyl ketone, or

15
ethanol toluene azeotrope.
rubber
10
DISCUSSION - A rubber in its
modified state, free of diluents, 5
1 min
retracts within 1 min to less than 1,5
times its original length after being 0
stretched at room temperature (18 to 0 50 100
29°C) to twice its length and held for 1
min before release. Elongation [%]
Comparison of Materials According to ASTM D 1566
300 ε = ε residual
Residual Elongation [%]
200
TPO
Definition of „Rubber“
according to Thermoplastic
ASTM D 1566 - 98 TPV Elastomers
100
SBS
NR/BR based tyre tread
0 NR gum stock
0 100 200 300
Elongation (εε) [%]
My personal Definition of “Unvulcanized Rubber“,

“Vulcanized Rubber“, “Elastomer“, and “TPE“
Unvulcanized Rubber is an uncrosslinked, amorphous or partially
crystalline polymer (synthetic or natural) with a Tg < temperature of use
Vulcanized Rubber (or: „Crosslinked Rubber“ or „Elastomer“) is obtained

by chemically crosslinking (vulcanization) of unvulcanized rubber
Thermoplastic Elastomers (TPE) are physically crosslinked rubbers

Thermoplasts are unvulcanized polymers (synthetic or natural) with a softening
temperature (Tg oder Tm) > temperature of use
Thermoset resins (or duroplasts) are highly crosslinked polymers which do not soften with
increasing temperature, but will deteriorate at high temperatures
In English, the term „Rubber“ is ambiguous as this term refers to unvulcanized

as well as to vulcanized rubber:
• rubber tree unvulcanized (=uncrosslinked) rubber

• natural rubber
• rubber boot vulcanized (=crosslinked) rubber
Tgs of Polymers with a Saturated C-C Main Chain
Polyethylene ~ -130°C
Polypropylene -18°C
(atactic / amorphous)
CH3 CH3 CH3 CH3

O O O O
O O O
Polyvinylacetate +30°C
O O O O
O O O O
CH3 CH3 CH3 CH3
Polystyrene +100°C
(ataktisch / amorph)
O O O O O O O
Si Si Si Si Si Si Si Silicon Rubber -120°C
Tgs of Polymers with an Unsaturated C=C Main Chain
-115°C
Polybutadiene (100% 1,4-cis)
-75°C
Polyisoprene (100% 1,4-cis)
Cl Cl -45°C
Polychloroprene (100% 1,4-trans)
Cl
Cl
CN
-50°C bis -5°C

Nitrile Rubber (depending on ACN-content)
CN
Influence of Tg on Rebound of Vulcanized Rubbers
(50 phr carbon black,
black, without plasticizer)
80
1,4-cis BR
SBR NBR
NR
60
Rebound [%] EPDM
40
IIR
20
0
-75 -50 -25 0 25 50 75 100
Temperature [°C]
• With increasing temperature rebound elasticity passes throug a minimum

• The temperature at the rebound minimum correlates with Tg, except for butyl rubber
• The temperature at the rebound minimum is significantly higher than the Tg of the respective rubber
• In this respect, butyl rubber performs different from the other rubbers
Source: Butyl And Halobutyl Compounding Guide For Non-Tyre Applications, 12/92 Bayer AG -KA
Schematic Presentation of the Dependence of the

Shear Modulus on Temperature
10000 NR (raw rubber)

NR/5 phr DCP
Polystyrene
1000
Shear Modulus [MPa]
100
10
0,1
-150 -100 -50 0 50 100 150 200
Temperature [°C]
Designation of Rubbers (DIN/ISO 1629)
Class- Chemical Description Examples

Designation
M Rubbers with fully saturated main chain CM, CSM, EAM, ACM,
(polymethylene type rubbers) EPM, EPDM,
N Nitrogen containing rubbers NBR, HNBR
O Rubbers with oxygen in the main chain CO, ECO, GPO
(Polyether type rubbers)
Q rubbers with a polysiloxane main chain MQ, MVQ, PMVQ, FMQ
R Rubbers with an unsaturated main chain NR, SBR, BR, NBR,
(double bond containing rubbers) CR, IIR
T Rubbers with sulfur in the main chain OT, EOT
(Polythioether type rubbers)
U Rubbers which contain carbon, nitrogen AU, EU
and oxygen in the main chain
(polyurethane type rubbers)
Z Rubbers with phosphorus and oxygen in FZ
the main chain (polyphosphazenes)
Abbreviations (DIN / ISO 1629) and Examples

BR Butadiene-Rubber
CR Chloroprene Rubber
CM Chlorinated Polyethylene
CSM Chlorosufonated Polyethylene
EPM Ethylene/Propylene-Rubber
EPDM Ethylene/Propylene/Diene-Rubber
ENR Epoxidised Natural Rubber
IR Synthetic Polyisoprene
IIR Butyl rubber
NR Natural Rubber
NBR Nitrile-Butadiene-Rubber
SBR Styrene-Butadiene-Rubber (E-SBR und S-SBR)
FPM Fluoro Rubber (DIN / ISO 1629)
FKM Fluoro Rubber (ASTM D-1418)
Annual Consumption of NR and Synthetic Rubber
14000
Annual Consumption [1000 metric tons] Natural Rubber

12000
Synthetic Rubber (Solid + Latex)
10000
8000
6000
4000
2000
0
1920 1930 1940 1950 1960 1970 1980 1990 2000 2010 2020
Sources:
•IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions
•Outlook for Elastomers 1996-97 (Wembley 1998)
•Rubber World, 21916 (1999) 13-14
•European Rubber Journal (Quotation of IISRP Statistics), various editions
•LMC International Ltd, Rubber March 2005: Verbrauch 2001-2005
Application Areas of Solid Rubber

(rubber latex not included)
Automotive
15%
Modification
Tyres of Plastics
45% 14%
Others
Cable and 15%
Wire
Construction Machine
3%
3% building
5%
Price and Volume of Rubbers (without Latex)
FZ Volume Shares
FQ High General Purpose Rubbers: 82%
FKM Performance
HNBR Q
AU/EU EVM
Rubbers
CR (0.3 Mio t)
Price
NBR (0.32 Mio t) Special Special

High Performance
IIR/X-IIR (0.5 Mio t)Rubbers Rubbers 1%
Rubbers
17%
EPM/EPDM (0.9 Mio t)
Shares in Turnover
BR (2,8 Mio t) General Purpose Rubbers: 60%
General
SBR (2,7 Mio t) Purpose
NR (6.7 Mio t) Rubbers
Volume High
Performance Special
Rubbers 10% Rubbers 30%
Source: Rubber World, 21916 (1999) 13-14
Oil – and Temperature Resistance of

Vulcanizates According to ASTM D 2000
General
GeneralPurpose
PurposeRubbers
Rubbers
250 Special Rubbers
Special Rubbers
max. service temperature [°C]
FKM MVQ High

HighPerformance
PerformanceRubbers
Rubbers
225
FMVQ
200
FZ 80 % VAc 40 % VAc
175 EVM
ACM AEM
HNBR
150 EPDM
CO/ECO 18 % CM (H)IIR
44 %
ACN CSM
125 NBR ACN
100 CR
EU SBR BR
NR
75 AU
50
0 20 40 60 80 100 120 140 no
requirement
Degree of Swelling in ASTM-Oil Nr. 3 [Vol %]
Evaluation of Vulcanizate Properties
1 2 3 4 5 6 7 8 9 10
Improvement
Criteria of Evaluation:
• Maximal Service Temperature
• Low Temperature Flexibility
• Oil Swell
• Mechanical Properties
• Ozone Resistance
Evaluation of Vulcanizate Performance*

Rubber Low Max. Service Mechanical Oil Swell Ozone Price Performance
temperature Temperature Properties (ASTM 2000-90) Resistance Index
performance
Tg Rating T max. Rating Tear Rating Rating Rating Rating
Resistance
[°C] [°C] [MPa] [Vol.% ] [€/kg]
NR -72 8 80 1 25 10 >140 (70) 1 1 1,1 21

SBR ca. -40 6 95 3 22 7 130 2 1 1,1 19
BR -120 10 85 2 20 6 >140 1 1 1,3 20
EPDM -60 5 145 6 24 8 >140 1 8 2,2 28
IIR -60 6 135 5 15 3 >140 1 6 2,7 21
NBR -40 5 125 5 22 7 20 bis 50 7 6 2,5 30
CR -39 4 115 4 22 7 55 bis 65 3 2 3,4 20
CM -25 3 140 6 15 4 80 4 5 3,1 22
CSM -25 3 135 5 16 4 80 4 9 3,8 25
EVM -35 4 170 8 14 3 20 bis 100 6 9 3,8 30
AEM -35 4 170 8 15 4 50 5 9 6,9 30
ECO -50 5 130 5 15 4 30 6 8 6,9 28
AU -30 4 80 1 25 10 3 bis 25 7 9 7,5 31
VMQ -120 8 250 10 10 1 30 bis 50 6 10 7,5 35
ACM -35 4 170 8 14 3 20 bis 40 7 9 9,4 31
HNBR -26 3 160 6 25 10 15 bis 40 8 9 28,1 36
FKM -20 2 250 10 14 3 5 9 10 43,8 34
FMVQ -70 8 215 9 10 1 10 9 10 125 37
FZ -65 8 180 8 16 4 10 9 10 500 39
E-SBR and S-SBR may not be evaluated according to these criteria as SBR is designed for high Tgs (improvement of wet skid)
*Ullmann‘s Encyclopedia of Industrial Chemistry, VCH Weinheim 1993, Vol. A23, Rubber 3. Synthetic; W. Obrecht „Introduction“
Correlation of Rubber Price and Vulcanizate
Performance
45
40 FZ
FMVQ
35 HNBR
MVQ FKM
Performance Index
EVM ACM
30 NBR AEM AU
EPDM ECO
25 CSM
NR IIR CM
20 BR CR
SBR
15
10
0
0,1 1 10 100 1000
Price of Rubber [€/kg]
Ranking of Top 10 Tyre Producers

Rank Company Sales of Tyres Share Return Market
of on Shares
Tyres Sales in Capitalization of Shares
Sales
[%] Tyres
[Mio US $] [%] [%] [%]
1 Michelin 13.425,0 95,0 6,6 19,6 20
2 Bridgestone 12.950,0 74,0 5,5 18,9

15
3 Goodyear * 12.470,0 86,7 2,4 18,2
4 Continental 4.901,0 49,0 -4,2 7,2 10
5 Sumitomo** 2.598,2 72,7 7,7 3,8
6 Pirelli 2.534,5 39,0 6,1 3,7 5
7 Yokohama 2.272,2 71,0 5,7 3,3 0

8 Cooper Tire 1.705,3 54,0 3,4 2,5
Bridgestone
Michelin
Goodyear
9 Toyo 1.247,6 61,5 2,1 1,8

Continental
10 Kumho 1.246,5 60,3 -13,1 1,8

11 Hankook 118,9 88,9 8,5 0,2
Sums: 55.469,2 81,0

Total Sales: 68.500,0 100,0 Source: FAZ 18.08.2003
* Dunlop is not included
** Goodyear und Sumitomo operate in NA und WE in 75/25 joint ventures (Dunlop)
Source: European Rubber Journal, vol. 184, no. 10, Oktober 2002, S. 28-30
Ranking of Top 22 Producers of Technical Rubber Products
(without Tyres)
Rank Company Company Sales 2001 Return on Sales
Site [Mio US$] [%]
1 Hutchinson SA France 2156 *)

2 Bridgestone Corp. Japan 2065 0,8
3 Freudenberg Group Germany 2060 3,7
4 Tomkins plc. UK 1855 5,7
5 Parker Hannifin US 1500 5,7
6 Cooper Tire & Rubber US 1477 2
7 Trelleborg AB Sweden 1446 2,9
8 Continental AG Germany 1270 *)
9 Federal Mogul Corp. US 1160 *)
10 Goodyear Tire & Rubber US 1122 *)
11 NOK Inc. Japan 1120 *)
12 Tokai Rubber Industries Ltd. Japan 987 2,7
13 Metzeler Automotive Profile Syst. Germany 900 *)
14 Toyoda Gosei Co. Ltd. Japan 897 1,3
15 Mark IV Automotive US 812 *)
16 GenCorp. Inc. US 808 8,6
17 Ansell Ltd. Australia 759 *)
18 Sumitomo Rubber Ind. Japan 750 *)
19 Yokohama Rubber Co Ltd. Japan 703 1,8
20 Dana Corp. US 695 *)
21 Toyo Tire Rubber Co. Ltd. Japan 670 1,3
22 Phoenix AG Germany 662 *)
*) not available
Source: European Rubber Journal 184,9 September 2002
Producers of Synthetic Rubber and

Capacities
Lanxess 8.7%
Others Exxon Mobil 5.7%

30%
Goodyear 5.3%
Total: JSR Corporation 5.2%
12,097 KMT
Sinopec 5.2%
ISP Elastomers 2.2%

Bridgestone/Firestone 2.8% Sibur 5.1%
Nizhnekamskneftekhim Inc. 3.1
Korea Kumho 4.8%
Zeon Corporation 3.2%
Petroflex 3.3% Dow 4.5%
Michelin 3.3% Polimeri 4.2%
Petro-China
3.6%
Source:
R. J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008„Globalization of Synthetic Rubber Industry“
Chemical and Technological Features of
Rubber Manufacturing Processes
Chemical Technological Features
Aspects
Emulsion Solution Dispersion Bulk Gas-Phase
E-SBR, CR, NBR, AEM

Radical E-BR, ACM, FKM,
EVM EVM EVM
Polymerization EVM
G-EPM
Ziegler/Natta- BR, EPM, EPM, BR* G-EPDM
Polymerization EPDM EPDM
G-BR**
Anionic BR, L-SBR. Q
Polymerization IR
Cationic ECO, CO IIR Q

olymerization
Polyaddition and AU, EU EU AU Q
Polycondensation
Polymer CIIR, BIIR, CM, CSM,
Modification CM, CSM, H-NBR*
H-NBR, FZ
* Technology not established (only patents for the hydrogenation of NBR-latex)

** Technology not established (only patents for the gas phase polymerization of butadiene)
Flow Diagram of an EPDM Solution Process

Water
Temperature:
Temperature: 35-65°C
35-65°C
Condenser
Pressure:
Pressure: 5-10
5-10bar
bar
Settler
Residence
Residence Time: 30min
Time: 30 min
Azeotropic-
Destillation Solids
SolidsContent:
Content: 10
10-12
-12wt.%
wt.%
Moisture Content: < 3 ppm
Moisture Content: < 3 ppm
Waste Water
Flash
Condenser Vessel Stripper
Dewatering
screw
Waste Air
Ethene Propene Waste Expeller

Reactor water
Hexane External steam
Oil
cooler PH- Air bed
Purification Control Dryer
Purification Abwasser
Antioxydant
Stripping
aid
Dryer Dryer Baler
Modifier
Reactivator Wrapper
Purification/ Purification/ EASC
Drying Drying
VOCl3
Hexane ENB
Evaluation of Rubber Manufacturing Processes
Polymerization Process
Aspect
Slurry
Viscosity 8 2 8 1 10
Heat Removal 10 3 8 3 5
max. Solids Cont. 5 2 5 9 5
Stereoregularität 0 10 10 8 10
Waste Water 0 5 5 10 10
Waste Air 5 5 5 8 5
Sum 28 27 41 39 45
Ranking: (Gas-Phase) > Dispersion > Bulk >> Emulsion > Solution
Prerequistes: comparable running times
Available Vulcanization Methods for the

Different Types of Rubber
Example Method of Vulcanization
Sulfur Peroxide Resin Other
“R“- Rubbers NR XXX - X (X)

BR XXX X (X) (X)
CR XX - (X) XX
SBR XXX (X) (X) (X)
NBR XXX X (X) (X)
HNBR XXX XX (X) (X)
IIR XX - XX (X)
XIIR XX XX XX XX
“M“-Rubbers EPDM XX XX X (X)
EPM - XXX - -
FKM - XX - XX
CM X X X X
Other
MVQ (X) XX (X) XX
Rubbers
Influence of Vulcanization Method and Crosslinking
Density on Tensile Strength (unfilled NR-Vulcanisates)
30
Tensile Strength [MPa]
20
Sx accelerated sulfur cure

S1 TMTD-cure
C C peroxide cure
10 C C high energy radiation cure
0
0,2 0,4 0,6 0,8 1,0 1,2 1,4
Reciprocal chain length 1/Mc x 10-4
• For high moduli and high tensile strength the vulcanization method and the length of rubber
chains between two crosslinking sites are decisive factors
• There is an optimum in tensile strength for Mc ~10.000 g/mol
• The tensile strength of rubber vulcanizates is only 1/100 - 1/1000 of the theoretical values
Sources: R. Houwink, H. K. de Dekker „Elasticity, Plasticity and Structure of Matter“ University Press, Oxford 3. Auflage (1971)
K. Dinges, Kautschuk und Gummi. Kapitel 2 in H. Batzer „Polymere Werkstoffe“
Georg Thieme Verlag Stuttgart, New York (1984)
Schematic Presentation of the Deformation of a

Rubber Network
Type of Bond Bond

Energy
[ KJ/Mol]
C-C 350
C-O 350
C-N 282
C-S-C 272
C-S-S-C 266
-S-S-S-S- < 266
Type of Bond Bond

Energy
[KJ/Mol]
covalent 260 - 350
TSexpt. = 1/100 - 1/1000 TStheor. physical 10 - 20

Influence of Compound Ingredients on Vulcanizate
Performance
•Oil Resistance Filler

•Low temperature flexibility
•Resistance to heat- and ageing
•Adhesion to cord, fibres and fabrics
•Covulcanisation of layers
Rubber •Tensile Strength
•Elongation at break
•Static and dynamic moduli
•Shore A Hardness
•Abrasion Resistance
•Compression Set
•Cut growth Resistance during dynamic stress
•Heat-buid-up
•Electical conductivity
• …….
•……..
•……..
•…….
Vulcanization
Method
2.1. Natural Rubber
• Microstructure and Property Profile
• NR-Market
–Designation of Grades and Glossary
–Development of Market and Price
–NR-Production, Areas of Application and Important Grades
• NR-Production
–NR-Latex and Latex Finishing
–General Features of NR and Hevea brasiliensis
–NR Grades and Specifications
• Chemical and Physical Properties of NR
–Solution Fractionation of NR
–Mastication of NR
–Crystallization (Spontaneous-and Strain induced)
• Chemically Modified NR-Grades
–CV-Grades
–SP-Grades
–ENR-Grades
• Vulcanization of NR
NR: Microstructure and Property Profile
Positive:
• Low price and good ratio of price versus performance
• Standardized NR-grades
• High level of mechanical properties
(Tensile Strength, Modulus Abrasion) 5
• Good Dispersability of Fillers H3C 2 3
(due to high viscosities at the start of the mixing cycle) C CH
1 4
• Low rolling resistance (truck tyres)
• High abrasion resistance (truck tyres)
CH2 CH2
• Slow spontaneous crystallization
• Significant strain induced crystallization
Negative:
• Poor resistance to swelling with hydrocarbons Physical Properties:
(fuels, oils and grease) Tg: -72°C
• Need for mastication prior to compounding 1,4-cis-content ~ 97%
• bad wet skid performance Tm (equilibrium): + 30 °C
• Poor resistance to heat ageing max. rate of crystallization: -25°C
max. degree of crystallinity: ~ 30 %
Strain induced crystallization
NR: Designation of Grades and Glossary
General Purpose Grades:

TSR Technically Specified Rubber (TSR 10, TSR 20, TSR 50)
SMR Standard Malysian Rubber (SMR 5, SMR 10, SMR 20, SMR 50)
SCR Standard Chinese Rubber (SCR 5, SCR 10, SCR 20, SCR 50)
GP General Purpose Grade
ADS Air Dried Sheet
RSS Ribbed Smoked Sheet
Special Grades:
OENR Oil Extended NR
L-Grades „Light“ Grades (with colour specification) produced by the
selection of latices and removal of carotinoids by latex creaming,
addition of Na-HSO3, and intenisve wash etc.
SP-Grades „Superior Processing“ (Sol/Gel-Blends)
CV-Grades „Constant Viscosity“ NR
obtained by the addition of hydroxyl amin prior to latex finishing
ENR Epoxidized NR
NR: Annual Consumption (incl. Latex)

14
Naturkautschuk
12
Synthesekautschuk (Fest + Latex)
10
Mio tons
0
1880 1900 1920 1940 1960 1980 2000 2020
Source:
• IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions
• Outlook for Elastomers 1996-97 (Wembley 1998)
• Rubber World, 21916 (1999) 13-14
• European Rubber Journal (Quotation of IISRP Statistics), different editions
• Consumption 2001-2005: LMC international Ltd. „Rubber, March 2005“
Source: European Rubber Journal, January/February 2011, 16
NR: Production
3500 Malaysia
Indonesia
3000 Thailand
x 1000 metric tons
2500 others
2000
1500
1000
500
0
Sources: 1980 1985 1990 1995 2000 2005
• K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical
Technology, vol 21, 4th ed., 562-591
• LMC International Ltd; Rubber April 2005
1997 2004 1997 2004 1997

Thailand 1.934 31,90% 2.988 34,50% India 570 9,40% 741 8,60% Ivory coast 87 1,40%
Indonesia 1.530 25,20% 1.942 22,40% China 400 6,60% 585 6,70% Philippines 60 1,00%
Malysia 1.070 17,60% 1.175 13,58% Sri Lanka 113 1,90% 92 1,10% Camerun 56 0,90%
Vietnam 110 1,80% 423 4,90% Cambodsha 49 0,80%
Brasil 35 0,60%
Liberia 25 0,40%
Burma 21 0,40%
Nigeria 13 0,20%
Total 4.534 75% 6.105 70% 1.193 20% 1.841 21% 346 5,7%
Source: Römpp Lexikon Chemie; Version 1.5; Stuttgart/New York Thieme-Verlag 1998
LMC International Ltd; Rubber April 2005
NR: Application Areas
Tyres
71%
Automotive
(other than tyre)
2%
Shoes Latex-Products
None automotive Others
4% 11%
5% 7%
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer
Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
Use of NR in Truck Tyres
Year Tread [wt.%] Side Wall [wt.%] Carcass [wt.%]

NR SBR BR NR SBR BR NR SBR BR
1974 45 21 34 48 37 15 71 20 9
1981 60 12 28 44 19 37 84 11 4
1983 77 7 16 58 6 36 100
1985 86 5 9 62 38 100
1990 86 5 9 75 25 100
1994 100 60 40 100
The major application of NR is in truck tyres
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer
Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
NR: Production
Share of smallholders
in rubber production:
Thailand 95%
Indonesia 83%
India 83%
Malaysia 81%
Brasil 70%
Sri Lanka 33%
Ivory Coast 29%
Source: International Rubber Study Group
Source: http://www.therubbereconomist.com
NR-Production by smallholders:
Area cultivated per smallholder: 1,25 ha;
Number of trees: 625 trees in total; 520 trees under tap
Annual tappings per tree: 180/a
Total number of tappings per year: 95.000 tappings for 625 trees/a
Annual yield: 850 kg/a
Annual earnings: ca. 250 €/a (0,30 €/kg)
Earnings/different source*: 1020 €/a (1,2 €/kg)
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk Othmer Encyclopedia
of Chemical Technology, vol 21, 4th ed., 562-591
*Broadcast in German TV (ZDF) “Mission“ about Charles Goodyear on 17.10.2004
As of today, only Bridgestone, Michelin und Goodyear run NR-plantations
Features of the Rubber Tree (Hevea Brasiliensis)
• Botanical Family: Euphorbiaceae

• Habitat: Equator + 15°
–Height: < 300 m
–Temperature: 25-30°C
–Humidity: > 70%
–Rain fall: 1800-2000 mm/year
–Soil: good drainage (not at the bottom of vallleys)
• max. age of tree: 30-40 Jahre (plantation), 100 Jahre (rain forest)
• Height of tree: 20 m (plantation), 40 m (rain forest)
• tapping age of tree: 5-7 years
•Tappings: every 2nd day = 180 days/year
• Yield per tree: 1-2 kg/a
• Yield per tap: 5-11g
• density of trees: 500/ha
• Rubber yields: 400-1.200 kg/ha
–Plantation: 1.000 kg/ha
–Maximum yield: 3.000 kg/ha
–Smallholder: 850 kg/ha
• Fungal infection: Dothidella Ulei (Yellow leaf blythe)
• Spread of fungus: so far, endemic and restricted to Brasil
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer, Encyclopedia of Chemical
Features of NR-Latex
• Total solids concentration:(25) 30-40 wt. % (dependent on many parameters)
• Rubber content: 90 - 95 wt. % of total solids
• Particle diameter: 150-3000 nm (dependent on many parameters)
• Gel content: dependent on many parameters (latex age, finishing method)
• Molar mass: 105-107 g/mol (not constant, dependent on many parmaters)
• Latex stability without the addition of additives (NH3, formaldehyde, boric acid,
phenolates, Na2SO3 (0,05 Gew.%), etc.) latex coagulation occurs
as a consequence of encymatic decay
Latex Finishing
• Dilution of the latex to 15-20 wt. % solids
• Removal of heavy impurities such as sand by sedimentation
• Removal of impurities such as wood, leafs, insects, etc. by filtration
• Latex fractionation for the removal of carotinoids for „L“ (light = colourless) grades
• Addition of:
• Na2SO3 (0,15 wt.%) for pale-crepe-grades
• [HONH3]2 SO4 for CV- grades (“Constant Viscosity“)
• Discontinuous latex coagulation with formic or acetic acid (5 wt. %) in pH-range 5,0 - 5,2
• Completion of coagulation by maturing for 12-16 h
• Mechanical water removal by riffle mills (6-9 passes)
• Drying in smoke at 60°C/1 week for RSS-production (“RSS” = Ribbed Smoked Sheet)
• Drying in air at 40°C/2 months (“ADS“ = Air Dried Sheet)
NR: Range of Grades
Latex- Acid Coagulation Acid Coagulation Natural

concentration (factory) (Plantation/Smallholder Coagulation of latex
centrifugation,
creaming, Sheet-Material „Cup lump“
evaporation of (RSS, ADS)
water „Smallholder‘s
lump“
SMR 5
60% 40%
Baled or Crumb wet and dry field grades

Rubber blending processes
Sales latex SMR L SMR CV 50 SMR GP SMR 10 SMR 20

(60 wt. % solids) SMR CV 60
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
Comminution Process: multi-stage wet blending process with mechanical generation of

crumbs, crumb blending and washing with subsequent crumb drying at 100-120°C/4-5 h is
used for the homogenization and purification of cup lumps
NR: SMR-Grades und Specifications
• The content of none rubber like residues is an important quality

criterium for NR
• As a consequence, the content of impurities is a feature in the
designation of NR grades
NR Grade SMR 5 SMR GP SMR 10 SMR 20 SMR 50

Strainer Residue [wt.%] 0,05 0,10 0,10 0,20 0,50
(mesh width: 45 mm)
Besides NR purity, price is also an important factor for the selection of

an appropriate NR grade. As a consequence of price and quality, the
ranking of NR grades for tyre building is as follows:
SMR 20 > SMR 10 > SMR GP > SMR 5 > RSS
NR: Vulcaniaztion of Different SMR-Grades

Typ Monsanto-Rheometer (160°C)
Delta F [J/cm2] TS 2 [min] t90 [min]
Impurity Level
SMR CV 29,4 2,2 11,6

SMR L 33,9 1,8 9,7
SMR 5 37,2 1,5 7,8
SMR 10 40 1,3 6,8
SMR 20 41,1 1,2 6,8
The impurities in NR perform like a vulcanization accelerator
ACS 1- Compound With increasing impurity level, the following

NR 100 phr features are observed:
Stearic Acid 0,5 phr • reduction of scorch time
ZnO 6,0 phr • reduction of vulcanization time
Sulfur: 3,5 phr
MBT 0,5 phr • Increase of crosslinking density
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical
Technology, vol 21, 4th ed., 562-591 (ISO 1658: Natural Rubber - Test Recipes and Vulcanization Characteristics,
International Organization for Standardization, Geneva, Switzerland, 1973
Chemical and Physical Composition of NR
Solution fractionation of NR by sequential coagulation:

1. Preparation of a NR solution in toluene
2. Incremental addition of methanol
Fraction share 1,4-trans Viscosity 1,2-

Nr.: content (toluene/25°C) content
[wt.%] [%] [dl/g] [%]
bale 100 2,2 11,5 0,6
1 24,4 2,0 7,7 0,6
2 19,7 2,0 3,9 0,5
3 15,5 2,0 1,9 0,5
4 8,0 3,4 1,16 0,7
5 12,9 4,0 0,62 0,6
6 12,8 5,0 0,3 0,5
Soluble portion 6,7 - - -
Source: Rubber Chem. Technol. 57, 104 (1984)

Source: Rubber Chem. Technol. 82, 283-314
• NR has a broad distribution of molar masses (“polydispersity“ or “physical inhomogenity“)

• The polydispersity increases with the age of the tree
• NR fractions with a low molar mass have a higher content of 1,4-trans moieties
than the fractions with a higher molar mass (“chemical inhomogenity“)
NR: Vulcanization with Multifunctinal Isocyantes
NR (TSR 5, Defo 700) [phr] 100 100 100 100 100 100
Carbon black/Corax N 2200 [phr] - - - - 50 50
Stearic Acid [phr] 3 3 3 3 3 3
Zinc oxide [phr] 3 3 3 3 3 3
Antilux 654 [phr] 1,5 1,5 1,5 1,5 1,5 1,5
IPPD (Vulkanox® 4010 NA) [phr] 1 1 1 1 1 1
TMQ (Vulkanox® HS/LG) [phr] 1 1 1 1 1 1
Mineral oil/Enerthene 1849 [phr] 3 3 3 3 3 3
Sulfur [phr] 1,6 1,6 1,6 1,6 1,6 1,6
TBBS (Vulkacit® NZ) [phr] 1 1 1 1 1 1
Desmodur® TT [phr] 0 0 15 25 0 10
OOOO
OOOO
CCCC
NNNN
CCCC
HHHH
CCCC HHHH CCCC
HHHH
NNNN
3333CCCC
HHHH
CCCC
NNNN
NNNN
CCCC
HHHH
3333
NNNN
HHHH
NNNN
HHHH
CCCC
SSSS
NNNN
HHHH
HHHH
3333
3333
3333
SSSS
HHHH
CCCC
HHHH
OOOO
NNNN
CCCC
OOOO
3333
3333
IPPD (Vulkanox® 4010 NA) TBBS (Vulkanox® NZ) Desmodur® TT (TDI Uretdione)
First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272
NR: Vulcanization with Multifunctional Isocyantes
NR (masticated TSR 5) 100 100 100 100 100 100
Carbon black (Corax N 220) 0 0 0 0 50 50
Desmodur TT 0 0 15 25 0 10
Fmin [dNm] 0,30 0,18 0,54 0,96 1,06 1,78

Fmax-Fmin [dNm] 7,41 6,30 24,20 20,06 15,94 36,26
t10 [min] 4,34 4,82 0,74 0,71 1,96 0,34
t80 [min] 6,21 6,77 15,23 15,56 4,22 7,47
t90 [min] 7,53 8,24 17,60 19,08 4,99 9,07
Tensile Strength [MPa] 17,8 15,3 25,7 21,8 27,8 25,2

Elongation at break [%] 605 650 635 565 540 480
M50 [MPa] 0,6 0,4 1,5 1,8 1,5 1,9
M100 [MPa] 0,9 0,6 2,0 2,4 2,7 3,1
M200 [MPa] 1,4 0,7 2,9 3,7 7,3 8,0
M300 [MPa] 2,2 1,2 5,0 6,0 13,4 14,4
Shore A Härte/23°C 43 40 66 68 66 75
Shore A Härte/70°C 45 38 - 65 - -
Rebound/23°C [%] 74 69 59 55 - -
Rebound/70°C [%] 81 78 - 60 - -
DIN-Abrasion [mm3] 183 327 155 123 102 133
NR contains polymer bound functional groups (-NH2, -COOH, -OH, -CONH2)

which react with isocyanates
Mastication of NR
184 kJ/mol 343 kJ/mol
*C
C* C* *C
Pentachlorothiophenol 2,2'-Dibenzamidodiphenyl-Disulfide
(DBD)
Degree of Mastication
SH S S
Cl Cl
NH HN
Cl Cl O O
Cl
• By the use of mastication additives the mastication of NR

is accelerated (oxidation catalysts and radical scavengers)
0 100 200 • Pentachlorothiophenol is an effective mastication aid; it is
Temperature [°C] banned in WE
• Today, disulfides as well as Fe-complexes are used for the
• At low temperatures (<120°C) mechanical chain acceleration of NR mastication
scission prevails
• At temperatures >120°C thermo-oxidative chain Source:
scission prevails C. Clarke, M. Hensel, Rubber World, November 2009, 28-31
• In the temperature range 100-130°C the mastication „Improved natural rubber processing and physical properties
effect shows a minimum by use of selected compounding additives“
NR: Crystallization at -25°C
35
30
Crystallinity [%]
25
20
15
Pale Crepe
10 pale crepe after acetone extraction
0
0 5 10 15 20 25 30
time [h]
• The Shore A Hardness of NR increases due to crystallization during storage at low temperatures
• NR can only be processed in the uncrystallized state
• Decrystallization can be achieved by storage at elevated temperatures (40°C-50°C)
• The decrystallization in the interior of bales needs 2 weeks at 30°C
• The maximum degree of crystallinity of unvulcanized NR is ~ 30%
• NR contains impurities which accelerate the speed of crystallization
• The crystallization accelerators can be removed by acetone extraction (e.g. stearic acid)
NR: Dependence of Crystallization Rate and Crystallite Melting

Temperature on Storage Temperature
1000 40
30
melting temperature [°C]
20
100
half time [h]
10
10 -10
-20
-30
1 -40
-50 -30 -10 10 -50 -30 -10 10 30
storage temperature [°C] storage temperature [°C]
Source: Source:
U. Eisele Intorduction to Polymer Physics, Springer-Verlag 1990 K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural
in Kirk-Othmer Encyclopedia of Chemical Technology,
Vol. 21, 4th ed., 562-591
Stress/Strain-Performance of Unfilled NR- and SBR-
Vulcanizates (gum stocks)
30
25
NR
stress [MPa]
20 SBR
Strain induced crystallization
15
10
0
0 200 400 600 800 1000
strain [%]
Dependence of Tack on Testing Temperature

(Unvulcanized NR- and SBR-Compounds)
25
20
NR
SBR
Tack-Index
15
10
0
0 20 40 60 80 100 120
temperature [°C]
Chemically Modified NR-Grades
Modification Application
Hydroxyl amine (“CV”-Grades) improved compounding, no mastication
required
Blend with NR-gel (“SP”-Grades) Improved processability of NR-compounds
Epoxydation (ENR) Improved oil resistance
Improved wet skid
Improved silica interaction
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
NR: CV-Grades
10 SMR 20
9 IR/Natsyn 2200 (IR / Ti)
Mooney- Increase [MU]
H
H + H2 N H 8
O
7
6
- H2 O 5
4
3
H 2
H 1
N H
0
0 5 10 15 20
storage time [days]
• During storage at ambient and elevated temperatures, the viscosity of NR increases to

a greater extent than for synthetic IR (storge hardening)
• It is assumed that the viscosity increase of NR is caused by the chemical reaction of
polymer bound –NH2 and polymer bound –CH=O groups
• By the addition of hydroxylamine to the NR latex prior to latex coagulation –CH=O
groups are chemically eliminated
•CV-Grades (“Constant Viscosity“) exhibit an improved storage stability
NR: CV-Grades
140
Mooney-Viscosity ML1+4
130
120
(100°C) 110
100
90
80
70 before hot air ageing
60 after hot air ageing
50
0 0,02 0,04 0,06 0,08
Hexanediamine [mol/kg]
H
Specification of CV-Grades
H NH2
H + H2 N + H
O O Grade Ml 1+4 (100°C)
- 2 H2 O Minimum Maximum
CV 50 45 55
CV 60 55 65
H
H
CV 70 65 75
N
N H LV 50 54 55
H
NR: CV-Grades
70
Increase of Mooney Viscosity [%]
60
H
H C + H2N OH 50
O
40
- H2O
30
H 20
H C 10
N OH
0
0 0,05 0,1 0,15 0,2
hydroxyl amine [wt. %]
NR CV-Grades (“Constant Viscosity“) are obtained by the addition

of hydroxylammonium chloride to the latex prior to latex finishing
ENR: Dependence of Properties on the Degree of Epoxidation
40
20
Tg [°C]
Epoxidation with -20
peracids in the
latex stage
-40
O O
-60
-80
O 0 20 40 60 80 100
Degree of Epoxidation [%]
Epoxydation of NR has the following effects:

• Increase of polarity (Reduction of the swelling in oil)
• Increase of Tg (Improvement of wet skid and reduction of gas permeation)
• Resistance to ageing is unchanged (as bad as for unmodified NR)
• Processability is reduced (supposedly this problem has been solved)
Source: Ullmann‘s Encyclopedia of technical Chemistry
ENR: Dependence of Vulcanizate Properties on the

Degree of Epxidation
NR [phr] 100 - -
ENR 25 (Degree of Epoxidation: 25%) [phr] - 100 -
ENR 50 (Degree of Epoxidation: 50%) [phr] - - 100
Carbon black (N 220) [phr] 30 30 30
Shore A Härte/23°C 59 56 59
M300 [MPa] 7,8 6,9 8,8
Tensile Strength [MPa] 27,1 25,9 27,8
Elongation at break [%] 550 590 560
Elasticity/23°C [%] 78 25 15
Goodrich HBU [°C] 44 60 52
CS/24h/70°C [%] 17 46 17
Volume Swell (70h/70°C)

ASTM-Oil No. 1 [%] 66 73 -5
ASTM-Oil No. 2 [%] 114 28 6
ASTM Oil No. 3 [%] 191 108 21
Air permeability/23°C [1018 x m4/s.N] 27,0 8,0 2,0

NR: SP-Grades
• SP-Grades (“Superior Processing“) are obained by blending crosslinked NR
with uncrosslinked NR in the latex stage.
• The crosslinked NR-latex (NR-gel) is obtained by sulfur cure in the latex
• The SP-series of grades comprises different blend ratios of ucrosslinked

and unrosslinked NR as well as oil extended grades
Grade Precrosslinked Uncrosslinked Oil

NR NR
[wt.%] [wt.%] [phr]
SP 20 20 80 0
SP 21 40 60 0
SP 22 50 50 0
SP 23 80 20 40
SP 24 80 20 0
SP-grades have the following advantageous properties:

• reduced die-swell
• Increased extrusion out-put
• Reduced roughness on surface and edges
Source: BP 880739; Natural Rubber Producers‘ Association, Appl.: 28.03.1957,

Inv.: B. C. Sekhar „Improvement in the Preparation of Superior Processing Rubbers“
NR: Impact of Vulcanization Systems on Vulcanizate

Properties
Schwefel Sulfur Sulfur Peroxide Capped
(conv.) (Semi EV) (EV) Di-Iso-
Cyanate
NR (SMR 5) [phr] 100 100 100 100 100

N 330 [phr] 50,0 50,0 50,0 50,0 50,0
Oil [phr] 4,0 4,0 4,0 3,0 3,0
ZnO [phr] 5,0 3,5 5,0 5,0 5,0
Stearic Acid [phr] 3,0 2,5 2,0 - -
Sulfur [phr] 2,5 1,2 0,33 - -
TBBS [phr] 0,5 - - - -
CBS [phr] - 0,8 0,8 - -
TMTD [phr] - 0,4 0,4 - -
Santoflex 13 [phr] 2,0 2,0 2,0 - -
TMQ [phr] - - - 2,0 2,0
DCP [phr] - - - 2,5 -
Novor 924 [phr] - - - - 6,7
Caloxol [phr] - - - - 5,0
ZDMC [phr] - - - - 2,0
ZMBT [phr] - - - - 2,0
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical
NR: Vulcanization with A Capped Diisocyanate (Novor 924)
O
N N
O N O NH O HN O N O
Novor 924: TDI based diisocyanate O O
Novor 950: MDI based diisocyanate
Thermal Cleavage
Due to health and safety reasons Novor
924 has been replaced by Novor 950 O
N N
O N O H H O N O
O C N O N C O
Tautomerization Tautomerization
H O N O
O N O H
H H
O
- H2 O - H2 O
N N
N O NH O HN O N
O O
Sources:
•F. Barlow „Rubber Compounding“ 2nd edition, Marcel Dekker, Inc. Chapter 7, page 96-98
• Vulcanization with Novor 924, NR Technical Bulletin, MRPRA, Brickendonbury, England
• Novor Application Data Sheet, Solid Tyres, ADS-5H, Rubber Consultants, Brickendonbury, England
• C. S. L. Baker, Novor Vulcanizing Systems: Their Technical Development and Application Areas, Rubber Manufacture and Technology Seminar, P. R. I.
(Malaysian Section), Kuala Lumpur, July 21-23-1981
NR: Dependence of Vulcanizate Properties on

Vulcanization System
Sulfur Sulfur Sulfur Peroxide Capped

(konv.) (Semi EV) (EV) Di-Iso-
cyanate
Shore A Hardness/23°C 65 65 67 61 70
M100 [MPa] 2,08 2,22 2,34 2,28 2,60
Tensile Strength [MPa] 28,8 30,1 24,2 21,4 24,0
Elongation at break [%] 515 485 390 310 460
Rebound/23°C [%] 70 77 67 72 66
Fatigue to Failure [kZ] 223 106 68 51 90
Goodrich HBU [°C] 29 32 36 34 -
CS/24h/70°C [%] 27 14 10 11 -
∆ TS (7d/100°C) [%] 73 54 24 49 30
2.2. Synthetic Polyisoprene (IR)
Contents:
• Differences between IR and NR
• IR-Grades, Catalysts and Microstructures
• Price, Producers, and Production Capacities
• Comparison of Unvulcanized NR- and IR- Properties
• Vulcanizate properties of NR and IR
• Compound and Vulcanizate Properties of Poly-3,4-Isoprene
IR grades and chemical differences between NR und IR:
IR
NR
Li Ti Nd
cis-1,4-content [mol % ] 98 93 97 99
Need for Mooney adjustment before use yes no mastication needed
Gel yes - - -
functional groups yes - - -
2.2. Synthetic Polyisoprene (IR)

Isoprene Poly-3,4-Isoprene
H 3C
3
C2 C
C
1
C4
Poly-cis-1,4-Isoprene Poly-trans-1,4-Isoprene
Type of IR Catalyst Solvent Microstructure
Trade Name cis-1,4 trans-1,4 1,2- 3,4-
1)
Cariflex IR-309 Li unpolar (benzene) 93 0 0 7
1)
Natsyn 200 Ti unpolar hydrocarbon 97 0 0 3
2)
Vestogrip Li Hexane/Additive 60
3)
IR Nd unpolar hydrocarbon 99 - - -
Sources:
1) E. Schoenberg, H. A. Marsh, S. J. Walters, W. M. Saltman, Polyisoprene, Rubber Chemistry and Technology, Vol 52, S. 526-604
2) Data sheet of Hüls AG: “Vestogrip“ (Production by Karbochem / South Africa: ca. 3.000t)
3) WO 02/38635 A1 (Michelin), Erf.: P. Laubry, Prior.: 13.11.2000
3) WO 02/48218 A1 (Michelin), Erf.: P. Laubry, Prior.: 28.11.2001
IR: Development of Prices, Producers and Production
Capacities
3
2,5
Price [US $ / kg]

2
1,5
0,5 IR
NR (RSS)
0
1980 1985 1990 1995 2000 2005 2010
Company Plant Location Capacity [kt]

Goodyear Beaumont/Texas/USA 90
Kraton Polymers Rotterdam-Pernis/Nederland 25
Kauchuk Sterlitamak Sterlitamak/Russia 100
Nishnekamskneftekhim Nishnekamsk /Russia 200
Togliattikauchuk Togliatti 130
JSR Corporation Kashima / Ibaraki Pref. 36
Zeon Corporation Mitzushima / Okayama Pref. 40
Karbochem Newcastle / Natal /South Africa 3
Total Capacity [kt] 624
Source: R.J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008 „Globalization of Synthetic Rubber Industry“
Comparison of NR and IR: Stress/Strain-

Stress/Strain-Curves of Unvulcanized
Polyisoprene Compounds
7 NR (SMR 5)
High cis-IR/Ti (97%)
Stress [MPa]
6 Low cis-IR/Li (93%)
0
0 100 200 300 400 500
Strain [%]
Evaluation of Compound- and Vulcanizate Properties of
NR and IR
Compound Properties
IR
NR
Li Ti Nd
Mastication - + + +
Mixing cycle - + + +
Die swell - + + +
Tack + - - +
Green strength + - - +
Vulcanizate Properties
IR
NR
Li Ti Nd
Modulus + - - +
Tensile Strength + - - +
Cut growth resistance + - - +
Rebound Elastivity + - - +
Abrasion resistance + - - +
Poly-3,4-Isoprene: Compound and Vulcanizate Properties

3,4-content (NMR): ca. 60 % 3,4-Polyisoprene 100 phr Compound Properties
ML 1+4(100°C) [MU] 77
ML 1+4 (100°C): 65 MU CB (Corax N 330) 50 phr t10/150°C [min] 13,8
Tg -8°C HAR-oil 10 phr t90/150°C [min] 27,5
Zinc oxide 3 phr
Source: Vulcanization (30 min/150°C)
Stearic acid 2 phr Shore A Härte (22°C) 67
Data sheet of Hüls AG
CBS 1 phr Shore A Härte (75°C) 52
„Vestogrip M 100 [MPa] 2,1
(3,4-Polyisopren-Kautschuk)“ Sulfur 2 phr M 300 [MPa] 8,4
TS [MPa] 14,7
εb [%] 510
Cut growth resistance [N/mm] 25

Residual elongation [%] 20
Rebound / 22°C [%] 2

Rebound / 75°C [%] 44
tan δ/25°C 0,26

tan δ/75°C 0,11
Source: P. Roch (Goodyear) KGK 48,6 (1995) 430-434“Compounding for Wet Grip“
3.0. Overview on Emulsions Rubbers
• Emulsion Rubbers and Features of the Emulsion Process

• Essentials of the Emulsion Polymerization
• Mechanism of Emulsion Polymerization
• Kinetic Aspects of the Emulsion Polymerization
• Flow Diagram of Continuous Emulsion Polymerization
• Flow Diagram of Latex Finishing
• Finishing of CR-Latex
• Legal Aspects of Water Usage
Emulsion Rubbers and Features of the Process

Features of the Emulsion
Process
Advantages:
• high reactor output Emulsion- Latex
• good heat removal rubber Coagulation
• low viscosities
• high solids E-SBR electrolyte
• high molar masses NBR electrolyte
• high reproducibility CR freezing
Disadvantages: ACM electrolyte
• Waste water FKM electrolyte
• Product impurities (residuals from
emulsifier and coagulants)
• no water resistant catalysts
available (Stereospecifity)
Application Areas for Rubber Latices:

• Carpet backing, paper-, textile- and leather finishing (X-SBR)
• Latex dipping process for improvement of cord adhesion
• Manufacture of dipped articles such as protection gloves etc. (NR, NBR, CR)
Principles of Emulsion Polymerization
Emulsifier
Initiator
Monomer
Polymerization
Wasser
Monomer emulsion Polymer dispersion

(Latex or rubber latex)
Mechanism of Emulsions Polymerization

Monomer containing emulsifier micelle Latex particle
Diameter: 5-10 nm Particle diameter: 10-500 nm
concentration: 1021 lw-1 concentration: 1017 lw-1
M M
M M M M
Monomer droplet
Diameter: 0,1-10*10 -6 m
concentration: 1013 lw-1 M M
M M M
Literature: Polymerization occurs only in
• P. E. Lovell, M. S. El-Aasser, Emulsion Polymerization, Wiley 1998
• Blackley, Emulsion Polymerization, 1975 monomer loaded micelles and
• H. Gerrens, Advances in Polymer Science, volume 1 not in monomer droplets
Phases in Emulsion Polymerization
Phase I Phase II Phase III

80
70
Surface tenison
60
pressure
Arbitrary Units
polymerization rate
50
40
30
20
10
0 20 40 60 80 100
Monomer Conversion [%]
Literature: P. E. Lovell, M. S. El-Aasser, Emulsion Polymerisation, Wiley 1998

Blackley, Emulsion Polymerisation, 1975
H. Gerrens, Fortschritte der Hochpolymerforschung
Kinetic Aspects of Emulsion Polymerization

Phase I: NL and Vbr increase
„free“ emulsifier reduces surface tension
Phase II: NL und Vbr remain constant
the monomer concentration in latex particles remains constant
the latex particles grow and soap coverage decreases
surface tenison increases
Phase III: the monomer droplets have disappeared
the monomer contained in latex particles is consumed
the number of latex particles remains constant
Number of latex particles formed:

x y
NL = k * (E-CMC) * I
Polymerization rate in Phase II:
VBr = NL * kw* [n]* [M]
Prediction by the Smith Ewart Theory: x = 0,4; y = 0,6
[n]= 0,5
NL: number of latex particles [lw-1]
E-CMC: effective emulsifier concentration [lw-1]
I: Initiator concentration [lw-1]
kw: propagation rate constant [l * mol-1 * sec-1]
[n]: average concentration of radicals per particle [without dimension]
[M]: monomer concentration in latex particle [Mol * l-1]
Flow Diagram of a Continuous Emulsion
Polymerization (E-SBR)
Recovered styrene
Vapour
Mixer/Settler condensation
Waste water treatment

Recovered butadiene
Aqueous emulsifier solution
Aqueous catalyst solution
Mixer/Settler Brüdenkondensation Stripping

column
Wate water
Flash
Hydroperoxide
treatment
evaporation
Butadiene
-tionskessel
Polymerisa
Abstopp-
Styrene
kessel
-tionskessel
Polymerisa
-tionskessel
Polymerisa
-tionskessel
Polymerisa
-tionskessel
Polymerisa
Short stop
Vapour
Latex-
storage
Flow Diagram of Latex Finishing

(E-SBR, NBR)
Latex
AO
Wash water
Mass Balance:
Additives (oil, etc)
Latex volume : 400.000 t

Rubber (25%): 100.000 t
Puffertank Water serum (75%): 300.000 t
Coagulants
Wash water: 100.000 t

Wash- Waste water: 400.000 t
tank
Dewatering dryer
Coagulation screw
tank
Baler and
packaging
stripped
Latex
Finishing of CR-Latex
dryer
Latex-surge dewatering rolls

tank
Acidic acid
Freezing
roll
Powdering Chopper
packaging
Legal Aspects of Water

Surveillance in Germany
Wasserhaushaltsgesetz (WHG)
“Legislation on the regulation of the water household"
of September 23rd, 1986, BGB1. I, S. 1654
Abwasserabgabegesetz (AbwAG)
“Legislation on Charges for the emission of polluted water“
of November 6th, 1990, BGB1. I, S. 2432
Abwasserherkunftsverordnung (AbwHerkV)
“Legislation on the provinence of waste water"
Of July 3rd, 1987, BGB1.I, S. 1578
Trinkwasserverordnung (TrinkwV)
“Legislation on the quality of drinking water and on water which is used in
food production”
of December, 5th, 1990, BGB1. I, S. 2612
Source:
W. Guhl und U. Werner; Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH,
D-69469 Weinheim, 1997
“Legislation on the regulation of the water household“
of September 23rd, 1986, BGB1. I, S. 1654
Water is a natural ressource. It has to be used in a sustainable

manner for the benefit of the community as well as for the benefit
of individuals. Negative impacts have to be avoided.
Everybody who uses water is obliged under the necessary

circumstances to act in a careful and responsible manner in order
to avoid water pollution and negative impacts on the properties of
water.
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
Legal Aspects of Water Surveillance in

Germany
“Legislation on Charges for the emission of polluted water“
of November 6th, 1990, BGB1. I, S. 2432
By law, in 1990 one “pollution unit“ was fixed at 70 DM. According to
this law, one pollution unit was defined to correspond to:
• 50 kg O2 (COD)
• 3 kg Phosphorous
• 25 kg Nitrogen
• 2 g organic halides
• 20 g Hg
• 100 g Cd
• 500 g Cr
• 500 g Ni
• 500 g Pb
• 1 kg Cu
• etc.
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
1. COD = 0
2. BOD = 0
3. COD = BOD
4. COD < BOD
5. BOD < COD
Which equation does not make sense?
COD: Chemical Oxygen Demand

BOD: Biological Oxygen Demand

Explanation:
COD = 0 no impurities present which can be chemically

oxidized (very pure water)
BOD = 0 no biologically degradable substances present
(substances which are not biodegradable might
be present)
COD = BOD all impurities are biodegradable
COD < BOD this is not possible
BOD < COD The impurities are only partially biodegradable
3.1. Emulsion-SBR (E-SBR)
• Overview
–Microstructure and Property Profile
–Market
–Application Areas, Market, Products and Important Grades
–Producers and Production Capacities
• Polymerisation
–Polymerization Recipe („Cold Rubber“)
–Ingredients of a Polymerization Recipe
–Sequence of Reaction Steps
–Copolymerisation of Styrene und Butadiene
–Influence of Chain Modification Agents
• Product Properties
–Tg
–Influence of None Polymeric Residues on Compound and
Microstructure of E-SBR
4
CH2
2 CH
1 2 1
HC CH2 3 CH
3 3
HC 4
CH CH CH
C 2 2
CH
H2 CH2 CH2 CH2
2
4 1
1
1,4-cis 1,4-trans Vinyl Styrene

E-SBR: Property Profile and Application Areas
Positive:
• good mechanical properties of filled vulcanizates (TS, Modulus, Abrasion
Resistance)
• Good wet skid properties (dependent on amount of incorported styrene/Tg)
• short sequences of incorportated styrene (low hysteresis losses and low
rolling resistance)
• Availability of high Mooney-grades which allow for high loadings of mineral
oil (oil extended grades with reduced price)
• Great variety of standardized grades
• Many competitors/low price (commodity)
Negative: Application Areas in Western Europe

• poor ageing resistance Tyres
• poor resistance to swelling in oils 72%
• no variation of microstructure
• low / no profits / no R&D-activities
Others
mechanical
2%
Buildings parts
Shoes Automotive
5% 8%
5% 8%
E-SBR: Producers and Production Capacities

Produer Site Country Capacity
Copolymer (DSM) Baton Rouge USA 150.000
Goodyear Houston USA 267.000
Ameripol Synpol Port Arthur/Odessa USA 336.000
Bayer Sarnia Can. 20.000
Petroquimica Argentina Pto. Gral, San Martin Argentinia 53.500
Petroflex/Coperbo Duque de Caxias/Triunfo Brasil 255.000
Negromex Altamira Mexico 74.500
Bayer France La Wantzenau France 90.000
Dow Schkopau Germany 120.000
Enichem. Ravenna Italy 295.000
Shell Pernis Netherlands 120.000
Dwory Oswiecim Poland 104.000
Chemopetrol Kralupy Czech Rep. 76.000
HIP Petrohemija Zrenjanin Crotia 40.000
Combinatul Petrochimic Onesti Rumania 100.000
Neftochim Burgas Bulgaria 20.000
JSR Kawasaki Japan 195.000
Mitsubishi Kasei Corp. Yokkaichi Japan 65.000
Zeon Corp. Tokuyama/Kawasaki Japan 200.000
Sumitomo Chemical Comp. Chiba Japan 50.000
Korea Kumho Ulsan Korea 190.000
Hyundai Daesan Korea 60.000
Taiwan Synthetic Kaohsiung Taiwan 105.000
BST Elastomers Mab Ta Phut, Rayong Thailand 60.000
Gadjha Tunggal Indonesia 60.000
Quenos Altona Australia 35.000
Apar und Synthetics &Chemicals Bombay/Bareilly India 75.000
V/O Raznoimport Omsk/Sterlitamak/Togliatti/Voronezh USSR 486.000
SINOPEC und Petro China Lanzhou/JiLin China 200.000
Sum 3.902.000
Market: 2,0 Mio t
Capacity: 3,9 Mio t
Capacity utilization: 51%
Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.
E-SBR: Producers and Capacities in Europe
(without Latex Capacities):
700
Company Site Country Capacity
Lanxess France La Wantzenau France 45.000
600 Dow Schkopau Germany 120.000
Enichem. Ravenna Italy 295.000
Dow (prior owner: Shell) Pernis Netherlands 120.000
500
Sum 580.000
Production [t]
415.000
400 Dwory Oswiecim Poland 104.000
Chemopetrol Kralupy Czech Republic 76.000
HIP Petrohemija Zrenjanin Croatia 40.000
300
Combinatul Petrochimic Onesti Rumania 100.000
Neftochim Burgas Bulgaria 20.000
200 Sum 340.000
100
Market Volume in WE: 666 k t

0 Capacities in WE: 415 kt
1990 1992 1994 1996 1998 2000 2002 Formal Capacity Utilization in WE: 160 %
Dow Chemical shuts down ESBR-Plant in Pernis/ end of March 2004 (Chemical Week of 24.03.2004)
Lanxess shuts down E-SBR production in La ‚Wantzenau effective by July 2008
Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.
Range of E-SBR Grades
Cold Rubber
Hot Rubber
High Styrene Rubber
number of Cold Rubber Hot High

grade Rubber styrene
without Carbon Black- Oil-extension Oil extension
assignation rubber
additives Masterbatch (<14 phr) (>14 phr)
1000 - - - - X -
1500 X - - - - -
1600 - X X - - -
1700 - - - X - -
1800 - X - X - -
1900 - - - - - X
Source: The Synthetic Rubber Manual, 14th edition IISRP (International Institute of Synthetic Rubber Producers, Houston (1999)
E-SBR: Selected Grades
E-SBR Styrene- ML 1+4 Antioxydant Mineral Oil Carbon Black Remarks & Application
grade content (100°C) System grade loading grade loading Areas
[wt.%] [MU] - [phr] - [phr]
General purpose rubber for
1500 23,5 50-52 S - - - - tyre treads and for technical
rubber goods
1502 23,5 50-52 NS - - - - uncoloured technical goods
Compounds with good
processability
1507 23,5 30-35 NS - - - - (calandered and injection
moulded products)
E-SBR with low ash content

1509 23,5 30-35 NS - - - - and low water swell (cables
and electronic industry)
lught colourd rubber goods
1707 23,5 49-55 NS NAPH 37,5 - -
(hoses and profiles)
1712 23,5 49-56 S HAR 37,5 - - Tyre treads, transportation
1721 40 50-55 S HAR 37,5 - - belts, dark colured technical
Abrasion resistant
1609 23,5 61-68 S HAR 5 N 110 4
compounds für retreading
tyre treads, dark colured
1808 23,5 48-58 S HAR 47,5 N 330 76
technical rubber goods
S: staining NAPH: naphthenic oil

NS: none staining HAR: highly aromatic
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
E-SBR: Recipe for Cold Rubber Production

Monomers:
Butadiene 23,2 wt.%
Styrene 9,5 wt.%
Modifier: t-DDM 0,07 wt.%
Reaction medium:
Water 65,4 wt.%
Emulsifier System:
K-salt of disproportionated rosin 1,5 wt.%
Na-salt of methylen-bis-naphthalinsulfonic acid 0,03 wt.%
Initiator-System:
p-Menthylhydroperoxide 0,04 wt.%
FeSO4 * 7 H20 0,01 wt.%
Di-sodium salt of ethylenediaminotetraacetic acid 0,02 wt.%
Na-salt of Formaldehydesulfoxylate 0,03 wt.%
Na3PO4*12 H2O 0,16 wt.%
E-SBR: Ingredients of Polymerization Recipe I
(Emulsifiers)
Disproportionation of Abietic Acid
CH3 Na-Salt of Methylene-bis

(Naphthalin-sulfonic Acid)
(Baykanol PQ(R))
H
CH3 COOH -
SO3
Abietic Acid Na
CH2 2 Na +
Pd -
SO3
Na
CH3 CH3 CH3
+ +
H H H
CH3 COOH CH3 COOH CH3 COOH
Dehydroabietic Acid Dihydroabietic Acid Tetrahydroabietic Acid
E-SBR: Ingredients of Polymerization Recipe II
p-Menthanehydroperoxide (p-MHP)
CH2 CH2 CH3

Oil soluble hydroperoxide CH3 CH CH O O H
CH2 CH2 CH3
Na-Formaldehydesulfoxylate
Na-Hydroxymethanesulfinate
H O
Reducing agent +
H O S O Na
Ethylenedinitrilotetraacetic Acid (EDTA)

O O
HO CH2 CH2 OH
Sequestering agent N CH2 CH2 N
for Fe-Ions HO CH2 CH2 OH
O O
E-SBR: Sequence of Reaction Steps
Redox Initiation:
R-OOH + Fe2+ R-O* + OH- + Fe3+
Fe3+ + Reducing agent Fe2+ + oxydized reducing agent
R-O* + Monomer R-O-Mon*
Growth Reaction:
R-O-Mon* + n Monomer P*
Regulation of Molar Mass with Mercaptanes:

P* + HS - R P- H + R - S*
R - S* + n Monomer R - S - Mn*
R - S - Mn* + HS - R R - S - Mn - H + R - S*
Transfer Reaction:
P* + R-H R - H + P*
Termination Reaction:
P* + P* P- P
E-SBR: Influence of Thiols
100 175
(ML 1+4 (100°C) [ME]
80
Gel content [wt.%]
140
60 105
40 70
20 35
0 0
0 0,2 0,4 0 0,2 0,4
Tert-dodecylmercaptane [phm] Tert-dodecylmercaptane [phm]
E-SBR: Styrene/Butadiene-Copolymerization (Differential
Styrene Incorporation)
Styrene Content of Polymer [wt. %]
100
Copolymerization Parameters
90 (Styrene = M1; Butadiene = M2)
80 r1 = 0,7
r2 = 1,4
70
60 As a Consequence of these
copolymerization parameters
50 there is no azeotropic composition
40
30
k11
20 r1 =
k12
10
k22
0 r2 =
k21
0 10 20 30 40 50 60 70 80 90 100
Styrene Content of Monomer Feed [wt. %]
E-SBR: Copolymerization of Butadiene and Styrene

(Integral Styrene Incorporation)
100
Copolymerization Parameter:
Integral Styrene Content [wt.%]
r1 (Styrene) = 0,78
80 r2 (Butadiene) = 1,39
60
Ideal (random) Copolymerization for Monomer Feed
Monomer Feed Styrene/Butadiene: 30/70 Styrene/Butadiene:
40
30/70
20 Polymerization Temperature:
+ 50°C Hot Polymerisation
- 20°C (Cold Polymerisation)
0
0 20 40 60 80 100
E-SBR: Distribution of Styrene Sequences
in E-SBR 1502
Copolymerization-
parameter
Styrol = M1
80 Butadien= M2
r1 = 0,7
70 r2 = 1,4
Probability [%]
60
k11
50 r1 =
k12
40 k22
r2 =
30 k21
20
10
0
1 2 3 4 5 6 7 8 9 10 11 12
Number of Styrene Units
E-SBR: Microstructure
Polymerization- BR-Microstructure
temperature 1,4-cis 1,4-trans Vinyl
[°C] [%] [%] [%]
-20 0,8 79,6 19,6

5 7,7 71,5 20,8
50 14,8 62,0 23,2
100 27,6 51,4 21,0
Source:
The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
E-SBR: Dependence of Tg on Styrene Content
100 expt. data

Tg of atactic
80 Fox-Flory-equation polystyrene
60
40
Tg [°C]
20
0
-20 Fox-Flory-Equation
1 w w2
-40 = 1 +
Tg Tg1 Tg2
-60 Tg: Tg of copolymers in K
Tg1: Tg of homopolymer 1 in K
-80 Tg2: Tg of homopolymer 2 in K
Tg of wn: weight fraction of copolymers 1 und 2
-100 E-BR
0 20 40 60 80 100
Styrene Content [Gew.%]
Source: T. G. Fox, P. J. J. Flory; Appl. Sci., 21,581 (1950)
Influence of None Polymeric Residues on Compound and

Vulcanizate Properties: Analytical Data
Product Mw Mw/Mn ML 1+4 Tg 137,5 phr

[g/mol] (100°C) of Krynol 1712
[ME] [°C] contains
37,5 phr oil
Krylene 1500 424.280 3,46 45 -51
mod. Krylene 1500* 429.210 3,51 51 -53 ==>
Krylene 1712 740.170 3,69 52 -50 27,27 wt.% oil
mod. Krynol 1712* 716.760 3,74 54 -50
Product Ash cont. Na Al chloride water- acetone-

(850°C) extract extract
[wt.%] [ppm] [ppm] [ppm] [wt.%] [wt.%]
Krylene 1500 0,33 1105 - 0,110 0,33 6,9

mod.* Krylene 1500 0,23 910 - 0,079 0,23 2,4
Krynol 1712 0,41 1502 655 0,230 0,41 32,3
mod.* Krynol 1712 0,20 355 1 0,045 0,20 30,1
* Modification of latex finishing (coagulation and crumb wash) in order to obtain

a rubber with a reduced content of residues with low molar mass
Influence of None Polymeric Residues on Compound and
Vulcanizate Properties: Compound Composition
Krylene 1712 [phr] 103,13 - 68,75 -

Krylene 1500 [phr] 25,0 - 50 -
mod. Krylene 1712* [phr] - 103,13 - 68,75
mod. Krylene 1500* [phr] - 25,0 - 50
Carbon black N 339 [phr] 80,0 80,0 - -
Carbon black N 234 [phr] - - 80 80
Mineral oil [phr] 10,0 10,0 20,0 20,0
TMQ [phr] 0,5 0,5 0,5 0,5
IPPD [phr] 0,75 0,75 0,75 0,75
DTBD [phr] 0,75 0,75 0,75 0,75
Stearic acid [phr] 2,5 2,5 2,0 2,0
Zinc oxide [phr] 2,5 2,5 2,5 2,5
Sulfur [phr] 1,9 1,9 1,9 1,9
CBS [phr] 1,1 1,1 1,2 1,2
DPG [phr] 0,55 0,55 0,3 0,3
* Modification of latex finishing (coagulation and crumb wash) in order to obtain

a rubber with a reduced content of residues with low molar mass
Influence of None Polymeric Residues on

Compound on Vulcanizate Properties
Krylene 1712 [phr] 103,13 - 68,75 -
Krylene 1500 [phr] 25,0 - 50 -
mod. Krylene 1712* [phr] - 103,13 - 68,75
mod. Krylene 1500* [phr[ - 25,0 - 50
Compound-Mooney ML1+4 (100°C) [MU] 67,0 71,0 73,5 77,0
Rheometer (160°C)
ΜL [dNm] 8,3 8,8 9,1 10,1
∆F [dNm] 35,3 38,2 37,3 39,2
ts1 [min] 4,8 4,3 4,7 4,5
t50 [min] 7,5 6,8 8,2 7,9
t90 [min] 11,2 9,3 12,6 11,1
Vulcanizate Properties:
Tensile Strength [MPa] 17,3 18,5 17,9 18,9
Elongation at break [%] 425 410 480 470
M100 [MPa] 2,5 2,7 2,3 2,3
M300 [MPa] 12,6 14,3 10,9 11,8
Shore A Hardness/23°C 69 71 72 71
Shore A Hardness/70°C 63 64 64 64
Rebound/23°C [%] 25 27 22 25
Rebound/70°C [%] 38 42 33 36
3.2. Polychloroprene (CR)
• Overview
– Property Profile and Application Areas
– Producers and Poroduction Capacities
– Grades and Application Areas
• Manufacturing
– CR-Microstructure
– Monomer Manufacturing Processes
– Basic Features of Polymerization Recipes
• Influence of CR-Microstructure on Chemical and Physical Properties
– Crystallization, Glass Transition Temperature, CR-Vulkanization
• Rubber Grades
– Standard Grades
– Sulfur Grades
– Precrosslinked Grades
• CR-Vulcanization
– Mechanism
• Substitution of CR
Sources:
- W. Obrecht, Houben Weyl-Müller Makromolekulare Stoffe (1987), volume E20/Teil 2, S. 842-859
- P. R. Johnson, Rubber Chem. Technol. 49 (1976) 650-702
CR: Property Profile and Application Areas

Positive Aspects:
• High loadability
• gute Vulkanisationsfähigkeit
• Adjustable crystallization rate
• Good vulcanizate properties
• Good dynamic properties
• High weather an ozone resistance
• Good adhesion to metals
• Good resistance against fungi, mould and bacteria
• Fair insulation properties
• Excellent fire resistance
• Low gas permeability
• Broad range of grades
Negative Aspects:
• High density (2,5 g/cm3)
• High compound price
• Modest resistance against chemicals and oils
• Crystallization at low temperatures
• poor ageing resistance at elevated temperatures
CR: Producers and Production Capacities (2010)
Producer Capacity Site Butadiene Acetylene
Denki Kagaku Kogyo KK 100 Omi/Japan - X
Lanxess 75 Dormagen/Germany X -
DuPont 45 Pontchartrin/USA X -
Tosoh 32 Nanyo/Japan X -
Chonquin Changshou Chemicals 28 Chongquing/China - X
Shanxi Syntheic Rubber Co 25 Datong/China - X
Pidilite 25 India X -
Showa Denko KK 20 Kawasaki/Japan X -
Nairit Scientific Industrial 10 Yerewan/Armenia - X
Total 360
Plant Closures
Stagnant CR-Consumption in WE and USA Producer Capacity Site
Growing Consumption in South-East Asia DuPont 30 Maydown/N.-Ireland
50 Louisville/USA
Bayer 25 Houston/USA
Source: Various Press Releases Polimeri (BP) 25 Grenoble/France
Monomer Manufacturing Processes

2-Chlorobutadiene-1,3 (Chloroprene) 2,3-Dichlorobutadiene 1,3
Acetylene Route (1930) Butadiene Route (DCB)
(Gas phase chlorination / 1956)
2 HC CH H 2C CH CH CH2 Cl
+ Cl2 H2C C CH CH2

CuCl/NH4Cl/HCl
Nieuwland Cl Cl Cl Cl
+ + Cl2
CH2 CH CH CH2+ CH2 CH CH CH2
(ca. 40 %) (ca. 60 %)
Cl Cl Cl
HC CH CH2 Side products: chlorinated C8-Compounds
Tetrachlorobutane H 2C C CH CH2
CuCl
+ NaOH/85°C - HCl
HCl/CuCl Cl Cl
(30-60°C)
H2C CH CH CH2
+ NaOH - HCl Cl Cl
(85°C) H2C C C CH2
Cl Cl
Only DuPont, Lanxess und Denki
H2C CH CH2 + HC CH CH CH2
produce DCB
2-Chloroprene 1-Chloroprene (impurity)
DE 1149001; Knapsack AG, Prior.:10.07.1961 GB 804254; Distillers Co. Ltd. , Prior.:21.03.1956;

Erf.: W. Vogt, K. Kaiser, H. Weiden Erf.: F. J. Bellringer
CR: Grades and Aplication Areas
CR Application Areas (2006)
Latex Rubber
applications Applications
5% 60%
Latex based 50
adhesives
Polymerization Temperature [°C]

5% 45
Latex
Solvent 40 Grades Rubber Grades
based 35 (Standard Grades,
adhesives precrosslinked grades
30% 30 and sulfur grades)
25
Application Areas of Rubber Grades 20
Adhesive
15 Grades
Profiles Hoses 10
11% 44%
0 2 7
0 1 3 4 5 6
Belts
12% Conveyor DCB-Content of Monomer Feed [phm]
Cables Belts
21% 12%
CR: Influence of Polymerization Temperature on

Microstructure
Polymerization 1,4-trans- 1,4-cis 1,2 3,4
CH2 H temperature [°C] [%] [%] [%] [%]
1,4-trans C C +12 94,5 3,8 1,0 0,8
Cl +30 93,5 4,5 1,2 1,0
CH2 +42 93,5 4,5 1,2 1,1
Cl +57 91,5 5,8 1,4 1,3
H +75 88,5 8,4 1,5 1,4
1,4-cis C C
CH2 CH2 95
1,4-trans-Content [Mol %]
1,2 Cl 3,4 H
CH2 C 2 CH2 C 3
3
C H 2
C Cl 90
CH2 CH2
Adhesive Rubber- and Latex Grades
Microstructure trans-1,4 cis-1,4 grades
> 89% > 95%
Tg [°C] -45 -20 85 0 10 20 30 40 50 60 70 80
Tm [ °C] 105 70
For commercially available CR-grades small differences in the

polymerization temperature and in the 1,4-trans content are an important
factor
CR: Basic Features of CR-Polymerization Recipes
Recipe Ingredients [wt.-parts] Adhesive Latex Standard Sulfur Precrosslinked
grade grade grades grades grades
Chloroprene 100 100 90-100 90-100 100
2,3-Dichlorobutadiene - - 0 - 10 0 - 10 -
Water 100-200 100-200 100-200 100-200 100-200
Disproportionated abietic acid 2,5-5,0 2,5-5,0 2,5-5,0 2,5-5,0 2,5-5,0
NaOH or KOH 0,5-1,0 0,5-1,0 0,5-1,0 0,5-1,0 0,5-1,0
Na-methylene-bis(naphthalinsulfonate) 0,3-0,7 0,3-0,7 0,3-0,7 0,3-0,7 0,3-0,7
n-dodecylmercaptane 0,05-0,5 0,05-0,5 0,05-0,5 0,05-0,5 0,05-0,5
Potassiumpersulfate 0,2-1,0 0,2-1,0 0,2-1,0 0,2-1,0 0,2-1,0
Na-Anthrachinon-2-Sulfonate 0,0125 0,0125 0,0125 0,0125 0,0125
Sulfur - - - 0,3-0,7 -
Dimethacrylates of alkanediols - - - - 0,1-0,3
Polymerization temperature [°C] 5 - 20 20-50 30-50 30-50 30-50
Monomer conversion [%] 60 - 85 60 - 85 60 - 85 60 - 85 70 - 85
-
SO3
CH3 CH3 CH3
Na
+ CH2 2 Na +
+
H H -
H SO3
CH3 COOH CH3 COOH CH3 COOH
Na
Dehydroabietic Acid Dihydroabietic Acid Tetrahydroabietic Acid Na-Methylene-Bis(Naphthalinsulfonate)

(Baykanol PQ R)
CR: Determination of Crystallization Rate

Dependence of Shore A Hardness Mercury dilatometry for the determination
on Crystallization Rate of crystallization rate
(Tc =-5°C pretreatment: 30 min at 80°C)
He 0
10
Shore A Hardness
He-Hi
20
Volume [mm3]
30
1/2(He- Hi) 40
Hi 50
60
t1/2
70
80
0,1 1 10 100 1000 10000 0,1 1 10 100 1000
Storage time [h]
Storage time [h]
Source: U. Eisele: Internal Bayer-Reporting System
CR: Crystallization Rate and Crystallite Melting Temperature
Dependence of t1/2 on Storage Dependence of Crystallite Melting
Temperature Temperatures on Polymerization
(Baypren 210; Pretreatment: 1 h / 60°C) Temperature
30 80
Crystallite melting temperature [°C]

25 70
60
20
50
15
t1/2 [h]
40
10 30
5 20 lowest figures
highest figures
10
0
-20 -15 -10 -5 0 5 10 15 20 0
-60 -10 40
Storage Temperature [°C]
Polymerization temperature [°C]
Source: U. Eisele „Introduction to Polymer Physics“ Springer Verlag
Dependence of Tg and Crystallization Rate at -10°C on

Monomer Feed and Polymerization Temperature
Polymerization-
Sym- T temperature [°C]
- 31 bol [°C] 103
45
- 33 35
25 45 35 25 15 5
15 102
- 34 5
t 1/2 [h]
Tg [°C]
- 35 101
- 36
100
- 37
- 38 10-1
0 3 6 9 12 15 0 3 6 9 12 15
DCB-Content of Monomer Feed [%] DCB-Content of Monomer Feed [%]
Crystalliaztion Rates of Unvulcanized CR, Unvulcanized CR-
Compounds and CR-Vulcanizates at - 10°C
500
B. 110 VSC
400 lcanizates
s
nd
R
ou
C
p
vu
d
300 -c o
ze
t1/2 [h]
CR
CR-bases
ni
ca
d
ize
ul
nv an
lc CR 100,0 phr
vu
U
200 Un Carbon black (N 762) 75,0 phr
Polyetherthioether 10,0 phr
B. 110 Vulkanox DDA 2,0 phr
Vulkanox 4010 NA 0,5 phr
KA 8418 Stearic acid 0,5 phr
100 Magnesium oxide 4,0 phr
B. 112 Zinc oxide 5,0 phr
B. 210
0
0 100 200 300 400 500 600 700 800
t1/2 [h] (unvulcanized CR)
Dependence of Crystallization Rate on Blending Ratio of Two

CR-Grades and on Type of Plasticizer
Unvulcanized ISO- 2475-1975 Compounds; Influence of Plasticizers
Measurements at - 10°C (CR-grade: Neoprene® W (~ Baypre® 210)
25
CR 100 phr
Stearic acid 0,5 phr 300
Magnesium oxide 0,5 phr
20 Phenyl-2-Naphthylamin 2,0 phr Neoprene® W + mineral oil
Carbon black (N 772) 30 phr 250
Zinc oxide (active) 5,0 phr
Vulkacit® NP 0,5 phr
15 200
t1/2 [h]
t1/2 [h]
10 150
100
5
Neoprene® W + Butyloleate
50
0
0
100 80 60 40 20 0
Baypren 110 VSC (slowly crystallizing) -20 -15 -10 -5 0 5 10 15 20
Temperature [°C]
0 20 40 60 80 100 Source:
Baypren 210 (normally crystallizing) R. M. Murray, J. D. Detenber Rubber Chem . Technol. 34 (1961)
668-685 “First and Second Order Transitions in Neoprene“
Dependence of Compression Set (CS) of Different CR-
Grades on Storage Temperature
100
CS (168 h / variable temperatures)
90
80 DCB-containing rubber grade (Baypren® 110)
DCB-free rubber grade (Baypren® 210)
70
CR Adhesive grade (Baypren® 320)
60
50
40
30
20
10
0
-60 -40 -20 0 20 40 60 80 100 120 140 160 180
Temperature [°C]
Bayer-Brouchure: „Chloropren-Kautschuk von Bayer: Der vielseitig einsetzbare Werkstoff“
Recipe Features which are specific for Different

CR-Rubber Grades
Cl
2 - Chloro - 1,3 - Butadiene CH2 CH CH2
• Standard CR-Grade
Cl Cl
2,3 - Dichloro - 1,3 - Butadiene CH2 CH2
S S
S S
• Sulfur Grade Sulfur
S S
S S
CH3 O O CH3
• Precrosslinked CR-Grade Dimethacrylate CH2 O CH2 O CH2
n
Molar Mass Control by Mercaptanes and by
Xanthogendisulfides
Molar mass control by mercaptanes
P* + HS - R P- H + R - S*
R - S* + nM R - S - M n*
R - S - Mn* + HS - R R - S - Mn - H + R - S*
Molar mass control by Xanthogendisulfides

P* + (RO - CS - S -)2 P - S - CS - OR + RO - CS - S*
RO - CS - S* + Mn RO - CS - S - Mn*
RO - CS - S - Mn* + (RO - CS - S -)2 RO - CS - S - Mn - S - CS - OR + RO - CS - S*
Molar mass control by Xanthogendisulfides results in the formation of polymer molecules with
two identical (xanthate) end groups. Xanthate end groups participate in vulcanization. As a
consequence, vulcanizates based on xanthate modified CR exhibit better mechanical properties
than mercaptane modified CR
CR: Influence of End Groups on Vulcanizate

Properties
ISO-Compound 2475
CR 100,0 phr
Carbon black N 762 30,0 phr CR-grade with xanthate end groups
Stearic Acid 0,5 phr
MgO 4,0 phr Mercaptan modified CR-grade
Phenyl-2-Naphthylamine 2,0 phr
ZnO active 5,0 phr
Vulkacit NPV/C 0,5 phr
16
Vulcanization: 40 min/150°C 22
15
21
14
M300 [MPa]
13 20
12
19
11
10 18
30 40 50 60 70 80 90 100 110 10 11 12 13 14 15
ML 1+4 (100°C) Modulus M300 [MPa]
Dynamic Resistance of CR-Standard Grades (Monsanto Test)
Xanthate modified CR-Grade (Baypren 121) unaged
7 days / 100°C
Mercaptane modfied CR-grade (Baypren 110 VSC) unaged
250
7 days / 100°C
ISO-Compound 2475
Cycles until failure [kcycles]
200 CR 100,0 phr

Carbon black N 762 30,0 phr
Stearic Acid 0,5 phr
MgO 4,0 phr
150 Phenyl-2-Naphthylamine 2,0 phr
ZnO active 5,0 phr
Vulkacit NPV/C 0,5 phr
100 Vulcanization: 40 min/150°C
50
0
52 54 56 58 60 62 64 66 68
Strain Amplitude[%]
Source: R. Musch presented at the 140th ACS Rubber Division Meeting, Detroit October 8-11, 1991
CR-Sulfur Grades
S Cl Cl S
NR2 C S ( CH2 C CH CH2 ) S (CH2 C CH CH2 ) x Sy C NR2
u v w
Application:
Vulcanizates which are based on CR sulfur grades perform particularly well in dynamic
applications. As a consequence, belts which meet the requirements of different applications are
a major application area (conveyor belts, V-belts, poly-v-belts, timing belts)
Production:
CR-Sulfur Grades are obtained by two consecutive production steps (1. Polymerization and 2.
Chemical break down of high molar masses)
In the 1st production step chloroprene and sulfur are copolymerized. The copolymers obtained
have a high molar mass and long sulfur bridges. In the 2nd production step, the molar mass of
the copolymers is reduced by a break down of sulfur bridges (peptization). As a consequence of
the chemical breakt down of the sulfur bridges dithiocarbamate end groups are incorporated.
These end group participate in vulcanization.. As a consequence, the number of dangling chain
ends is reduced and vulcanizate properties are improved.
Compounding and Vulcanization:
During compounding residual sulfur bridges are broken down "Mastication". Sulfur grades
can be vulcanized by the addition of ZnO and/or MgO (without the addition of accelerators).
Critical Aspects:
During storage, the Mooney viscosity of sulfur modified CR can increase or decrease. Heat
resistance of vulcanizates based on sulfur modified CR is inerior to that of standard CR.
Production of CR-Sulfur Grades
1) Copolymerization of Chloroprene and Sulfur
Cl
CH2 C CH CH2 + S8
2) Chemical break down of high molar masses by the use of disulfides,

particularly Thiuramdisulfides
Cl Cl
Sa ( CH2 CH CH2 )n Sv Sw ( CH2 CH CH2)x
S S
NR2 S S NR2
Cl S S
Sa ( CH2 CH CH2)n S v S NR2 NR2 S Sw ( CH2 CH CH2) x
Impact of the Amount of Incorporated Sulfur on Mastication

and Ageing Performance
50 80
Baypren 510
48
70
ML 1+4 (100°C) [ME]
Baypren 610
Change of M100 (7d/100°C) [%]
46
Incorporated Sulfur
60
44
42 50
40 40
38 30
36
20
34
10
32
30 0
0 2 4 6 8 10 0 0,2 0,4 0,6
Sulfur [phm]
Mastication time [min]
Compound Ingredients:
Mastication: CR 100 phr
Ruß (N 762) 75 phr
Mill size: 200 x 400 mm Polyetherthioether 10 phr
Friction: 1:1,2 Vulkanox DDA 2,0 phr
Revolutions: 20 min-1 Vulkanox 4010 NA 0,5 phr
Width: 1,2 mm Stearic acid 0,5 phr
Amount: 600 mg Magnesium oxide 4,0 phr
Zinc oxide 5,0 phr
Vulcanization of CR-Sulfur Grades
H H
CR-Sulfur grades (which are fully
commercially available) contain
dithiocarbamate end groups which are
H C attached via sulfur bridges. These end
S
groups are active in vulcaniaztion.
N N
CR-Sulfur grades can be considered as
S Sx
"rubber bound intermediates“ which are
S S known from theoretical considerations
H
H
on the mechanism of sulfur cure.
As a consequence, CR sulfur grades are
H
C
vulcanized by the use of ZnO and MgO
N
(+ Stearinsäure) without using
S N accelerators.
S
S
Sx CR sulfur grades exhibit a critical
S stability of Mooney viscosities during
storage particularly at elevated
N temperatures.
SH
S
Precrosslinked CR-Grades
Production:
Precrosslinked CR-rades are blends of CR-Gel
gelled CR and ungelled (soluble) CR. The
two blend components are produced
separately by emulsion polymerization.
Prior to finishing, the two latices are
blended. By the latex blending process a
good dispersion of the gelled CR paricles Ungelled
in the soluble CR phase is achieved. (soluble)
CR
Application:
Unvulcanized CR compounds which
contain CR gel exhibit good processing
features, particularly a low die swell. de
Die swell = x 100
do
Major application areas are extruded
articles (wiper blades as well as window
and door seals In these applications CR Rubber d0 de
is being substituted by EPDM and TPEs. Compound
Properties of Precrosslinked CR-Grades
20
50

46 18
Die Swell [%]
42 16
38
14
34
12
30
26 10
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Gel content [wt.% %]
Gel content [wt.% %]
CH2
Mechanism of CR-Vulcanization
according to Pariser/Du Pont CH Vulcanization of CR
CH2
S
Cl
Chemicals for CR-Vulcanization
Cl S
+
CH2 + NH NH S
CH CH2 CH2 NH NH
CH2
CH2 CH2 NH NH Ethylenethiourea
CH2
CH2 (ETU/Vulkacit(R) NPV)
CH
CH2CH2
CH
+ ZnO CH2
S
CH2
- ZnCl + O S "cyclic Dithiocarbamate"
Cl S
S N CH3 (Vulkacit(R) CRV)
NH NH
NH NH
CH2CH2
CH2 CH2
CH2 CH2
CH2
CH2
CH
End groups which participate in
CH CR-Vulcanization
O CH2
CH2
S
S
O S - NH NH Dithiocarbamate end groups are
CH2
present in sulfur modified CR
NH NH
CH2 CH2 S NR2
CH
CH2 CH2 Cl
+ ZnCl + CH2 Sx
CH2 + CH2
- ZnCl2 S
S
CH CH Xanthate end groups are present
CH2 in in xanthate modified CR
CH2 CH2 S O
CH
S
CH2 R
Substitution of CR
250
FKM MVQ
max. service temperature [°C]
225
FMVQ
200
FZ Resistance
80 % VAc to high temperatures
175 EVM
ACM AEM to high temperatures, flame resistance
Resistance
150 HNBR
CM (H)IIR EPDM
Resistance to dynamic stress CSM
125 NBR
Price
100
EU CR SBR BR
NR
75 AU
50
0 20 40 60 80 100 120 140 no
requirements
max. Volume Swell in ASTM-Öl Nr. 3 [Vol %]
Nitrile Rubber (NBR)
• Overview
– NBR-Microstructure
– Basic Features of NBR and Range of NBR Grades
– Application Areas of NBR and Market
– Producers and Production Capacities
– Range of NBR Grades
– Dependence of Properties on Acrylonitrile Content
• Polymerisation
– Emulsifiers
– Initiator systems
– Molar mass regulation
– Copolymerization
• Product groups and Properties
– Standard grades
– Carboxylated grades
– Precrosslinked grades
• Vulcanization and Vulcanizate Properties
NBR: Microstructure
N
C
C
N
4
2 CH
1 2
CH2 δ−
HC CH2 δ+ N
3 CH
3
CH CH C
HC 4
CH
C CH2 2 CH2
H2 CH2 CH
1 2
1
1,4-cis 1,4-trans Vinyl Acrylonitrile

Dependence of the Microstructure of Incorporated
Butadiene Moieties on Polymerization Temperature
Polymerization- Microstructure of Butadiene Sequences

temperature 1,4-cis 1,4-trans Vinyl
[°C] [%] [%] [%]
-20 0,8 79,6 19,6

5 7,7 71,5 20,8
50 14,8 62,0 23,2
100 27,6 51,4 21,0
Source:
The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
Basic Features of NBR

Standard
grades Fast curing / Low mould
fouling
(Injection moulding)
slow cure
peroxide cure
Special grades X-NBR
Precrosslinked NBR
Positive:
• Low degree of swelling in oil, fuels, greases and fats
NBR/PVC-Blends
•High kevel of mechanical properties
•High abrasion resistance especiall for carboxalated
NBR-powder grades
grades
• Broad range of grades
• Low gas permeability liquid NBR
-HO-terminated
• Low price level / high competition -COO-terminated
-NH2-terminated
Negative: NBR
mit bound antioxydant
• Maximal service temperature: < 110 °C
(Criterium: 1000 h / εb=0,5*εεb0)
• Standard grades are not applicable for outdoor use
(contrary to NBR/PVC-Blends)
NBR-Application Areas in Western Europe
Automotive Rubber Goods
35% (without
automotive)
34%
Rubber
Adhesives modification of
1% Thermoplastic
and
Others duroplastic
Cable and shoes
4% 5% building polymers
wiring
5% 11%
5%
300
NR
Volume swell [%]
250
200
150
100 SBR
50 CR
NBR
0
0 7 14 21
time in ASTM-ÖL3 [days]
NBR:Market- und Development

450
400
350
Consumption [j/y]
300
250
200
150
100
50
0
85
90
95
00
05
10
19
19
19
20
20
20
NBR: Production Capacities
(European Rubber Journal 181, no
no 4, April, S. 10 1999; updated in July 2010)
Zeon Tokuyama / JP 45 Nipol

Kawasaki /JP 20 Nipol
Louisville / USA Goodrich 35 Hycar
Houston / USA Goodyear 28 Chemigum
Barry/Wales / GB BP 15 Breon
(Baton Rouge / USA) (Copolymer) 15 (Nysin)
Lanxess La Wantzenau / FR Polysar 100 Perbunan / Krynac
Leverkusen / DE Bayer 35 Perbunan
Sarnia / CAN Polysar 25 Perbunan / Krynac
Triunfo / BRA Petroflex 30 Perbunan
JSR Yokkaichi / JP 35 JSR NBR
Polimeri Porto Torres / IT 30 Europrene
Paratec Altamira / Mexico Negromex/Uniroyal 25 Paratec
Korean Kumho Ulsan 20 Kumho NBR
Lucky Gold Hyundai 16
President Kaoshing / Taiwan 15
Eliokem Sandouville / FR Goodyear 11 Chemigum (Powder)
Valia /Gujarat - Indien Goodyear 25 Chemigum (bales)
Nitriflex Duque de Caxais / BRA 10 Nitriflex/Nitriclean
PASA Santa Fe 5
S&C Bareilly 2
Sibur Omsk
Total: 424
NBR-Standard Grades
50
Acrylonitrile content [wt. %]
45
40
35
30
25
20
15
20 30 40 50 60 70 80 90 100 125
Mooney Viscosity ML 1+ 4 (100°C)
without pretreatment (DIN 53523)
NBR: Dependence of Tg on Acrylonitrile Content
100 PAN
80
60
40
s
Tg [°C]
a de
20
l gr Gordon-Taylor-Equation*
ci a
+0 er TgCopolymer = w1*Tg1 + w2*Tg2
m
-20 Com
o f
e TgE-BR = - 80°C
-40 ang TgPAN = + 100°C
R
-60 *Gordon M., Taylor J. S., J. Appl. Sci., 21, 581 (1950)
-80 E-BR
-100
0 10 20 30 40 50 60 70 80 90 100
Acrylonitrile content [wt.%]
NBR: Dependence of Volume Swelling on

Acrylonitrile Content
90
Expt. Conditions:
80 14 days
70 Fuel B and C: 20°C
vvvvvWeight Change[%]
ASTM-Oils: 140°C
60
50
40
30
20 Fuel C (Isooctan/Toluene: 50/50)
Fuel B (Isooctan/Toluene: 70/30)
10
ASTM Öl Nr. 3 (aromatic/naphthenic)
0 ASTM Öl Nr. 1 (paraffinic)
-10
0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile content [wt.%]

Dependence of Shore A-Hardness and Rebound on
Acrylonitrile Content
90 50
75°C
80 40
20°C
Rebound [%]
Shore A Hardness
70 30
60 75°C 20
50 10 20°C
40 0
0 5 10 15 20 25 30 35 40 45 50 0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile content [wt.%] Acrylonitrile [wt.%]
Source: Rubber, 3 Synthetic Ullmann‘ s Encyclopedia of Technical Chemistry, Vol A 23 (1993)
Dependence of Compression Set on Acrylonitrile

Content
50
Compression Set (70 h/100°C) [%]
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile-content [wt.%]
Source: Rubber, 3 Synthetic Ullmann‘ s Encyclopedia of Technical Chemistry, Vol A 23 (1993)

NBR-Polymerization: Activation of Polymerization,
Molar Mass Regulation and Deactivation
Redox Initiation:
R-OOH + Fe2+ R-O* + OH- + Fe3+
Fe3+ + Reducing agent Fe2+ + oxydized Reducing agent
R-O* + Monomer R-O-Mon*
Growth reaction:
R-O-Mon* + n Monomer P*
Molar Mass Regulation by Mercaptanes:

P* + HS - R P- H + R - S*
R - S* + n Monomer R - S - Mn*
R - S - Mn* + HS - R R - S - Mn - H + R - S*
Transfer Reaction:
P* + R-H R - H + P*
Deactivation:
P* + P* P- P
Emulsifiers for NBR-Polymerization

Disproportionated Abietic Acid
CH3 CH3 CH3

CH3
Pd + +
H H H
H CH3 COOH CH3 COOH
CH3 COOH CH3 COOH
Abietic Acid Dehydro abietic acid Dihydro abietic acid Tetrahydro abietic acid
Partially hydrogenated tallow fatty acids
Producer Brand name C14 ges. C14 ges. C18 ges. C18 unges.
BAX AG IS/1 3,1 32,5 33,5 31
Holm THT 1618W 0,4 27,5 34,8 37,3 Methylen-Bis (Naphthalin-
Oleon Radiacid 40 3,5 35,1 24,8 36,6 sulfonsäure), Na-Salz
Unichema Prifac 5910 2,6 37,7 31,5 28,3
(Baykanol PQ(R))
Cognis Edenor C1618 1,2 40,3 26,4 32,1
-
SO3
Na
Sulfates- und Sulfonates (Examples) 2 Na +
CH2
Na-Laurylsulfate (Texapon)
Na-Alkylarylsufonate (Marlon) -
SO3
Na-Alkylsufonate (Mersolat) Na
Activatator Systems for NBR-Polymerization
“Organic“ Activation System
p-Menthylhydroperoxide (p-MHP) “Inorganic“
CH2 CH2 CH3 Activation System
CH3 CH CH O O H (NH4)2 S2O8
CH3 CH2 CH2 Ammoniumperoxodisulfate

Na-Formaldehydesulfoxylate
Na-Hydroxymethanesulfinate
H O CH2 OH
+ CH2
H O S O Na
N
H CH2 CH2
Ethylenedinitrilotetraacetic acid (EDTA)
O O CH2 CH2
HO OH
HO CH2 CH2 OH
N CH2 CH2 N
Triethanolamine
HO CH2 CH2 OH
O O
Ion-(II) sulfate Fe SO4
Copolymerization Diagram for the Copolymerisation of

Butadiene/ACN- (for incremental conversions)
100
Acrylonitrile content of polymer [wt. %]
Copolymerization Parameters
90 Ideal
Copolymerisation (ACN = M1; Butadiene = M2)
80 5°C: r1 = 0,02; r2 = 0,28
50°C: r1 = 0,04; r2 = 0,42
70
Azeotropic Azeotropic composition:
60 Composition
(calculated for 5°C)
50 Acrylonitrile: ca. 38+5 Gew.%
40 Butadiene: ca. 62+ 5 Gew.%
30
k11
20 r1 =
k12
10
k22
0 r2 =
k21
0 10 20 30 40 50 60 70 80 90 100
Acrylonitrile content of monomer feed [wt.%]
Source: W. Hofmann, Nitrilkautschuk, Berliner Union Verlag

NBR: Dependence of Integral Copolymer
Composition on Monomer Conversion
Modellierungsparameter
Acrylonitrile Content of Polymer [Gew. %] 100 (ACN = M1; Butadien = M2):
90 r1 = 0,02; r2 = 0,28
80 Acrylonitrile content
of monomer feed:
70
60 wt.%
60
50 wt.%
50
40 38 wt.%
33 wt.%
30 28 wt.%
20 20 wt.%
10 10 wt.%
5 wt.%
0
0 10 20 30 40 50 60 70 80 90 100
W. Hofmann, Nitrilkautschuk, Berliner Union Verlag
NBR: Dependence of Incremental and Integral

Acrylonitrile Content on Monomer Conversion
Acrylnitrilonitrile content of polymer [wt. %]
Incorporation of ACN during batch-polymerization

100 Incremental composition
90
80 Integral composition
70
Monomer Feed:
60 Acrylonitrile: 73,7 wt.%
50 Butadiene: 26,3 Gew.%
Copolymerizatin parameters:
40 r1 = 0,023; r2 = 0,30
30
For the production of a NBR-grade with
20 a high chemical homogenity one or both
of the two monomers (ACN respectively
10 butadiene) have to be incrementally added
during the course of the polymerization in
0 order to compensate for changes in the
0 10 20 30 40 50 60 70 80 90 100 composition of the monomer feed, unless
polymerization is performed in the azeo-
Monomer conversion [%] tropic monomer composition
NBR: Dependence of Tg on Polymerization Parameters
(Batch-Polymerization)
Sample Bound Polymerization ACN-addition Monomer Tg

ACN temperature during Conversion Lower Tg Upper Tg
polymerization
[wt.%] [°C] - [%] [°C] [°C]
A 38,9 5 - >57 -19
B 32,8 5 - >57 -22
C 25,8 5 - >57 -61 -33
D 44,8 50 - >57 -13
E 34 50 - >57 -26
F 29,2 50 - >57 -46 -32
G 28,5 50 - >57 -49 -33
H 23 50 - >57 -64 -40
I 21,1 50 + >57 -53
K 31,4 50 - 57 -31
Batchwise NBR-Polymerization may result in chemically

inhomogenous blends which exhibit two separate Tg-peaks
Source:
V. R. Landi (Uniroyal) Presented at a meeting of the Divison of Rubber Chemistry of the American Chemical Society, Cleveland, Ohio, October 12-15 (1971)
Rubber Chemistry and Technology
Influence of TDM-Quality on the Efficiency of

Molar Mass Regulation
160
140
Mooney Viscosity
120
ML1+4 (100°C)
100
TDM / Lanxess
80
TDM / Phillips Chevron
60
40
20
0
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
Amount of TDM [phm]
• For NBR-Production C12-Mercaptans are efficient molar mass modifiers

• Tert.-Dodecylmercaptane (TDM) is specifically important
• TDM by Chevron Phillips is based on propene-tetramers
• TDM by Lanxess is based on isobutene-trimers
Molar Mass Regulation by TDM Based on TIB
1. TIB- Production by Isobutene-Oligomerisation
Wagner- Meerwein-
+ 2 Rearrangement
H + +
+
- H+
+ +
"Triisobutene (TIB)"
2. TDM-Production by the Addition of H2S to TIB
H2S / Cat. SH
+
"Triisobutene (TIB)" 2,2',4,6,6'-Pentmethylheptanthiol-4

Patent No. Company Priority Patent Title
Jp 07 316 126 Zeon 27.12.1994 Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol
DE 102007024009 Lanxess 22.05.2007 TDM-Mischung: Herstellung und Anwendung
Reaction of Incorporated TDM-End Groups During

Vulcanization
3. Thermal Decomposition of TDM-End Groups
CH3
H3C C CH3
CH2 CH CH CH2 SH
CH2
Vulcanization +
CH2 CH CH CH2 S C CH3
CH3 CH3
CH2
H3C C CH2 C CH C CH3
H3C C CH3
CH3 CH3 CH3
CH3
TDM derived end groups result in:

• Acceleration of speed of cure
• Reduction of free (dangling) chain ends / Improvement of mechanical properties
• During vulcanization TIB is released which causes odour

EP 0692496 Zeon 30.03.1993 (Jp)
Unsatuarated Nitrile/Conjugated Diene copolymer,
EP 0779300 Zeon 29.08.1994 (Jp) process for Producing the same, and Rubber Composition
EP 0779301 Zeon 29.08.1994 (Jp)
Dependence of NBR-Properties on Content of
Metal Ions
cCa cMg cNa cK ppm

_
Ion-Number = 3 + +
40 24 23 39 Atomic weight
weight
Influence of Ions on Speed of Cure:

accelerating: Na-, K- Ions
retarding: Mg-, Ca- Ions

DE 102007024011 Lanxess 22.05.2007 Nitrile Rubber with Specific Ion Number
Dependence of NBR-Properties on Content of

Metal Ions
cCa cMg cNa cK ppm
_
Ion-Number = 3 + +
40 24 23 39 Atomic Weight
70
Mooneyscorch MS5 (120°C)
60
50
40
[min]
30
20
10
0
0,00 20,00 40,00 60,00 80,00 100,00 120,00
Ion-Number (IN)
Dependence of NBR-Properties on Metal Ion
Content
cCa cMg cNa cK ppm
_
Ion-Number = 3 + +
40 24 23 39 Atomic Weight
10
9
8
7
M300 [MPa]
6
5
4
3
2
1
0
-20 0 20 40 60 80 100 120
Ion-Number (IN)
NBR: Peroxyde Curable Grades

Rubber Crosslinking
efficiency
O O 2 O (R*) NBR 1,0
Avoidance of phenol-
C
2 O + + 2 R-H and amine based antioxydants
C (=radical scavengers)
C H
O
C
Number of x-links
X-linking efficiency = H H
O O
Peroxide-
Peroxide-functions
Type of Rubber Theoretical X-linking

efficiency H H
O O
M - Rubber 1 S
R - Rubber >1
Degradating rubbers <1
Vulcanization of NBR: Compound Study
Ingredients EV 1 EV 2 EV 3 Peroxide
NBR (18 wt.% ACN)* [phr] 100 100 100 100
Zinc oxide [phr] 5,0 5,0 5,0 -
Stearic acid 0,5 1,0 0,5 -
Vulkanox OCD - - 2,5 -
TMQ 1,0 1,5 - 1,0
Vulkanox MB-2 - 1,5 2,5 -
Carbon black (N 550) 50 30 80 40
Carbon black (N 772) - 50 - -
Dioctylphthalat (Vestinol/Hüls) 5,0 - - 5,0
Etherthioether (Vulkanol OT) - 6,0 20 -
Vulkalent E - 1,0 1,0 -
Sulfur (Rhenocure IS-60-50) 0,4 0,3 0,3 -
Vulkacit CZ 2,0 - 1,5 -
Vulkazit NZ - 1,5 - -
Vulkacit Thiuram 2,0 2,0 2,5 -
Perkadox BC 40 (Akzo) - - - 4,0
Vulcanization t [min]/T [°C] 25/160 16/160 25/160 12/180
* Perbunan NT 1845 (ACN; 18 Gew. %; ML 1+4 (100°C): 50 ME; MR: 14%)
Vulcanization of NBR: Results of Compound Study
Vulcanization System EV 1 EV 2 EV 3 Peroxide
ML1+4 (100°C) [ME] 78 87 67 77

ts [min] 3,2 1,8 3,4 0,6
t90 [min] 7,2 2,6 7,0 4,9
Shore A 71 72 71 70
TS [MPa] 16,9 19,5 15,8 18,3
εb [%] 310 365 310 260
M100 [MPa] 4,3 4,4 4,7 4,2
M300 [MPa] 16,3 17,3 15,4 13,0
CS (70h/100°C) [%] 12 20 16 -
CS (70h/120°C) [%] - - - -
CS (70h/125°C) [%] - 31 - 14
Brittleness Point [°C] -60 -62 -62 -

Tg [°C] -49 -53,5 -60 -
CS (24h/-20°C) [%] - 17 20 -
Carboxylated NBR (X-NBR)
N Carboxl-containing monomers:
C • Methacrylic acid
• Itaconic acid
C
• Maleic Acid
N COOH
Advantages:
• High tensile strength
• High moduli
• Good dynamic performance (cut growth resistance)
• High abrasion resistance
Disadvantages:
• Scorchiness of Compounds
• Cost of ZnO2 in relation to ZnO
• high Compression Set
• high heat-built-up bei dyn. Beanspruchung
• Reduced ageing resistance
Application
ApplicationAreas:
Areas:
••Spinning
SpinningCods
Codsund
undspinning
spinninghoses
hoses
•• high
highperformance
performanceshoe
shoesoles
soles
•• pump
pump stators / Pumpseals
stators / Pump seals
•• belts
belts
•• Hydraulic
Hydraulichoses
hoses
Chemistry of Vulcanization with Metal oxides

CH2
CH2
C
C CH3
CH3 CH3 _
OOC _ CH3
C _ _
CH2 COO COO 2+ OOC C
CH3 Zn +
2+ ZnO ZnOH
+ ZnO CH3 Zn_ CH2
ZnO 2+
8 CH2 C _ Zn _ CH3
- H2O C COO _
ZnOH
+ OOC
COO C
COOH __ CH3
CH2 H3C OOC
C C CH2
CH2
CH2
• Vulcanization with metal oxides is used for X-NBR and CSM.

• The following metal oxides are used: CaO, MgO, ZnO and ZnO2
• For scorch safety ZnO2 is superior over ZnO
• Usually, vulcanization with metal oxides is combined with sulfur cure
• Dual vulcanization results in a „hybride-network-structure“
• In a hybride network chemical as well as physical networks are present.
Sources: Eisenberg, A. Macromolecules, Vol 3, 2 (1974) 147 „Clustering of Ions in Organic Polymers - A Theoretical Approach“
Ibarra, L., Alzorriz, M. Polym. Int. 48: 580-586 (1999)
Naskar, N., Debnath, S. C., Basu, D. K.; J. Appl. Pol. Sc., Vol 80, 1725-1736 (2001)
Brown, H. P. Rubber Chemistry and Technol, 30 (1957) 1347 Crosslinking Reactions of Carboxylated Elastomers“
Compound- and Vulcanizate Properties of NBR and X-NBR
X-NBR 100,0 50,0 0
NBR 0 50,0 100,0
Fmin. [Nm] 9,0 10,2 8,0
X - NBR 100 50 0 Fmax. 86,3 78,7 60,0
NBR 0 50 100 ts [min] 3,0 2,7 2,8
CB (N 660) 40 40 40 t90 [min] 10,0 7,0 6,8
Dibutylphthalate 5 5 5 t95 [min] 21,5 11,0 8,3
2 2 2 Shore A 83 80 67
Stearic acid
M100 [MPa] 5,2 4,5 1,7
Wingstay 29 1 1 1
M200 [MPa] 11,0 10,0 4,8
Sulfur 0,5 0,5 0,5
M300 [MPa] 18,6 15,5 11,0
TMTD 2 2 2
TS [MPa] 25,5 21,0 18,2
MBS 1 1 1 εb [%] 430 415 500
Zinc oxide 5 5 5 Abrasion Index 493 159 73
Ageing at 70h/121°C
∆ elongation [%] - 42 - 35 - 30
CS [%] 34,1 27,1 14,7
Precrosslinked NBR
Properties:
Properties:
••Reduction
Reductionofofdie
dieswell
swell
••Increased
Increased dimensionstability
dimension stabilityafter
afterextrusion
extrusion
••Improvement
Improvement of surface quality of extruded/calenderedarticles
of surface quality of extruded/calendered articles
••Increase of Moduli
Increase of Moduli
••Improvement
ImprovementofofCS CS
••Reduction
ReductionofofTS
TS
••Reduction
Reductionofofelongation
elongationatatbreak
break
Precrosslinked NBR High Mooney NBR

Krynac 34.80
Precrosslinked NBR-grades provide for high dimensional stability after extrusion which is
only matched by standard NBR-grades with considerably increased Mooney viscosities
Precrosslinked NBR: Compound Study
NBR* (34 Gew.% ACN) Krynac VP KA 8769 phr 10 20 30 40
NBR (34 Gew.% ACN) Krynac 34.50 phr 90 80 70 60
Zincoxide Lanxess phr 3,0 3,0 3,0 3,0
Stearic acid Henkel KGaA phr 1,0 1,0 1,0 1,0
TMQ (Vulkanox HS) Lanxess phr 1,5 1,5 1,5 1,5
Zincmethylmercaptobenzimidazol Lanxess phr 1,5 1,5 1,5 1,5
Carbon black (Corax N 550) Degussa phr 30 30 30 30
Vulkanol 81 Lanxess phr 10 10 10 10
Sulfur Kali Chemie phr 0,3 0,3 0,3 0,3
TBBS (Vulkacit NZ) Lanxess phr 1,5 1,5 1,5 1,5
TMTD (Vulkacit Thiuram) Lanxess phr 1,5 1,5 1,5 1,5
* Precrosslinked NBR
Source: Bayer AG, Marinelli/Welle, KALIS-Nr.: 9588 vom 05. 10. 2000
Precrosslinked NBR: Results of Compound Study

NBR* (34 Gew.% ACN) 10 20 30 40
NBR (34 Gew.% ACN) 90 80 70 60
Compound-ML [ME] 42 44 47 51
Mooney-Relax. [%] 5,8 5,6 5,5 5,7
Die swell /linear [%] 42,9 31,7 31,2 16,8
Fmin. [dNm] 0,77 0,95 1,15 1,44
Fmax. [dNm] 10,63 11,31 12,1 13
ts1 [min] 1,85 1,77 1,68 1,64
t90 [min] 5,31 4,76 4,58 4,5
t95 [min] 6,61 5,84 5,57 5,48
Shore A/23°C 51 53 55 57
Shore A/70°C 49 50 52 54
M100 [MPa] 1,2 1,4 1,5 1,7
M200 [MPa] 2,4 2,9 3,2 3,6
M300 [MPa] 4,5 5,2 5,8 6,4
Rebound/23°C [%] 40 39 39 39
Rebound/70°C [%] 54 56 57 61
CS (70h/23°C) [%] 13 13 13 12
CS (70h/100°C) [%] 34 32 30 28
4. Overview on Solution Rubbers
• Features of the Solution Process
• Definition of “Solution Rubbers“
• Isolation of Rubbers from their Solutions
– Dry Finishing with Extruders
– Dry Finishing with Heated Mills (under vacuum)
– Solvent Removal by „Steam Striping“
– Expeller Screw for Mechanical Water Removal from Rubber
Advantages:
• Use of water sensitive catalyst systems (Z/N, anionic, cationic)
• evaporation cooling
• low cooling costs if semi- or total adiabatic processses are applied
Disadvantages:
• low content of solids
• high viscosities
• reactor fouling
• waste air
• waste water (depending on finishing technology)
• high drying costs for recycled solvents (depending on finishing technology)
Definition of Solution Rubbers and Examples

A “solution rubber” is prepared in the presence of an organic solvent
in which the rubber is either dissolved or dispersed.
Examples
Rubber Reaction Catalyst/Process
Medium
Z/N*
Solution-BR
Ti-BR solvent
High-cis-
1,4-BR
Ni-BR solvent Z/N*

Co-BR solvent Z/N*
Solution Rubbers
Nd-BR solvent Z/N*
Li-BR solvent anionic
L-SBR solvent anionic

EPM/EPDM solvent Z/N*
CM/CSM solvent polymer modif.

HNBR solvent polymer modif.
IIR solvent cationic

* Z/N = Ziegler-Natta Catalysis
Dry Finishing with Extruders (Under Vacuum)
Dry Finishing:
Recovery of rubbers from their solutions by direct evaporation
with extruders without the use of steam
Vent for Devolatilizing Srew press
US 4124306
(French Oil Mill Machinery)
Prior.: 30.11.1977
Inv.: D. K. Bredesen, G. C. Craig,
W. W. Gilius, C. R. Johnson
Dry Finishing with Hot Mills (Under Vacuum)

Dry Finishing:
Recovery of rubbers from their solutions by direct evaporation
under vacuum with „heated mills“without the use of steam
Source:
DE 4032598 (Bayer AG)
Prior.: 16.04.1992
Inv.: B. von der Linden, K. Goth
Solvent Removal by Steam Stripping
Isolation of CSM from Solution
Stripping
unit Dewatering
(expeller)
screw
Steam oil
Expander
Antioxydant screw US 2,592,814
Steam (Du Pont)
Prior.: 20.12.1947
PH- Waste water Inventor: J. L. Ludlow
Control
Stripping
aid
Process for Precipitating Polymers
US 5266211
Bunawerke Huels GmbH
Prior.: 13.06.19990
Inventor: W. Breuker,
H. Wagner, E. Moeller,
B. Schleimer
Expeller Screw for Mechanical Removal of

Water from Rubbers
After steam stripping a dispersion of rubber crumbs in water is Source:
otained. Before thermal drying water is removed mechanically US 2003007709 (Bayer AG)
Prior.: 05.07.2001
Inv.: N. Schweigler H.
Goebel, T.-O. Neuner
In order to obtain rubber crumbs a cutting device

is often attached at the end of a dewatering screw
Source:
US 3672641 (French Oil Mill Machinery)
Prior.: 14.09.1970
Inv.: R. K. Slaby
4.1. Overview on Polybutadiene Rubbers (BR):
CH2
CH
CH2 CH2 CH2
CH CH CH CH CH CH CH2 CH
CH2 CH2 CH2

1,4-cis 1,4-trans 1,2- bzw. Vinyl
• BR: Overview
– Property Profile and Areas of Application
– Microstructure, Glass Transition Temperature and Crystallization
– Producers and Production Capacities
– Market- und Market Development
• Application of BR for Tyres and for Impact Modification (HIPS/ABS)
– Comparison of BR grades in Tyre Performance
• Unvulcanized Compound Properties (Green Strength and Tac)
• Vulcanizate Performance (Dynamic Performance and Abrasion Resistance)
– Comparison of BR-Grades for the Impact Modification of Thermoplastics
(HIPS/ABS)
• Principle of Rubber Toughening
• BR Branching and Viscosity of Solutions
• Correlation of Mooney- and Solution Viscosities
• Performance Requirements for Tyres and Impact Modification
• Comparison of Production Technologies for High-cis-BR
• Summary
Property Profile and Areas of Application

Positive:
• Low price and good performance/price-ratio
• Broad range of BR-grades with different molar masses, oil extenison, Tgs etc.
• Brod spectrum of applications(tyres, modification of thermoplastics, TRP, golf balls)
• Dependence of strain induced crystallization on 1,4-cis content
• Low glass transition temperature
Negative:
• Poor resistance to heat and ageing
• High degreee of swelling in fuels, oils and greases
• high gas permeability
•Spontaneous crystallization
Application Areas
Technical Tyres
Rubber 71%
Products
5%
Rubber
Toughening
23% Golf ball cores
1%
BR: Microstuctures and Glass Transition
Temperatures 2
1
CH2 CH2 CH
1
1
4 3
CH2 CH2 CH CH
2
3
CH
CH CH
2 3 CH2
4
CH2 4
1,4-cis 1,4-trans 1,2- bzw. Vinyl

Catalyst Li* Co Ni Ti Nd E-BR**
Tg -93 -106 -107 -103 -109 -80
Microstructure (according to manufacturer‘s product specifications) [%]

1,4-cis 36-38 97 97 93 98 12,9
1,4-trans 52 1 2 3 1 68,3
Vinyl 10-11 2 1 3-4 <1 18,8
Microstructure (according to Thorn-Csanyi et al.) [%]

Vinyl/1H-NMR*** 10,4 1,9 4,0 <1 18,1
Vinyl/FT-IR*** 11,4 1,0 5,4 0,6 17,7
Vinyl/Metathese*** 10,7 1,7 4,6 0,7 17,8
* aliphatic, cycloaliphatic aromatic solvents without polar additives

** Polymer Handbook/Polymerisation temperature: 25°C
*** E. Thorn-Csanyi, H.-D. Luginsland, Rubber Chem. Technol. (1977) 222-230
Crystallization Rate of Unvulcanized and Vulcanized BR

(Nd catalyzed BR)
100
Raw Rubber
Vulcanizate
10
t 1/2 [min]
0,1
-100 -80 -60 -40 -20 0
Temperature [°C]
Source: U. Eisele Introduction to Polymer Physics, Springer-Verlag 1990

BR: Impact of 1,4-cis-Content on Crystalization Rate and
Melting Temperature of Crystallites
250 0
Melting temperature of crystallites

Nd Nd
Ni Ni
200 -5
Co
Co Ti
t 1/2 (-20°C) [min]
Ti
150 -10
[°C]
100 -15
50 -20
0 -25
90 92,5 95 97,5 100 90 92,5 95 97,5 100
1,4-cis-content [%] 1,4-cis-content [%]
BR: Producers and Production Capacities

500
450
400
350
300
Capacity [kt]
250
200
150
100
50
0
im
lin
rs
hi
R
c
r
ur
ho
nd
on
oo s
FS
be
C
ow
er
ea
pe
es
JS
sa
R
he
ch
ib
he
im
Ze
um
U
ila
S/
dy
TS
no
nx
ot
fte
ic
ha
ol
K
La
Si
M
ne
T
G
sk
am
ek
hn
iz
N
Source: IISRP Worldwide Rubber Statistics 2001 / Amendments 2011

Selected BR-Producers and BR-Grades
Polimeri, Ravenna, IT
Lanxess, Dormagen, DE
Chemizna Dwory, SA, Kralupy, CZ Li

Ube, Chiba, JP Ni
Nizhnekamskneftechim Ti
Michelin, Bassens, FR Co
Dow, Schkopau, DE Nd
Petroflex, Cabo, BR Li/Co/Nd
Lanxess, Port Jérôme, FR Ni/Nd
Korea Kumho, Yeochin, Yeosu
BS/FS, Lake Charles, La
Lanxess, Orange, Texas
Sinopec, GaoQiao, Caojing
ASRC (Michelin), Louisville, Ky
Goodyear Tyre&Rubber Co., Beaumont, Tx
0 50 100 150 200 250 300 350 400
Capacity [kt]
BR: Application Areas

Application Areas of BR
Technical
Rubber Tyres
Goods 71%
5%
HIPS/ABS
23% Golf balls
1%
Tyre Market (2.2 Mio t) HIPS/ABS-Market (0,68 Mio t)

not Ni-BR
assigned 38%
7%
Li-BR Li-BR
7% 48%
Nd-BR
8% Ti-BR
Co-BR 18% Co-BR
22% 52%
Anatomy of a Passenger Tire and Use of BR
Tread
SBR/BR: 70/30
Sub Tread
NR/BR: 80/20
Sidewall Carcass
NR/BR: 60/40 NR/BR: 90/10
Rim Cushion
NR/BR: 80/20
Apex
NR/BR: 80/20
Source:
Comparison of BR-Grades for the Application

in Tyres (ASTM-Compound 3189 – 90)
BR (Nd-, Co-, Ti-, Li-) 100,0 phr
Zinc oxide 3,0 phr
Sulfur 1,5 phr
Stearic acid 2,0 phr
Carbon black (NBS 378) 60,0 phr
TBBS 0,9 phr
Oil (ASTM Type 103) 15,0 phr
Vulcanization: 145°C/35 min
Source:
Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
ASTM Designation: D 3189 - 90 „Standard Test Methods for Rubber-Evaluation of Solution BR
Green Strength of BR-Compounds
3
Stress [MPa]
1
Li-BR Ti-BR Co-BR Nd-BR
0
0 250 500 750 1000
Strain [%]
Source:
Tack of Unvulcaniuzed BR-Compounds

350
Li-BR
time until separation [sec]
300
Ti-BR
250 Co-BR
Improvement
Nd-BR
200
150
100
50
0
100 1000 10000
critical load for separation [g]
Source:
„
Vulcanizate Properties of BR Grades
BR Grade Nd Co Ti Li
Vulcanizate properties
M300 [MPa] 9,4 8,6 8,1 8,0
Shore A-Hardness 65 63 64 66
Rebound [%] 49 47 45 47
DIN-Abrasion [mm3] 23 27 33 52
Pendulum -Skid
Asphalt, dry 85 85 85 89
Asphalt, wet 33 33 33 35
Dynamic properties
Goodrich-HBU [°C] 27 32 36 18
De-Mattia crack growth [mm/kc] 1,9 6,0 1,5 5,6
Monsonto-FTF/εε =100% [cycles] 460 50 115 63
Source:
“
1,4-cis BR: Dynamic Performance of BR-

Vulcanizates (Monsanto Fatigue to Failure Test)
Number of Kilocycles until Failure
40
35
30
Improvement
25
20
15
10
5
0
Ti Ni Co Nd
Source: D. J. Wilson „Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes“

Makromol. Chem., Macromol. Symp. 66, 273-288 (1993)
1,4-cis BR: Abrasion Resistance of BR-Vulcanizates
(DIN-Abrasion)
50
Ti-BR
45 Ni-BR
Improvement
Abrasion [mm3]
Co-BR
40
Nd-BR
35
30
25
20
0 5 10 15
Modulus at 300% elongation [MPa]
Source:
D. J. Wilson „Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes“ Makromol. Chem.,
Macromol. Symp. 66, 273-288 (1993)
Phase Morphology of Rubber Modified

Thermoplastics and Thermoset Resins
Rubber Modified Thermoplastics
Grafted Shell
Soft Hard Examples
„Compatibilizer“
Phase Phase
Hard Phase
(coherent phase BR SAN ABS
or matrix) BR PS HIPS
EPDM SAN AES
Soft (dispersed) EPM PP EPM/PP
Phase NBR PP NBR/PP
The impact resistance of hard and brittle thermoplastic

and duroplastic polymers is improved by rubber particles
Source:
Prerequisites for an efficient impact modification are: C. Schade, H.-J Renner, W. Heckmann
1) good dispersion of the rubber phase in the matrix (BASF)
2) good mechanical bonding across the phase boundaries „Predictive property Adjustment“
Kunststoffe international 7/2010, 36-39
3) x-linking of the rubber phase
Influence of Rubber Content on Notched Impact
Resistance of EPM/PP-Blends
Notched impact resistance [kJ/m2]
80 52 47 37 33
25
60
Rubber content
[wt.%]
40
20 ho
20
he
0 -20 0 20
-40
Temperature [°C]
Source:
H. Schwager (BASF); Kunststoffe 82, 499 (1992)
T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“
Impact of Branching on Solution Viscositiy

of Li-BR in Styrene
100000
10000
Viscosity [mPa*s]
1000
100
10 HX 565 Mooney: 65 Degree of Branching: 50-55

HX 501 Mooney: 40 Degree of Branching: ca. 18
HX 530 Mooney: 65 Degree of Branching: ca. 10
1
5 7 9
Solid Contents of BR solution [wt.%]

Source: Rubbers as Impact Modifiers for Plastics Bayer AG Rubber Business Group Order No.: KA 34271e
Correlation of Solution and Mooney Viscosities of
Different BR-Grades
260
Solution Viscosity (5,43 wt.% in toluene) [mPa*s] 240 Li-BR (commercial grades)
220 Co-BR (commercial grades)
200
180
160
140
120
100
80
60
ad y
es
gr htl
g
Star shaped BR
BR sli
40
ed nd
ch a
20
an ear
br in
0
L
0 10 20 30 40 50 60 70 80
Mooney-Viscosity (ML1+4/100°C) [MU]
Source: „Rubbers as Impact Modifiers for Plastics“ Bayer AG, Rubber Business Group, Order No.: KA 34271e
Performance Requirements for the

Application of BR in Tyres and HIPS/ABS
Property Performance Requirements
for tyres for HIPS/ABS
Tg as low as possible as low as possible
Vinyl content - > 1 Mol%
Gel content not crical <500 ppm
Solution viscosity - <21 mPas (5,2% / toluene)
colour - colourless
Tack yes -
Green strength yes -
Strain induced crystallization yes -
dynamic resistance yes -
Abrasion resistance yes -
The performance profiles for HIPS/ABS und for tyres

differ significantly
High-cis-BR Production Technologies
Transition Metal Co Ni Ti Nd
Solvent Benzene, Benzene Benzene Hexane
Toluene Toluene Toluene Aliphatics
(Aliphatics) Hexane
Residence time [min] 150 120 120 100-120
Conversion [%] 55-80 <85 <95 <100
Tendency towards high high low Very low

gel formation
Heat removal partially partially partially fully
adiabatic adiabatic adiabatic adiabatic
Solids Content 14-22 15-16 11-12 18-22
Molar Mass yes yes no no
Control agents
Formation of 4- high high Very low
VCH high
Transition metal [ppm] 10-50 50-100 200-250 100-200 Positive
content feature
Formation of 4-VCH by
a Diels-Alder-Reaction
Butadiene 4-Vinylcyclohexene (4-VCH)
Summary
From the different BR grades, Nd-BR is advantageous from two points of view:
• Tyre applications (particularly tyre treads)
• Production technology
For the impact modification of thermoplatics (HIPS and ABS)

• Li-BR and Co-BR are superior
• for Nd-BR a highly branched grade with a low solution viscosity is required
4.2. LiBR and S-SBR
With a Special Emphasis on Integral Rubber
• Selected Milestones in Rubber History
• Capacities of Multi-Purpose Solution Plants
• Origins of S-SBR Technology and Basic Features
• Chemical Aspects of the Anionic Polymerization and Consequences
– Reaction Mechanism and Catalyst Costs
– Vinyl-Content and Impact on Tg
– Branching and Impact on Processability
– Styrene/Butadiene-Copolymers, Preparation and Properties
– Integral Rubber
• Green Tyre Technology
• Recent Developments in S-SBR Technology Towards Improving Tyre Performance
–Functionalisation of S-SBR
Selected Milestones in Rubber History with a

Special Emphasis on Anionic Polymerization
1839 Charles Goodyear discovers the vulcanization by sulfur
1888 John Dunlop patents pneumatic tire
1910 Matthews, Strange (England), Harries (Germany) and Schlenk
(Germany) discover sodium as a catalyst for polymerization
1914-18 Start-up of Methyl-Rubber production in Germany
(2,3-dimethylbutadiene/Na-catalyst)
1926 Butadiene rubber developed in Germany (Buna)
1929 Ziegler discovers BuLi to be a polymerization catalyst
1929 First laboratory scale E-SBR by Tschunkur & Bock (Buna S)
1936 Ziegler describes the features of the anionic polymerization
1938 Invention of redox activation by Bock (“cold E-SBR“)
1939-45 BR-production in Russia (catalysts based on Na and K)
1952 Start-up of R&D into diene base rubbers/Li-metal by Firestone
1960ies Start- up of commercial productions using anionic initiators by
Firestone, Shell and by Phillips Petroleum
Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization,

Principles and Practical Consequences, Marcel Dekker Inc. New. York, Basel 1996
Capacities of Multi-Purpose Solution Plants*
(BR/S-SBR-SBS-TPE‘s)
Plant Location Capacity [kt] Remarks Origin of basic technology
Western Europe Firestone/Asahi
EniChem Ravenna 100.000 incl. TPE‘s Phillips-Petroleum
Grangemouth 80.000
Bayer Lillebonne 120.000 technology origin not assigned
Michelin Bassens 85.000
Repsol Qimica Santander 80.000 incl. TPE‘s
Fina Polymers Antwerp 80.000 incl. TPE‘s
Dow Schkopau 60.000
Americas
ASR Louisville, Ky 110.000
Bridgestone/Firestone Lake Charles 180.000
Orange 125.000 incl. TPE‘s
Bayer Orange 30.000
Goodyear Beaumont, Tx 360.000
Petroflex Cabo 35.000 incl. TPE‘s
Negromex Salamanca 30.000
Altamira 10.000
Japan
Asahi
Japan Elastomer Oita 48.000 incl. TPE‘s
Nippon Zeon Tokuyama 296.500 incl. E-SBR
JSR Yokkaichi 30.000 incl. Hydrogenated polymers
Others
Korean Kumho Yeochon 145.000
Taiwan Synthetic Kaohsiung 210.000 incl. TPE‘s
Dow (Carbochem) Newcastle 30.000
Total Capacity 2.274.500
* Source: IISRP Worldwide Rubber Statistics 2001
Origin of S-SBR-Technologies and Basic Features

Feature Technology
Firestone/Asahi Phillips
Initiator n-Bu-Li sec.-Bu-Li
Solvent n-hexane cyclohexane
Randomizer none glymes
branching agent/chain end coupling DVB DVB, SiCl4, SnCl4
short stop water stearic acid
process continuous discontinuous, batch
temperature control adiabatic isotherm
sequential monomer addition butadiene one shot
Vinyl content of BR-moieties ~ 10% > 20%
molar mass distribution of base polymer broader narrower
Until today, the technologies have merged and there are only
small differencies in the technologies of the leading companies
Basic Patents:
Firestone: US 3317918, CA 966949, US 3205211, FR 1546396, FR 1539429, FR 1539427, BE 718549,
US 3681304, OS 2134656, US 3558575, US 3726844, US 3726844, US 3787377
Phillips: US 3458490, US 3438952, US 3502746
Bridgestone: JP 75-015271
Mechanism of the Anionic Polymerization
Initiation:
+
CH2 +
R Li + R Li
Chain growth:
CH2 +
CH2 +
n R Li
Li +
R n
Transfer reactions: ideally none
Termination reactions: ideally none
• Under ideal polymerization conditions, there is neither chain transfer nor

termination reactions and the active species are truly living.
• All polymer chains are initiated at the start of the polymerization and all
chains grow up to total monomer consumption.
• The resulting polymer molecules have a narrow molar mass distribution
and a high chemical homogeinity
Features of a “Living Polymerization“

nMonomer DP: degree of po0lymerization
Mn: number average of molar mass
DP = X X: monomer conversion
nInitiator * f
Molar Mass (Mn) [g/mol]
nMonomer : amount of monomer [moles]

MWMonomer: molar mass of monomer
nMonomer * MWMonomer nInitiator : amount of initiator [moles]
Mn = X f: functionality of initiator
nInitiator * f u, v, w: amounts of initiator
Mn = m *X + C
nInitiator = u
C = 0
nInitiator = v
n Monomer * MGMonomer
m =
nInitiator * f nInitiator = w
u<v<w
0 0,5 1,0
Monomer Conversion X
Living Polymerization: Rational for Uniform Terminology T.r. Darling, T. P. Davis, M. Fryd, A. A. Gridnev, D. M.
Haddleton, S. D. Ittel, R. R. Matheson, jr., G. Moad, E. Rizzardo, Journal of Polym. Chemistry, Vol 38, 1706-1708 (2000)
Impact of Initiator Concentration on Molar
Masses and on Catalyst Costs
rubber]
25 Basis of calculation:
[[Pf/kg] • 65 DM/kg BuLi (4 DM/mol BuLi; MwBuLi: 61 g/mol)
• Ideally “Living Polymerization“
20
[Pf/kg
BuLi
15
Bu-Li
for for
10
Costs
5
Costs
0
0 50000 100000 150000 200000 250000 300000 350000 400000
Molar mass [g/mol]
Molar mass [g/mol]
Consequences from the living nature of the polymerization:
• Catalyst costs increase with decreasing molar masses.
• Star shaped polymers are obtained by the coupling of low molar mass
polymers. Therefore star shaped polymers are bound to be more expensive
than standard rubbers at the same molar mass.
Impact of the Gegenion and of the Solvent

on the Vinyl-Content
Gegen- Microstructure 1,4-insertion:
ion (Benzene) -
P
cis-1,4 trans-1,4 1,2-
[%] [%] [%] Li + Li +
P
-
Li 35 55 10
Na 10 25 65
K 15 40 45 1,2-insertion:
Cs 6 35 59
- -
P P
+ +
Solvent Microstructure Li
Li
cis-1,4 trans-1,4 1,2-
[%] [%] [%] X X
X X
Hexane 35 55 10
X X
Toluene 35 52 13 Ether with two coordination sites
THF 0 9 91
Sources:
R. Casper in Ullmann‘s Encyclopedia of Technical Chemistry
G. Sylvester u. P. Müller in Houben Weyl, Methoden der organischen Chemie,
Band E 20/Teil2, Makromolekulare Stoffe, S. 801
Dependence of the Vinyl-Content on Polymerization
Temperature and Modifier (Type and Concentration)
90
80
DME THF
30°C
Vinyl-Content [mol%]
70 30°C
60 DME THF
50°C 50°C
50
THF
DME 70°C
40
70°C
30 Modifier:
DME: Dimethoxyethane
20
THF: Tetrahydrofuran
10
0
0,1 1,0 10 100
Ether [mol/mol Li]
Source: Ullmann‘s Encyclopedia of Technical Chemistry
Impact of the Vinyl Content of Li-BR on Tg

+0 VI-BR
-10
-20
Range of commercial
-30 Vinyl-BR grades
-40
Tg [°C]
-50
-60
-70
-80
-90 Standard-Li-BR (without modifiers)
-100
0 10 20 30 40 50 60 70 80 90 100
Vinyl-Content [%]
S. L. Aggarwal, T. G. Hargis, R. A. Livigni, H. J. Fabris, L. F. Marker, „Advances in

Elastomers & Rubber Elasticity, J. Lal a. J. E. Mark, Eds., Plenum Press, New York, 1986, p. 17
Li-BR: Dependence of Wet Skid and Abrasion Resistance
on Vinyl Content
Vinyl-BR SBR
1712
Vinyl Content 10 47 64 66 88 18
1,4-cis 40 26 21 18 7 8
1,4-trans 50 27 15 16 5 74
Wet Skid Performance (Laboratory)

Portable Test Device* - 84 109 104 120 100
Retreaded Tyre
Concrete 70 95 92 93 - 100
Asphalt 70 90 92 93 - 100
Abrasion Resistance 140 100 80 100
* Road Research Laboratory Instrument, on wet Syenite-Glass Surface
Branching by the Copolymerization with

Divinylbenzene
Copolymerization with multifunctional monomers (DVB):
+ +
R CH2 Li R Li
n n CH
+
+
R CH2 Li R CH Li
n n
Branching by Chain End Coupling
Chain end coupling with SiCl4, SnCl4 etc.:
Coupling with SiCl4:
• Reduction of Cold-Flow
4 C +
• low viscosity of BR-solutions
Li
• Application for HIPS and Bulk-ABS
SiCl 4 • Highly filler loaded rubber compounds
(SnCl4 as alternative) with good processability and high Shore-
A Hardness (roll covers, tyre beads etc.)
Coupling with SnCl4:

exclusive úse is for tyres; during compound
preparation the Sn-C bonds seems to break
+ and the bound rubber content is increased.
Si + 4 Li Cl As a consequence hysteresis of vulcanizates
is reduced.
Many patents in this area, for example:
US 6271317 (Goodyear) Prior.: 19.01.1998,
Inv.: A. F. Halasa, S. Futamura, W. L. Hsu,
B. A. Matrana „Asymmetrical Tin-Coupled
Rubbery Polymers and Method of Making“
(Star shaped rubbers with at least 3
brances; 1 branch with MW <40.000 g/mol
and 1 branch with MW>80.000 g/mol)
Impact of Chain Branching on Processability

Cold Mooney- Com- Calan- Ex- Injection Spin-
flow measure- pression dering trusion moulding drawing
ment moul-
Improvement
ding
Improvement
Viscosity
Narrow molar
mass distribution
Broad molar mass
Highly branched
distribution
(Star shaped)
100 101 102 103 104 105 106

Shear rate [sec-1]
Source: U. Eisele, Introduction to Polymer Physics, Springer Verlag 1990
Li-BR: Influence of Branching on Cold Flow
14
Linear Chain
12
10
Cold Flow [mg/min]
8 Star shaped
polymer with
Divinylbenzene
6 3 branches
[phm]
4 0,03
2 0,06
0
0 20 40 60 80 100
Mooney-Viscosity ML 1+4 (100°C) [MU]
Linear BR has an extremely high cold flow which results in the instability of
rubber bales. BR has to be branched in order to improve the stability of bales.
Properties of Linear and Star Branched Li-BR
Li-BR linear star branched
Coupling agent without SiCl4
Mw [g/Mol] 256.000 310.000

Mn [g/Mol] 188.000 158.000
Mw/Mn 1,4 2,0
Cold flow [mg/min] 16 0
ML 1+4(100°C) 53 54
Compound-Mooney ML 1+4 (100°C) 98 80
Shore A Hardness 64 61
S300 [Mpa] 8,0 8,1
Tensile Strength [Mpa] 16,5 16,2
heat-build-up [°C] 32 40
Rebound [%] 77 71
Compound Preparation:
BR: 100 phr, Ruß (IRB Nr. 2): 50 phr, Zink oxide: 3 phr, Mineral oil : 10 phr, Stearic acid: 2 phr,
Sulfur: 1,75 phr, Accelerator: 0,8 phr; Vulcanization: 135 °C/35 min
S-SBR: Solution-SBR
L-SBR: Market and Market Development

Introduction of “Green Tyre Technology by Michelin“
700
600
Consumption [t]
500
400
300
200
100
0
1989 1991 1993 1995 1997 1999 2001
Source: IISRP; Evaluation by Bayer AG (Wachholz/BPO-IIS-BPSC-SP)

Copolymerization of Styrene and Butadiene at
Differential Monomer Conversions
100
Styrene content of polymer [wt. %]
90
Parameters of copolymerization
80 (styrene = M1; butadiene = M2)
70
Radical copolymerization
60 (emulsion)
50 E-SBR r1 = 0,7
r2 = 1,4
40
S-SBR Anionic colymerisation in
30 in hexane hexane
20 (Bu-Li/no randomizers/50°C)
10 r1 = 0,04
r2 = 11,8
0
0 10 20 30 40 50 60 70 80 90 100
Styrene-content of monomer feed [wt. %]
Copolymerization of Styrene and Butadiene
The anionic copolymerization of styrene and butadiene in an unpolar

solvent (hexane) yields a block copolymer with the following features:
• high chemical homogeinity
• narrow molar mass distribution
• tapered intermediate sequence
Course of the copolymerization in hexane (full batch process):

start up of the reaction
Butadiene block tapered sequence styrene block
For tyre applications block styrene blocks have to be

avoided as they cause high hysteresis losses.
Styrene/Butadiene-Copolymerisation
Differential styrene content in the polymer

100
90
80
70
60
[wt. %]
50 E-SBR
40
Ra ize
S-SBR
m
30 in Hexane
nd rs
o-
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Styrene content in the monomer feed [wt. %]
Impact of Randomizers on the Copolymerization

Behaviour of Styrene and Butadiene
(Styrene = M1; Butadiene = M2) Cyclohexane; 25/75 Styrene/Butadiene
70
T r1 r2 n-Butyl-Lithium
[°C] t-BuOK/n-Buli: 0,067/1
Total Styrene Content of Polymer
60
t-BuOK/n-Buli: 0,38/1
Benzene 25 0,04 10,8
Cyclohexane 25 0,04 15,5 50
Hexane 25 0,03 12,5
40
[wt.%]
THF 25 4,0 0,3

Diethylether 25 0,4 1,7 30
Triethylamine 25 0,5 3,5
Anisol 25 0,3 3,4 20
Diphenylether 25 0,1 2,8
10
THF -78 11,0 0,04
THF 0 5,3 0,2
0
THF 25 4,0 0,3 0 20 40 60 80 100
Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization, Principles and Practical Applications, Marcel Dekker, Inc.
Y. Melenevskaya, V. Zgonnik, V. Denisov, E. Dolinskaya, K. Kalnish; Polym. Sci. (USSR), 21, 2215 (1979)
Tg of S-SBR: The Impact of Styrene and Vinyl
Content
40
+10°C
Standard Emulsion Technology

Styrene Content [wt. %]
Solution technology without

+ 0°C
30
- 10°C
randomizers
Solution technology with
- 20°C
20 randomizers
- 30°C
10 - 40°C
- 70°C - 60°C - 50°C

0
0 10 20 30 40 50 60
Vinyl [%]
In the variation of the microstructure (vinyl-content) the S-SBR
technology has a greater versatility than the E-SBR-technology.
Source: H. Mouri, J. E. Hall, (Firestone) 146th ACS meetin in Pittsburgh, PA., USA
Impact of Tg on Important Tyre Tread Properties

-20 S-SBR (25% Styrene, 55% Vinyl)
E-SBR 1516 (40% Styrene)
-40 S-SBR (34% Styrene, 32% Vinyl)
Tg [°C]
E-SBR 1500 (23.5% Styrene)

-60 E-SBR (15% Styrene)
S-SBR (18% Styrene, 10% Vinyl)
-80 Emulsion BR
Li-BR
-100 high cis Nd-BR
Decrease of Rolling Resistance
and Abrasion
Increase of Heat Build Up
and Wet Skid Resistance
In order to comply with many conflicting tyre tread properties the

preparation of rubber blends is essential in rubber technology. An
alternative to macroscopic blending would be microscopic blending
as with integral rubber.
The „Integral Rubber“ Concept
Li- NR SBR SBR
BR 1500 1700
1
10-1
tan δ
10-2
Integral-
rubber
10-3
-100 -80 -60 -40 -20 0 20 40 60 80 100

Temperature [°C]
Integral Rubber is a multi block copolymer the building blocks of

which have well defined Tgs
Source: K. H. Nordsiek, K. M. Kiepert, Kautschuk Gummi Kunststoffe 38 (1985), p. 178-185
Routes for the Preparation of Integral Rubbers

Integral-Rubber 1 based on butadiene, styrene and isoprene
(full batch process without the sequential addition of either monomer or modifier)
Segment: Vinyl-BR S-SBR 3,4-IR

Tg [°C] -90°C -20°C ~ 0°C
Integral-Rubber 2 based on butadiene, styrene and isoprene

(batch process with sequential monomer- and modifier addition)
butadiene randomizer styrene isoprene
Segment: Medium-cis BR Vinyl-BR S-SBR 3,4-IR

Tg [°C] -90°C -50°C -20°C ~ 0°C
Performance Comparison of Standard S-SBR with
E-SBR in a Carbon Black Compound
E-SBR S-SBR
Processability
Black incorporation time + -
Tack + -
Green Strength + -
Vulcanization
t10 + - In a carbon black loaded compound
t90 - + there is no real advantage for S-SBR.
t90 - t10 0 +
Mechanical Properties Therefore there was no major break-
break-
Moduli + - through for S-SBR until the green tyre
Tensile Strength + - technology emerged.
emerged.
Tear resistance + -
Abrasion resistance + -
Heat build up - +
Rolling resistance - +
Wet grip + +
Price +* -
* fully depreciated plants
Green Tyre Technology

Et-O CH2
Et-O Si CH2 CH2 S
Si OH Et-O S
SiO2
Si OH Et-O S
Et-O Si CH2 CH2 S
Et-O CH2
Performance of the green tyre Additional costs for the green tyre
Rolling Resistance Ruß Silica
Compound Compound
150
Rubber E-SBR L-SBR
Carbon black - NR
loaded tread 100 Filler
- BR
Green tyre Ruß Silika
Silane - Si 69
50 Additive - DPG
Raw Materials ++ --
Mixing Costs ++ --
0
Patents:
DE 2447614; Degussa, Prior.: 05.10.1974; Erf.: K. Burmester, S. Wolf,
E. Klötzer, F. Thurn
US 4,709,065; Shin-Etsu; Prior.: 20.09.1985; Erf.: H. Yoshioka et al.
EP 299074; Bridgestone; Prior.: 03.10.1987; Erf.: T. Hamada et al.
Abrasion Wet DE 3813678; Bridgestone; Prior.: 23.04.1987; Erf.: M. Takeshita et al.
Resistance Skid EP 501 227; Michelin, Prior.: 25. 02. 1991; Erf.: R. Rauline
EP 447066; Bridgestone; Prior.: 27.02.1991; Erf.: T. Hamada
Recent Developments in S-SBR Technology
Towards Improving Tyre Performance
Functionalisation of S-
S-SBR
• Partial or total substitution of activator
• Improvement of silica dispersion
• Iprovement of silica reinforcement
• Reduction of hysteresis loss
• Improvement of wet skid
• Reduction of abrasion loss
Functionalization of Living Chain Ends

OR
R1 N Si OR
+ C CH2 OR
R C Li +
91
n
R2
+
Li
OR
N Si OR
R n C 80
CH2 OR
R1 R2
EP 1113024 A1; Prior.: 02.12.1999, Bridgestone, Inv.: K. Morita, H. Kondo "Polymer

process for making the polymer and rubber composition using the polymer“
Functionalization with Polyether Segments
O
+
2 R CH2 Li + Cl Cl
n n
+
- 2 Li Cl
O
R n nR
n
DE 10057508; Bayer AG, Prior.: 21.11.2000; Erf.: T. Scholl, W. Obrecht, Braubach,

E. Giebeler, Grün, A. Müller, M. Graf
„Polyether/Diolefin-Kautschuke enthaltende Kautschukmischung“
Incorporation of Aminoisoprene
CH3 CH3
N
CH2
CH2 C
CH CH2
Dimethyl-Aminoisoprene
• is incorporated initially at the chain end
• it acts as a randomizer during the whole course of the polymerization
• the aminoisoprene containing rubber exhibits increased interaction with silica
EP 01165641; Bayer AG, Prior.: 03.02.1999; Erf.: T. Scholl, W. Obrecht, R. Stadler,

R. Morschhäuser, G. Mannebach "Kautschukmischungen basierend auf Aminoisopren"
Functionalization of the Living Chain End
with a Polysiloxane Building Block
H3C CH3
Si
O O
R CH2
+
Li + H3C CH3
Si Si
n O
H3C CH3
D3
CH3 CH3 CH3 CH CH3 CH3

3
Si Si Si
+
R O O O Li
n
Source: EP 0778 311; Michelin, Prior.: 07.11.1995; Erf.: J.-L. Cabioch „Composition de caoutchouc
à base de silice et de polymère diénique fonctionnalisé ayant une fonction silanol terminale“
Modification of S-SBR with Hydroxyl-Moieties
H
X
S
X SH
X: - OH (US 6252008)
X: - COOH (US 6365668)
Sources:
US 6252008; Bayer AG; Prior.: 18.07.1998; Inv.: T. Scholl, U. Eisele, J. Trimbach, S. Kelbch
WO 02/31028 A1; Bayer AG; Prior.: 10. 10. 2000; Inv.: Th. Scholl, J. Trimbach, W. Nentwig, R. Engehausen
US 6365668; Bayer AG; Prior.: 16.11.1998; Inv.: Th. Scholl, J. Trimbach
4.3. Chemistry and Production Technology of High-
cis-1,4 BR with an Emphasis on Nd-BR
• Technically Relevant Catalyst Systems for the Production of High cis-1,4 BR

– Influence of Halides on 1,4-cis Content
– Role of Halides and Electron Donors on Microstructure
– Trans-1,4 BR: Dependence of Melting Temperature on 1,4-cis-Content
– Reaction Scheme of Butadiene Insertion
• Mechanism of Nd-Catalyzed Butadiene Polymerization

– Activity of Rare Earth Naphthenates (Cocatalyst: RnAlCl3-n)
– Influence of Solvents
– Influence of Molar Neodymium/Chloride-Ratio on 1,4-cis Content
– Reaction Scheme of Butadiene Polymerization by Nd-Catalysis
– Mechanism of Nd-Catalyzed Butadiene Polymerization
• Technical Options for the Control of Molar Mass in Nd-BR-Production
Technically Relevant Catalyst Systems for the

Production of High cis-BR
BR Catalyst System Molar cis-1,4

Ratios Content
Li-BR nBu-Li 36 - 38
Co-BR Co(II)Octanoate / DEAC / H20 1 / 7 0-80 / 20-30 97
Ni-BR Ni(II)Naphthenate /Bu2O.HF/TIBA 1 / 100 / 40 97
Ti-BR TiJ3(OEt) / TiCl4 / TEA 1 / 0,7 / 5 93
Nd-BR Nd(III)Versatate / DIBAH / EASC 1 / 10-15 / 3 98
Abbreviations:
nBu-Li n-Butyl-Lithium
DEAC Diethyl Aluminum Chloride
TIBA Triisobutyl Aluminum
TEA Triethyl Aluminum
DIBAH Diisobutyl Aluminum Chloride
EASC Ethylaluminum Sesquichloride
Influence of Halides on 1,4-cis-Content
98
cis-1,4-Content [%]
Metal Component of
97
Halide Catalyst System
96
Ti Co Ni Nd
95
F 35 93 98 95,7
Cl 75 98 85 96,2 94
Br 87 91 80 96,8 93
J 93 50 10 96,7 92
0 1 2 3 4
Molar Cl/Nd - Ratio
Source: Sources:
Zhinquan Shen, Jun Ouyang, Fasong Wang, •Lars Friebe: Diploma Thesis TU Munich 2000
Zehnya Hu, Fusheng Yu, Baogong Qian; •L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;
J. Pol. Sci., Chem. Ed. 18 (1980) 3345-3357 Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Role of Halides and Electron Donors on Microstructure
Nd(OR)3 + TIBA trans -1,4-BR For the achievement of

Nd(OR)3 + DIBAC cis -1,4-BR high 1,4-cis contents the
Nd(COOR)3 + TIBA trans -1,4-BR presence of a halide
Nd(COOR)3 + DIBAC cis -1,4-BR source is essential
Nd(COOR)3 + Mg (Allyl)2 trans -1,4-BR Source:

Shiro Kobayashi; Transition in
Nd(COOR)3 + Mg (Allyl)2 + R-Cl cis -1,4-BR
Precision Polymerization (1997)
Nd(CH2Ph)3 + TIBA trans -1,4-BR Part 1. H. Watanabe, T. Masuda,
Diene Polymerization, pages 55-66
Nd(CH2Ph)Cl2 + TIBA cis -1,4-BR
Co(Oct)2 + AlR2Cl + H2O cis - 1,4-BR The coordination of electron

Co(Oct)2 + AlR2Cl + H2O + PPh3 s - 1,2 - BR donors to vacant catalyst
Co(Oct)2 + AlR3 + CS2 s - 1,2 - BR sites results in a significant
reduction of 1,4-cis contents.
As a consequence, syndiotactic
Ni(Oct)2 + BF3 - OEt2 + AlR3 cis - 1,4 - BR BR or trans-1,4 BR are
Ni(Oct)2 + BF3 - OEt2 + AlR3 + PPh3 trans - 1,4 - BR obtained.
Trans 1,4-BR: Dependence of Melting Temperature
on 1,4-trans Content
160
120
Data from:
US 5134199 Enoxy Chem Ltd.
80
GB 2161169 (Asahi)
Tm [°C]
US 4931376 (Asahi)
US 5596053 (Bridgestone/Firestone)*
40
Goodyear
+0
- 40
60 70 80 90 100
1,4 - trans-content [Mol %]
*US 5596053 (Bridgestone/Firestone) Prior. 31. 05. 1995; Erf.: J. W. Kang; J. T. Poulton
"High Trans-1,4-BR and Catalyst and Process for Preparing Crystalline High Trans-1,4-BR“
US-A-5089574 (trans-1,4-BR-Herstellung/Goodyear)
EP-A-1092565 Prior.: 11.10.99 D. J. Zanzig, P. H. Sandstrom, J. J. Verthe, E. J. Blok, G. M. Holtzapple
„Tire with silica-reinforced tread comprised of trans-1,4-BR, solution-SBR, polyisoprene and defined amount
of carbon black and amorphous silica“
Reaction Scheme of Butadiene Insertion

Allyl-Komplex
Bd
Bd
M M M
M
8
C
15
C
C
29
C
22
`
Bd
Bd M
M M M
54 60
36
C 43
C C C
For the achievement of high 1,4-cis contents, a vacant coordination site

on the transition metal is a prerequisite. To this site butadiene has to be
coordinated in a cisoid mode.
The formation of trans-1,4-BR is thermodynamically favourable
whereas the formation of 1,4-cis-BR ist kinetically controlled.
Source: Porri, Giarrusso, J. Polymer Science, Vol. 4, 93

Mechanism of Neodymium Catalyzed Butadiene
Polymerization
Activity of Rare Earth Napthenates (Cocatalyst: RnAlCl3-n)
100 Only rare earth metals in the oxydation state

90 +III show polymerization activity
80 Al-alkyls reduce Pm, Sm and Eu salts to the

oxydation stage +II
70
U m satz [% ]
60
50
40
30
20
10
0
La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Source:
Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian
J. Pol. Sci., Chem. Ed. 18 (1980)3345-3357

Polymerization: Influence of Solvents
Contrary to other Ziegler–Catalysts,

aromatic solvents have a negative im-
pact on Nd-based catalyst systems
Source: F. Cabassi,G. Ricci, L. Porri; Transition Metal Catal. Polym. (Proc. Int. Symp. 1988, 2nd vol. 655-670)
„Neodymium Catalysts For 1,3-Diene Polymerization. Some Observations On their Activity And Steoreospecificity“
Polymerization
O R1
Et Cl Cl
Nd O R2 H Al Al Al
Et Cl Et
R3
3
NdV DIBAH EASC
1 10 - 15 3
Literature:
http://dx.doi.org/10.1007/12_094
1) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner; Adv. Polym. Sci. (2006) 204, 1-154 (Review);
Neodymium-Based Ziegler/Natta Catalysts and their Application in Diene Polymerization

2) Friebe, Lars; Mueller, Julia; Nuyken, Oskar; Obrecht, Werner; Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (2006), 43(6), 841-854.
Comparison of the solvents n-hexane, tert-butyl benzene and toluene in the polymerization of 1,3-butadiene with the Ziegler catalyst system
neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride.
3) Friebe, Lars; Mueller, Julia M.; Nuyken, Oskar; Obrecht, Werner. Pure and Applied Chemistry (2006), 43(1), 11-22.
Molar mass control by diethyl zinc in the polymerization of butadiene initiated by the ternary catalyst system
neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride. Journal of Macromolecular Science, Part A:
4) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner. Macromolecular Science, Part A: Pure and Applied Chemistry (2005), A42(7), 839-851.
A Comparison of Neodymium Versatate, Neodymium Neopentanolate and Neodymium Bis(2-ethylhexyl)phosphate
in Ternary Ziegler Type Catalyst Systems With Regard to their Impact on the Polymerization of 1,3-Butadiene.
5) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2004), 45(1), 758-759.
Novel investigations and applications for neodymium based catalysts.
6) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Abstracts of Papers, 227th ACS National Meeting, Anaheim, CA, United States, March 28-April 1, 2004 (2004)
Novel investigations and applications for neodymium based catalysts.
7) Friebe, Lars; Windisch, Heike; Nuyken, Oskar; Obrecht, Werner. Journal of Macromolecular Science, Pure and Applied Chemistry (2004), A41(3), 245-256.
Polymerization of 1,3-Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/Ethylaluminum Sesquichloride: Impact of the Alkylaluminum Cocatalyst Component.
8) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Materials and Engineering (2003), 288(6), 484-494.
In situ preparation of a compatibilized poly(cis-1,4-butadiene)/poly(e -caprolactone) blend.
9) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Chemistry and Physics (2002), 203(8), 1055-1064.
Polymerization of 1,3-butadiene initiated by neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride: kinetics and conclusions about the reaction mechanism.
Reaction Scheme of Butadiene Polymerization

by Nd-Catalysis
1) Formation of Nd-Alcoholate by the Reduction od Nd-Versatate
Nd ( OOC - R )3 + 6 H Al Nd (O-CH2- R )3 + 3 Al O Al
O Al
Nd ( OOC - R )3 + 3 H Al Nd (O-CHR- R )3 + 1 Al O
O Al
2) Formation of a Nd-Hydrodo Compound (Precursor of Active Nd-Species)
(R-CH2-O)3 Nd + H Al (R-CH2-O)2 Nd - H + RCH2 O Al
H
Nd (O-CH2- R )3 + H Al (R-CH2-O)2 Nd + R-CH2-O Al
CH3
CH2 C CH3 CH3
(R-CH2-O)2 Nd (R-CH2-O)2 Nd - H + H2C
H CH3
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
by Nd-Catalysis
3) Hydride transfer and Formation of a Nd-Allyl Compound

CH3
AlR 3
(R-CH2 - O)2 Nd - H + (R-CH2 - O)2 Nd
4) Halogenation of the Nd-Allyl Compound

CH3 CH3
(R-CH2 - O)2 Nd Al2Et3Cl3

Cl2 Nd
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

by Nd-Catalysis
5) Formation of polymerization active Nd species (cationic Nd allyl complex)
and first butadiene insertion
AlR3 -
ClAlR3
Cl Cl +
AlR3 Nd
Nd Nd Cl
Cl Cl AlR3
AlR3 R
R R
- - ClAlR3
-
ClAlR3 ClAlR3
+ +
+ Nd Nd
Nd Cl Cl
Cl AlR3 AlR3
R
AlR3
R
R
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
by Nd-Catalysis
6) Control of Molar Mass by Al-Alkyls and by Al-Hydrido Compounds
Nd L + H Al H Nd L + R Al
L L
R
Nd L + Al Nd L + R Al
L L
R
Active “living“ inactive “dormant“

polymer chain polymer chain
(attached to Nd) (attached to Al)
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht, Journal of Macromol. Sci.
Mechanism of Nd-Catalyzed Butadiene Polymerization

Solvent n-Hexane Addition Sequence:
Butadiene 1,85 mol/l 1. Hexane
Experimental NdV 0,20 mmol/l 2. Butadiene
Conditions: 3. DIBAH
EASC 0,13 mmol/l (nCl/nNd = 2/1)
4. Neodymversatate
2,0; 4,0; 6,0; 10,0 mmol/l
DIBAH 5. EASC
nDIBAH/nNd = 10, 20, 30, 50 Polymerization temperature: 60°C
Conversion/time-plots Plot for 1st order monomer consumption
100
0
80
-1
60 -2
ln(1-x)
40 -3
nDIBAH/nNd = 10 nDIBAH/nNd = 10
20 nDIBAH/nNd = 30 -4 nDIBAH/nNd = 30
0 -5
0 50 100 150 200 250 0 50 100 150 200 250 300
time [min] Time [min]
Sources:
Lars Friebe: Diplomarbeit and der TU München, Dezember 2.000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Dependence of Molar Mass Dependence of PDI (Mw/Mn)
Distribution on Monomer on Monomer Conversion
Conversion
c o n v e r s io n / %
nDIBAH/nNd = 10
8 2 .5
nDIBAH/nNd = 20
4,0 nDIBAH/nNd = 30
index Indices
6 6 .4
nDIBAH/nNd = 50
5 5 .1 3,5
Refractive
5 0 .0
3,0
Mw/Mn
inof refraction
4 3 .5
2,5
3 5 .6
difference
2,0
Difference
3 0 .7
2 2 .7 1,5
1 2 .2
1,0
7 .8 0 10 20 30 40 50 60 70 80 90 100
4 .8
30 35 40 45 50 55 60 65
30 35 40 45 50 55 60 65
e lu t io n t im e / m in
Elution time[min]
Source:
L. Friebe: Diploma Thesis at TU Munich, December 2.000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Dependence of Mn on Molar Mass Control

Monomer Conversion with Al-Component
2,5*105
Chains formed per Nd-Atom
16
Formal Number of Polymer
nDIBAH/nNd = 20 14 nDIBAH/nNd = 20
2,0*105 nDIBAH/nNd = 30
12 nDIBAH/nNd = 30
Mn [g . mol-1]
1,5*105 10
8
1,0*105
6
4
0,5*105
2
0 0
0 10 20 30 40 50 60 70 80 90 100
0 10 20 30 40 50
Monomer Conversion [%] nDIBAH/nNd
nDIBAH/nNd = 4,4
Source:
L. Friebe: Diploma Thesis at TU Munich, December 2000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Technical Options for the Control of Molar Mass in
Nd-BR Production
Influence of Polymerization Temperature
G. Sylvester, B. Stollfuss ACS, Rubber Div. Dallas 1988 „Synthesis of
Contrary to Catalysts based on Co, cis-1,4-Polybutadienes by rare earth catalysts“
Ni and Ti, for Nd-based catalysts 2500
there is no agents for the control of
Molar Mass (Mv)

2000
molar mass available.
[kg/mol]
Therefore in Nd-BR technology 1500
molar mass has to be controlled by:
• Nd/Al-ratio 1000
• Monomer/Nd-ratio
500
• Monomer Conversion
• Polymerization temperature 0
0 10 20 30 40 50 60 70 80 90
Influence of Butadiene/Nd-ratio Influence of Monomer Conversion

D. J. Wilson, Polymer 1993, 34,16, 3504-3508 M. Bruzzone ACS Symposium Series No. 3 (1982)
900 60 33-55
800
Molar Mass (Mv)
ML 1+4 (100°C)
50
700
[kg/mol]
600 40
500
30
400
300 20
200
10
100
0 0
0 0,05 0,1 0,15 0,2 0,25 0,3 0 20 40 60 80 100
Nd (mmol/100 wt.-parts of butadiene] Monomer Conversion [%]
Comparison of Technologies for the Production of

High cis-1,4-BR
Co Ni Ti Nd
Solvents Benzene Benzene Benzene N-Hexane
Cylcohexane
Toluene Hexane Toluene
Aliphates Toluene
Residence time 150 min 120 min 120 min 100-120 min
Monomer 55-80 % < 85% < 95% < 100%
conversion
Gel formation high high low Very low
process Partially adiabatic Partially Partially fully
/isothermal adiabatic adiabatic adiabatic
Max. solids concentation 14-22% 15-16% 11-12% 18-22%
Molar mass regulator yes yes none none
Formation of VCH high high very high low
Residual transition metal 10-50 50-100 200-250 100-200
Content [ppm]
Advantage * Formation of VCH by

Diels-Alder-Reaction
Butadiene Vinylcyclohexene (VCH)
4.4. Ethene/Propene-Co- and Terpolymers (EPM/EPDM)
• Overview
– EPM and EPDM, Termonomers, Market, Range of Grades and
Property Profiles
• EPDM-Production
– Chemistry of Polymerization , Producers, Capacities, Brand
Names and Production Technologies
• Production Technologies (Flow Charts)
– Solution Process
– High Temperature Solution Process
– Gase Phase Process
– Comparison of Manufacturing Technologies
• Metallocenes
– Ovewrview on Metallocene Patents
– Metallocene Activation
– Comparison of Catalyst Costs
Ethene/Propene-Co- und Terpolymers

(EPM/EPDM)
Method of
Vulcanization
EPM
Peroxides
EPDM Sulfur
Peroxides
Phenol resins
etc.
EPM (15%) EPDM (85%)

Ethene/Propene-Copolymers Ethene/Propene/Diene-Terpolymers
(30% of grades are oil extended)
Major areas of application: Major areas of application:

• Oil additives
• Impact modification of thermoplastic • Technical rubber goods
polymers (PP) • Cables and wires
• TPEs
EPDM-Termonomers
Relative polymerization rates of
termonomer double bonds
in Vanadium catalysed
polymerizations
5-Ethyliden-2-norbornene
~ 40 : 1
(ENB)
Dicyclopentadiene
(DCPD) ~ 15 : 1
1,4-Hexadiene
(HD) ~5:1
Criteria for the selection of the termonomer:

• Large reactivity difference of double bonds during polymerization
• Low impact on the reduction of the polymerization rate
• Low impact on the reduction of the molar mass during polymerization
• Sufficiently long scorch time and high crosslinking efficiency during vulcanization
• Low termonomer costs
Impact of the Termonomer on the Curing

Characteristics
ENB DCPD HD
70
ENB
60 DCPD
50 1,4-HD
Torque [Nm]
40
30
20
10
0
0 1,0 2,0 3,0 4,0 5,0 6,0
time [min]
Property Profile of EPM/EPDM based
Vulcanizates
Advantages:
– good price/performance-ratio
– high maximum service temperature
– good low temperature performance
– broad spectrum of grades (oil extended grades etc.)
– ability for vulcanization with sulfur, peroxides and others
– high loadability with extender oils and fillers (reduction of compound price)
– good mechanical properties of vulcanizates
– good weathering and ozone resistance (outdoor applications)
– good electrical insulation (low salt content)
– Low density
Disadvantages:
– low resistance to oil and chemicals
– fair ability to covulcanization
– low resistance to fungi and bacteria
Main Application Areas of EPM/EPDM
700 EPDM Consumption (world) 55

13% 9% Automotive Production / Mio.
EPDM-Consumption / kt
15% 6% 600
500
50
16% 400
41%
300
Automotive production (world) 45
200
Automotive
Thermoplast Modification 100
Building 0 40
1987
1988
1995
1991
1993
1986
1989
1990
1992
1994
Technikcal Rubber Goods

Electro/Electronics
Oil Additives
Market: 1,050 Mio t (2004)
Growth rate: 3,5 %/a
Source: European Chemical News 10, März 2005, 13

Range of EP(D)M-Grades
Ethene Content [wt.%] 50 - 75

ENB-Content: [wt.%] 0 1,7 - 3 4-7 8 - 12
Mooney Viscosity: [MU]
16 - 20 20 - 60 60 - 90
[ML 1+4 (125°C)]
Oil Content: [phr] 0, 25, 30, 50, 100
Dependence of Tg on the Ethene- and the ENB-Content

(V-catalysed commercial products)
products)
-45 EPDM/2% ENB
EPDM/1% ENB
-47,5 EPM /0% ENB
-50
-52,5
Tg [°C]
-55
-57,5
-60
-62,5 Tg(EPDM) = Tg(EPM) + 1,2°C/wt.% ENB

-65
40 45 50 55 60 65 70
Ethene content [wt.%]
Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001

Dependence of the Cristallinity on the Ethene Content and
on the Polymerization Temperature of V-Catalysed EPM
30
35-39°C
25
Enthalpy of fusion [J/g]
40-44°C
45-49°C
20 50-54°C
55-59°C
15 60-64°C
65-70°C
10
0
46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64
Ethene content [wt.%]
Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001
Chemical and Process Aspects in EPM/EPDM-

Manufacturing Technologies
Chemical Process Features

Aspects
free radical E-SBR, CR, NBR, EVM EVM AEM,

E-BR, ACM,FKM, EVM,
Polymerization EVM (ENM)
Ziegler/Natta- BR (G-BR)
Polymerization EPM/EPDM EPM/EPDM (G-EPM/EPDM)
anionionic BR, L- Q
Polymerization SBR.
IR
cationic ECO, CO IIR Q
Polymerization
Polyaddition und AU, EU EU AU, Q
Polycondensation
Polymer- CIIR, BIIR, CM, CSM,
modification CM, CSM, (H-NBR)
H-NBR,
FZ
Features of the EPDM-Manufacturing
Technologies
Source: R. T. Sylvest, J. A. Riedel, J. R. Pillow; GAK 6/1997 (50) 478-483
Process Solution Slurry High temperature Gas phase

solution (Dow) (UCC)
Solvent: Hexane Propene/ethene Hydrocarbon mix. -

Catalyst System Ziegler/Natta CGC/Borane Ziegler/Natta
Catalysts: VOCl3, VCl4, V(acac)3,VO(OR)3, TiCl4 CGC-Catalyst V(acac)3
Cocatalysats: EASC, DEAC Borane (MMAO) Al-Alkyl
Reactivators: PDCAE, TCAE, BPCC - CHCl3
Modifier: H2, ZnEt2, (NH3) - H2
Short stos: Stearic acid, water, antioxidants ?
Antioxidans: sterically hindered phenols, phosphites ?
Stripping aids: water soluble polymers etc. - -
Oil: mineral oil fraction with high b. p. - -
Reactivators:
PDCAE BPCC TCAE
Cl O Cl O Cl O
O C2H5 Cl O C4H9 9
Cl O C 2H 5
Cl Cl Cl Cl Cl
Speculation on the Active Species in the

Vanadium-Catalysed EPDM-Polymerization
+V VOCl3
+IV VCl4
+III VX3 + R2 AlX {R2VX} {R2V }

+ + R2AlX2
-
Aktivator
heat
heat
+II VX2 + R3 Al [R2V] [RVX]

R2AlX R3Al
{homogeneously soluble species} [heterogeneous species]
Source: K.J. Cann, J.W. Nicoletti, X. Bai, F.D. Hussein, K.H. Lee, D.P. Zilker, Presentation at FLEXPO `97
EPDM
Producers, Capacities (kt) and Brand Names
Baton Rouge, Louisiana 180
Exxon Vistalon
Notre Dame de Gravenchon 85
Geleen, Niederlande 135 Keltan
DSM
Triunfo, Brasilien 35 Nitriflex EP
Plaquemine, Louisiana 100 Nordel-IP
DPDE
Seadrift, Texas 90 Elastoflo (UCC)
Marl, Deutschland 60 Buna EP G
Lanxess
Orange, Texas 55 Buna EP T
Lion Copolymer Geismar, Louisiana 91 Royalene / Trilene
Polimeri Ferrara, Italien 85 Dutral
Mitsui Chiba, Japan 60 Mitsui EPT
JSR Kashima, Japan 25
JSR EP
Yokkaichi, Japan 45
Sumitomo Chiba, Japan 40 Esprene
Kumho Yeochon, Südkorea 40 KEP
Petro China Jilin, China 30
Nizhnekamsk Nizhnekamsk, Russland 30
Herdillia Maharashtra, Indien 10
total capacity 1076
Source: European Chemical News 10, März 2005, 13
EPDM-Solution-Process with Fully Flooded Reactor

Water containing
azeotrope ENB
Condenser
Boiling point: 146°C
Settler Max. exposure limit/MAK: 1 ppm
External Smell limit: 3-5 ppm
cooling
loop
Waste water
Azeotropic Condenser Flash
destillation drum
Stripper
Propene Waste air
dewtering
screwg
destillation
Hexane Ethene Steam
Polymerization
reactor Expeller
Settler
Steam
oil
destillation PH-
drier Control drier
Waste water Antioxydant Waste water
Stripping
aid
Precoller
drier -32/-35°C
Water
Modifier
Process Features baling
Propene precooling: -32°C/-35°C
Reactivator Temperature: 20-65°C
Pressure: 5-10 bar
Drier drier EASC
Residence time: 6-15 Min.
VOCl3 /VCl 4 Packaging
3/1 Soldis conc.: 3 -7 Gew.%
H2 O: < 3 ppm
Hexane VNB/ENB
Dow‘s High-Temperature Solution Process
(Source: Dow-Patents, Publications etc.)
Plant location: Plaquemine/Lousiana In the Dow-HT-Process low
amounts of CGC- catalyst
Destillation are required. The catalyst
is not washed out and no
Solvent Condenser steam stripping is applied
and
monomer („leave-in-catalyst“)
Evaporator Evaporator
Flash-
High boiling drum
residue
(ENB, AO, etc.)
Ta
Antioxidant
(AO)
Polymerization
reactor
baler
Ageing
drum
"Insite-Kat." packaging
Scavenger
Temperature: 40 - 80 °C
Purification Purification Purification Ta: 80°C (>130°C)
Pressure: 9-15 bar
Residence time: < 20 Min.
Ethene Propene ENB MMAO Borane
Metal Content of Commercial EPDM
Activation of Metallocenes
Cl R
Alkylation
Zr
Cl
Zr Product V Ti Fe Al Ca Na Sum
R
Dow-CGC <1 1,0 1,3 1,7 <1 <1 8,0
Activation by MAO Activation by EPDM # 2 8,0 <1 4,3 31 1,7 1,8 22,3
(molar excess of MAO: Borane/Borates:
10.000 - 10.000 fold) (with molar
B/Zr-ratios) EPDM #3 1,9 <1 4,3 31 1,7 1,8 48,8
EPDM #4 2,4 <1 2,0 6,7 64 5,7 82,8
EPDM #5 5,1 <1 2,8 9,6 160 4,6 184,1
R EPDM#6 4,8 1,9 63 440 64 9,4 584,1
Zr + A
Source: J. G. Pillow (Dow) „Ethylene Elastomers made using Constrained Geometry Catalyst Technology“
Kautschuk Gummi Kunststoffe 51, 12/98, 855-859
Crystallinity of Metallocene-Based EPDM
30
EBTHI-Cat.
CH2 CH2 DOW-Insite-Cat.
CH2
25
CH2
Enthalpy of fusion [J/g]
ZrCl2
CH2 Me2Si X
20 Ti
CH2 N
X
CMe3 V-Catalysis
15 CH2 CH
2
10
0
40 42 44 46 48 50 52 54 56 58 60 62
Ethene Content [wt.%]
Impact of Cristallinity on Low-Temperature

Compression Set of EPDM-Based Vulcanizates
DOW-Insite-Cat.
100
Low-Temperature-Compression-Set [%]
90
80 Me2Si
Ti X
70 N
X
60 CMe3
50
40
EPDM/V-Cat.
30 EPDM/CGC (Dow)
20
10
0
0
0
,5
,5
,5
5
12
18
21
35
0
,0
,5
8,
8,
32
37
47
10
37
Enthalpy of Fusion [J/g]

UCC‘s EPDM-Gas-Phase-Process (now Dow)
Flow-Chart:
US 4994534
Filter Plant location: Seadrift/Texas

Compressor Temperature: < 90 °C (40°C-60°C)
Pressure: 9-15 bar
Residence time: 0,5 - 1 h
Cooler
Purification
Patents:
ENB Product EP 1099715
Fluidizing Aid Desactivation EP 1099473
Suported Catalyst Monomer EP 1086995
degassing EP 1083192
unit
US 6180738
WO 0000333
WO 9965953
Ethene Purification
Propene Purification ENB

Boiling point: 146°C
Modifier Purification
Maximum exposure level: 1 ppm Baling of
Product etc.
Smell limit 3-5 ppm
Source: „Carbide starts up Seadrift plant with new technology“ European Chemical News, 1-8 February 1999 ($
12m charge for replacing the purge unit)
Comparison of EPM/EPDM-Manufacturing
Technologies
Ranking: 1-10; 1= modest; 10=excellent
Process Solution Slurry HT-Solution Gas-Phase
V-Catalysis V-Catalysis CGC/Dow V-Catalysis
Process Economy 4 5 7 10
EPM 10 10 10 10
EPDM 10 10 10 0
Low Mooney 10 8 10 0
High Mooney 5 10 3 10
Oil Extended Grades 7 10 3 0
Process Flexibility 42 48 36 20
Overall Process
Performance 46 53 43 30
••The
Thewell
wellestablished
establishedvanadium
vanadiumbased
basedsolution
solutionand
andslurry
slurryprocesses
processes
are
are inferior in investment and operation costs, but provideaahigher
inferior in investment and operation costs, but provide higher
flexibility.
flexibility.
••The
TheHT-solution
HT-solutionandandthe
thegas-phase
gas-phasetechnology
technologyarearelow
lowcost-
cost-
technologies,
technologies, which are superior in the production of specificgrades
which are superior in the production of specific grades
Metallocene-Patents 1980-2000 (Oct. 2000)
250
2.923 Documents
Number of Patents (US) + Pat. - Appl.
US-
US-Patents and EP-
EP- and WO-
WO-Patent Applications
200
150
100
50
0
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em
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al i
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ay
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il l i
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on
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WPIDS-Recherche Dr. Karjetta vom 29. 09. 2000
Cl Alkylation
R Alkylation
(BuLi, AlR3 or MAO) (BuLi, AlR3 or MAO) R
Zr Zr Zr
Cl
Cl R
Activation by MAO Activation by borates and boranes
R
Zr
+ A
Cossee-Mechanism of Metallocene Catalysed
Olefin Insertion
R
R R
CH2 CH2
Zr Zr
+ Zr
+ CH2 + CH2
CH2
CH2
R
+
Zr CH2
CH2
Key Patents in Metallocene- und Single-Site-Catalysts

1.1. Bis Cyclopentadienes
X Me2C
X
Zr B Zr ZrCl2 Me2Si ZrCl2
X X
B = Bridge
EP 35242 EP 129368 EP 468537 EP 351392 EP 4858821

(29.12.1980) (06.06.1983) (30.01.1987) (15.07.1988) (12.11.1990)
BASF Exxon Exxon Fina Hoechst
(Kaminsky) (Ewen) (Turner) (Ewen, Razavi) (Spaleck)
EP 69951
(09.07.1981)
Hoechst
(Kaminsky)
MAO- MAO- Borate- MAO-Activation
Activation Activation* Activation
HDPE, LLDPE, a-PP HDPE, LLDPE, i-PP, EP(D)M HDPE, s-PP, COC HDPE, i-PP
* H. C. Welborn, Jr.; J. A. Ewen US 5324800 (Exxon) Prior.: 30.08.1991 „MAO-Activation of Bridged Metallocenes“
1.2. Isoelectronic Bicyclopentadienyl Systems
Y Cl
E N R B Me
B Cl
X X Cl Me Me
R´ Zr X B
Zr Zr Zr P
X X Cl Me2Si Ph
X P ZrCl2
E B N Ph
R B
E = N, P R´ Y Ph SiMe3
EP 638593 US 5554775 WO 96/34021 WO 98/01455 WO 98/50392

(02.08.1993) (17.01.1995) (25.04.1995) (05.07.1996) (08.05.1997)
Shell Lyondell Lyondell Bayer AG Nova Chemicals
(Ostoja-Starzewski) (Spence)
US 5539124 WO 97/2351
(19.12.1994) (22.12.1995)
Lyondell Hoechst AG
(Herberich)
MAO-/Borate- MAO-/Borate-
Activation Activation
Polyolefins HDPE, PP PE, PP HDPE, LLDPE, PP, HDPE, LLDPE,

EPM, EPDM, COC PP, EPM, EPDM

2. 1. Mono-Cyclopentadienyl Systems
Me2Si III
(IV) Ti
Ti Ti X Ti X
MeO N X
OMe X RxE X
X NR2
MeO CMe3
E= N, O
EP 210615 EP 416 815 US 5132380 WO 96/13529

(29.07.1985) (31.08.1998) (12.09.1991) DSM
Idemitsu Kosan Dow Dow (Lovocat)
US 5206197 EP 420436
Dow (13.09.1989)
(04.03.1991) Exxon
MAO- MAO-/Borate- Borate-Activation MAO_/Borate-
Activation Activation Activation
S-PS HDPE PO HDPE
LLDPE LLDPE
EP(D)M EPM
ES
2.2. Mono Cyclopentadienyl Systems
F
F CH3
Ti
F CH3
N O
CH3
F F Ti N C Ti
N CH3
t-Bu N N
P X
t-Bu P
t-Bu
WO 2005/005496 WO 2008/095687 US 6063879

DSM DSM (29.10.1997)
Nova
MMAO-Activation MMAO-Activation MMAO-Activation
EP(D)M EP(D)M PE, LLDPE

3.1. Post Metallocenes
Ar Ar Ar
S
P N
X X X
Ti N
Pd Ti
X X
X´ X O O
P N Zr
O X
t-Bu
O
Ar Ar Ar
t-Bu N
EP 121965 WO 92/12162 JP 5230133 EP 606125 US 5637660

(05.04.1983) (27.12.1990) (19.02.1992) (08.01.1993) (17. 04. 1995)
Shell Exxon Mitsui Toatsu Shell Lyondell
EP 571945
(29.05.1992)
Sumitomo
Alternating Polyolefins Polyacetylens Polyolefins, HDPE, PP
Olefin/CO-Copolymers Polyacetylens
(„Carilon“)
3.2. Post Metallocenes
R
R´ R
N X´ N
M Cl Cl Cl
N X N Fe
R´ R Cl N N
Ti
R N O O
M = Ni, Pd
WO 96/23010 DuPont BP EP 0874005 EP 1881014
(24. 01. 1996) (Brookhart) (24.01.1998) (10.05.2006)
DuPont Mitsui Mitsui
(Brookhart)
polar/unpolar HDPE, (PP) HDPE(PP) HDPE, EPM EPM, EPDM
Copolymers, LDPE
Features of the Activation by MAO

Chemical Structure of Methylalumoxane (MAO):
(CH3)2 Al - [O - Al - CH3]n- O - Al(CH3)2 n : 6 - 20

(CH3) Al - [O - Al - CH3]n- O - Al(CH3) MW : 2.000-2.500
Features of the activation by MAO:

• The details on the mechanism of the activation by MAO are not known
• A 1.000-10.000 fold molar excess of MAO is needed in solution polymerizations
• A 50-100 fold molar excess is needed for supported catalysts (gas phase)
• MAO is capable of alkylating metallocenedichlorides
• MAO is able to abstract chlorides from metallocenemono- or dichlorides
• MAO is an efficient scavenger for impurities
(Polymerizations performed in the presence of MAO are very robust towards impurities)
Activation of Metallocenes by Boranes and Borates
Abstraction of Alkyl-Anions by Borane and Borates
R F
F F
Zr Borane
F F
F F
R F
B F
F F F F
- F F
-R H F F
_
N+ B F Anilinium Borate
Ph
Me
Me
R F F 4
_
F F
+ Ph
Zr + Ph
B F Triphenylcarbenium
Ph Borate
F F 4
• For the Activation of metallocenes molar quantities of borane/borates are

required
• Polymerizations activated by boranes/borates are very susceptible to impurities
R. F. Jordan Turner M. Bochmann M. D. Rausch, T. J. Marks (1991;
(1986) Turner (1990) J. C. W. Chien JACS 113, 3623)
R 1987
1987 (1991) F5
Zr H
- Ph + Ph
+ N+ -
R Ag BPh4 A
Me A
Ph B
Me Ph
F5 F5
-R
-
+R
- - - -
+R +R +R
CH3CN - RH
R -
R R
- - F5
Zr + Ag+1/2 R2 + BPh4 Ph
N - Ph Ph
A
B F5
Me A
Me Ph
F
F5
- F EP
EP468
468537
537 (Exxon)
(Exxon) Priorität:
Priorität:1987
1987
A : F EP 561 479 (Exxon)
EP 561 479 (Exxon) Priorität:1987
Priorität: 1987
F Nicht
F
F F F Nicht oder
oderschwach
schwachkoordinierende
koordinierendeAnionen
Anionen
"NCA"oder
"NCA"oder"WCA"
"WCA"
F - F
F B
F
(insbesondere:
(insbesondere:Tetrakis(Pentafluorophenylborat)
Tetrakis(Pentafluorophenylborat)
F FF
F US
F
F US5599761
5599761(Exxon)
(Exxon) Priorität:
Priorität:04.02.1987
04.02.1987
F Erfinder: H. W. Turner
Erfinder: H. W. Turner
F „Ionic
„IonicMetallocene
MetalloceneCatalyst
CatalystCompositions“
Compositions“
Key Patents for the Activation of Metallocenes
Year of
Priority
1980 Activation of Cp2ZrCl2 by MAO (BASF/Kaminsky) EP 35242; Prior. 29.12.80
Activierung of Cp2ZrRCl by MAO (Hoechst/Kaminsky) EP 69951; Prior.: 09.07.81
Activation of metallocenes by Alkyl/R<C6- Al-Oxanen (Exxon)
Activation of CGCby MAO (Dow/Stevens) EP 416815; Prior.: 31.08.89
1985
Activation of metallocenes EP 468 537; Prior.: 30.01.87 [Cp2MX]+ [BR4]
by borates (Exxon/Turner) EP 561 479; Prior. 30. 01. 1987
US 559 976; Prior. 04. 02. 1987
Ionic metallocene catalyst comosition
Activation by borates (Dow/Stevens) EP 418044; Prior.: 14.09.89 [Cp1MXn]+ [BR4]-
Activation by boranes (Fina/Ewen) EP 427 697; Prior.: 10. 10. 1989
1990
CGC-Activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993
CGC/Diene-activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993

Activation of metalloenes by Al- Alkyls R >C8 - Al-Oxanes (Montell)
1995
Non Coordinating Anions

F
F F
F 4 -
F F
F F
F
F F F
F F F
F F
- F F
B
F F
F FF
F F F F
F
F F F F F B FF
F F F F F F FF
F F F
F
- F F
F
F Si F
F B
F
F
F - F
F F F B F
F
F
F FF F F F
F
F
F F
F F F B F
F F F
F
F F FF
F
F F F FF
F F F
F F F F
F F F F
F
F
EP 468537 (Exxon) WO 01/08691 (Bayer AG) EP 1066296 (Bayer AG)

Prior.: 30.01.1987 Prior.: 18.08.2000 Prior.: 24.03.1998
Inv.: Turner, Hlatky Inv.: Becke, Kahlert, Inv.: Becke, Denninger,
Denninger, Windisch, Obrecht Mager, Windisch
EP 561479 (Exxon) WO 01/10124 (Bayer AG) EP 111927 (Bayer AG)

Prior.: 30.01.1987 Prior.: 11.09.2000 Prior.: 23.06.1999
Inv.: Turner, Hlatky Inv.: Becke, Denninger, Inv.: Becke, Mager, Zahalka
Kahlert, Obrecht, Schmid,
Windisch,
Comparison of Catalyst Costs
Example Catalyst Cocat. Reactivator Total Cat-Costs
[EUR/100 kg] [EUR/100 kg] [EUR/100 kg] [EUR/100 kg]
Plant 1 VOCl3 EASC DCPEE
[EUR/kg] 0,50 3,75 2,00 6,25
Plant 2 V(acac)3 DEAC TEA
[EUR/kg] 1,25 1,30 0,65 3,20
Exxon- Pat. Et(Ind)2ZrCl2 MAO -
[EUR/kg] 13,00 151,00 - 164,00
Exxon- Pat. Et(Ind)2ZrMe2 Borate -
[EUR/100 kg] 2,25 3,45 - 5,70
•• MAO-activation
MAO-activationof ofmetallocenes
metallocenesisisnot
noteconomical
economicalininaasolution
solutionprocess
process
•• Borate-activation
Borate-activation results in catalyst costs which are comparablewith
results in catalyst costs which are comparable with
Vanadium-systems
Vanadium-systems
•• For
Foran
animprovement
improvementin inoverall-economy
overall-economymetallocene-technology
metallocene-technologyhashastotobe
be
combined with process improvements
combined with process improvements
•• Increased
Increasedcatalyst
catalystcosts
costsmight
mightbe
becompensated
compensatedby bythe
theimproved
improvedproperty
property
profile of new products
profile of new products
4.5. Butyl- and Halobutyl Rubber
Abbreviations:
Butyl Rubber: IIR
Bromo Butyl Rubber: BIIR
Chloro Butyl Rubber: CIIR
Brominated Isobutene Paramethylstyrene Rubber: BIMS
IIR-Terpolymer (mainly with Divinyl benzene): XLIIR
Contents
• Overview
– Products, Property Profiles and Areas of Application
– Market, Market Shares, Producers and Range of Grades
• Polymerization Mechanism and Production Technologies
– Standard-Butyl Rubber (IIR)
– Halo Butyl Rubber (XIIR)
• Vulcanization and Vulcanizate Properties
Butyl- and Halo Butyl Rubber

CH3 CH3 CH3 CH3
CH2 C CH2 C CH2 C CH CH2 CH2 C 20 39 H3C

CH3 CH3 29
30
n
CH3
CH3 CH2
CH3 CH3 45
CH 2
C
Butyl Rubber (IIR) 19 123° 15
C C27 CH 23
C 28
CH
35 2 CH CH H3C
21 2 26 2
38 CH3 16 CH3
CH3 CH3 CH2 CH3
CH2 C CH2 C CH2 C CH CH2 CH2 C Standard Angle: 109,5°

CH3 CH3 n X CH3
X = Cl: Chloro Butyl Rubber (CIIR)

X = Br: Bromo Butyl Rubber (BIIR)
Basic Features:
Isoprene content: 0,5 - 2,5 Mol%
CH3 CH3 CH3 Incorporation of Isoprene: random 1,4-trans
CH2 C CH2 C CH2 CH CH2 CH CH2 C Tg: ca. -72°C
CH3 CH3 n CH3 Mw/Mn: 3-5
CH2Br CH3
Brominated Isobutene-co-p-Methylstyrene Rubber (BIMS)
Isobutene-Terpolymers
Butyl- and Halo Butyl Rubber (X)IIR: Property Profile and
Areas of Application
Property Profile
Positive:
• Low gas permeability
Tyres Pharmaceutical • high resistance to heat and vapour
Others Adhesives • high resistance to chemicals
Chewing gum Automotive • good insulation properties
• good covulcanization (XIIR))
• product purity
5% 4% 3% 1%1%
(grades without antioxydants)
Negative:
low elasticity /highly damping
Areas of Applications:
• XIIR based Innerliners (passenger tyres)
• IIR b ased tubes (truck tyres)
86%
• bladders (IIR)
• ABC-protection clothes
• Cable and wiring
• Pharmaceutical stoppers
Source: • Adhesives and sealants
CHEManager 20/2006, Seite 8 (GIT Verlag Darmstadt) • absorbers for noise and fenders
• chewing gum
Butyl and Halobutyl Rubber (X)IIR: Grades

CH3 CH3 CH3 CH3
CH2 C CH2 C CH2 C CH CH2 CH2 C
CH3 CH3 CH3

n
Butyl Rubber (IIR)
X2 (Cl2 / Br2)
CH3 CH3 CH2 CH3
CH3 CH3 X CH3

n
Halo Butyl Rubber (XIIR)

X = Cl: Chloro Butyl Rubber (CIIR)
X = Br: Bromo Butyl Rubber (BIIR)
Advantages of XIIR over IIR:

• Higher speed of vulcanization
•Improved covulcanization without deterioration of basic IIR properties
Characteristic Features of IIR based Vulcanizates
Air permeability of vulcanized rubbers

(50 phr SRF, without plasticizers)
Rebound
(50 phr SRF, without plasticizer) Temperature [°C]
70 60 50
100
80
1,4-cis BR 1,4-cis-BR
Luftdurchlässigkeit(Q x 10exp8)
SBR
NR
Rebound Elasticity [%]
NR NBR EPDM
60
10 SBR
EPDM
NBR/28 ACN
40
NBR/33 ACN
IIR NBR/38 ACN
IIR
20 1
0
-75 -50 -25 0 25 50 75 100
Temperature [°C] 0,1
0,0029 0,00295 0,003 0,00305 0,0031
1/T x 10exp4
Source: Butyl And Halobutyl Compounding Guide For Non-Tyre Applications, 12/92 Bayer AG -KA 34 166)
(X)IIR: Market, Market Development, Producers

and Production Capacities
Main Areas of Application:
Market Growth (Basis: 2.000): (90%: Tyres and Tyre Production)
IIR: - 2,3 %/ p.a. •XIIR: Inner liners
XIIR: + 2,3 % p.a. •IIR: Truck tyre tubes
•IIR: heating bladders
Sum: + 1,2 % p.a.
Pricing (1996):
700 •IIR: ca. 1,80 €/kg
IIR •XIIR: ca. 2 €/kg
XIIR
•BIMS: ca. 3,5 €/kg
600
Sum Production capacities (2008)
500
Consumption [kt]
Company Butyl Halo- Total

400 butyl [kt]
Exxon X X 414
300 Lanxess X X 252
Nizhnekamsk X X 180
200
Togliatti X 50
100 Sinopec X (X) 45
Japan Butyl Co. X X 80
0
Total Capacity 1.041
79
82
85
88
91
94
97
00
19
19
19
19
19
19
19
20
Range of Commercial IIR and XIIR Grades
Range of Standard Butyl Grades Range of XIIR Grades
100 100
90 90
80
bu l
80
om uty
tyl
Mooney Viscosity
70
ML (1+8) 125°C
Mooney Viscosity
70
Br lorb
ML (1+8) 125°C
60 60
Ch
50 50
40 40
30 30
20 20
10 10
0 0
0 2 4 6 8 10 0 2 4 6 8 10
Content of double bonds [Mol%] Halogen Content [Mol%]
IIR: Flow Chart of Slurry Polymerization

(Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)
CH3Cl compressor dryer compressor
AlCl3- Al2O3
solution
drum
Cond
enser
“catalyst cocatalyst
drum“
H2O „slop isoprene“ H2O
Storage tank
for
„mixed feed“
Storage
units for
IIR-slurry
NH3- Ethene- in water
Heat exchangers
Isobutene- Isoprene Reactor Steam- Flash- Stripping-
drying unit unit unit
Features of IIR Production Technology
Process: Slurry polymerization
Catalyst: AlCl3
Cocatalysts: HCl (Exxon)
H2O (Lanxess) Ethylene
(gas)
Diluents: CH3Cl (Exxon and Lanxess)
„mixed feed“(GUS)
Make-up of AlCl3-solution 30 - 45 °C
Polymerization temperature: -90 °C bis - 100 °C
Residence time 0,5 - 1 h
Conversion of monomers:
Isobutene 75 - 95 %
Isoprene 45 - 85 %
Concentration of IIR-Slurry 25 - 35 wt.%
Reactor output: 2 - 4 t/h*Reactor
Operation time of reactors: 18 - 60 h
Additives:
Antiagglomerants: (Stearic acid/Zn-stearate) Ethylene
(liquid)
0,4 - 1,0 wt.%
Antioxydants: 0,02-0,15 wt.%
-discolouring: alkylated Phenylene Diamines
-None discolouring: phenolic AO Inlet and Drain
for light
(+ alk. Phenyl phsophites) hydrocarbon
-chewing gum: without AO wash
catalyst mixed feed catalyst

Sources:
Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993
US 2,356,128; US 2,491,752; US 2,491,710; US3,968,076; US 4,474,924; US 4,068,051; US 5,532,312
IIR: Reaction Scheme of Cationic Polymerization

Formation of Cation:
AlCl3 + HCl
+
H + AlCl4
-
AlCl3 + H2O +
+ AlCl3OH
-
H
Initiation of Polymerization: CH3

CH3 -
+ - CH3 C
+
AlCl4
H + AlCl4 + CH2 C
CH3 CH3
Chain Propagation (Growth) Reaction:
CH3 CH3
CH3
CH3
- + -
+
CH3 C AlCl4 + n CH2 C H CH2 C CH2 C AlCl4
CH3 n
CH3 CH3 CH3
Transfer Reaction:
CH3 CH3 CH3 CH3 CH3
CH3
+ - + -
H CH2 C CH2 C AlCl4 +CH2 C H CH2 C CH C + CH3 C AlCl4
n CH3 n
CH3 CH3 CH3 CH3 CH3
Termination Reaction:
CH3 CH3 CH3 CH3
+ -
H CH2 C CH2 C AlCl4 H CH2 C CH2 C Cl + AlCl3
n n
CH3 CH3 CH3 CH3
IIR: Living Cationic Polymerization
Generation of Carbo Cation:
R - Cl + MX n + -
R + MX n+1
Initiation: CH3
CH3
+
+ CH2 C
+
MX n+1
-
R R CH2 C
CH3
Propagation: CH3
CH3 CH3 CH3
CH3
R CH2 C MX n+1
+ - + n CH2 C R CH2 C CH2 C
+ -
MX n+1
CH3 n
CH3 CH3 CH3
Reversible Termination:
CH3 CH3 CH3 CH3
R CH2 C CH2 C
+ -
MX n+1 R CH2 C CH2 C Cl + MX n
n n
CH3 CH3 CH3 CH3
MXn (Metal halides) and R-Cl used for the preparation Cl

of Isobutylene based blockcopolymers:
BCl3 and TiCl4 Cl Cl Cl
Cl
Influence of Polymerization Temperature on Molar Mass

(Polyisobutylene / without Isoprene)
13 -25 -50 -75 -90 -106 -120 -143
107 EtAlCl2/H2O
γ-Strahlung AlCl3/H2O
Mn [g/mol]
106
105
Molar Masses:
BF3/H2O
γ-Strahlung > EtAlCl2 > BF3 > AlCl3
104
3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0
1/T *10 [K-1]
3
Source: J. Kennedy, P. D. Trivedi, Adv. Pol. Sci. (1978) 28, 113-151

XIIR: Flow Chart of IIR-Halogenation
Storage tank Halogenation reactor Neutralization reactor
Br2 bzw. Cl2
IIR-solution
in hexane
Addition of AO
Hexane
water
X-IIR-
Slurry
in water
Antiagglo- steam Caustic

merants soda
Source: Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)
XIIR: Mechanism of IIR-Halogenation CH3

CH3 CH3 CH3

n
Reaction Conditions:
CH3 CH3 X2 CH3
CH3
Solvent: Hexane
CH3 CH3 CH3 H
X IIR-solids 20 - 25 wt.%:
CH2 C CH2 C CH2 C C CH2 CH2 C Ratio of Halogen/Isoprene: 1:1 Mol/Mol
+
CH3 CH3 n
CH3 Reaction temperature : 40 – 60 °C
X
Residence time: lh
Stripping-Vapour : 2 - 2 kg/ kg XIIR
CH3 CH3 CH3 H CH3 Antioxydants / stabilizers: Ca-Stearate,
X
Epoxydized Soy
CH2 C CH2 C CH2 C C CH2 CH2 C
+ bean oil (ESB)
n
CH3 CH3 X CH3
- HX Source:
Kirk-Othmer Encyclopedia of Chemical Technology,
CH3 CH3 CH3 X CH3
Fourth Edition, Volume 8, 1993
CH3 CH3 n X - HX CH3

Patents:
CH3 CH3 CH2 X CH3 US 2631984; US 3099644; US 4288575; US 4554326;
US 4632963; US 4681921; US 4650831; US 4384072;
US 4513116; US 5681901
CH3 CH3 n CH3
Crosslinking Efficiencies in Vulcanization by
Peroxides (Dicumyl Peroxide)
Rubbber X-linking
O O 2 O (R*)
efficiency
C Vi-BR ~ 100 1)
2 O + + 2 R-H
C
(98% Vinyl)
C
SBR 12,5
C
cis 1,4-BR 10,5
Number of crosslinks EPDM 1,5
X-linking efficiency =
Peroxide Functions EPM 0,4 - 0,7
NBR 1,0
Type of Rubber Theoretical Cross- IR 1,0
linking efficiencies CR 0,5
M - Rubbers 1 IIR <<1
R - Rubbers >1 PE 1,0
Degradating polymers <1 PP <<1
1) Dissertation Th. Früh, TU Hannover 1995
Properties of Sulfur- and Peroxide Cured IIR and XLIIR
IIR Polysar Butyl 402 100 -

IIR -Terpolymer* Polysar Butyl XL 10000 - 100
N 762 Carbon black 50 50
Hard Clay Silicate - 20
Polarite 102R/EEC Int Silanised calcinated Clay 130 80
Pb3O4 - 10 -
Stearic acid - 1 1
Bis(t-butylperoxy-isopropyl)benzene Perkadox 14-40 B/Akzo - 1,5
Trimethylolpropanetrimethacrylate Sartomer 350/Sartomer - 1,5
Dibenzoyl chinone dioxime Actor DQ/Kawaguchi 6 -
Dibenzo thiazyldisulfide Vulkacit DM / Lanxess 1 -
* IIR-Terpolymer mit Divinylbenzol (XLIIR)
Source: C. A. Moakes, Bayer „Polynotes“ No B11 „An Improved Seal for Chemical Condensers
Based on Polysar Butyl Terpolymer“
Properties of Sulfur- and Peroxide Cured IIR and XLIIR
Butyl Rubber Grade IIR XLIIR
Compound Properties
Compound Mooney (ML 1+4/100°C) 105 98
Mooney-Scorch (125°C) [min.] 4,0 6,2
Vulkanizate Properties (160°C/12 min.)
Shore A Härte (23°C) 81 76
S100 [MPa] 6,0 6,5
Elongationat break [%] 155 105
Tensile Strength [MPa] 6,8 7,5
Compression Set (70h/105°C [%]) 75 15
Hot air ageing (100°C/96h)
Shore A Härte (23°C) 83 78
S100 [MPa] 7,8 -
Elongation at break [%] 110 95
Tensile Strength [MPa] 8,0 8,2
Electrolyte permeability (g*mm/day*m2)
Ethylenglycol 0,38 0,21
g-Butyrolactone 1,0 0,8
Dimethyl formamide 7,8 1,8
Vulcanization of BIIR by Peroxides
CH3 CH3 CH2 CH3

CH3 CH3 CH2 CH3
CH3 CH3 n
X CH3
+ DCP CH3 CH3 n CH3
- 2 X* CH3 CH3 CH3

CH3 CH3 X CH3
n
CH3 CH3 CH2 CH3
n
CH3 CH3 CH2 CH3
Vulcanization of BIIR by ZnO/NN‘-m-Phenylene
Bismaleic Imide
CH3 CH3 CH3
CH3 CH3 CH2 CH3 CH2 C CH2 C CH2 C CH CH CH2 C

n
CH2 C CH2 C CH2 C CH CH2 CH2 C CH3 CH3 CH2 CH3
O
CH3 CH3 n
X CH3 C
+ ZnO C N
- ZnOHX O
CH3 CH3 CH2 CH3

O
CH2 C CH2 C CH2 C CH CH CH2 C
C N
n
CH3 CH3 CH3
C
O
CH3 CH3 CH2 CH3
CH2 C CH2 C CH2 C CH CH CH2 C

n
CH3 CH3 CH3
IIR and XIIR: Methods of Vulcanization and

IIR (Lanxess Butyl 301) [phr] 100 100 100 - - - -
XIIR (Bromo butyl - - - 100 100 100 100
Carbon black (N 330) [phr] 50 50 50 - - - -
Carbon black (N 774) [phr] - - - 50 50 50 50
Zinc oxide [phr] 5 5 5 - 5 5 5
Lead Oxide (Pb3O4) [phr] - 10 6 - - - -
Stearic Acid [phr] 1,0 1,0 1,0 1,0 1,0 1,0 1,0
Sulfur [phr] 1,25 - - - - - -
MBT [phr] 1,5 - - - - - -
Benzochinondioxim [phr] - 6 - - - - -
PF-Resin (Amberol) [phr] - - 10 - - - -
CR (Baypren 110) [phr] - - 5 - - - -
Dicumyl peroxide [phr] - - - 1,5 -
Zinc oxide [phr] - - - - 5 - -
Dicumyl peroxide [phr] - - - - - 1,5 -
BMI (HVA 2) [phr] - - - - - 0,5 1,5
temperature [°C] 160 150 190 180 180 180 180
time [min] 25 12 30 15 3 4 20
Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92
J. Rogers, W. H. Waddell (Exxon) „Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682
IIR und XIIR: Methods of Vulcanization
and Vulcanizate Properties
IIR [phr] 100 100 100 - - - -
XIIR [phr] - - - 100 100 100 100
Carb. black (N 330) [phr] 50 50 50 - - - -
Carb. black (N 774) [phr] - - - 50 50 50 50
Vulcanization
S/MBT Chinon Resin ZnO DCP DCP/BMI ZnO/BMI
Compound Properties
91 94 82 83 88 88 89
ML 1+4 (100°C) [MU]
17 7 >30 - - - -
MS5 (125°C) [min]
- - - 16 12 14 16
MS5 (135°C) [min]
Physical Properties
66 64 64 48 40 54 58
Shore A Hardnes
2,5 2,1 1,9 0,9 0,5 0,12 0,19
M100 [MPa]
M300 [MPa] 5,2 1,8 9,5 10,2
Tensile Strength [MPa] 16,6 12,8 15,8 12,4 8,9 10,5 13,6
Elongation at break [%] 530 400 590 580 680 325 360
CS (70h/150°C) [%] 68 68 12 58 53 28 13
Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92
J. Rogers, W. H. Waddell (Exxon) „Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682
Influence of Oil Loading on Properties of BIIR-

Vulcanizates
BIIR Polysar Brombutyl 2030 100 100

Carbon black N 660 60 60
Paraffin Oil Sunpar/Sunoco Inc. - 7
Resin Pentalyn A / Hercules 4 4
Stearic Acid 1 1
MBTS Vulkacit DM / Lanxess 1,3 1,3
Zinc oxide 3 3
Sulfur 0,5 0,5
Influence of Oil Loading on Properties of BIIR-
Vulcanizates
Butylkautschuk-Typ BIIR BIIR
Paraffinöl - 7
Mischungseigenschaften
Compound-Mooney (ML 1+4/100°C) 72 62
Mooney-Relaxation (MR30) [%] 5,1 5,5
Monsanto-Tack [N] 2,3 2,2
Vulkanisateigenschaften (160°C/12 min.)
Zugfestigkeit [MPa] 10,5 8,9
Bruchdehnung [%] 650 670
S 50 [MPa] 0,9 0,8
S 100 [MPa] 1,7 1,1
S 300 [MPa] 5,4 4,0
Shore A Härte/23°C 60 58
Shore A Härte/70°C 47 40
Rückprallelastizität/23°C [%] 9 9
Rückprallelastizität/70°C [%] 30 29
Luftdurchlässigkeit/70°C (DIN 53536) [m2/s*Pa]) 2,3 3,0
Influence of Carbon Black Loading on BIIR

Vulcanizates
BIIR Polysar Brombutyl 2030 100 100 100 100 100

Carbon Black N 660 60 40 30 20 0
Paraffin Oil Sunpar/Sunoco Inc. - - - - -
Resin Pentalyn A / Hercules 4 4 4 4 4
Stearic Acid 1 1 1 1 1
MBTS Vulkacit DM / Lanxess 1,3 1,3 1,3 1,3 1,3
Zinc Oxide 3 3 3 3 3
Sulfur 0,5 0,5 0,5 0,5 0,5
Influence of Carbon Black Loading on BIIR Vulcanizates
BIIR (Butyl rubber 2030) 100 100 100 100 100
Carbon black (N 660) 60 40 30 20 0
Compound Properties
Compound-Mooney (ML 1+4/100°C) 72 62 56 51 40
Mooney-Relaxation (MR30) [%] 5,1 7,4 7,6 7,8 7,2
Monsanto Rheometer MDR 165°C
minimal torque [Nm] 2,3 1,7 1,4 1,2 0,8
t50 [min] 2,9 3,3 1,3 3,3 3,3
t90 [min] 6,2 6,8 7,1 7,8 6,8
Maximal torque [Nm] 7,9 5,5 4,3 3,4 2,2
Vulcanizate properties (160°C/12 min.)
M50 [MPa] 0,9 0,7 0,7 0,6 0,4
M100 [MPa] 1,3 0,9 0,8 0,7 0,5
M300 [MPa] 5,4 2,4 1,8 1,2 0,6
Rebound at 23°C [%] 10 10,7 11,9 12,2 13,8
Rebound at 70°C [%] 32 39 42 44 49
Air permeation at 70°C/E+17 [m2/s*Pa]) 2,14 2,27 2,39 2,58 2,78
tan δ / 0°C (Roelig-test) 0,647 0,809 0,863 0,900 0,945
tan δ /70°C (Roelig-test) 0,251 0,215 0,190 0,178 0,151
Influence of (X)IIR/NR-Blend Ratio on Vulcanizate

Properties
BIIR 100 - 80 - 60 - 40 -
CIIR 0 100 0 80 0 60 0 40
NR 0 0 20 20 40 40 60 60
Carbon black (N 660) 60 60 60 60 60 60 60 60
Paraffin oil 7 7 7 7 7 7 7 7
Pentalyn A* 4 4 4 4 4 4 4 4
Stearic acid 1 1 1 1 1 1 1 1
Zinc oxide 3 3 3 3 3 3 3 3
MBTS 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0
Sulfur 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5
Source: W. Hopkins, R. H. Jones, J. Walter “Bromobutyl and Chlorobutyl. A Comparison of Their Chemistry,
Properties and Uses“ paper 16A10 presented at IRC ‘85 Kyoto; International Rubber Conference
Influence of (X)IIR/NR-Blend Ratio on Vulcanizate
Properties
BIIR [phr] 100 - 80 - 60 - 40 -
CIIR [phr] - 100 - 80 - 60 - 40
NR [phr] - - 20 20 40 40 60 60
Unaged:
M300 [MPa] 4,2 3,7 5,7 5,1 7,1 5,7 8,9 4,3
Tensile Strength [MPa] 9,3 9,9 10,0 10,7 12,8 10,3 14,7 9,7
Elongation at break [%] 740 770 620 620 560 560 490 580
Aged (168h/100°C)
M300 [MPa] 6,8 5,5 7,6 7,9 8,4 7,7 6,7 3,6
Tensile Strength [MPa] 10,0 10,9 9,8 11,0 9,3 9,2 8,8 5,8
Elongation at break [%] 550 640 420 465 320 365 370 475
Air permeation at 2,9 2,9 5,4 5,7 9,2 7,5 13,8 13,2
50psi/65°C (Q x 10-8]
Adhesion at 100°C
Self adhesion / tack [kN/m] 16,8 4,4 14,7 4,7 15,2 9,1 15,4 5,2
Adhesion to NR [kN/m] 7,5 1,3 10,0 1,6 14,7 1,9 20,8 2,9
Fatigue to failure after
ageing at 168h/120°C [kcycles] 61,8 72,7 23,6 3,9 0,3 0,1 0,0 0,0
5. Rubber Specialities:
Performance Profiles of Vulcanizates
Maximal Service Temperature

100
80
60
Processability Low Temperature Performance
40
20
0
Mechanical Properties Ozone Resistance
Oil Swelling
Silicon Rubber
Hydrogenated Nitrile Rubber
Fluoro Rubber
Ethylene-Vinylacetate-Copolymers
5.1. Fluoro Rubber (FKM / FPM)
Bond Bond Radius
energy of atoms Maximum Service Temperature:
[J/mol] [A]
3.000 h 232°C
C-H 413 0,37 1.000 h 260°C
240 h 288°C
C-F 485 0,72 48 h 316°C
Properties of FKM-Vulcanizates: Areas of Application:

Positive: 60 % Automotive (75% in Europe)
•Excellent resistance to ozone, UV- and weather 10 % Aviation and Aerospace
•High service temperature 10 % Chemical planty s (Fume treatment
•Low oil swell of incineration and power plants)
•High resistance to chemicals and acids 20 % rest
•High flame resistancy Rubber goods:
Negative: 30-40 % O-Rings and seals
•High price 30-40 % crank shaft seals
•Poor low temperature flexibility (except Kalrez) 10-15 % hoses and profiles
•Poor resistance to amines and bases ~5% Modification of polyolefins
•Poor compounding 4.5 % pipes and tubings
•Necessity to oven ageing after vulcanization 10 % rest
Sources: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons
A. L. Logothetis „Chemistry of Fluorocarbon Elastomers“ Prog. Polym. Sci., Vol. 14, 251-296 (1989)
Fluoro Rubber: Market, Producers and Capacities

USA
Market: 2002: ca. 15.000 t World Market
45%
Prices: 20 - 50 EUR/kg
(correlated with F-content)
Top price: ~ 500 €/kg (Kalrez) Asia W-
Growth: 8 - 10% p. a. 22% Europe
Return on Sales: 20 - 25% 33%
Source: Kunststof En Rubber; 11 November 2003
Producer Trade Market Site Capacity*
names Share [%] [kt]
Du Pont Viton/Kalrez 43 Deepwater, NJ 3,0
Dordrecht, NL 1,0
Utsonomiya, Jp 1,0
DuPont-Showa Kawasaki, Jp
Dyneon Fluorel 22 Decatur, AL 2,0
Zwijndrecht, BE 2,1
Gendorf, DE
Solvay Tecnoflon 15 Spinetta, I 2,0
(Ausimont)
Daikin Kogyo Daiel 10 Osaka, Jp 1,0
Asahimont Chiba, Jp 2,0
Asahi Glass Aflas 5 Chiba, Jp 1,0
Unimatec Noxtite 5 Jp 1,0
Estimated total capacity: 20 kt; capacity utilization: 80-100%
FKM: Composition of Standard Grades
HFP Fluorine containing monomers
H F
VD
C C VDF
20
80
F[
H F
wt
Z F F
.%
60
40
]
C C TFE
Am olymbers)
.t%
]
P
F F
orp er
(ru
[w
F CF3
40
ho s
P
60
HF
C C
us
HFP
X F F
80
20
Y
Copolymers fluorine cont.
TFE [wt.%]
80 60 40 20 VDF TFE/P 54
TFE [wt.%] VDF/HFP 65
VDF/HFP/TFE 67
VDF TFE HFP
[%] [%] [%] VDF/HFP/TFE/CSM* 69
X 33 33 33 TFE/PMVE/CSM* 71
Y 55 23 22
Z 22 12 65 *Cure Site Monomer
Soures: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons
A. L. Logothetis „Chemistry of Fluorocarbon Elastomers“ Prog. Polym. Sci., Vol. 14, 251-296 (1989)
FKM: Performance of Standard Grades

Copolymers Fluorine Cont. Volume swell Tg [°C]
[wt.%] benzene gear oil
21°C 121°C
VDF/HFP 65 20 171 -18
VDF/HFP/TFE 67 15 127 -8
VDF/HFP/TFE/CSM* 69 7 45 -5
TFE/PMVE/CSM* 71 3 10 -19
TFE/P 54 - - -2 (0)
Storage in motor oil which contains amines (163°C)

180
Benzene/21°C 10
reduction of elongation at
160 Gear Oil/121°C

Volume Swell [%]
0
140
-10
120
-20
break [%]
HNBR
100 -30
FKM (68% F)
80 -40
60 d -50
40 -60
20 -70
0 -80
60 65 70 75 0 200 400 600 800 1000
Fluorine Content [wt.%] time [h]
FKM: Glass Transition Temperatures
H F
0 VDF Vinylidene fluoride
Glass transition temperature [°C]
TFE/VDF/PMVE (59% fluorine)

H F
-5 TFE/VDF/HFP
F CF3
HFP Hexafluoropropene
-10 (76% fluorine)
F F
-15 F F TFE Tetrafluoroethylene
(76% fluorine)
-20 F F
-25 F O CF3
PMVE Perfluoromethyl-
-30 F F vinyl ether
(69% fluorine)
H CH3
-35
0 0,5 1 1,5 2 P Propen
H H
Hydrogen content [wt.%]
Source: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons
Range of FKM-Grades and Vulcanization

Ageing Resistance in Media with Basic Additives
Vulcanization with
Peroxides
peroxi-
Vulcanization with
disch
Bisphenols
Vulcanization
with Diamines
Aflas Viton A Viton B, GF Viton GLT

PVDF Kalrez PTFE
55 65 75
Fluorine Content [wt. %]
FKM: Vulcanization with Diamines
1. Elimination of HF by MgO, CaO und PbO.
CF3 CF3 CF3
- HF - HF
CF2 CH2 CF2 CH2 CF2 CF2 CH CF2 CH2 CF2 CF2 CH CF CH CF2
F
2. Crosslinking by Diamines, which are used in "capped form" (such as carbamates) in

order to increase scorch resistance CF CF 3 3
CF2 CH CF CH2 CF2 CF2 CH CH2 CF2

CF3
NH N
CF2 CH CF CH CF2 H2N R NH2 - 2HF
R R
CF2 CH CF CH CF2 NH N
CF3 CF2 CH CF CH2 CF2 CF2 CH CH2 CF2
CF3 CF3
Diamine cure yields crosslinks which are liable to hydrolysis (not steam resistant)
CF3
CF3
CF2 CH CH2 CF2
CF2 CH CH2 CF2
O
N NH2
H2O
R R
N NH2
O
CF2 CH CH2 CF2
CF2 CH CH2 CF2
CF3
CF3
Sources: W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978)
W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979)
FKM: Vulcanization with Bisphenols

1. Elimination of HF by MgO, CaO and PbO
CF3 CF3 CF3
- HF - HF
CF2 CH2 CF2 CH2 CF2 CF2 CH CF2 CH2 CF2 CF2 CH CF CH CF2
F
2. Crosslinking with Bisphenols ( such as Bisphenol AF) in the presence of BTPPC (Benzyl
triphenyl phosphonium chloride)
BTPPC acts as phase transfer catalyst and is often referred to as "accelerator"
+
CF3
CF3
+ - HCl
HO OH + CH2 P Cl CH2 P
+
HO O
CF3
CF3
n n
CF3
CF2 CH CF CH2 CF2

CF3
CF3 O
HO O
CF2 CH CF CH CF2
CF3
CF2 CH CF CH CF2
CF3 CF3
CF3
Sources: T. L. Smith, W. H. Chu, J. Polym. Sci A-2, 10, 133 (1972)

A. W. Fogiel, J. Polym. Sci., Symp., 53, 333 (1975) O
W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978) CF2 CH CF CH2 CF2
W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979) CF3
A. Neppel, M. v. Kuzenko, J. Guttenberger, Rubber Chem. Technol., 56, 866 (1983)
D. J. Plazek, I. C. Choy, F. N. Kelley, ‚E. von Meerwall, L.-J. Su, Rubber Chem. Technol., 56, 866 (1983)
A. N. Theodore, M. Zinbo, R. O. Carter, III, J. Appl. Polym. Sci., 61, 2065 (1996)
FKM: Vulcanization with
CF
Peroxides
CF3 3
CF2 CF2 CF CF2 Br Br/J-Content:

CF2 CF
CF2 CF2 CF2 CF2 0,5-1 wt.%
J CF2 CF2
n
C H2J2 Type of Bond energy CF2 CFBr

bond [kJ/mol]
C-F CF2 CHBr
C F2J2 480
C-H 405 CF2 CF O CF2 CF2 Br
C-Br 270
J-( C F 2 ) - J Br CF2 CF2 Br
4 -6 C-J 200
• C-F bonds have a high bond energy. As a consequence, F-radicals cannot be abstracted by peroxides and
FKM with high fluorine contents (> 70 wt.%) cannot be vulcanized by the use of peroxides.
•For the vulcanization of FKM with F-contents > 70 wt% special cure sites are required. For this purpose
bromine and iodine are incorporated into FKM. C-Br and C-I bonds have a lower bond energy thqn C-F
bonds. Therefore Br- and I-radicals can be abstracted by the use of peroxides.
• Br- and I- based cure sites are incorporated by chain modifiers and by special comonomers which
contain Br- and/or iodine.
In the presence of Br- and I- containing compounds (modifiers and monomers) the polymerization
proceeds as a „living radical polymerization“ (this probably was the first example of a living radical
polymerization). During the course of the polymerization Br- and I are incorporated as end groups.
During peroxide cure of Br- and I- containing FKM and during subsequent annealing toxic compounds
are released which contain bromine and iodine.
Source: D. F. Lyons GAK 3/2005, Jahrgang 58 „ Einfluss der Molmasse auf die Eigenschaften von Bisphenol-AF-vernetzten Fluorkautschuken“
FKM: Vulcanization
•The method of FKM-cure depends on the fluorine content.
•Copolymers based on vinylidene fluoride and propene (Aflas) are crosslinked by

the use of peroxides.
•Fluoro rubbers with a fluorine content<70 wt.% (such as copolymers based on

VDF and HFP) are liable to HF-elimination which is a prerequisite for the
vulcanization with diamines and bisphenols. MgO and Ca(OH)2 are added to the
rubber compound in order to react with HF which is eliminated during
vulcanization.
•FKM vulcanizates which are cured by diamines and bisphenols contain double
bonds. As a result, their resistance to heat and ageing is inferior to FKM without
double bonds. Also, diamine cured FKM is liable to hydrolysis.
•Fluor rubbers with a fluorine content > 70 wt. % (FKM which contains no or only
a small amount of VDF) cannot elimiminate HF. Therefore vulcanization cannot
be achieved by diamines or bisphenols. FKM with F-contents > 70 wt.% requires
special cure site monomers which enable peroxide cure.
Source: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons
5.2. Silicon Rubber (Q)
CH3 CH3
Grade Tg [°C] Tm [°C]
( Si O Si O ) MQ - 120 - 45
n MQ VMQ - 120 - 45
CH3 CH3 PVMQ - 120 - 70
FMQ - 69
CH3 CH3
Vulcanizate Properties:
( Si O Si O ) VMQ Positive:
n
Low temperature performance
CH3 CH High temperature resistance
CH2 Low dependence of properties on temperature
changes
Ozone-, UV- and Weather resistance
Hydrophopic character
Physiological inertness
CH3 Negative:
Low reistance against acids, bases, vapour and
( Si O Si O ) PVMQ hydrocarbons (significant improvement with
n FMVQ)
Mechanical properties
CH3 CH RTV: poor HTV: better / DVR !
CH2 High gas permeability
CH2 CH2 CF3 Bond energies [kJ / mol]

CH3
Si-O 444
( Si O Si O ) C-O 339
n FMQ C-C 348
CH3 C-S 272
CH3
S-S 266
Silicon Rubber: Properties and Application Areas
Haushalt Application Areas:

20% Automotive
industry
40% Pharmaceutical- and medical rubber
goods
Medical
Applications Rubber goods with food contact
25% Machine building
15%
Cable insulation
Adhesives
Temperature [°C] duration
90 40 years Moulded articles
121 10-20 years
150 5-10 years Hoses, sealants (Automotive, Machine
200 2-5 years building and E&E)
250 3 months
315 2 months
Sources:
•K. Polmanteer, Rubber Chemistry Technology, Vol 61: 471-502“Silicon Rubber, its Development and Technological Progress“
•T. Maxson GAK 12/1995, Jahrgang 48, 873-884 „Fluor-Silikonkautschuk“
•D. Klages, U. Raupbach, GAK 4/1995, Jahrgang 48, 49-51 „Fluorsilicon-Kautschuk: Ein sehr moderner Werkstoff“
•E. L. Warrick, O. R. Pierce, K. E. Polmanteer, J. C. Saam, Rubber Chemistry Technology, Vol 52: 437-526 „Silicone Elastomer Developments 1967-1977“
•Winnacker/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Producers Capacities and Silicon Rubber Market
Manufacturer* Site Siloxane- Silicone
Capacity Rubber-
[kt] Brand Name
Dow Corning Carollton, USA 260.000 Silastic®
Barry, GB 110.000
Waterford, 110.000
Momentive USA
(formerly: GE + Bayer) Ohta, Japan 40.000
Leverkusen, 65.000 Silopren®
DE
Shin-Etsu Isobe, Japan 95.000 KE, Sylon®
Wacker Burghausen, 90.000 Elastosil®
DE
Nünchritz, DE 30.000
Rhodia Rousillon, FR 60.000 Rhodorsil®
S Western World (2000) 850.000

*Evonik and Crompton are active in this market without proprietary siloxane production
Japan
25% Nord-
amerika
44% Year 1995 2005
Consumption /t: ~ 110.000 ~ 200.000
Growth rate 2005: ca. 3,5 % / a; LSR ca. 10 % / a
Europe
Source: 31%
Winnacker/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Silicon Rubber: Production

Synthesis of Silicium:
SiO2 + C Si + 2 CO
Rochow-Process: CH3
2 CH3-Cl + Si Cl Si Cl
CH3
H3C CH3
Si
O O D3
H3C CH3
Si Si
H3C O CH3
H3 C O CH3
CH3
- HCl H3C Si Si CH3
n Cl Si Cl + 4 H2O O O D4
CH3 Si Si
H3C O CH3
H3C CH3
H3C CH3
Si O n Dn
Silicon Rubber: Production
H3C O CH3
H3C Si Si CH3 85 % CH3 CH3
O O O Si O Si OH
n
Si Si 15 % CH3 CH3
H3C O CH3
H3C CH3
Katalysatoren: Übliche Temperaturen:

Säuren, Lewis Säuren, Saure Silikate, KOH 140°C
Basen NaOH 170°C
After short-stopping of the „polymerization“ residual monomers are removed under vacuum.
For standard grades residual monomer contents are specified < 1 wt.% (for specialities: <0,5 wt.%)
CF3 CF3
CH2 CH2
H3C CH3
HC CH H2C O CH2
O O
H3C Si Si CH3 Si Si H3C Si Si CH3
O O O O O O
Si Si Si Si Si Si
H3 C O CH3 O H3C O CH3
CH CH H3 C CH3 CH2 C
H2
CF3 CF3
CH2 CH2
Modified silicon rubbers are obtained by the copolymerization with the respective cyclic monomers. As a
consequence multibloc copolymers are obtained initially. At extended reaction times randomization occurs.
Silicon Rubber: Vulcanization

HTV-Kautschuk Liquid Rubber RTV-Rubber
Chain length [nSi] 10.000 1.000 200
Viscosity Greasy/Highly viscous Highly viscous liquid / pourable
processing Transfer moulding Transfer moulding
Extrusion
Transfer Moulding
Crosslinking method
Peroxides predominantly predominantly
Addition 1C- und 2C-systems 2C-Systeme RTV-1: Condensation
RTV-2: Addition
Cure temperature 110 -300 °C 110 - 200 °C 25 - 150 °C
Vulcanization Method Products

Condensation at room temperature Silanol containing
(RTV) Silicon rubbers
Platinum catalyzed hydrosilylation Silicon rubbers with
at low or elevated temperature silanol and vinyl
(RT to 80°C, LSR: 110-200°C) groups
High temperature-Vulcanization MQ, PVMQ, MVQ,

with peroxides (HTV: 120-180°C) FVMQ
RT-Vulcanization of Silicon Rubber (2K-System)
1a) Condensation of polysiloxanes which contain silanol groups by multifunctional

alkoxysilanes
R R
R R Si
Si
Si OH OR HO Si R O O R
- 4 ROH
R R
Si
RO Si OR
R O O R
R R
OR
Si Si
Si OH HO Si
R R
R R
Typical mulftifunctional alkoxysilanes are:
OR R OR OR
RO Si OR RO Si OR RO Si O ( Si O ) R = Me, Et
n
OR OR OR OR
Metal carboxylates are often used for catalysis :

Metals: Pb, Zn, Zr, Sb, Fe Sn Ba, Ca
Carboxylates: Naphthenate, Octoate, Hexoate, Laurate, Acetate
Typical examples are:
Tin-(II)-octoate und Dibutyl tin dilaurate in the presence of chloroacetic acid
RT-Vulcanization of Silicon Rubber

(1K- und 2K-Systems)
1b) Condensation of polysiloxanes which contain capped silanol groups by
multifunctional alkoxysilanes
R O O R
R R
Si O C CH3 CH3 C O Si Si Si
+ H 2O O O R
R R R
RO OR - CH3COOH
Si
Si O R
R O
R O RO OR O R Si
Si
R R
Si O C CH3 CH3 C O Si
R R
For the condensation reaction the catalysts quoted under 1a) are being used.
RTV-Vulcanization of Silicon Rubber
(2K-System)
1c) Condensation of polysiloxanes with silanol groups by means of multifunctional

silanes (with evolution of hydrogen)
R O
R O
Si OH H Si R
- H2 Si O Si R
R O R
R O R
R Si H HO Si
R Si O Si
O R
O R
For the condensation reaction the catalysts quoted under 1a) are being used.
Application for Bladder coatings
LT-Vulcanization of Silicon Rubber

(1K und 2K-Systems)
2) Platinum catalyzed hydrosylization (50-150°C)
CH3 CH3 CH3 CH3

( Si O ) Si O ( Si O ) Si O
n n
Pt-Compounds as
CH3 CH H2PtCl6 (ca. 10 ppm) CH3 CH2
CH2
CH3 H CH3 CH2
( Si O ) Si O
n ( Si O ) Si O
n
CH3 CH3 CH3 CH3
Inhibitors:
HT-Vulcanization of Silicon Rubber
3) Peroxide Cure (120-180°C)
Typical Peroxides Temperature °F

(t1/2) = 1 min.)
Bis(2,4-dichlorobenzoyl)Peroxide 234
Di-Benzoylperoxide 271
Di-Cumylperoxide 340
2,5-Dimethyl-2,5-bis(t-butyl peroxy) hexane 354
Di-t-Butylperoxide 379
R R R R R R
R R R
Si O Si O Si Si O Si O Si
Si O Si O Si
R R R R R* R
Peroxide R R R
- 2 H* R R R
R R R R R* R
Si O Si O Si
Si O Si O Si Si O Si O Si
R R R
R R R R R R
Impact of Vulcanization Method on Cost of Articles

Comparison of Peroxide-
Peroxide- (HTV) and platinum catalysed LTV-
LTV-Cure
Cost Factor HTV LTV
Raw materials [$/pound] 3,50 5,00
Vulcanization time [sec] 120 60
Overhead-Costs [$/h] 60,00 60,00
salaries [$/h] 12,00 12,00
Hours per shift 10 10
Shifts per week 8 8
Number of nests per mould 3 3
Weight per article + 10% loss 59,5 59,5
Number of articles per week 7200 14.400
Material consumption per week 885 1.770
Raw material costs per week [$] 3.097,31 8.849,45
Total cost per week [$] 8.857,31 14.609,45
Cost per article [$] 1,23 1,01
Savings per article [%] 0 21,25
Financial result per year [$] 44.286,55 230.563,76
Increase of financial result [%] 0 420,62
Source: Rubber World, 12/1994, S. 20-24

5.3. Hydrogenated Nitrile Rubber (HNBR)
Range of Products: HNBR (partially and fully hydrogenated grades)
XHNBR
Low-Tg-HNBR
Low-Mooney-HNBR
Overview:
• Microstructure, Property Profile and Appliecation Areas
• Catalytic Hydrogenation of NBR
• Sequence of Process Steps in NBR- and HNBR-Production
• Producers and Production Capacities
• Chemical and Physical Properties
• Comparison of NBR- and HNBR Properties
»Speed of Ageing
»Tg
»Crystallization
»Stress/strain-Performance
• Vulcanizate Properties of Sulfur- und Peroxide crosslinked Vulcanizates
• Performance of HNBR in Power Transmission Belts
HNBR: Microstructure
N
C
C
N
δ−
CH2 H H
δ+ N
C
CH CH CH
C C CH 2
H3C CH2 H2 H2 CH
1 2
Butylidene-Moiety Ethylidene-Moiety Nitrilo-Ehylidene-

Moiety
HNBR: Property Profile and Application Areas
Positive:
• Broad range of grades (Mooney, degree of hydrogenation, acrylonitile content)
• excellent mechanical properties of vulcanizates (high TS, high abrasion resistance and high
dynamic resistance)
• high oil resistance (depending on acrylonitrile content)
• good adhesion to fibres and cords (Covulcanization)
• Low temperature flexibility
• High filler loadability of compounds
Negativ:
• Max. service temperature < 155°C
• High Tg >-30°C
• Bad incorporation of softeners
• High price (~ € 20/kg)
HNBR: Application Areas and Articles

Expansion Blow Out Preventer
Joints 15%
45%
25%
Ship Couplings 7% 4% 4%
Riemen Schläuche Dichtungen
Kabel Ölförderung Sonstige
Rotor/Stator- Pumps
Roll Covers Oil well Packers

Catalytic Hydrogenation of NBR
Requirements for Hydrogention Catalyst:
Selective Hydrogenation of C=C bonds • Selective and quantitative hydrogenation
of C=C- double bonds in the presence of
nitrile groups without gel formation
• Low catalyst loadings and/or catalyst
recovery
N Homogenous Catalyst Systems:
C
(PPh3)3 RhI Cl and (PPh3)4RhI H
(US 3700637, DE 2539132, EP 134023, DE 3541689, DE
C 3540918, EP 298386, DE 3529252, DE 3433 392, US 4,464,515,
N US 4,503,196, DE 3921264, US 6084033)
H2/Catalyst Heterogenous(Supported) Catalyst Systems:

N
Pd/SiO2; Pd/C; Pd/CaCO3; Pd/BaSO4
C (DE 3229871, US 4337329, US 4384081, US 4510293, DE
3227650, DE 3046008, EP 0298386)
C Relative prices of noble metals [€/g]:
N Rh (150) > Ru (75) > Pd (12,50)
Unselective Hydrogenation of Nitrile-Groups Results in Gel Formation
H
H
C NH2 + HN
C N
- NH3
HNBR Grades with Low Mooney Viscosities

During hydrogenation the Mooney viscosity
increases by a factor 2. Due to high stickiness
the production of NBR-grades with a Mooney
viscosity > 30 MU is not possible. Therefore
R N
the range of standard HNBR viscosities was
C limited to >60 MU until recently.
C Cross-metathesis of NBR with olefins allows

N for the production of NBR with Mooney
viscosities < 30 MU. In-situ hydrogenation of
theseNBR-feedstocks yields HNBR-grades
Catalyst with Mooney viscosities < 60 MU.
As a consequnece of low TONs, large

amounts of catalysts are required for the
N cross-metathesis of NBR.
R C
CH 2 H C Metathesis catalysts which are robust
C towards nitrile groups are protected by
N patents. Their use implies the payment of
licence fees.
Catalysts without Activity in NBR-Metathesis *
PCy3
PPh 3
Cl
Cl Ru
BH 3
2-
Ru Cl Ph Ph
Cl PCy3 S
P
PPh 3
Ciba-Catalyst Cl
Ru
+
Cl 2 K
Grubbs-I-Catalyst P
PCy3 Ph Ph
BH 3
BF 4
-
Cl Cl
Ru Ru
R1 Cl
Cl +
Catalyst from Prof. Berke' s
P R2 PCy3 group (University of Zurich)
PCy3 Ph
R3
Piers-Catalyst Fürstner-(I)-Nolan-Catalyst (Umicore)
2- + 2- +
SnCl3 Ph SnCl 3
Ph
Cl Cl
Ru P Ru
Ph
Cl Cl
N N
SnCl3 SnCl 3
Ph
P
Ph
Ph
2 2
Catalyst from Prof. Berke' s group (University of Zurich) Catalyst from Prof. Berke' s group (University of Zurich)
*Source: Julia-Maria Müller, Dissertation TU München
Catalysts which are Active in NBR-Metathesis*

(„Number of Catalytic Steps (TON)“)
Mes N N Mes Mes N N Mes Mes N N Mes
Cl
CF 3 COO Cl
Ru Ru
Ru Cl
CF 3COO Cl R1
+ PCy 3
O P R2
R3
Buchmeiser-Nuyken-Catalyst Piers-II-Catalyst Grubbs-II-Catalyst

TON = 8 / 23°C TON=12 / 55°C TON=40 / 23°C
Mes N N Mes
Mes N N Mes Mes N N Mes
Cl
Cl
Ru Cl N Ru
Ru
Cl
Cl Cl
O N
O
Br
NO 2
Br
Grubbs-Hoveyda-Catalst Grela-Catalyst Grubbs-III-Catalyst
TON=53 / 23°C TON=78 / 23°C TON=120 / 23°C
*Sources: Julia-Maria Müller, Dissertation TU München; M. Schneider, Dissertation TU München,

M. Kellner, MSc-Thesis TU München; K. Langfeld, MSc-Thesis TU München; C. Gantner, MSc-Thesis TU München
Sequence of Process Steps in NBR and HNBR-
Production
NBR-Production: Sequence of Process Steps:

Removal of Latex- Thermal Bale wrapping
Emulsions- Mechanical Bale
residual coagulation drying Packaging
polymerization dewatering pressing
monomers + crumb wash and storage
HNBR-Production: Sequence of Process Steps

Make-up of
Hydrogenation Catalyst recovery
catalyst solution
Removal of
Cemement Solvent removal
Bale cutting oxygen and dilution Catalyst recovery
preparation- by evaporation
hydrogenation
Wet Mechanical Thermal Bale wrapping

Bale Packaging
solvent dewatering crumb-
pressing and storage
stripping of crumbs drying
HNBR-Producers and Capacities

Producers and Capacities
Company Site Capacity [t]
Takaoka Japan 2.800
Zeon
Houston USA 2.000
Leverkusen Germany 3.000

Lanxess
Orange USA 3.600
Total 11.400
Markt- und Marktentwicklung

14000
12000
10000 Consumption
Volume [t]
capacity
8000
6000
4000
2000
0
1992 1994 1996 1998 2000 2002 2004
Ageing of Unvulcanized NBR and HNBR
(Increase of Mooney Viscosity ML 1+4/100°
1+4/100°C))
+1 NBR Hydriergrad: 0 %
+0 HNBR Hydriergrad: 96 %
HNBR Hydriergrad: 99,5 %
-1
-2
-3
-4
ln Vbr
-5
-6
-7
-8
1/T *103 [K-1]
2,0 2,4 2,6 2,8 3,0 3,2
T [°C]
180 160 140 120 100 80 60 40
Source: W. Obrecht, H. Buding, U. Eisele, Z. Szentivani, J. Thörmer, Angew. Makromol Chem. 145/146 (1986) 161-179 (2373)
„Hydrierter Nitrilkautschuk: Ein Werkstoff mit neuen Eigenschaften“
Tg of HNBR and NBR

100 E/ACN-Copolymers 100 NBR
HNBR (fully hydrogenated)
80
80
60
60 40
20
40
Tg [°C]
0
20
-20
0 -40
-60
-20
-80
-40 -100
0 20 40 60 80 100 0 20 40 60 80 100
Acrylonitrile Cont. [wt.%] Acrylonitrile Cont. [wt.%]
Data for Ethene/Acrylonitrile-Copolymers from: R. E. Uschold, I. B. Finlay, Appl. Polym. Symp. 25 (1974) 205
Tg of Ethene/Vinylacetate- und Ethene/Vinylchloride-Copolymers
100 Ethene/Vinylacetate-Copolymers 100 Ethene/Vinylchloride-Copolymers
80 80
Levapren
Nielsen et al.*
60 60
40 40
Tg [°C]
20 20
0 0
-20 -20
-40 -40
0 20 40 60 80 100 0 20 40 60 80 100
Vinylacetate Cont. [wt.%] Vinylchloride Cont. [wt.%]
Source: Ethene/Vinylacete Copolymers: L. E. Nielsen, J. Pol. Sci. 42 (1960) 357-366
Ethene/Vinylchloride Copolymers: F. P. Reding, J. A. Faucher, R. D. Whitman, J. Pol. Sci. 57 (1962) 483-498
Influence of ACN-Content on Crystallinity of HNBR (DSC)
16
14
1. DSC-Aufheizung
12
2. DSC-Aufheizung
Crystallinity [%]
10
0
0 10 20 30 40 50 60
Acrylonitrile Content [wt. %]
Tgs of Ethylene-Copolymers
100
50
0
Tg [°C]
-50
EPM
-100
HNBR
EVC
EVM
-150
-200
0 10 20 30 40 50 60 70 80 90 100
Comonomer Content [wt.%]
Influence of Nitrile Content on Tg of HNBR

100
50
0
Tg [°C]
-50
HNBR (fully hydrogenated)
NBR
-100
?
-150
0 10 20 30 40 50 60 70 80 90 100
Acrylonitrile Content [wt. %]

Dependence of Tg on Degree of NBR-Hydrogenation (ACN-
Cont.: 34 wt. %)
-20
dyn. mech. (11 Hz)
-22
DSC
-24
-26
Tg [°C]
-28
-30
-32
-34
0 20 40 60 80 100
Degree of Hydrogenation [%]
Source:
U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation Between
Network Structure and Properties of Sulfur- and Peroxide-Cured HNBR Vulcanizates“
Influence of Residual Double Bond Content on Stress/Strain-

Properties of HNBR-based Vulcanizates
(34 wt.% ACN; unfilled; sulfur vulcanized)
100 phr HNBR
12 0,07 phr Schwefel
2,63 phr TMTD
2,07 phr DTDC*
10 * Dithiodicaprolactam
stress [MPa]
8 11,0%
7,9%
4,0%
6
1,9%
0,5%
4
0
0 100 200 300 400 500 600 700
strain [%]
Source:
U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation Between
Network Structure and Properties of Sulfur- and Peroxide-Crosslinked HNBR Vulcanizates“
Dependence of E‘ and E‘‘ on Temperature (HNBR with
38,5 wt .% ACN)
10000
1000
E' and tan δ [MPa]
E'
E''
100
10
0,1
-200 -150 -100 -50 0 50 100
Temperature [°C]
NBR and HNBR: Impact of ACN-Content on

Stress/Strain-Properties of Unvulcanized Raw Rubbers
0,8 50
NBR HNBR
0,7 45
40
0,6
35 18,9 wt.%
28 wt.%
0,5
Stress [MPa]
stress [MPa]
30 33,9 wt.%
38,5 wt.%
0,4 25
48,3 wt.%
0,3 19,2 wt.% 20

28 wt.%
15
0,2 34,2 wt.%
39,1 wt.% 10
0,1 49 wt.%
5
0 0
0 1000 2000 3000 4000 0 500 1000 1500
elongation [%] elongation [%]
Influence of ACN-Content of Unvulcanized NBR and HNBR on
Maximum Stress (Yield-Stress) on “True“ Tensile Strength
300
"True" Tensile Strength [MPa]

250
200
150
100
50
0
1
Yield-Strength
0,8
[MPa]
0,6
0,4
0,2
0
0 10 20 30 40 50
Acrylonitrile Content [wt.%]
Influence of Extention on Permanent Elongation of Fully

Hydrogeanted, Unvulcanized HNBR (Variation of ACN-Content)
extension
160 120
280%
140 ε = ε bleibend 48,3 %
permanent elongation [%]
100
permanent elongation [%]
120
80
100 200%
80 ASTM D 1566 - 98 18,8 % 60

Kautschukdefinition
60 40
39,0 % 120%
28,2 %
40
20 80%
34,9 %
20
0
0
0 20 40 60
0 100 200 300 400
elongation [%] ACN-content [wt.%]

Influence of Sulfur- and Peroxide Vulcanization
on Properties of Partially Hydrogenated HNBR
H-NBR 100,0 phr HNBR-Grade (Therban) 1706 S 1706 S
Sulfur 0,5 phr ACN-content [wt.%] 33,7 33,7
Stearic acid 1,0 phr RDB-content [Mol.%] 4,3 4,3
ZnO 2,0 phr ML 1+4(100°C) [MU] 60 60
MgO 2,0 phr Compound Properties
OCD 1,0 phr Compound Mooney/ ML 1+4(100°C) 64 66
ZMB-2 0,4 phr Mooney-Scorch (120°C) [min.] 12,5 14
N 550 45,0 phr Fmax [N] 56,4 51,2
TMTD 2,0 phr Vulcanizate-Properties
CBS 0,5 phr 72
Shore A Hardness(23°C) 72
Vulcanization time: 20 min Shore A Hardness (70°C) 69 70
temperature: 160°C M 100 [MPa] 3,4 5,6
M 200 [MPa] 8,8 17,8
M 300 [MPa] 14,7 -
H-NBR 100,0 phr TS [MPa] 27 26
ZnO 2,0 phr elongation [%] 510 295
MgO 2,0 phr Rebound [%] 38 36
DDA 1,0 phr Compression Set
ZMB-2 0,4 phr 70h/-10°C [%] 73 68
N 550 45,0 phr 70h/23°C [%] - 10
TAIC 1,5 phr 70h/100°C [%] 73 -
Perkadox 1440* 7,0 phr 70h/150°C [%] - 27
Vulcanization time: 15 min Hot air ageing
D/D0 (150°C/ 5 d) [%] 55 -
Temperature: 180°C
Annealing: 6h/150°C D/D0 (150°C/24 d) [%] - 54
Degree fo vol. swelling in fuel
Perkadox 1440 100*(V/ V0-1) (48h/50°C) [%] 75 65
Bis(t-butylperoxyisopropylbenzol 40%ig
Vulcanizate Properties of Sulfur- and Peroxide

Cured HNBR (Partially and Fully Hydrogenated)
HNBR-Grade (Therban) 1706 S 1706 S 1706
ACN-content [wt.%] 33,7 33,7 34,5
Residual double bond cont. [Mol.%]4,3 4,3 0,4
ML 1+4(100°C) [ME] 60 60 63
Compound Properties
Compound Mooney [ML 1+4(100°C)]64 66 74
Mooney-Scorch (120°C) [min.] 12,5 14 16
Fmax [N] 56,4 51,2 52
Sulfur Core (Press 160°C/20`)
Peroxide Cure (Press 180°C/15`)
Shore A Härte (23°C) 72 72 73
M 100 [MPa] 3,4 5,6 6,9
M 200 [MPa] 8,8 17,8 17,7
M 300 [MPa] 14,7 - -
Tensile Strength [MPa] 27 26 24
Elongation [%] 510 295 280
Rebound [%] 38 36 34
Compression Set
70h/-10°C [%] 73 68 -
70h/23°C [%] - 10 12
70h/100°C [%] 73 - -
70h/150°C [%] - 27 28
Hot Air Ageing
D/D0 (150°C/ 5 d) [%] 55 - -
D/D0 (150°C/24 d) [%] - 54 59
Degree of Vol. Swelling in Fuel
100*(V/V0 -1) (48h/50°C) [%] 75 65 70
Performance of HNBR in Power Transmission Belts
200 180 160 140 120 100 [°C]
Materials used for 10.000
power transmission
log t/h for ε b = 50%

belts HNBR / peroxide cured
1.000
Leather HNBR / sulfur cured
100
SBR CR
10
1 -1
CR 2,1 2,2 2,3 2,4 2,5 2,6 10 -3 ( K )
-1 T
1000
rate of crack growth
HNBR CR HNBR
(Sulfur cured) 100
10 Tear-Analyzer-Test / Exp. Conditions

Frequency: 4 Hz
HNBR Strain Ampli tude: 20%
(Peroxide cured) 1 Attenuation mode: sinuoidal
Rate of crack growth: 1/co (dc/dn)
0,1
-20 0 20 40 60 80 100
Temperature [°C]
Source:
M. Mezger; D. Achten “Therban: The high performance elastomer in power transmission systems”
9. Tagung “Zahnriemengetriebe” am Institut für Feinwerktechnik und Elektronik-Design der TU Dresden
5.4. EVM: Profile of Properties and Applications
O O O
O C O C C O
CH3 CH3 CH3

VAc-content: 40-90 wt.%
radical polymerization in solution
Positive: Random monomer incorporation
Ozone-, UV-, and weather resistance Low molar masses
Maximum service temperature 175°C Significant degree of short chain branches
High filler loadability
FRNC-applicability Application Araeas:
(Flame resistant non corrosive) Automotive- and engineering: seals and
membrandes
Resistance to water/glycole Hoses in high temperature environment
Braod range of grades FRNC-products: cables and floorings
No necessity for post cure in oven Sound protection
FRNC Conveyor belts
Negative: Hot Melt and pressure sensitive adhesives
fair mechanical properties Protecting foils
Low temperature flexibility (depending on VAc- Blending component for HNBR, EPDM, CM,
content) NBR)
Fair oil resistance Rubber modification of thermoplasts (PVC,
TPU, SAN, PC etc.)
Range of products limited to ML 1+4 = 20 - 35 Oil additive
Vulcanization only peroxides Shoe soles
Source: H. Bartl, J. Peter, Über Äthylen/Vinylacetat-Copolymerisate und ihre Vernetzung; Kautschuk und Gummi, Jahrgang 14, 2 (1961) WT 23-32
Production Routes Towards EVM and EVA

10000
Producer Process Products
Exxon, BP, High pressure Escorene
Mitsui ctc.
High pressure bulk process
750-3000 bar Du Pont High pressure Elvax
120-300°C USI High pressure Vynathene
1000
Lanxess Solution Levapren
Mitsui Solution
Solution process
pressure [bar]
100-500 bar High pressure process:

50-120°C
100 • Preferred mprocess for EVA
Emulsion process (thermoplastic polymers with
10-100 bar VAc-content <40 wt.%)
30-70°C • Monomer conversion: < 20%
• Molar mases decrease with
increasing VAc-content
10
Solution process:
EVM-Rubbers • Preferred process for EVM-r
rubbers (VAc-cont. 40-90%)
• Monomer conversion: 60- 70%
1 • Solvents: t-Butanol; Methanol
0 20 40 60 80 100
Emulsion Process:
Vinylacetate content [wt.%] • Preferred process for latices with
high gel content (paints)
High Pressure Bulk Process: • Monomer conversion: ~ 100%
US 5089579 (Bayer AG), Prio.: 11. 12.1989; Erf.: H. Sutter, A. Kolwert, W. Obrecht
Solution Process:
US 4937303 (Bayer AG), Prio.: 01.05.1989; Erf.: B. A. Wolf, B. Will, W. Obrecht, R. Casper, W. Baaade, G. Sylvester, K-P. Meurer, H. Zimmermann
EP 0632067 (Bayer AG), Prio.: 30.06.1993; Erf.: R. Steiger, E. Asch, W. Baade, W. Obrecht
EVM: Physical Properties
Thermoplast Rubber
100
Temperature (Tg) [°C]
Enthalpy of fusion
80
Glass Transition 60
(DH)[J/g]
40
20
0
-20
-40
0 20 40 60 80 100
Vinyl acetate content [wt.%.]
100
Temperature of Fusion
80
60
(Fp)[°C]
40
20
0
-20
-40
0 20 40 60 80 100
Vinyl acetate content [wt.%]
EVM: Maximum Service Tempeature

0
-10
-20
weight loss [wt.%]
O CH3 O CH3 -30
O - HAc O -40
O CH3 -50 350 °C
-60
O
-70
-80
-90
-100
200 300 400 500 600
Temperature [°C]
Elastostab H 02 OCN N C N NCO
time till elongation becomes <50 % in h
106
100000
Stabaxol P 200 n n = ca. 4
O O
20000 h
H3C O nO N N C N
135 N O O nCH3 10000
H H
n
n = ca. 4
1000
1000 h
The addition of acid scavengers

such as carbodiimides and > 170°C 137°C
100
isocyanates does not improve hot 190 180 170 160 150 140 130 120 110
200
air performance temperature in °C
EVM: Dependence of Oil Swell and LOI (Limiting
Oxygen Index) on Vinyl Acetate Content
Storage time in SAE-oil SAE 90 (3 d/125°C)
LOI according to ASTM-D 2863
80 60
Delta F/F0 x 100 [%] Al2O3: 190 phr
60 Delta D/D0 x 100 [%]
Limiting Oxygen Index (LOI) [%]

50 Al2O3: 0 phr
Change of Properties [%]
Delta V/ V0 x 100 [%]

40 40
20 30
0 20
-20
10
-40
0
0 20 40 60 80 100 0 20 40 60 80 100
Vinyl acetate content [wt.%]
Vinyl acetetate content [wt.%]
Source: E. Rohde; DKG-Bezirksgruppentagung; NRW in Bad Honnef; 07.-08. Mai 1992
EVM: Dependence Properties on Vinyl Acetat

Content
EVM 100,0 phr Vinyl acetate content [wt.%] 40 45 50 60 70 80
MgO 2,0 phr
Compound properties
Stearic acid 1,0 phr
Mooney ML 1+4(100°C) 20 24 23 25 20 20
Carbon black/N 550 65,0 phr t10/180°C [min] 1,2 1,2 1,2 1,2 1,3 1,3
Vulkanox DDA 1) 1,0 phr t90/180°C [min] 7,2 6,6 6,6 6,2 6,9 6,1
Plasticizer DOS 2) 7,5 phr FH-FL/180°C [N] 17 20 19 21 19 17
Plasticizer ODTM 7,5 phr
Vulcanised properties
PE-Wax 2,0 phr
(ISO-Stab Nr. 2, 2mm)
Aktiplast PP 2,0 phr Shore A Härte (23°C) 75 74 68 71 68 72
TAIC 1,5 phr S 100 MPa] 5,0 5,7 4,4 5,4 4,2 4,7
Peroxide (40%ig) 3) 6,0 phr Elongation at break [%] 295 275 285 280 300 300
Vulkanization time: 10 min Tenjsile Strength [MPa] 11,7 13,6 12,6 12,8 11,5 10,5
Temperature: 180°C
Compression Set
no post vulcanization storage 70h/100°C [%] 23 20 20 22 21 27
in hot air
70h/125°C [%] 25 23 25 26 24 31
70h/150°C [%] 41 38 41 40 46 51
1) Styrenated Diphenyl amine (SDPA)
2) Dioctylsebacate (DOS)
3) 1,3-Bis(tert.-butylperoxyisopropyl)-
Hot air ageing (14d/150°C)
∆F/F0 x100 [%] -3 -12 -10 -11 10 -8
benzene (Perkadox 14/40) ∆D/D0 x100 [%] -2 -2 2 -2 -7 -15
∆H/H0 x100 [%] 10 9 11 12 15 14
Source:
E. Rohde Storage in SAE Oil90
DKG-Bezirksgruppentagung (3d/150°C)
NRW in Bad Honnef ∆F/F0 x100 [%] -26 -12 -8 8 6 10
07.-08. Mai 1992 ∆D/D0 x100 [%] -19 -4 -4 2 8 -12
∆V/V0 x100 [%] 69 47 31 13 3 -4
EVM/HNBR-Blends
Therban 1707 100 75 50 25 -
Levapren 500 - 25 50 75 100
EVM/HNBR 100,0 phr Rhenogran P 50 - 1,5 3 4,5 6
1)
Rhenogran P 50 var.
Compounc properties
Carbon black/N 550 50,0 phr Relative compound price 100 80 60 40 20
Carnuba Wax 2,0 phr ML 1+4(100°C) [ME] 123 99 58 40 32
t2/177°C [min] 1,5 1,6 1,5 1,6 1,6
MgO 10,0 phr t90/177°C [min] 11,7 11,0 10,2 10,2 9,5
ZnO 2,0 phr
TAIC 1,75 phr Vulcanized properties
Shore A Härte (23°C) 78 80 80 81 77
Peroxide (40%ig) 2) 7,0 phr S 100 [MPa] 10,7 13,1 12,6 12,0 8,3
Vulcanization time: 15 min Elongation at break [%] 240 190 170 145 165
Tensile Strength [MPa] 26 24 22,5 18,8 18,5
Temperature: 177°C
Anealing: 16 h Compression Set
70h/23°C [%] 12 12 12 14 14
1) Carbodiimide 70h/150°C [%] 20 17 17 14 9
2 Vulcup 40 KE 70h/175°C [%] 27 27 25,5 20 15
Hot air ageing(14d/150°C)

F/F0 x100 [%] -2,3 -3,8 -10 -7,5 -1,6
D/D0 x100 [%] -37 -26 -29 -21 -12
H/H0 x100 [%] +6 +5 +4 +3 +2
Source: Storage in ASTM oil Nr. 3
Test Report WR 26/83 (7d/150°C)
(Mobay, Chem. Corp.) ∆F/F0 x100 [%] -10 -17 -36 -50 -56
∆D/D0 x100 [%] -4 -11 -29 -34 -45
∆V/V0 x100 [%] +24 +34 +49 +67 +83
EVM: Influence of Post Cure on Physicals

15
O-Ring: Mechanical properties
without post with post
e cure cure
ur r e
10
stc cu Tensile Strength [MPa] 10,4 11,8
Stress [MPa]
p o ost εb [%] 285 230

th t p
wi ou M100 [MPa] 1,8 3,1
ith
w CS 72 h / 150°C [%] 63 31
5
CS 168 h / 150°C [%] 71 50
0
0 50 100 150 200 250 300
strain [%]
10
9
8
7
torque [dNm]
6
5
= 75 % of
4 total cure
3 Sources:
2 cycle time
for IM H. Meisenheimer, Kautschuk Gummi Kunststoffe,
1 52 (1999) 724
0 P. J- Pazur, L. Ferrari, H. Meisenheimer, ACS Rubber
0 20 40 60 80 100 120 140 160 180 200 220 240 Div. 165th Spring Meeting, Grand Rapids, Michigan
time [sec ] H. Magg, A. Welle, Nordic Rubber Conf. 2005, Köge,

Denmark
EVM: „Acrylate Reinforcing Technology“ (ART)
Levapren grade 500 500HV 500HV
Z in c d ia c ryla te Levapren 100 100 100
S a re t 6 3 3 TMQ 1,0 1,0
N 762 35 35
S a rto m e r 7 0 5 ZnO 10 10
O ZMB-2 3) 1,0 1,0
Ficon 153 1) 20 -
2+ Saret SR 633 2) - 20
H2C CH C O Zn Vul-CUP 40 KE 6,5 6,5
2
Compound properties
1) 1,2-BR (liequid rubber) Mooney ML 1+4(100°C) [MU] 23 9,9 26,8
2) Zn diacrylate 3)
For further ompound ingredients see Vulcanized properties

„Stuey on variation of vinyl acetate (ISO-Stab Nr. 2, 2mm)
content“ Shore A Härte (150°C) - 72 73
Source: Tensile strength [MPa] 12,6 13,5 20,8
T. A. Brown, Polysar Rubber Corporation, Elongation at break [%] 285 80 175
Technical Report TR 552.92,17 vom M 50 [MPa] - 6,6 4,2
22.05.92 M100 [MPa] 4,4 - 10,5
Rebound/23°C [%] - 43 46
„Acrylate-Reinforcing“ is used for Rebound/100°C [%] - 62 61
golf ball cores based on high Hot air ageing (14d/150°C)
F/F0 x100 [%] -10 1 -5
ART based “Golf-Ball-Core“-Patents D/D0 x100 [%] 2 -8 -29
EP 0496947, Prior.: 29.01.1991 (Bridgestone) H/H0 x100 [%] 11 6 8
US 6426387, Prior.: 04.08.2000 (Taylor Made Golf
Co. Storage in SAE-oil 90 (3d/150°C)
EP 1227121, Prior.: 24.01.2001 (JSR) ∆F/F0 x100 [%]
US 6525141, Prior.: 02.04.2001 (Bridgestone) ∆D/D0 x100 [%] -8 -13 -22
US 6270428, Prior.: 07.08.2001 ∆V/V0 x100 [%] -4 -6 -29
US 6517451, Prior.: 11.02.2003 (Titleist) 31 13,7 12,1
6. Thermoplastic Elastomers (TPE)
• Principle of Physical Crosslinking, Phase Morphology and Property Profile

• Nomenclature and Range of Available Grades
• Selection of Commercially Available TPEs, Producers and Brand Names
• Market, Areas of Applications and Prices
• Phase Morphology of Rubber Modified Thermoplastics and Thermoset Resins
• Comparison of Technological Properties of Different Classes of Engineering
Polymers
– Dependence of Shear Modulus on Temperature
– Dependence of Residual Elongation on Original Elongation
– Comparison of Technological Properties of Chemically and Physically
Crosslinked Rubbers (Data from Product Data Sheets)
• TPE-O and TPE-V
– PP-Performance and Price of EPDM/PP-Blends
– Mechanical Properties
• Advanced technologies for the production of PP-based TPEs
• TPEs from the viewpoint of a producer of technical rubbber goods
TPE: Phase Morphology and Property Profile

A coherent soft or rubber phase (coherent matrix) is
representative for most TPEs
The hard phase which contains the physical cross-links
is dispersed within the soft phase. The hard phase is
only physically and never chemically crosslinked
The soft phase can either be uncrosslinked or
crosslinked
Examples for physical crosslinks

Soft Segment • Hydrogen bonds /Crystallization
Hard Segment
• Dipol/Dipol - Interaction
Scheme of the Phase Morphology • Glassy Hardening (vitrification)
of A-B-A, (A-B)n and (A-B)x- • Ionomers
Multiblock Copolymers
Positve:
• Good vulcanizate properties at low / moderate temperatures Type of Bond energy
• No compounding and vulcanization know-how necessary bond [kJ / Mol]
• Short cycle times no time consuming vulcanization covalent 260 - 350
• Recycling of waste (due to thermo labile/reversible crosslinks) physical 10 - 20
Negative:
• High permanent set after (tension set, compression set)
• Poor mechanical properties at elevated temperatures (tensile strength, compression set)
• Deterioratioon of mechanical properties in appropriate solvents
• High heat-build-up in dynamic applications
• Limited range of grades (particularly no soft grades available)
• Anisotropic properties of injection moulded articles (particularly for TPEs with uncrosslinked rubber phase)
Nomenclature and Range of Available TPEs
Examples
TPE-O EPM / PP
mechanical and
reactor-blends EPDM / PP
(unvulcanized)
Thermoplastic
Polyolefins EPDM / PP
Olefin TPE-V NBR/ PP
(dynamically vulcanized)
NBR / PVC
EVM / PVC
Polyblends1 PVC based blends ACM / PVC
(without dynamic vulcanization)
High Performance HNBR / PA

HNBR / PBT
TPE-V NBR / PA
(without polyolefines EVM / PA
Thermoplastic (dynamically vulcanized) EVM / PBT
Elastomers SBC
TPE-S (SBS, SIS, SEBS, SIBS)
Styrenic Block-Copolymers
TPE-U Polyester-Urethanes,
Polyurethane Block Copolymers Polyether-Urethanes
Multi-Block-
Copolymers2
COPE based on aromatic
TPE-E Polyesters (Terephthalates)
Copolyester Block Copolymers PBT´/ PTHF; PET / PTHF
TPE-A PEBA based on

PA 6 and PA 12
Polyamide Block Copolymers
1 Consists of an elastomer finely dispersed in a thermoplastic matrix
2 Rubber and thermoplastic segments are chemically bonded by block- or graft copolymerization
Sources: SRI Elastomers Overview 2008; Stratley Consultants
Selection of Commercially Available TPEs, Producers

and Brand Names
Type of TPE Crosslinking Producer Brand Name
Principle
TPE-O (reactor blends) Crystallization UCC Flexomer®
Bassell Spherilene®
Exxon Exxtral®
TPE-V Crystallization AES (Advanced Elastomer Systems) Santoprene®
AES (Advanced Elastomer Systems) Geolast®
PVC-based blends Dipol/Dipol Denki KK Denka LS®
High performance TPE-V Zeon ?

TPE-S Glassy hardening Shell Kraton®
SBS, SIS, SEBS (vitrification) BASF Styrolux®
Firestone, Polimeri
Dow
SIBS Kaneka Sibstar®
Boston Scientific Taxus®
Innovia SIBS®
TPE-U Hydrogen bonds / Bayer Desmopan/Texin®
Crystallization BASF Elastollan®
Goodrich Estane®
TPE-E Crystallization DuPont Hytrel®
Toyobo Pelprene®
TPE-A Hydrogen bonds / Atochem Pebax®
Crystallization Dow Estamid®
Ionomer Du Pont Surlyne®
TPE: Market, Application Areas and Range of Prices
WO-TPE-Market: 1,5 Mio t Areas of Application
IRP Shoe
SBC Hoses 18% 15%
TPO-V TPU
5%
COPE
PEBA Cables
Rest 3%
Medical Auto-
TPO- Appl. Ad- motive
Blends Asphalt hesives 32%
3%
Mod. 12%
12%
W.-Europe:: 576a t (2001)
TPE Price [€/kg]
Type 2.000 2.005 Growth
PP/EPM-Reactor Blends 0,90-1,20
[%] PP/EPM-TPE-V 2,00-2,50
SBC's 195 226 3 SBC 1,00-3,30
TPO's 135 172 5 SBS 1,30-1,50
TPV's 36 59 10,5 SIS 1,50-1,70
TPU's 62 79 5 SEBS 2,60-3,30
COPE's 20 30 8
COPA's 7,5 10 5 TPE-U (TPU) 3,00-4,00
Sonstige TPE-E (COPE) 3,50-4,40
Sum 455,5 576 4,5 TPE-A (PEBA) 3,60-7,00
Source:
European Rubber Journal 184,no.1 (January 2002)
Schematic Presentation of the Dependence of the

Shear Modulus on Temperature
104
103
Shear Modulus [MPa]
Tempeature Temperature of
of Use Processability
102
101
100
10-1
Temperature Softening
Tg of Temperature of
Rubber Thermoplast Phase
Phase
Dependence of Modulus on
Temperature: Target and Reality
104
103
Shear Modulus [MPa]
102
101 Target
Reality
100
10-1
-100 - 50 0 50 100 150 200
Temperature [°C]
Schematic Presentation of the Dependence of the Shear

Modulus on Temperature for Different Engineering Polymers
104
103
Shear Modulus [MPa]
4 3 2 1
102 5
6
101
7
100
10-1 8
- 100 - 50 0 50 100 150 200
Temperature
Dependence of Shear Modulus on Temperature for Different
Engineering Polymers
104
1. Thermoplastic Polymer
103 (Polycarbonate, PP.PA)
2. Thermoplastic
Shear Modulus [MPa]
(Polystyrene, PMMA)
4 3 2 1
102 5 3. Rubber Modified
Thermoplastic
6
4. Elastomer (crosslinked)
101
5. TPE
7 6. TPE
100
7. Elastomer (crosslinked)
10-1 8 8. Unvulcanized Rubber

- 100 - 50 0 50 100 150 200
Temperature
Schematic Presentation of Stress/Strain Diagrams

of Block Copoymers
elongation
A-B-A, (A-B)n und (A-B)x-
Block Copoymers
Residual elongation
stress [MPa]
A-B Block Copolymers
strain [%]
Dependence of Residual Elongation on Original
Elongation for Different Engineering Polymers
300 εresidual = εoriginal

εResidual ) [%]
200
TPE-O (EPDM / PP: 60/40)
residual elongation (
ASTM D 1566 - 98
„Definition of Rubber“ TPE-V (EPDM / PP: 78/22)
100
SBS with 27 wt.% styrene

NR/BR-tyre tread (with filler)
0 vulcanized gum stock
(unfilled NR)
0 100 200 300
original elongation ( εoriginal ) [%]
Compression - Set
ho h1 h2
ho- h2
CS = x 100 [%]
ho- h1
ho- h2
ho- h1
ho In compression set (CS) measurements ho ,
h2
h1, compression, exposition time, and
h1 exposition temperature are well defined
(DIN, ASTM). Most commonly, the
deformation is 25%. In order to achieve the
same deformation „ho-h1“ the pressure has
to be adjusted to the degree of x-linking
Comparison of Technological Properties of
Chemically and Physically Crosslinked Rubbers
(Data from Product Data Sheets)
S BC T P E -U T PO
me ch. T PV T PV
Cla ssica l
P rope rtie s T P E -A T P E -E E P D M/ P P E P D M/ P P E P D M/ P P
E la stome rs S BS S IS S E BS E ste r E the r
ble nd (pa rtia lly (highly
x-linke d) x-linke d)
S hore A 10 to 80 71 52 75 92 93 78 72 75
S hore D - 44 42 25 40 63 32 54
T e nsile S tre ngth [MP a ] 10 to 35 32 20 34 45 40 79 36 51 15,4 47 12 5,5 8,5
E longa tion a t bre a k [% ] 300 to 800 880 1200 500 450 380 715 485 380 880 660 650 350 490
CS (22h/ 70°C) 5 to 30 75 60 38
CS (24h/ 70°C) 5 to 40 60 60 62 21 5 90 53
CS (22h/ 100°C) 5 to 40 88 44
CS (70h/ 150°C) 30 (H N BR , FKM)
Technologische Eigenschaften von TPEs

und von Hauptvalenzelastomeren
klassische
200 Elastomere
Gebrauchstemperatur [°C]
PEBA
TPO
100 TPU
COPE
SBC
0
-100
0 50 80 100
Shore A Härte
30 40 50 60 70 80
Shore D Härte
PP-Performance and Price of EPDM/PP-Blends
180 7
TPE-V
(EPDM / PP-blend,
highly crosslinked)
160
6
140
Performance [arbitrary units]

Melting temperature [°C]
5 TPE/SEBS-
120
Blends
4
100
TPE-V
(EPDM/PP partially
cross-linked)
80 3
60
2 TPE-O
(mechanical
40 PP-Properties:
PP-Properties: blends)
• Low Price
• Low Price
• •High 1 TPE-O
HighSoftening
SofteningTemperaure
Temperaure (Reactor-
20 • •Good
Good AgeingResistance
Ageing Resistance
(Residual Catalyst Content) Blends)
(Residual Catalyst Content)
0 0
20 40 60 80 100 0 0,5 1 1,5 2
Isotacticity [%] Price [$/kg]

Source: T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced
Technologies 4, pp. 406-414 „New Polymers from New Source: Robert Eller Associates, Inc. 1996
Catalysts“
TPE-O and TPE-V: Basic Properties

TPE-O TPE-V TPE-V
Properties (Mechanical PP/EPDM (PP/EPDM-Blend with (PP/EPDM-Blend with
Blend) partially crosslinked highly crosslinked
EPDM-phase) EPDM-Phase)
Shore A-Hardness 78 72 75
Tensile Strength [MPa] 12 5,5 20
Elongation at break [%] 650 350 490
Compression Set 75 60 38
(22 h /70°C) [%]
Volume Swell in ASTM- soluble 90 50
Oil Nr. 3 [Vol%]
Uncrosslinked rubber phase Crosslinked rubber phase
n n
ir ectio ir ectio
D Flo w D Flo w
of of
TPE-O and TPE-V: Mechanical Properties
Properties no. of recycles

1 2 3 5
M100 [psi] 650 630 620 600 20
Tensile Strength [psi] 1530 1520 1500 1590 Shore D
Hardness: 50
15
35 Shore A
Hardness: 87
Stress [MPa]
30 1,0-1,5
Particle diameter [ µm] 10
25
5,4
20
17 5
15 Shore A
72 39 Hardness: 64
10
0
5
0 100 200 300 400 500
0
0 200 400 600 Elongation [%]
Elongation at break [%]
Gas Phase Technology

TPE-O: PP/EPM-Reactor-Blends PE* PP**
UCC Montell
BASF Fina
BP Phillips
Hoechst Solvay
Exxon UCC
Amoco BASF
Filter Filter Montell Amoco/Chisso
ventilator ventilator
Sumitomo
Sources:
* Ind Eng. Res. 33 (1994) 449-479
** Chem. Systems (April 1992)
Cooler "Polypropylene"
Product
outlet
Supported Removal
of
catalyst residual
monomer
Cooler
Propylene purification
Ethylene
purification
Temperature: < 90 °C (40°C-60°C)

Pressure: 9-15 bar packaging
Residence time per reactor: 0,5 - 1 h
Source: T. W. Klimek (Quantum Chemical Corp.) ANTEC `91, 1382-1384
Properties of PP/EPM- Reactor-Blends
1000
Catalyst Fragmentation
900 during Polymerization
800 Catalyst System A

E-Modulus [MPa]
700
600
Catalyst System B
500
400
300
20 30 40 50 60
Rubber Content [wt.%]
Source:
H. Schwager (BASF); Kunststoffe 82, 499 (1992)
T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“
Preparation of TPE-Vs by Reactive Processing

Blending
Definitions:
1) “Reactive Processing” stands for a chemical reaction in the course of which
polymers are modified without the use of solvents.
2) “Dynamic Blending” stands for the solvent free blending process during which
a chemical reaction occurs.
3) “Dynamic Vulcanization” is used for vulcanization reactions (without solvent)
with simultaneous shearing.
4) Every vulcanization method can be performed dynamically
5) Resin cure was the first vulcanization method applied for the production of
EPDM/PP based TPE-V
Preparation of a TPE-V by the Dynamic Vulcaniztion
of a EPDM/PP blend with Phenol Resin
1. Preparation of a PP/EPDM-Block Copolymer in order to partially compatibilize
PP and EPDM
1a) Reaction of PP with Dimethylol Phenol Resin in order to “activate” PP
OH
HOCH 2 CH2 OH
PP +
1) Melting PP at 185°- 190°C

2) Addition of dimethylol resin at 185°-190°C (5 Min.)
3) Addition of the catatalyst SnCl2 x 2H20 (2 Min.)
OH
PP CH2 CH 2 OH
Preparation of a TPE-V by the Dynamic Vulcaniztion of a

EPDM/PP blend with Phenol Resin
1b) Preparation of block copolymer by the reaction of “activated PP” with EPDM
OH
PP CH2 CH 2 OH + EPDM
1) Addition of EPDM and additional Phenol Resin at 185°- 190°C (5 Min.)

2) Addition of more SnCl2 x 2H20 at 185°- 190°C (5 Min.)
OH
PP CH 2 CH2 EPDM
Preparation of a TPE-V by the Dynamic Vulcaniztion of a
EPDM/PP blend with Phenol Resin
2) Addition of PP und EPDM with subsequent vulcanization of the EPDM-Phase
OH
PP CH2 CH2 EPDM
1) Addition of EPDM and PP at 185°- 190°C (5 Min.)

2) Addition of of more SnCl2 x 2H20 at 185°- 190°C (5 Min.)
PP - OH
EPDM-
PP CH2 CH2 EPDM
Phase Phase
In reality, the series of reactions from 1a), 1b) to 2) do not occur in a sequence
of reactions, which are well separated but rather in a concurrent fashion
Compatibilising Effect of Dimethylolphenol Resins in

Dynamic Vulcanization of PP/NBR-Blends
Polypropylene 185-190°C 0 50 50 50
Dimethylolphenol resin 5 min. 0 2 2 2
SnCl2 . 2 H2O 2 min. 0 0,4 0,4 0,4
Polypropylene 185-190°C 50 0 0 0
NBR + 5 min. 50 50 50 45
Aminino terminated NBR 0 0 0 5
Dimethylolphenol resin + 5 min. 0 0 1,67 5
SnCl2 . 2 H2O 0 0 0 0,5

M100 [MPa] 0 0 0 10,2
E-Modulus [MPa] 149 170 157 107
Permanent elongation [%] 0 54
Compatibilising Effect of Dimethylolphenol Resins in
Dynamic Vulcanization of PP/NBR-Blends
Polypropylene 185-190°C 25 37,5 50 62,5 75

Dimethylolphenol resin 5 min 1 1,5 2 2,5 3
SnCl2 . 2 H2O 2 min 0,2 0,3 0,4 0,5 0,6
Polypropylene 5 min 67,5 56,25 45 33,75 22,5

5 min 7,5 6,25
NBR + 5 3,75 2,5
Aminino terminated NBR 9,38 7,81 6,25 4,69 3,13
Dimethylolphenol resin + 1,13 0,78 0,5 0,28 0,13
SnCl2 . 2 H2O 5 min 1,13 0,94 0,75 0,56 0,38

M100 [MPa] 15,8 15,7 15,2 16,2 17,1
E-Modulus [MPa] 33 92 221 320 456
Permanent elongation [%] 20 33 50 63 70
Reactive Blending von EPDM/SAN: Results

SAN EPDM Reactive Processing
2 wt.% PF-Harz/0,2 wt.% Catalyst/130°C
(without fillers/without oils)
EPDM-grade: EP T 2370 (Lanxess)
elongation at break
1000
100
[%]
10
1
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
EPDM-content [wt.%]
Sources:
• M. Vierle: MSc Thesis TU Munic December 2001
• DE 10127402, Bayer AG, Prior.: 06.06.2001, Inv.: M. Vierle, N. Steinhauser, O. Nuyken, W. Obrecht
• M. Vierle, N. Steinhauser, O. Nuyken, W. Obrecht, Macromol. Mater. Eng. 2003, 288, 209-218„Blend Preparation by Reactive Processing
Advanced technologies for the production of PP-
based TPEs
608 R
R2 ataktisches Preparation of PP-Blockcopolymers by the
Zr Polymer
R1 use of the „Waymouth-Catalyst“
The length of building blocks is determined
622 R
by the ratio of propagation rates versus
Rotation rate
595 R
Source:
R2 Isotaktisches
R. Waymouth, J. Coates, A-L. Mogstad, K. Stein, D. Fischer,
Zr Polymer
R1 S. Borkowsky
Stepol `94; Milano June 6-10, 1994 "Stereospecific
R Polymerization and Copolymerization of Functionalized Olefins"
BP/Amoco started to manufacture PP- PP-based multi-

multi-block copolymers in the pilot-
pilot-plant scale in
California (Menlo Park)
Baxter Healthcare Corp., Round Lake, IL cooperates in the performance of tests towards the
replacement of soft PVC in medical devices
A. Khare;
Khare; S. Y. Ding; M. T. K. Ling; L. Wood; Modern Plastics,
Plastics, September 1999; 94-
94-99
„Heat-
Heat-resistant,
resistant, flexible olefins meet tough medical demands“
demands“-Single-
Single-Site metallocene catalysts
yield autoclavable,
autoclavable, high-
high-clarity elastomers with cost/performance benefits of flexible PVC.
Advanced technologies for the production of PP-

based TPEs
Cl
Cl
Cl B
Cl Temperature Cl
B Cl Zr
Zr Cl Cl
P
Et P
Et
Et Et
Polymers with high tacticity atactic polymers
PP-based multi-block copolymer

Preparation of PP-
PP-based multiblock copolymers by the
use of Donor/Acceptor Metallocenes (Ostoja Starzewski)
Starzewski)
PP-Based TPE
4
10
Elastomeric PP
Komplex modulus (G*) [MPa]

G'
3
10
Schubmodul (MPa)
2
10
G''
1
10
0
10
-120 -80 -40 0 40

0
10
tan δ
-1
10
-2
10
-160 -120 -80 -40 0 40
Temperatur[°(°C)
Temperature C]
Sample from Prof. Aladyshev
PP-Based TPE
6
Elast.PP
2] ]
2
[N/mm
4
stress σσ[N/mm
Spannung
Probenform: S1-Stab
Anlieferzustand: Platte
Meßdatum: 05.06.02
Dateiname: S14308sd (Graph 1)
0
0 200 400 600 800
strain (εεε) [%]
Dehnung [%]
Abb.
Sample from Prof. Aladyshev
PP-Based TPE 4
10
modulus (G*) [MPa]

G' G" HAIFA 1
G' G" HAIFA 2
3
komplexer Schubmodul [MPa]

10
2
10
1
10
Komplex
0
10
-1
10
0 -120 -80 -40 0 40 80

10
-1
10
tan(δ) -2
10
-3
10
-160 -120 -80 -40 0 40 80 120
Temperatur [°C]
Temperature [°C]
Sample from Prof. Eisen/Haifa
PP-Based TPE
6
HAIFA-1
HAIFA-2
2] ]
4
2
[N/mm
stress σσ[N/mm
Spannung
0
0 100 200 300 400 500 600 700 800 900
strain εε [%]
Dehnung [%]
Sample from Prof. Eisen/Haifa
TPEs from the Viewpoint of a Producer of Technical
Rubber Goods
• Reduction of Manufacturing Costs
– Reduction in number of raw materials and associated costs for logistics (ordering,
transportation and storage,)
– Reduction/elimination of compounding costs including energy savings
– Significant reduction of cycle time and increase of output (seconds instead of minutes)
– Cost reduction by recycling of waste (no costs for incineration and land fill)
• New Technology for Rubber Processors

– Installation of equipment for the processing of thermoplastic materials
– Know-how in thermoplastics and their processing not available
– Know-how for the compounding and processing of rubbers becomes abundant
• TPE- Range of Products and Proeprties

– Limited availability of soft grades with Shore A Hardness < 50
– Open questions on the production of composites
– High hysteresis which results in p high permanent set (after elongation and compression)
– Losses on dynamic stress bei dynamischer Beanspruchung
– Irreversible damage of articles if service temperature is increased above threshold
temperature
7. Test Questions
Please do not forget to write your name

on each page of the questionnaire
Family Name
Given Name
1
Which Abbreviations Are Used for the Following

Rubbers?
Nr. Rubber Abbreviation
1 Polybutadiene
2 Polychloroprene
3 Chlorinated Polyethylene
4 Chlorosulfonated Polyethylene
5 Ethene/Propene/Diene-Terpolymers
6 Ethene/Propene-Copolymers
7 Epoxydized Natural rubber
8 Fluororubber
9 Acrylic Rubber
10 Synthetic Polyisoprene
11 Isobutene/Isoprene-Copolymers
12 Styrene/Butadiene-Copolymers
13 Natural Rubber
14 Silicon Rubber with Viny Groups
15 Butadiene/Acrylonitrile-Copolymers
16 Brominated Isobuylen/Isoprene-Copolymers
17 Vinylmethylsilicon Rubber, which also contains fluorine
18 Polyphosphazene modified with perfluorinated alcohols
19 Standardized NR from Vietnam
20 Smoked Sheets based on NR
Family Name
2
Given Name
Please Assign the following Rubbers to the
Correct Position in the Matrix:
ACM, BIIR, BR, CM, CSM, EVM, FKM, HNBR, IIR, SBR
Chemical Process Features
Features Emulsion Solution Dispersion Mass or Gas-
(slurry) Bulk Phase
Radical
Polymerization
Ziegler/Natta-
Polymerization
anionic
Polymerization
Cationic
Polymerization
Polyaddition und
Polycondensation
Polymer-
modification
Family Name
Given Name 3
Which of the Curves Matches the Performance of the

Materials Mentioned Below ?
300 1
Residual Elongation [%]
200 2
100 3
4
5
0 6
0 100 200 300
elongation [%]
Nr.: Questions Answers
1 Thermoplastic Polymer ?
2 Unvulcanized HNBR at 20°C ?
3 Unvulcanized HNBR at 120°C?
4 Unvulcanized BR with Mn = 10 kg/mol at 50°C ?
5 Unvulcanized BR with Mn = 500 kg/mol at 20°C?
6 SBS at 20°C?
7 SBS at 120°C
8 TPU at 20°C
9 NR (unfilled and vulcanized) at 60°C
10 NR (filled and vulcanized) at 60°C
Family Name
4
Given Name
Natural Rubber
Please Mark „RIGHT“ or „WRONG“
Nr.: Frage Right Wrong

1 Unvulcanized NR does not crystallize
2 Today, Malaysia is NR-Producer No. 1
3 For NR plantations China is ideal.
4 For NR plantations Brasil is ideal.
5 A smallholder earns ~ 10000 €/a
6 SMR 20 is a NR-grade with high purity
7 SMR CV vulcanizes faster than SMR 10
8 NR has to be masticated before use
9 IR has to be masticated before use
10 For the mastication of NR, mastication aids have to be used
Family Name
Given Name
5
Natural Rubber

1 A tyre tread based on NR performs well on a wet road
2 A tyre tread based on NR exhibts a low rolling resistance
3 The vulcanizateion of NR with peroxides yields good dynamic properties
4 NR has a lower Tg than ENR
5 NR can be vulcanized with multifunctional isocyantes
6 CV grades can be vulcanized with diisocyantes
7 NR can be vulcanized with phenol/formaldehyde resins
8 NR based compounds have a higher tack than SBR-based compounds
9 NR crystallizes at 35°C
10 NR crystallizes faster at -50°C than at -20°C
Family Name
Given Name
6
Synthetic Polyisoprene
Nr.: Question RIGHT WRONG

1 The mechanical properties of IR do depend on the 1,4-cis-content
2 Li-based catalysts produce IR with a high 1,4-cis-content
3 Nd-based catalysts produce BR with a high 1,4-cis-content
4 Ti-based catalysts produce IR with the highest 1,4-cis-content
5 Tg of IR does not depend on 1,4-cis content
6 IR has to me masticated before use
7 IR can be crosslinked with diisocyantes
8 IR with a high 3,4-content is good for tyres with a high wt grip
9 IR with a high cis-1,4-content provides tyres with good wet grip
10 Poly-1,4-trans-Isoprene has a lower Tg than Poly-1,4-cis-Isoprene
Family Name
Given Name
7
Emulsion Rubbers

Nr.: Question Right Wrong
1 The term "emulsion" is used for a dispersion of polymer particles in water
2 The term "latex" is used for a dispersion of rubber particles in water
3 Polymer dispersions are obtained by slurry (precipitation) polymerization
4 Latices are obtained by emulsion poymerization
5 Latices with a solids content > 50 wt. % can not be made
6 The addition of emulsifier increases the stability of latices
7 The addition of emulsifier increases the stability of emulsions
8 At freezing temperatures latex stability is higher than at 23°C
9 At elevated temperatures (>100°C) latex stability is higher than at 23°C
10 The addition of electrolytes increases latex stability
Family Name
Given Name 8
Pollution of Water and Air:
Nr. Question Right Wrong
1 COD = 0
2 BOD = 0
3 BOD = COD
4 COD < BOD
5 BOD < COD
6 There are no biodegradable emulsifiers
7 Emulsion rubbers yield considerable amounts of water water
8 Dry finishing of solution rubbers does not cause water pollution
9 Rubber recovery from a solution by steam stripping causes waste water
10 Emulsion rubbers cause air pollution
Family Name
9
Given Name
Crystallization of Rubbers
Nr.:
Frage Right Wrong
1 Additives can increas the rate of crystallization
2 Additives can reduce the rate of crystallization
3 SBR is a crystallizing rubber
4 NBR is a crystallizing rubber
5 NR is a crystallizing rubber
6 Rubber compounds crystallize slower than raw rubbers
7 Vulcanizate crystallize faster then the respective rubber compounds
8 Strain induced crystallization is a wanted property
9 Low temperature performance of vulcanizates is improved by spontaneous
crystallization
10 The compression set performance of vulcanizates at low temperatures is
is improved by spontaneous crystallization
Family Name
Given Name 10
Crystallization of Rubbers

1 SBR exhibits spontaneous crystallization
2 NBR is a crystallizing rubber
3 CR is a crystallizing rubber
The rate of CR crystallization depends on polymerization temperature
4 NR is a crystallizing rubber
5 Spontaneous crystallization is a wanted property
6 Strain induced crystallization provides high abrasion resistance
7 The rcrystallization rate of CR depends on temperature
The crystallization rate of rubbers shows a temperature maximum
8 The crystallization rate of rubbers shows a temperature minimum
The rate of crystallite nucleation increases with increasing temperature
9 The rate of crstallite growth decreases with increasing temperature
10 The rate of crystallization of vulcanizates can be monitored
by Shore A measurements
Family Name
Given Name 11
NBR

1 NBR which is polymerized under azeotropic conditions has 2 Tgs
2 NBR which is polymerized under azeotropic conditions has 1 Tg
3 A batch polymerization with incremental monomer addition can result in 2 Tgs
4 Low monomer conversions result in NBR with chemical heterogenity
5 High amounts of emulsifier improve chemical homogenity
6 High amounts of modifier improve chemical homogenity
7 Rebound of NBR increases with the content of acrylonitrile
8 The degree of oil swelling increases with acrylonitrile content
9 Shore A hardness of NBR vulcanizates dempend on acrylonitrile content
10 The compression set of NBR vulcaniaztes depend on acrylonitrile content
Family Name
Given Name 12
NBR

1 The properties of NBR depend on the emulsifier used for polymerization
2 The properties of NBR depend on the electrolytes used for latex coagulation
3 The tendency to gelling increases with increasing polymerization temperature
4 The tendency to gelling decreases with increasing polymerization temperature
5 Molar masses increase with increasing monomer conversion
6 Molar masses do not depend on monomer conversion
7 Molar masses do not depend on modifier level
8 Molar masses decrease with increasing amounts of modifier
9 Molar masses increase with increasing amounts of modifier
10 The properties of NBR depend on the modifier used
Family Name
Given Name 13
NBR
In the literature you find the following Tgs for polybutadiene (BR) and
polyacrylonitrile (PAN:
BR (Li-catalysis) -90°C
BR (Ti-catalysis) -100°C
BR (Nd-catalysis) -110°C
BR (emulsion polymerization) -80°C
PAN +100°C
Please select the relevant Tgs and calculate the Tg of an NBR grade
which contains 50 wt.% acrylonitrile.
acrylonitrile.
The calculated Tg is:

is: ………..
………..°
°C
Family Name
Given Name 14
NBR:

1 The compatability of NBR and PVC depends on acrylonitrile content
2 Vulcanizates based on NBR perform well in ozone containing air
3 Vulcanizates based on CR perform well in ozone containing air
4 NBR/BIIR-Blends are useful for innerliners
5 Blends based on NBR and EPDM are compatible
6 Sulfur cure of NBR/HNBR-Blends result in high temperature resistance
7 Precrosslinked NBR yields compounds with low die swell
8 NBR can be vulcanized with phenol/formaldehyde resins
9 The swelling of NBR vulcanizates in oil increases with acrylonitrile content
10 The swelling of NBR vulcanizates in oil decreases with acrylonitrile content
Family Name
Given Name 15
CR

1 The properties of CR do not depend on the temperature of polymerization
2 Vulcanization with ETU* results in crosslinks which contain 1 sulfur atom
3 CR-based adhesive grades contain 2-3-Dichlorobutadiene-1,3
4 CR rubber grades are polymerized at a lower temperatures than
CR adhesive grades
5 CR-latices can not be coagulated with electrolytes
6 CR crystallinity is disturbed by copolymerized sulfur
7 Mercaptane modification results in higher tensile strength of vulcanized CR
than the modification with xanthogendisulfides
8 The ageing resistance of vulcanized CR sulfur grades is higher than those of
mercaptane modified CR grades
9 CR-sulfur grades have to be masticated prior to use
10 Precrosslinked CR grades are used for vulcanizates with good dynamic
performance
Family Name
Given Name 16
HNBR:

1 Tg of HNBR does depend on the degree of hydrogenation
2 The rebound of HNBR vulcanizates depends on ACN content
3 HNBR and EVM are fully compatible at all copolymer compositions
4 The compatibility of PVC and HNBR depends on the acrylonitrile content of HNBR
5 Compatibility of HNBR and EVM depends on the vinyl acetate content of EVM
6 The crystallinity of HNBR depends on acrylonitrile content
7 Ethene sequences are prone to crystallization
8 Tg of amorphous PE is at -200°C
9 Tg of amorphous PE ist at + 0°C
10 Unvulcanized HNBR with a low acrylonitrile content performs like a TPE
Family Name
Given Name 17
HNBR:

1 Pd-Catalysats can be used for the selective hydrognation of C=C bonds in NBR
2 Raney-Nickel can be used for the selective hydrogenation of C=C bonds in NBR
3 Li[AlH4] can be used for the selctive hydrogenation of C=C bonds in NBR
4 NN=NH can be used for the selective hydrogenation of C=C bonds in NBR
5 Supported catalaysts can be recovered by centrifugation
6 Supported catalaysts are not quantitatively recovered after hydrogenation
7 Homogeneous catalysts can be recovered by filtration
8 Ethene and acrylonitrile can be radically copolymerized
9 Metallocenene-based catalysts readily copolymerize ethene and propene
10 In the hydrogenation on NBR, gel formation is a major problem
Family Name
Given Name 18
IIR, CIIR and BIIR:

1 At a polymerization temperature of -100°C molar masses of IIR are too high
2 At a polymerization temperature of 23°C °C molar masses of IIR are too low
3 IIR is a feedstock for the preparation of BIIR
4 NR/BIIR-Blends are used for the production of innerliners
5 IIR has a good performancde in the covulcanization of layers
6 BIIR has a good performancde in the covulcanization of layers
7 IIR can be vulcanized by the use of peroxides
8 BIIR can be vulcanized by the use of peroxides
9 Bladders which are used for the vulcanization of tyres are based on
resin cured IIR
10 Bromination of IIR is performed in CH3Cl
Family Name
Given Name 19
Thermoplastic Elastomers:

1 The hard phase is not crosslinked
2 The hard phase is crosslinked
3 The soft phase can be polar
4 The soft phase can be crsslinked
5 Tg of soft phase > Tg of hard phase
6 Tg of soft phase < Tg of hard phase
7 Hard- and soft phase have to be mechanically coupled
8 Hard- and soft phase have to be compatible
9 Dynamic vulcanization can be performed in a twin
screw extruder
10 Dynamic vulcanization can be performed on a mixing mill
Family Name
Given Name 20
Please assign the Curves
104
1
103
Schubmodul [MPa]
4 3 2
5
102
6
7
101 8
9
100
10-1
-100 -50 0 50 100 150 200
Temperatur
Nr.: Frage Number of curve(s)
1 Which curve(s) matches the performance of unvulcanized NR ?
2 Which curve(s) matches the performance of unvulcanized SBR ?
3 Which curve(s) matches the performance of vulcanized SBR ?
4 Which curve(s) matches the performance of unvulcanized NBR ?
5 Which curve(s) matches the performance of vulcanized NBR ?
6 Which curve(s) matches the performance of isotactic Polypropylene?
7 Which curve(s) matches the performance of Polycarbonate?
8 Which curve(s) matches the performance of atactic Polytyrene?
9 Which curve(s) matches the performance of ABS with 30 wt.% BR ?
21
10 Which of the curve(s) matches the performance of SBS ?
Which series of modified rubbers and which modification

results in the following properties
Rubber A [phr 100 - -

Rubber B [phr] - 100 -
Rubber C [phr] - - 100
Carbon black (N 220) [phr] 30 30 30 Rubber A

Shore A Hardness/23°C 59 56 59 Rubber B
Modulus300 [MPa] 7,8 6,9 8,8
Tensile Strength [MPa] 27,1 25,9 27,8 Rubber C
Elongation at break [%] 550 590 560 modification
Rebound/23°C [%] 78 25 15
Goodrich HBU [°C] 44 60 52
CS (24h/70°C) [%] 17 46 17
Volume swell (70h/70°C) Family Name

ASTM-oil Nr. 1 [%] 66 73 -5 Given Name
ASTM-oil Nr. 2 [%] 114 28 6
ASTM oil Nr. 3 [%] 191 108 21
Air permeation/23°C [1018 x m4/s.N] 27,0 8,0 1,98

22
Which Metal is used for the production of BR in order to
obtain the Properties below ?
2
CH2
1
CH2 CH
1
1
4
CH2
3
CH2 CH CH
2
3
CH
CH CH
2 3 CH2
4
CH2
4
Metal
Microstructure [%]
1,4-cis 36-38 97 97 93 98 12,9
1,4-trans 52 1 2 3 1 68,3
Vinyl 10-11 2 1 3-4 <1 18,8
1
Vinyl/ H-NMR*** 10,4 1,9 4,0 <1 18,1
Vinyl/FT-IR*** 11,4 1,0 5,4 0,6 17,7
Vinyl/Metathese*** 10,7 1,7 4,6 0,7 17,8
Tg -93 -106 -107 -103 -109 -80
23
Please Assign Rubber A and Rubber B

Rubber A 100 75 50 25 -
Rubber B - 25 50 75 100
Compound Properties
ML 1+4(100°C) [MU] 123 99 58 40 32
t2/177°C [min] 1,5 1,6 1,5 1,6 1,6
t90/177°C [min] 11,7 11,0 10,2 10,2 9,5
Shore A Härte (23°C) 78 80 80 81 77 Rubber A
Modulus 100 [MPa] 10,7 13,1 12,6 12,0 8,3
Elongation at break [%] 240 190 170 145 165 Rubber B
Tensile Strength [MPa] 26 24 22,5 18,8 18,5
Compression Set
70h/23°C [%] 12 12 12 14 14
70h/150°C [%] 20 17 17 14 9
70h/175°C [%] 27 27 25,5 20 15
Heat ageing (14d/150°C)

F/F0 x100 [%] -2,3 -3,8 -10 -7,5 -1,6
D/D0 x100 [%] -37 -26 -29 -21 -12
H/H0 x100 [%] +6 +5 +4 +3 +2
Oil swelling (7d/150°C) Family Name

ASTM-Öl Nr. 3
∆F/F0 x100 [%] -10 -17 -36 -50 -56 Given Name
∆D/D0 x100 [%] -4 -11 -29 -34 -45
∆V/V0 x100 [%] +24 +34 +49 +67 +83 24
Rubber A 100,0 50,0 0
Rubber B 0 50,0 100,0
Fmin. [Nm] 9,0 10,2 8,0
Fmax. 86,3 78,7 60,0 Rubber A
ts [min] 3,0 2,7 2,8 Rubber B
t90 [min] 10,0 7,0 6,8
t95 [min] 21,5 11,0 8,3
Shore A 83 80 67
Modulus100 [MPa] 5,2 4,5 1,7
Modulus200 [MPa] 11,0 10,0 4,8
Modulu300 [MPa] 18,6 15,5 11,0
Tensile Strength [MPa] 25,5 21,0 18,2
Elongation at break [%] Family Name
430 415 500
Abrasion Index 493 159 73 Given Name
Ageing at 70h/121°C
∆ Dehnung [%] - 42 - 35 - 30
CS (70 h/121°C) [%] 34,1 27,1 14,7 25
Please assign 5 polymer blends for which the

scheme below applies
Hard phase
(coherent phase or matrix)
Soft phase
(dispersed phase)
Nr.: Hard phase Soft phase

1
2
3
4
5
Family Name
Given Name
26
Which Series of Rubbers Yields the Properties Given in
the Table Below?
Rubber A B C D E F
Compound properties
Mooney ML 1+4(100°C) 20 24 23 25 20 20
t10/180°C [min] 1,2 1,2 1,2 1,2 1,3 1,3
t90/180°C [min] 7,2 6,6 6,6 6,2 6,9 6,1
FH-FL/180°C [N] 17 20 19 21 19 17 Rubber
Vulcanised properties Variation
(ISO-Stab Nr. 2, 2mm)
Shore A Härte (23°C) 75 74 68 71 68 72
S 100 MPa] 5,0 5,7 4,4 5,4 4,2 4,7
Elongation at break [%] 295 275 285 280 300 300
Tenjsile Strength [MPa] 11,7 13,6 12,6 12,8 11,5 10,5
Compression Set
70h/100°C [%] 23 20 20 22 21 27
70h/125°C [%] 25 23 25 26 24 31
70h/150°C [%] 41 38 41 40 46 51
Hot air ageing (14d/150°C)

∆F/F0 x100 [%] -3 -12 -10 -11 10 -8 Family Name
∆D/D0 x100 [%] -2 -2 2 -2 -7 -15
∆H/H0 x100 [%] 10 9 11 12 15 14 Given Name
Storage in SAE Oil90
(3d/150°C)
∆F/F0 x100 [%] -26 -12 -8 8 6 10
∆D/D0 x100 [%] -19 -4 -4 2 8 -12
∆V/V0 x100 [%] 69 47 31 13 3 -4
Rubber A [phr] 100 80 60 40

Rubber B [phr] - 20 40 60
Unaged: Rubber A
M300 [MPa] 4,2 5,7 7,1 8,9 Rubber B
Aged (168h/100°C)
M300 [MPa] 6,8 7,6 8,4 6,7
Air permeation at 2,9 5,4 9,2 13,8
50psi/65°C (Q x 10-8] Family Name
Adhesion at 100°C
16,8 14,7 15,2 15,4 Given Name
Self adhesion / tack [kN/m]
Adhesion to NR [kN/m] 7,5 10,0 14,7 20,8
Fatigue to failure after
ageing at 168h/120°C [kcycles] 61,8 23,6 0,3 0,0 28
Please Assign Rubber A
Family Name
Rubber A
Given Name
Rubber A [phr] 100 100 100 100

Carb. black (N 774) [phr] 50 50 50 50
Vulcanization ZnO DCP DCP/BMI ZnO/BMI

Compound Properties
ML 1+4 (100°C) [MU] 83 88 88 89
MS5 (125°C) [min] - - - -
MS5 (135°C) [min] 16 12 14 16
Physical Properties
Shore A Hardnes 48 40 54 58
M100 [MPa] 0,9 0,5 0,12 0,19
M300 [MPa] 5,2 1,8 9,5 10,2
CS (70h/150°C) [%] 58 53 28 13
29

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“Chemistry and Technology of Rubbers”

Chemistry and Technology of Rubbers

2.1. Natural Rubber

3. Overview on Emulsion Rubbers

4. Overview on Solution Rubbers

5. High Performance Rubbers

• Definition of the Terms “Rubber“, “Elastomer“ and “Thermoplastic

Standard Terminology Relating to Rubber

rubber, n-a material that is capable of 30

benzene, methyl ethyl ketone, or

My personal Definition of “Unvulcanized Rubber“,

Vulcanized Rubber (or: „Crosslinked Rubber“ or „Elastomer“) is obtained

Thermoplastic Elastomers (TPE) are physically crosslinked rubbers

In English, the term „Rubber“ is ambiguous as this term refers to unvulcanized

• rubber tree unvulcanized (=uncrosslinked) rubber

CH3 CH3 CH3 CH3

Tgs of Polymers with an Unsaturated C=C Main Chain

-50°C bis -5°C

Rebound [%] EPDM

• With increasing temperature rebound elasticity passes throug a minimum

Schematic Presentation of the Dependence of the

10000 NR (raw rubber)

Class- Chemical Description Examples

Abbreviations (DIN / ISO 1629) and Examples

Annual Consumption [1000 metric tons] Natural Rubber

Application Areas of Solid Rubber

NBR (0.32 Mio t) Special Special

Oil – and Temperature Resistance of

FKM MVQ High

Evaluation of Vulcanizate Performance*

NR -72 8 80 1 25 10 >140 (70) 1 1 1,1 21

Price of Rubber [€/kg]

Ranking of Top 10 Tyre Producers

2 Bridgestone 12.950,0 74,0 5,5 18,9

7 Yokohama 2.272,2 71,0 5,7 3,3 0

9 Toyo 1.247,6 61,5 2,1 1,8

10 Kumho 1.246,5 60,3 -13,1 1,8

Sums: 55.469,2 81,0

1 Hutchinson SA France 2156 *)

Producers of Synthetic Rubber and

Others Exxon Mobil 5.7%

Total: JSR Corporation 5.2%

ISP Elastomers 2.2%

E-SBR, CR, NBR, AEM

Cationic ECO, CO IIR Q

* Technology not established (only patents for the hydrogenation of NBR-latex)

Flow Diagram of an EPDM Solution Process

Ethene Propene Waste Expeller

Dryer Dryer Baler

Available Vulcanization Methods for the

“R“- Rubbers NR XXX - X (X)

Sx accelerated sulfur cure

Schematic Presentation of the Deformation of a

Type of Bond Bond

Type of Bond Bond

TSexpt. = 1/100 - 1/1000 TStheor. physical 10 - 20

•Oil Resistance Filler

NR: Microstructure and Property Profile

General Purpose Grades:

NR: Annual Consumption (incl. Latex)

1997 2004 1997 2004 1997

Use of NR in Truck Tyres

Year Tread [wt.%] Side Wall [wt.%] Carcass [wt.%]