Chemistry and Technology of Rubber

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. 3.1. 3.2. 3.3. Overview on Emulsion Rubbers Emulsion-Styrene/Butadiene-Rubber Polychloroprene 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. 5.1. 5.2. 5.3. 5.4. 6. 7. High Performance Rubbers Fluoro Rubber Silicon Rubber Hydrogenated Nitrile Rubber Ethylene/Vinylacetate-Copolymers Thermoplastic Elastomers 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
recovering from large deformations quickly and forcibly, and can be, or already is modified to a state in which it is essentially insoluble (but can swell) in boiling solvent, such as benzene, methyl ethyl ketone, or ethanol toluene azeotrope. 30 25 20 Stress [MPa] 15 rubber 10 5 0 0 50 Elongation [%] 100 1 min 1 min
DISCUSSION
- A rubber in its modified state, free of diluents, retracts within 1 min to less than 1,5 times its original length after being stretched at room temperature (18 to 29 C) to twice its length and held for 1 min before release.
Comparison of Materials According to ASTM D 1566
300 Residual Elongation [%]
= residual
200 Definition of Rubber according to ASTM D 1566 - 98 100
TPO Thermoplastic Elastomers
TPV SBS
0 0 100 200 Elongation () [%]
NR/BR based tyre tread NR gum stock 300
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 natural rubber rubber boot unvulcanized (=uncrosslinked) rubber vulcanized (=crosslinked) rubber
Tgs of Polymers with a Saturated C-C Main Chain

Polyethylene Polypropylene (atactic / amorphous)
CH3 O O CH3 O O CH3 O O CH3 O
~ -130 C -18 C
Polyvinylacetate
+30 C
O O CH3
O O CH3
O O CH3
O O CH3
Polystyrene (ataktisch / amorph)
+100 C
Si
Si
Si
Si
Si
Si
Si
Silicon Rubber
-120C
Tgs of Polymers with an Unsaturated C=C Main Chain

Polybutadiene -115 C (100% 1,4-cis)
Polyisoprene
-75 C (100% 1,4-cis)
Cl Cl CN
Cl
Polychloroprene
Cl
-45 C (100% 1,4-trans)
Nitrile Rubber
-50 C bis -5 C (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 NR EPDM 40 IIR 20 SBR NBR
Rebound [%]
60
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)

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

BR CR CM CSM EPM EPDM ENR IR IIR NR NBR SBR FPM FKM Butadiene-Rubber Chloroprene Rubber Chlorinated Polyethylene Chlorosufonated Polyethylene Ethylene/Propylene-Rubber Ethylene/Propylene/Diene-Rubber Epoxidised Natural Rubber Synthetic Polyisoprene Butyl rubber Natural Rubber Nitrile-Butadiene-Rubber Styrene-Butadiene-Rubber (E-SBR und S-SBR) Fluoro Rubber (DIN / ISO 1629) 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% Tyres 45% Modification of Plastics 14%
Cable and Wire Construction 3% 3%
Others 15% Machine building 5%
Price and Volume of Rubbers (without Latex)

FZ FQ FKM HNBR Q AU/EU EVM
Volume Shares
High Performance Rubbers
General Purpose Rubbers: 82%
CR (0.3 Mio t)
Price
NBR (0.32 Mio t) IIR/X-IIR
Special (0.5 Mio t)Rubbers
High Performance Rubbers 1%
Special Rubbers 17%
EPM/EPDM (0.9 Mio t) Shares in Turnover
BR (2,8 Mio t) SBR (2,7 Mio t) NR (6.7 Mio t)

Volume
General Purpose Rubbers
General Purpose Rubbers: 60%
Source: Rubber World, 21916 (1999) 13-14
High Performance Rubbers 10%
Special Rubbers 30%
Oil and Temperature Resistance of Vulcanizates According to ASTM D 2000

250 225 200
FZ FMVQ
80 % VAc 40 % VAc
max. service temperature [ C]
FKM
MVQ
General GeneralPurpose PurposeRubbers Rubbers Special Rubbers Special Rubbers High HighPerformance PerformanceRubbers Rubbers
175 150 125 100 75 50 0

44 % ACN
ACM HNBR
EVM AEM CO/ECO 18 % ACN NBR CM CSM (H)IIR EPDM
EU AU
CR
SBR
BR
NR
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 Max. Service Low Temperature temperature performance Tg Rating T max. Rating [ C] NR SBR BR EPDM IIR NBR CR CM CSM EVM AEM ECO AU VMQ ACM HNBR FKM FMVQ FZ -72 ca. -40 -120 -60 -60 -40 -39 -25 -25 -35 -35 -50 -30 -120 -35 -26 -20 -70 -65 8 6 10 5 6 5 4 3 3 4 4 5 4 8 4 3 2 8 8 [ C] 80 95 85 145 135 125 115 140 135 170 170 130 80 250 170 160 250 215 180 1 3 2 6 5 5 4 6 5 8 8 5 1 10 8 6 10 9 8 Mechanical Properties Tear Rating Resistance [MPa] 25 22 20 24 15 22 22 15 16 14 15 15 25 10 14 25 14 10 16 10 7 6 8 3 7 7 4 4 3 4 4 10 1 3 10 3 1 4 Oil Swell (ASTM 2000-90) Rating [Vol.% ] >140 (70) 130 >140 >140 >140 20 bis 50 55 bis 65 80 80 20 bis 100 50 30 3 bis 25 30 bis 50 20 bis 40 15 bis 40 5 10 10 1 2 1 1 1 7 3 4 4 6 5 6 7 6 7 8 9 9 9 1 1 1 8 6 6 2 5 9 9 9 8 9 10 9 9 10 10 10 Ozone Price Resistance Rating [/kg] 1,1 1,1 1,3 2,2 2,7 2,5 3,4 3,1 3,8 3,8 6,9 6,9 7,5 7,5 9,4 28,1 43,8 125 500 21 19 20 28 21 30 20 22 25 30 30 28 31 35 31 36 34 37 39 Performance Index Rating
E-SBR and S-SBR may not be evaluated according to these criteria as SBR is designed for high Tgs (improvement of wet skid) *Ullmanns Encyclopedia of Industrial Chemistry, VCH Weinheim 1993, Vol. A23, Rubber 3. Synthetic; W. Obrecht Introduction
Correlation of Rubber Price and Vulcanizate Performance

45 40 35
FZ HNBR MVQ FKM ACM EVM AU NBR AEM EPDM ECO CSM CM IIR CR FMVQ
Performance Index
30 25 20 15 10 5 0 0,1 1
NR BR SBR
10
100
1000
Price of Rubber [/kg]
Ranking of Top 10 Tyre Producers

Rank Company Sales of Tyres Share of Tyres [%]
95,0 74,0 86,7 49,0 72,7 39,0 71,0 54,0 61,5 60,3 88,9
[Mio US $]
1 2 3 4 5 6 7 8 9 10 11 Michelin Bridgestone Goodyear * Continental Sumitomo** Pirelli Yokohama Cooper Tire Toyo Kumho Hankook 13.425,0 12.950,0 12.470,0 4.901,0 2.598,2 2.534,5 2.272,2 1.705,3 1.247,6 1.246,5 118,9
Return Market on Shares Sales in [%] Tyres [%] [%]

6,6 5,5 2,4 -4,2 7,7 6,1 5,7 3,4 2,1 -13,1 8,5 19,6 18,9 18,2 7,2 3,8 3,7 3,3 2,5 1,8 1,8 0,2
20 15 10 5 0
Capitalization of Shares Sales
Bridgestone
Michelin
Goodyear
Sums: Total Sales:
55.469,2 68.500,0
81,0 100,0
* 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
Source: FAZ 18.08.2003
Continental
Ranking of Top 22 Producers of Technical Rubber Products (without Tyres)

Rank Company Company Site
France Japan Germany UK US US Sweden Germany US US Japan Japan Germany Japan US US Australia Japan Japan US Japan Germany
Sales 2001 [Mio US$]

2156 2065 2060 1855 1500 1477 1446 1270 1160 1122 1120 987 900 897 812 808 759 750 703 695 670 662
Return on Sales [%]

*) 0,8 3,7 5,7 5,7 2 2,9 *) *) *) *) 2,7 *) 1,3 *) 8,6 *) *) 1,8 *) 1,3 *)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
Hutchinson SA Bridgestone Corp. Freudenberg Group Tomkins plc. Parker Hannifin Cooper Tire & Rubber Trelleborg AB Continental AG Federal Mogul Corp. Goodyear Tire & Rubber NOK Inc. Tokai Rubber Industries Ltd. Metzeler Automotive Profile Syst. Toyoda Gosei Co. Ltd. Mark IV Automotive GenCorp. Inc. Ansell Ltd. Sumitomo Rubber Ind. Yokohama Rubber Co Ltd. Dana Corp. Toyo Tire Rubber Co. Ltd. Phoenix AG
*) not available Source: European Rubber Journal 184,9 September 2002
Producers of Synthetic Rubber and Capacities

Lanxess 8.7% Others 30% Exxon Mobil 5.7% Goodyear 5.3%
Total: 12,097 KMT

ISP Elastomers 2.2% Bridgestone/Firestone 2.8% Nizhnekamskneftekhim Inc. 3.1 Zeon Corporation 3.2% Petroflex 3.3% Michelin 3.3%
JSR Corporation 5.2% Sinopec 5.2% Sibur 5.1% Korea Kumho 4.8%
Dow 4.5% Polimeri 4.2%
Source: R. J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008Globalization of Synthetic Rubber Industry
Petro-China 3.6%
Chemical and Technological Features of Rubber Manufacturing Processes

Chemical Aspects
Radical Polymerization Ziegler/NattaPolymerization Anionic Polymerization Cationic olymerization Polyaddition and Polycondensation Polymer Modification
Technological Features
Emulsion
E-SBR, CR, NBR, E-BR, ACM, FKM, EVM
Solution
EVM
Dispersion
EVM
Bulk
AEM EVM BR* Q
Gas-Phase
BR, EPM, EPDM BR, L-SBR. IR ECO, CO
EPM, EPDM
G-EPM G-EPDM G-BR**
IIR
AU, EU CIIR, BIIR, CM, CSM, H-NBR, FZ
EU CM, CSM, H-NBR*
AU
* 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 Condenser Settler AzeotropicDestillation
Temperature: 35-65C Temperature: 35-65C Pressure: 5-10 Pressure: 5-10bar bar Residence Time: 30 Residence Time: 30min min Solids 10 SolidsContent: Content: 10-12 -12wt.% wt.% Moisture Content: < 3 ppm Moisture Content: < 3 ppm
Stripper Dewatering screw Waste Air
Waste Water Condenser
Flash Vessel
Ethene Hexane
Purification
Propene
Reactor
External cooler steam PHControl Antioxydant Stripping aid Oil
Waste water
Expeller Air bed Dryer
Purification
Abwasser
Dryer
Dryer
Baler
Modifier Reactivator
Purification/ Drying Purification/ Drying Wrapper
EASC VOCl3
Hexane
ENB
Evaluation of Rubber Manufacturing Processes

Polymerization Process Aspect
Viscosity Heat Removal max. Solids Cont. Stereoregularitt Waste Water Waste Air Emulsion Solution 2 3 2 10 5 5 Dispersion Slurry 8 8 5 10 5 5 Bulk 1 3 9 8 10 8 Gas-Phase 10 5 5 10 10 5
8 10 5 0 0 5
Sum Ranking: Prerequistes:
28
27
41
39
45
(Gas-Phase) > Dispersion > Bulk >> Emulsion > Solution comparable running times
Available Vulcanization Methods for the Different Types of Rubber

Example Sulfur R- Rubbers NR BR CR SBR NBR HNBR IIR XIIR EPDM EPM FKM CM MVQ XXX XXX XX XXX XXX XXX XX XX XX X (X) Method of Vulcanization Peroxide X (X) X XX XX XX XXX XX X XX Resin X (X) (X) (X) (X) (X) XX XX X X (X) Other (X) (X) XX (X) (X) (X) (X) XX (X) XX X XX
M-Rubbers
Other Rubbers
Influence of Vulcanization Method and Crosslinking Density on Tensile Strength (unfilled NR-Vulcanisates)
30
Tensile Strength [MPa]
20
10
Sx S1 C C C C
accelerated sulfur cure TMTD-cure peroxide cure 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] 350 350 282 272 266 < 266
C-C C-O C-N C-S-C C-S-S-C -S-S-S-S-
Type of Bond
Bond Energy [KJ/Mol] 260 - 350 10 20
covalent
TSexpt. = 1/100 - 1/1000 TStheor.
physical
Influence of Compound Ingredients on Vulcanizate Performance

Filler
Rubber
Oil Resistance Low temperature flexibility Resistance to heat- and ageing Adhesion to cord, fibres and fabrics Covulcanisation of layers 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) Good Dispersability of Fillers (due to high viscosities at the start of the mixing cycle) Low rolling resistance (truck tyres) High abrasion resistance (truck tyres) Slow spontaneous crystallization Significant strain induced crystallization
H3C
C 1 CH2
CH 4 CH2
Negative:
Poor resistance to swelling with hydrocarbons (fuels, oils and grease) Need for mastication prior to compounding bad wet skid performance Poor resistance to heat ageing Physical Properties:
Tg: 1,4-cis-content Tm (equilibrium): max. rate of crystallization: max. degree of crystallinity: Strain induced crystallization -72 C ~ 97% + 30 C -25 C ~ 30 %
NR: Designation of Grades and Glossary

General Purpose Grades:
TSR SMR SCR GP ADS RSS Technically Specified Rubber (TSR 10, TSR 20, TSR 50) Standard Malysian Rubber (SMR 5, SMR 10, SMR 20, SMR 50) Standard Chinese Rubber (SCR 5, SCR 10, SCR 20, SCR 50) General Purpose Grade Air Dried Sheet 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 12
Naturkautschuk 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
x 1000 metric tons
3000 2500 2000 1500 1000 500
Malaysia Indonesia Thailand others
0 1985 1990 1995 2000 2005 Sources: 1980 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 Thailand Indonesia Malysia
1.934 31,90% 1.530 25,20% 1.070 17,60%
2004
2.988 34,50% 1.942 22,40% 1.175 13,58%
1997 India China Sri Lanka Vietnam

570 9,40% 400 6,60% 113 1,90% 110 1,80%
2004
741 8,60% 585 6,70% 92 1,10% 423 4,90%
1997 Ivory coast Philippines Camerun Cambodsha Brasil Liberia Burma Nigeria
87 1,40% 60 1,00% 56 0,90% 49 35 25 21 13 0,80% 0,60% 0,40% 0,40% 0,20%
Total
4.534
75% 6.105
70%
1.193
20% 1.841
21%
346 5,7%
Source:
Rmpp 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 4% None automotive 5% Others 7% Latex-Products 11%
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
1974 1981 1983 1985 1990 1994
Tread [wt.%]
NR 45 60 77 86 86 100 SBR 21 12 7 5 5 BR 34 28 16 9 9
Side Wall [wt.%]

NR 48 44 58 62 75 60 SBR 37 19 6 BR 15 37 36 38 25 40
Carcass [wt.%]
NR 71 84 100 100 100 100 SBR 20 11 BR 9 4
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 Indonesia India Malaysia Brasil Sri Lanka Ivory Coast 95% 83% 83% 81% 70% 33% 29%
Source: International Rubber Study Group
Source: http://www.therubbereconomist.com
Area cultivated per smallholder: Number of trees: Annual tappings per tree: Total number of tappings per year: Annual yield: Annual earnings: Earnings/different source*:
Source:
NR-Production by smallholders:
1,25 ha; 625 trees in total; 520 trees under tap 180/a 95.000 tappings for 625 trees/a 850 kg/a ca. 250 /a (0,30 /kg) 1020 /a (1,2 /kg)
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: Habitat:
Height: Temperature: Humidity: Rain fall: Soil:
Euphorbiaceae Equator + 15
< 300 m 25-30 C > 70% 1800-2000 mm/year good drainage (not at the bottom of vallleys)
max. age of tree: Height of tree: tapping age of tree: Tappings: Yield per tree: Yield per tap: density of trees: Rubber yields:
Plantation: Maximum yield: Smallholder:
30-40 Jahre (plantation), 100 Jahre (rain forest) 20 m (plantation), 40 m (rain forest) 5-7 years every 2nd day = 180 days/year 1-2 kg/a 5-11g 500/ha 400-1.200 kg/ha
1.000 kg/ha 3.000 kg/ha 850 kg/ha
Fungal infection: Spread of fungus:
Dothidella Ulei (Yellow leaf blythe) 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
Technology, vol 21, 4th ed., 562-591
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

Latexconcentration centrifugation, creaming, evaporation of water Acid Coagulation (factory) Acid Coagulation (Plantation/Smallholder Sheet-Material (RSS, ADS) Natural Coagulation of latex Cup lump Smallholders lump
SMR 5 60% Baled or Crumb Rubber wet and dry blending processes 40% field grades
Sales latex (60 wt. % solids)
SMR L
SMR CV 50 SMR CV 60
SMR GP
SMR 10
SMR 20
Comminution Process: multi-stage wet blending process with mechanical generation of

crumbs, crumb blending and washing with subsequent crumb drying at 100-120C/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
Strainer Residue [wt.%] (mesh width: 45 mm)
SMR 5
0,05
SMR GP
0,10
SMR 10
0,10
SMR 20
0,20
SMR 50
0,50
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
Impurity Level
Monsanto-Rheometer (160 C)
Delta F [J/cm2] TS 2 [min] 29,4 2,2 33,9 1,8 37,2 1,5 40 1,3 41,1 1,2 t90 [min] 11,6 9,7 7,8 6,8 6,8
SMR CV SMR L SMR 5 SMR 10 SMR 20
The impurities in NR perform like a vulcanization accelerator
ACS 1- Compound
NR Stearic Acid ZnO Sulfur: MBT 100 phr 0,5 phr 6,0 phr 3,5 phr 0,5 phr
With increasing impurity level, the following features are observed: reduction of scorch time reduction of vulcanization time 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 Nr.:
bale 1 2 3 4 5 6 Soluble portion
share [wt.%]
100 24,4 19,7 15,5 8,0 12,9 12,8 6,7
1,4-trans content [%]

2,2 2,0 2,0 2,0 3,4 4,0 5,0 -
Viscosity (toluene/25 C) [dl/g]

11,5 7,7 3,9 1,9 1,16 0,62 0,3 -
1,2content [%]
0,6 0,6 0,5 0,5 0,7 0,6 0,5 -
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) Carbon black/Corax N 2200 Stearic Acid Zinc oxide Antilux 654 IPPD (Vulkanox 4010 NA) TMQ (Vulkanox HS/LG) Mineral oil/Enerthene 1849 Sulfur TBBS (Vulkacit NZ) Desmodur TT
HHHH HHHH CCCC HHHH CCCC CCCC HHHH NNNN
[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr]
NNNN
100 3 3 1,5 1 1 3 1,6 1 0
100 3 3 1,5 1 1 3 1,6 1 0

HHHH CCCC
3333CCCC
100 3 3 1,5 1 1 3 1,6 1 15
100 3 3 1,5 1 1 3 1,6 1 25
100 50 3 3 1,5 1 1 3 1,6 1 0

OOOO
100 50 3 3 1,5 1 1 3 1,6 1 10
NNNN CCCC OOOO CCCC 3333 HHHH
NNNN
NNNN
HHHH CCCC
3333
IPPD (Vulkanox 4010 NA)
First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272
HHHH NNNN
SSSS SSSS
HHHH NNNN
HHHH
3333
3333
HHHH CCCC
OOOO
OOOO CCCC NNNN
3333
TBBS (Vulkanox NZ)
3333
Desmodur TT (TDI Uretdione)
NR: Vulcanization with Multifunctional Isocyantes

NR (masticated TSR 5) Carbon black (Corax N 220) Desmodur TT Fmin Fmax-Fmin t10 t80 t90 Tensile Strength Elongation at break M50 M100 M200 M300 Shore A Hrte/23 C Shore A Hrte/70 C Rebound/23 C Rebound/70 C DIN-Abrasion [%] [%] [mm3] [dNm] [dNm] [min] [min] [min] [MPa] [%] [MPa] [MPa] [MPa] [MPa] 100 0 0 0,30 7,41 4,34 6,21 7,53 17,8 605 0,6 0,9 1,4 2,2 43 45 74 81 183 100 0 0 0,18 6,30 4,82 6,77 8,24 15,3 650 0,4 0,6 0,7 1,2 40 38 69 78 327 100 0 15 0,54 24,20 0,74 15,23 17,60 25,7 635 1,5 2,0 2,9 5,0 66 59 155 100 0 25 0,96 20,06 0,71 15,56 19,08 21,8 565 1,8 2,4 3,7 6,0 68 65 55 60 123 100 50 0 1,06 15,94 1,96 4,22 4,99 27,8 540 1,5 2,7 7,3 13,4 66 102 100 50 10 1,78 36,26 0,34 7,47 9,07 25,2 480 1,9 3,1 8,0 14,4 75 133
NR contains polymer bound functional groups (-NH2, -COOH, -OH, -CONH2) which react with isocyanates
Mastication of NR
184 kJ/mol *C C*
Pentachlorothiophenol
343 kJ/mol
C*
*C
Degree of Mastication
2,2'-Dibenzamidodiphenyl-Disulfide (DBD)
S S
SH Cl Cl
NH Cl Cl Cl O O
HN
100 Temperature [ C]
200
At low temperatures (<120 C) mechanical chain scission prevails At temperatures >120 C thermo-oxidative chain scission prevails In the temperature range 100-130 C the mastication effect shows a minimum
By the use of mastication additives the mastication of NR is accelerated (oxidation catalysts and radical scavengers) Pentachlorothiophenol is an effective mastication aid; it is banned in WE Today, disulfides as well as Fe-complexes are used for the acceleration of NR mastication Source: C. Clarke, M. Hensel, Rubber World, November 2009, 28-31 Improved natural rubber processing and physical properties by use of selected compounding additives
NR: Crystallization at -25 C

35 30
Crystallinity [%]
25 20 15 10 5 0 0 5 10 15 20 25 30 Pale Crepe pale crepe after acetone extraction
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
melting temperature [ C]
-50 -30 -10 10
30 20 10 0 -10 -20 -30 -40

-50 -30 -10 10 30
half time [h]
100
10
storage temperature [ C]
storage temperature [ C]
Source:
U. Eisele Intorduction to Polymer Physics, Springer-Verlag 1990
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
Stress/Strain-Performance of Unfilled NR- and SBRVulcanizates (gum stocks)
30 25
stress [MPa]
20 15 10 5 0 0 200
NR SBR
Strain induced crystallization
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
Hydroxyl amine (CV-Grades)
Application
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
NR: CV-Grades
H H O
H2 N
- H2 O
H H N H
10 9 8 7 6 5 4 3 2 1 0 0
Mooney- Increase [MU]
SMR 20 IR/Natsyn 2200 (IR / Ti)
5 10 15 storage time [days]
20
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
Mooney-Viscosity ML1+4 (100 C)
140 130 120 110 100 90 80 70 60 50 0 0,02 0,04 0,06 0,08 before hot air ageing after hot air ageing
Hexanediamine [mol/kg]
H H O
H2 N
NH2
Specification of CV-Grades
H
Grade
Ml 1+4 (100 C) Minimum 45 55 65 54 Maximum 55 65 75 55
- 2 H2 O H H N N H H
CV 50 CV 60 CV 70 LV 50
NR: CV-Grades
Increase of Mooney Viscosity [%] 70 60 50 40 30 20 10 0 0 0,05 0,1 0,15 0,2 hydroxyl amine [wt. %]
H H C O - H2O + H2N OH
H H C N OH
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 0
Epoxidation with peracids in the latex stage
Tg [C]
-20 -40 -60 -80
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: Ullmanns Encyclopedia of technical Chemistry
ENR: Dependence of Vulcanizate Properties on the Degree of Epxidation

NR ENR 25 (Degree of Epoxidation: 25%) ENR 50 (Degree of Epoxidation: 50%) Carbon black (N 220) Shore A Hrte/23 C M300 Tensile Strength Elongation at break Elasticity/23 C Goodrich HBU CS/24h/70 C Volume Swell (70h/70 C) ASTM-Oil No. 1 ASTM-Oil No. 2 ASTM Oil No. 3 Air permeability/23 C [phr] [phr] [phr] [phr] [MPa] [MPa] [%] [%] [ C] [%] [%] [%] [%] [1018 x m4/s.N] 100 30 59 7,8 27,1 550 78 44 17 66 114 191 27,0 100 30 56 6,9 25,9 590 25 60 46 73 28 108 8,0 100 30 59 8,8 27,8 560 15 52 17 -5 6 21 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 (conv.) Sulfur Sulfur (Semi EV) (EV) Peroxide Capped Di-IsoCyanate
100 50,0 3,0 5,0 2,0 6,7 5,0 2,0 2,0
NR (SMR 5) N 330 Oil ZnO Stearic Acid Sulfur TBBS CBS TMTD Santoflex 13 TMQ DCP Novor 924 Caloxol ZDMC ZMBT
[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr]
100 50,0 4,0 5,0 3,0 2,5 0,5 2,0 -
100 50,0 4,0 3,5 2,5 1,2 0,8 0,4 2,0 -
100 50,0 4,0 5,0 2,0 0,33 0,8 0,4 2,0 -
100 50,0 3,0 5,0 2,0 2,5 -
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: Vulcanization with A Capped Diisocyanate (Novor 924)

O N N O
Novor 924: TDI based diisocyanate Novor 950: MDI based diisocyanate Due to health and safety reasons Novor 924 has been replaced by Novor 950
N O O
NH
HN O
O N
Thermal Cleavage
O N N O N O H O C N O N C O H O N O
Tautomerization
Tautomerization
O N H
O H O
H O
O H
- H2 O
N N N O O NH O HN O O
- H2 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 (konv.)
Shore A Hardness/23 C M100 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23 C [%] Fatigue to Failure [kZ] Goodrich HBU [ C] CS/24h/70 C [%] TS (7d/100 C) [%] 65 2,08 28,8 515 70 223 29 27 73
Sulfur (Semi EV)

65 2,22 30,1 485 77 106 32 14 54
Sulfur Peroxide (EV)

67 2,34 24,2 390 67 68 36 10 24 61 2,28 21,4 310 72 51 34 11 49
Capped Di-Isocyanate
70 2,60 24,0 460 66 90 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:

NR
cis-1,4-content [mol % ] Need for Mooney adjustment before use Gel functional groups 98 yes yes yes
Li
IR Ti
Nd
93 97 99 no mastication needed -
2.2. Synthetic Polyisoprene (IR)

Isoprene H 3C C2
1 3
Poly-3,4-Isoprene
C C4
Poly-cis-1,4-Isoprene
Poly-trans-1,4-Isoprene
Type of IR Catalyst Trade Name

Cariflex IR-309 Natsyn 200 Vestogrip IR
3) 2) 1) 1)
Solvent
unpolar (benzene) unpolar hydrocarbon Hexane/Additive unpolar hydrocarbon
Microstructure cis-1,4 trans-1,4 1,2- 3,493 97 0 0 0 0 7 3 60 99 -
Li Ti Li Nd
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 Hls 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
Sources:
IR: Development of Prices, Producers and Production Capacities

3
Price [US $ / kg]
2,5 2 1,5 1 0,5 0 1980 1985 1990 1995 2000 2005 2010
IR NR (RSS)
Company
Goodyear Kraton Polymers Kauchuk Sterlitamak Nishnekamskneftekhim Togliattikauchuk JSR Corporation Zeon Corporation Karbochem Total Capacity [kt]
Plant Location
Beaumont/Texas/USA Rotterdam-Pernis/Nederland Sterlitamak/Russia Nishnekamsk /Russia Togliatti Kashima / Ibaraki Pref. Mitzushima / Okayama Pref. Newcastle / Natal /South Africa
Capacity [kt]
90 25 100 200 130 36 40 3 624
Source: R.J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008 Globalization of Synthetic Rubber Industry
Comparison of NR and IR: Stress/StrainStress/Strain-Curves of Unvulcanized Polyisoprene Compounds
9 8 7
Stress [MPa]
6 5 4 3 2 1 0 0
NR (SMR 5) High cis-IR/Ti (97%) Low cis-IR/Li (93%)
100
200
300
400
500
Strain [%]
Evaluation of Compound- and Vulcanizate Properties of NR and IR

Compound Properties
NR
Mastication Mixing cycle Die swell Tack Green strength
Li + + + -
IR Ti + + + -
Nd + + + + +
+ +
Vulcanizate Properties
NR
Modulus Tensile Strength Cut growth resistance Rebound Elastivity Abrasion resistance
Li -
IR Ti -
Nd + + + + +
+ + + + +
Poly-3,4-Isoprene: Compound and Vulcanizate Properties

3,4-content (NMR): ML 1+4 (100 C): Tg ca. 60 % 65 MU -8 C 3,4-Polyisoprene 100 phr CB (Corax N 330) 50 phr HAR-oil 10 phr Zinc oxide 3 phr Stearic acid 2 phr CBS 1 phr Sulfur 2 phr Compound Properties ML 1+4(100 C) [MU] t10/150 C [min] C [min] t90/150 C) Vulcanization (30 min/150 Shore A Hrte (22 C) Shore A Hrte (75 C) M 100 [MPa] M 300 [MPa] TS [MPa] b [%] Cut growth resistance [N/mm] Residual elongation [%] Rebound / 22 C Rebound / 75 C tan /25 C tan /75 C [%] [%] 77 13,8 27,5 67 52 2,1 8,4 14,7 510 25 20 2 44 0,26 0,11
Source: Data sheet of Hls AG Vestogrip (3,4-Polyisopren-Kautschuk)
Source: P. Roch (Goodyear) KGK 48,6 (1995) 430-434Compounding 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 good heat removal low viscosities high solids high molar masses high reproducibility
Emulsionrubber
E-SBR NBR CR ACM FKM
Latex Coagulation
electrolyte electrolyte freezing electrolyte electrolyte
Disadvantages:
Waste water 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 Monomer Initiator
Polymerization
Wasser
Monomer emulsion
Polymer dispersion (Latex or rubber latex)
Mechanism of Emulsions Polymerization

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

Phase I
80 70
Phase II
Phase III
Arbitrary Units
60 50 40 30 20 10 0
Surface tenison pressure polymerization rate
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: Phase II: NL and Vbr increase free emulsifier reduces surface tension NL und Vbr remain constant the monomer concentration in latex particles remains constant the latex particles grow and soap coverage decreases surface tenison increases the monomer droplets have disappeared the monomer contained in latex particles is consumed the number of latex particles remains constant
Phase III:
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:
NL: E-CMC: I: kw: [n]: [M]:
x = 0,4; y = 0,6 [n]= 0,5
number of latex particles [lw-1] effective emulsifier concentration [lw-1] Initiator concentration [lw-1] propagation rate constant [l * mol-1 * sec-1] average concentration of radicals per particle [without dimension] monomer concentration in latex particle [Mol * l-1]
Flow Diagram of a Continuous Emulsion Polymerization (E-SBR)

Recovered styrene
Mixer/Settler
Vapour condensation
Waste water treatment
Recovered butadiene
Butadiene Styrene Aqueous emulsifier solution Hydroperoxide Aqueous catalyst solution
Mixer/Settler
Brdenkondensation
Stripping column
Wate water treatment
Flash evaporation
Abstoppkessel
Polymerisa -tionskessel
Short stop
Vapour
Latexstorage
Latex
AO
Flow Diagram of Latex Finishing (E-SBR, NBR)

Wash water
Mass Balance:
Latex volume : Rubber (25%): Water serum (75%): Wash water: Waste water: 400.000 t 100.000 t 300.000 t 100.000 t 400.000 t
Puffertank
Coagulants Additives (oil, etc)
Washtank
Coagulation tank
Dewatering screw
dryer
Baler and packaging
stripped Latex
Finishing of CR-Latex
dryer dewatering rolls
Latex-surge 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

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. 2. 3. 4. 5. COD = 0 BOD = 0 COD = BOD COD < BOD BOD < COD
Which equation does not make sense?
COD: Chemical Oxygen Demand BOD: Biological Oxygen Demand

Explanation: COD = 0 BOD = 0 no impurities present which can be chemically oxidized (very pure water) no biologically degradable substances present (substances which are not biodegradable might be present) all impurities are biodegradable this is not possible The impurities are only partially biodegradable
COD = BOD COD < BOD BOD < COD
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 Vulcanizate Properties
Microstructure of E-SBR
4
2
HC HC
3
CH 1 2
4
CH2 CH
2
CH2
CH CH2
1
C H2
CH CH
4
CH CH2
1 2
CH2
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:
poor ageing resistance poor resistance to swelling in oils no variation of microstructure low / no profits / no R&D-activities
Application Areas in Western Europe

Tyres 72%
Others 2%
Buildings Shoes Automotive 5% 5% 8%
mechanical parts 8%
E-SBR: Producers and Production Capacities

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

700 600 500
Company
Lanxess France Dow Enichem. Dow (prior owner: Shell)
Site
La Wantzenau Schkopau Ravenna Pernis
Country
France Germany Italy Netherlands
Capacity
45.000 120.000 295.000 120.000
Production [t]
Sum
Dwory Chemopetrol HIP Petrohemija Combinatul Petrochimic Neftochim Oswiecim Kralupy Zrenjanin Onesti Burgas Poland Czech Republic Croatia Rumania Bulgaria
580.000 415.000
104.000 76.000 40.000 100.000 20.000
400 300 200 100 0 1990 1992 1994 1996 1998
Sum
340.000
2000 2002
Market Volume in WE: Capacities in WE: Formal Capacity Utilization in WE:
666 k t 415 kt 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 grade assignation 1000 1500 1600 1700 1800 1900
Cold Rubber without Carbon Blackadditives Masterbatch X X X Oil-extension (<14 phr) X Oil extension (>14 phr) X X -
Hot Rubber X -
High styrene rubber X
Source: The Synthetic Rubber Manual, 14th edition IISRP (International Institute of Synthetic Rubber Producers, Houston (1999)
E-SBR: Selected Grades

E-SBR Styrenegrade content [wt.%]
1500 1502 23,5 23,5
ML 1+4 (100C) [MU]

50-52 50-52
Antioxydant Mineral Oil System grade loading [phr]

S NS -
Carbon Black grade loading [phr]

-
Remarks & Application Areas

General purpose rubber for tyre treads and for technical rubber goods uncoloured technical goods Compounds with good processability (calandered and injection moulded products) E-SBR with low ash content and low water swell (cables and electronic industry) lught colourd rubber goods (hoses and profiles) Tyre treads, transportation belts, dark colured technical Abrasion resistant compounds fr retreading tyre treads, dark colured technical rubber goods
1507
23,5
30-35
NS
1509
23,5
30-35
NS
1707 1712 1721 1609 1808
23,5 23,5 40 23,5 23,5
49-55 49-56 50-55 61-68 48-58
NS S S S S
NAPH HAR HAR HAR HAR
37,5 37,5 37,5 5 47,5
N 110 N 330
4 76
S: staining NS: none staining
NAPH: HAR:
naphthenic oil highly aromatic
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
E-SBR: Recipe for Cold Rubber Production

Monomers: Butadiene Styrene Modifier: Reaction medium: Water Emulsifier System: K-salt of disproportionated rosin Na-salt of methylen-bis-naphthalinsulfonic acid Initiator-System: p-Menthylhydroperoxide FeSO4 * 7 H20 Di-sodium salt of ethylenediaminotetraacetic acid Na-salt of Formaldehydesulfoxylate Na3PO4*12 H2O 65,4 wt.% t-DDM 23,2 9,5 0,07 wt.% wt.% wt.%
1,5 0,03
wt.% wt.%
0,04 0,01 0,02 0,03 0,16
wt.% wt.% wt.% wt.% 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
Abietic Acid
CH2
SO3 Na 2 Na + SO3 Na
Pd
CH3
CH3
CH3
+
H CH3 COOH H CH3 COOH
+
H CH3 COOH
Dehydroabietic Acid
Dihydroabietic Acid
Tetrahydroabietic Acid
E-SBR: Ingredients of Polymerization Recipe II

p-Menthanehydroperoxide (p-MHP) CH2 CH2 CH3 O CH3 O H
Oil soluble hydroperoxide
CH3 CH
CH
CH2 CH2
Na-Formaldehydesulfoxylate Na-Hydroxymethanesulfinate H O S H Ethylenedinitrilotetraacetic Acid (EDTA) O O CH2 N HO O CH2 CH2 CH2 N CH2 O OH CH2 OH O Na
+
Reducing agent
Sequestering agent for Fe-Ions
HO
E-SBR: Sequence of Reaction Steps

Redox Initiation:
R-OOH Fe3+ R-O* + Fe2+ + Reducing agent + Monomer R-O* + OH- + Fe3+ Fe2+ + oxydized reducing agent R-O-Mon*
Growth Reaction:
R-O-Mon* + n Monomer P*
Regulation of Molar Mass with Mercaptanes:

P* + HS - R R - S* + n Monomer R - S - Mn* + HS - R P- H R - S - Mn* R - S - Mn - H + R - S* + R - S*
Transfer Reaction:
P* + R-H R - H + P*
Termination Reaction:
P* + P* P- P
E-SBR: Influence of Thiols

100 175
Gel content [wt.%]
80 60 40 20 0
(ML 1+4 (100C) [ME] 0 0,2 0,4
140 105 70 35 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 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100
Copolymerization Parameters (Styrene = M1; Butadiene = M2) r1 = 0,7 r2 = 1,4 As a Consequence of these copolymerization parameters there is no azeotropic composition
r1 = r2 = Styrene Content of Monomer Feed [wt. %]
k11 k12 k22 k21
E-SBR: Copolymerization of Butadiene and Styrene (Integral Styrene Incorporation)

100
Integral Styrene Content [wt.%]
80
Copolymerization Parameter: = 0,78 r1 (Styrene) r2 (Butadiene) = 1,39
60 Ideal (random) Copolymerization for Monomer Feed Styrene/Butadiene: 30/70 40
Monomer Feed Styrene/Butadiene: 30/70 Polymerization Temperature: + 50C Hot Polymerisation - 20C (Cold Polymerisation)
20
0 0 20 40 60 80 100
E-SBR: Distribution of Styrene Sequences in E-SBR 1502

80 70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8
Copolymerizationparameter Styrol = M1 Butadien= M2 r1 = 0,7 r2 = 1,4
Probability [%]
r1 = r2 =
k11 k12 k22 k21
9 10 11 12
Number of Styrene Units
E-SBR: Microstructure
Polymerizationtemperature [C] -20 5 50 100
BR-Microstructure 1,4-cis 1,4-trans Vinyl [%] [%] [%] 0,8 7,7 14,8 27,6 79,6 71,5 62,0 51,4 19,6 20,8 23,2 21,0
E-SBR: Dependence of Tg on Styrene Content

100 80 60 40 expt. data Fox-Flory-equation
Tg of atactic polystyrene
Tg [C]
20 0 -20 -40 -60 -80 -100

Tg of E-BR Tg: Tg1: Tg2: wn:
Fox-Flory-Equation
1 w w2 = 1 + Tg2 Tg Tg1
Tg of copolymers in K Tg of homopolymer 1 in K Tg of homopolymer 2 in K weight fraction of copolymers 1 und 2
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 [g/mol] Mw/Mn ML 1+4 (100C) [ME] 45 51 52 54 Al [ppm] 655 1 Tg [C] -51 -53 -50 -50 chloride [ppm] 0,110 0,079 0,230 0,045
Krylene 1500 mod. Krylene 1500* Krylene 1712 mod. Krynol 1712* Product
424.280 429.210 740.170 716.760 Ash cont. (850C) [wt.%] 0,33 0,23 0,41 0,20
3,46 3,51 3,69 3,74 Na [ppm] 1105 910 1502 355
137,5 phr of Krynol 1712 contains 37,5 phr oil
==>
27,27 wt.% oil
waterextract [wt.%] 0,33 0,23 0,41 0,20
acetoneextract [wt.%] 6,9 2,4 32,3 30,1
Krylene 1500 mod.* Krylene 1500 Krynol 1712 mod.* Krynol 1712
* 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 Krylene 1500 mod. Krylene 1712* mod. Krylene 1500* Carbon black N 339 Carbon black N 234 Mineral oil TMQ IPPD DTBD Stearic acid Zinc oxide Sulfur CBS DPG [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] 103,13 25,0 80,0 10,0 0,5 0,75 0,75 2,5 2,5 1,9 1,1 0,55 103,13 25,0 80,0 10,0 0,5 0,75 0,75 2,5 2,5 1,9 1,1 0,55 68,75 50 80 20,0 0,5 0,75 0,75 2,0 2,5 1,9 1,2 0,3 68,75 50 80 20,0 0,5 0,75 0,75 2,0 2,5 1,9 1,2 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 Krylene 1500 mod. Krylene 1712* mod. Krylene 1500* [phr] [phr] [phr] [phr[ 103,13 25,0 67,0 8,3 35,3 4,8 7,5 11,2 17,3 425 2,5 12,6 69 63 25 38 103,13 25,0 71,0 8,8 38,2 4,3 6,8 9,3 18,5 410 2,7 14,3 71 64 27 42 68,75 50 73,5 9,1 37,3 4,7 8,2 12,6 17,9 480 2,3 10,9 72 64 22 33 68,75 50 77,0 10,1 39,2 4,5 7,9 11,1 18,9 470 2,3 11,8 71 64 25 36
Compound-Mooney ML1+4 (100C) [MU] Rheometer (160 C) L F ts1 t50 t90 Vulcanizate Properties: Tensile Strength Elongation at break M100 M300 Shore A Hardness/23C Shore A Hardness/70C Rebound/23 C Rebound/70 C [dNm] [dNm] [min] [min] [min] [MPa] [%] [MPa] [MPa] [%] [%]
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-Mller 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 Vulkanisationsfhigkeit 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
Denki Kagaku Kogyo KK Lanxess DuPont Tosoh Chonquin Changshou Chemicals Shanxi Syntheic Rubber Co Pidilite Showa Denko KK Nairit Scientific Industrial
Capacity Site
100 75 45 32 28 25 25 20 10 Omi/Japan Dormagen/Germany Pontchartrin/USA Nanyo/Japan Chongquing/China Datong/China India Kawasaki/Japan Yerewan/Armenia
Butadiene Acetylene
X X X X X X X X X
Total
360
Plant Closures
Stagnant CR-Consumption in WE and USA Growing Consumption in South-East Asia
Producer
DuPont Bayer
Capacity Site
30 50 25 25 Maydown/N.-Ireland Louisville/USA Houston/USA Grenoble/France
Source: Various Press Releases
Polimeri (BP)
Monomer Manufacturing Processes

2-Chlorobutadiene-1,3 (Chloroprene)
Acetylene Route (1930)
2 HC CH CuCl/NH4Cl/HCl Nieuwland
Butadiene Route (Gas phase chlorination / 1956)

H 2C CH CH CH2 + Cl2 Cl Cl Cl + (ca. 60 %) Cl
2,3-Dichlorobutadiene 1,3 (DCB)

Cl H2C C CH + Cl2 Cl H 2C C Cl CH Cl CH2 CH2
CH2 CH CH CH2+ CH2 CH CH CH2 (ca. 40 %) HC CH CH2 Side products: chlorinated C8-Compounds Tetrachlorobutane CuCl Cl Cl H2C CH CH CH2 - HCl
HCl/CuCl (30-60 C)
+ NaOH/85 C
- HCl
+ NaOH (85C) Cl H2C CH CH2 +
Cl H2C C
Cl C CH2
Cl HC CH CH CH2
Only DuPont, Lanxess und Denki produce DCB
2-Chloroprene
DE 1149001; Knapsack AG, Prior.:10.07.1961 Erf.: W. Vogt, K. Kaiser, H. Weiden
1-Chloroprene (impurity)
GB 804254; Distillers Co. Ltd. , Prior.:21.03.1956; Erf.: F. J. Bellringer
CR: Grades and Aplication Areas

CR Application Areas (2006)
Latex applications 5% Rubber Applications 60%
Polymerization Temperature [C]
Latex based adhesives 5% Solvent based adhesives 30%
50 45 40 35 30 25 20 15 10 0
0 1 2 3 4 5 6 7
Latex Grades
Rubber Grades
(Standard Grades, precrosslinked grades and sulfur grades)
Application Areas of Rubber Grades Profiles 11% Belts 12% Cables 21% Hoses 44%
Adhesive Grades
Conveyor Belts 12%
DCB-Content of Monomer Feed [phm]
CR: Influence of Polymerization Temperature on Microstructure

CH2 1,4-trans Cl Cl 1,4-cis C CH2 C C C CH2 H CH2 H
Polymerization temperature [ C] +12 +30 +42 +57 +75 1,4-trans[%] 94,5 93,5 93,5 91,5 88,5 1,4-cis [%] 3,8 4,5 4,5 5,8 8,4 1,2 [%] 1,0 1,2 1,2 1,4 1,5 3,4 [%] 0,8 1,0 1,1 1,3 1,4
1,2
Cl CH2 C
2 3
3,4
H CH2 C
3
C CH2
C CH2
Cl
1,4-trans-Content [Mol %]
95
90
Adhesive grades
Microstructure trans-1,4 cis-1,4 > 89% > 95%

Tg [ C] Tm [ C] -45 105 -20 70
Rubber- and Latex Grades
85 0
10
50 60 70 20 40 30 Polymerization Temperature [ C]
80
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]
Chloroprene 2,3-Dichlorobutadiene Water Disproportionated abietic acid NaOH or KOH Na-methylene-bis(naphthalinsulfonate) n-dodecylmercaptane Potassiumpersulfate Na-Anthrachinon-2-Sulfonate Sulfur Dimethacrylates of alkanediols Polymerization temperature [ C] Monomer conversion [%]
Adhesive grade
100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 5 - 20 60 - 85
Latex grade
100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 20-50 60 - 85
Standard grades
90-100 0 - 10 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 30-50 60 - 85
Sulfur grades
90-100 0 - 10 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 0,3-0,7 30-50 60 - 85
Precrosslinked grades
100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 0,1-0,3 30-50 70 - 85
CH3
+
CH3
+
CH3
CH2
SO3 Na 2 Na + SO3 Na Na-Methylene-Bis(Naphthalinsulfonate) (Baykanol PQ R)
H CH3 COOH
Dehydroabietic Acid
H CH3 COOH
Dihydroabietic Acid
H CH3 COOH
Tetrahydroabietic Acid
CR: Determination of Crystallization Rate

Dependence of Shore A Hardness on Crystallization Rate
He Shore A Hardness
Mercury dilatometry for the determination of crystallization rate (Tc =-5C pretreatment: 30 min at 80C)
0 10
Volume [mm3]
He-Hi 1/2(He- Hi) Hi

t1/2
20 30 40 50 60 70 80
0,1 1 10 100 1000
0,1
10
100 1000 10000
Storage time [h]

Source: U. Eisele: Internal Bayer-Reporting System
Storage time [h]
CR: Crystallization Rate and Crystallite Melting Temperature

Dependence of t1/2 on Storage Temperature
(Baypren 210; Pretreatment: 1 h / 60C) 30
Crystallite melting temperature [ C]
Dependence of Crystallite Melting Temperatures on Polymerization Temperature

80 70 60 50 40 30 20 10 0
-60 -10 40
25 20 t1/2 [h] 15 10 5 0 -20 -15 -10 -5 0 5 10 15 20 Storage Temperature [ C]
lowest figures highest figures
Polymerization temperature [ C]
Source: U. Eisele Introduction to Polymer Physics Springer Verlag
Dependence of Tg and Crystallization Rate at -10C on Monomer Feed and Polymerization Temperature
Sym- T bol [C] 45 35 25 15 5
- 31 - 33 - 34
103 45
Polymerizationtemperature [C]
102
35
25
15
t 1/2 [h]
0 6 9
Tg [C]
- 35 - 36
101
100
- 37 - 38 3 12 15
10-1 0 3 6 9 12 15
DCB-Content of Monomer Feed [%]
DCB-Content of Monomer Feed [%]
Crystalliaztion Rates of Unvulcanized CR, Unvulcanized CRCompounds and CR-Vulcanizates at - 10C

500
lcanizates
B. 110 VSC
s
400
CR-bases vu
t1/2 [h]
300
U nv ul ca ni ze d
200
Un
d ize n a lc vu
CR
nd ou p m -c o
B. 110 100 B. 210 0 100 200 300 400 500 KA 8418 B. 112
CR Carbon black (N 762) Polyetherthioether Vulkanox DDA Vulkanox 4010 NA Stearic acid Magnesium oxide Zinc oxide
100,0 75,0 10,0 2,0 0,5 0,5 4,0 5,0
phr phr phr phr phr phr phr phr
600
700
800
t1/2 [h] (unvulcanized CR)
Dependence of Crystallization Rate on Blending Ratio of Two CR-Grades and on Type of Plasticizer
25 20 15
Unvulcanized ISO- 2475-1975 Compounds; Measurements at - 10C

CR Stearic acid Magnesium oxide Phenyl-2-Naphthylamin Carbon black (N 772) Zinc oxide (active) Vulkacit NP 100 0,5 0,5 2,0 30 5,0 0,5 phr phr phr phr phr phr phr
Influence of Plasticizers
(CR-grade: Neoprene W (~ Baypre 210) 300 250 200
Neoprene W + mineral oil
t1/2 [h]
10 5 0 100 80 60 40 20 0 Baypren 110 VSC (slowly crystallizing)
t1/2 [h]
150
100 50 0 -20 -15 -10 -5 0 5 10 15 20

Neoprene W + Butyloleate
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 CRGrades on Storage Temperature

CS (168 h / variable temperatures)
100 90 80 70 60 50 40 30 20 10 0 -60 -40 -20 0 20 40 60 80 100 120 140 160 180 DCB-containing rubber grade (Baypren 110) DCB-free rubber grade (Baypren 210) CR Adhesive grade (Baypren 320)
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 Cl 2,3 - Dichloro - 1,3 - Butadiene CH2 CH CH2 Cl CH2
Standard CR-Grade
S S
S S S
Sulfur Grade
Sulfur S S S
CH3 O
O O CH2 O
n
CH3 CH2
Precrosslinked CR-Grade
Dimethacrylate
CH2
Molar Mass Control by Mercaptanes and by Xanthogendisulfides

Molar mass control by mercaptanes
P* R - S* R - S - Mn* + HS - R + nM + HS - R P- H R - S - M n* R - S - Mn - H + R - S* + R - S*
Molar mass control by Xanthogendisulfides

P* RO - CS - S* + (RO - CS - S -)2 + Mn P - S - CS - OR RO - CS - S - Mn* RO - CS - S - Mn - S - CS - OR + RO - CS - S* + RO - CS - S*
RO - CS - S - Mn* + (RO - CS - S -)2
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 Stearic Acid 0,5 phr MgO 4,0 phr Phenyl-2-Naphthylamine 2,0 phr ZnO active 5,0 phr Vulkacit NPV/C 0,5 phr
CR-grade with xanthate end groups Mercaptan modified CR-grade
16 Vulcanization: 40 min/150C
22

30 40 50 60 70 80 90 100 110
15 14
21
M300 [MPa]
13 12 11 10
20
19
18 10 11 12 13 14 15
ML 1+4 (100C)
Modulus M300 [MPa]
Dynamic Resistance of CR-Standard Grades (Monsanto Test)

Xanthate modified CR-Grade (Baypren 121) Mercaptane modfied CR-grade (Baypren 110 VSC) unaged 7 days / 100C unaged 7 days / 100C ISO-Compound 2475
CR 100,0 phr Carbon black N 762 30,0 phr Stearic Acid 0,5 phr MgO 4,0 phr Phenyl-2-Naphthylamine 2,0 phr ZnO active 5,0 phr Vulkacit NPV/C 0,5 phr Vulcanization: 40 min/150C
250
Cycles until failure [kcycles]
200 150 100 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
u
Cl
v w
Cl
NR2 C S ( CH2 C CH CH2 ) S (CH2 C CH CH2 ) x Sy C NR2

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 Sa ( CH2 CH CH2 )n S Sw ( CH2 v S NR2 S S S NR2 Cl CH CH2)x
Cl Sa ( CH2 CH CH2)n S v S
S NR2 NR2
S S Sw ( CH2 CH CH2) x
Impact of the Amount of Incorporated Sulfur on Mastication and Ageing Performance

50
ML 1+4 (100C) [ME]
48 46 44 42 40 38 36 34 32 30 0 2 4 6
Baypren 510
80
Change of M100 (7d/100C) [%]
Baypren 610
70 60 50 40 30 20 10 0 0 0,2 0,4 0,6
Incorporated Sulfur
10
Mastication time [min]

Mastication:
Mill size: Friction: Revolutions: Width: Amount: 200 x 400 mm 1:1,2 20 min-1 1,2 mm 600 mg
Sulfur [phm]
Compound Ingredients:
CR Ru (N 762) Polyetherthioether Vulkanox DDA Vulkanox 4010 NA Stearic acid Magnesium oxide Zinc oxide 100 75 10 2,0 0,5 0,5 4,0 5,0 phr phr phr phr phr phr phr phr
Vulcanization of CR-Sulfur Grades

H H H N S S H H C S Sx S N
CR-Sulfur grades (which are fully commercially available) contain dithiocarbamate end groups which are attached via sulfur bridges. These end groups are active in vulcaniaztion. CR-Sulfur grades can be considered as "rubber bound intermediates which are known from theoretical considerations on the mechanism of sulfur cure. As a consequence, CR sulfur grades are vulcanized by the use of ZnO and MgO (+ Stearinsure) without using accelerators. CR sulfur grades exhibit a critical stability of Mooney viscosities during storage particularly at elevated temperatures.
H C N S S S Sx S N SH S N
Precrosslinked CR-Grades
Production:
Precrosslinked CR-rades are blends of 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 in the soluble CR phase is achieved. CR-Gel
Application:
Unvulcanized CR compounds which contain CR gel exhibit good processing features, particularly a low die swell. Major application areas are extruded articles (wiper blades as well as window and door seals In these applications CR is being substituted by EPDM and TPEs.
Die swell Rubber Compound = de do x 100
Ungelled (soluble) CR
d0
de
Properties of Precrosslinked CR-Grades

20 50 Tensile Strength [MPa] 0 10 20 30 40 50 60 70 46 Die Swell [%] 42 38 34 30 26 Gel content [wt.% %] 18 16 14 12 10
0 10 20 30 40 50 60 70
Gel content [wt.% %]
Mechanism of CR-Vulcanization according to Pariser/Du Pont

S Cl CH2 CH CH2 CH CH2 Cl NH S NH
CH2
CH
CH2 S
+
Vulcanization of CR
Cl
Chemicals for CR-Vulcanization S
+ NH
NH NH NH
CH2 CH2
CH2
CH2 CH2 CH2 CH
NH
NH
+ ZnO - ZnCl +
O NH
CH2 S
CH2CH2 S S N CH3
Ethylenethiourea (ETU/Vulkacit(R) NPV)
"cyclic Dithiocarbamate" (Vulkacit(R) CRV)
NH
CH2 CH2 CH2 CH O CH2 O NH S NH Cl
CH2 CH2 CH2 CH CH2 S NH NH CH2 CH CH2 S CH2 CH2 CH CH2 CH2 CH2
CH2CH2
End groups which participate in CR-Vulcanization S S Sx S S O R

Xanthate end groups are present in in xanthate modified CR Dithiocarbamate end groups are present in sulfur modified CR
NR2
CH2 CH2 CH2 CH CH2 S
+ ZnCl +
- ZnCl2
CH2 CH
Substitution of CR
250
FKM
max. service temperature [ C]
MVQ
225 200 FZ 175 150 125 100 EU 75 50 0 20 40 60 80 100 120 140 no requirements AU FMVQ
Resistance to high temperatures 80 % VAc
ACM
HNBR
NBR
AEM to high temperatures, flame resistance Resistance CM CSM

Price
EVM
Resistance to dynamic stress
(H)IIR
EPDM
CR
SBR
BR
NR
max. Volume Swell in ASTM-l 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 Emulsifiers Initiator systems Molar mass regulation Copolymerization
Polymerisation
Product groups and Properties

Standard grades Carboxylated grades Precrosslinked grades
Vulcanization and Vulcanizate Properties
NBR: Microstructure
C C N N
HC HC
3
CH 1 2
4
CH2
+
CH2 CH CH CH2
CH CH
2
C H2
CH2
1
CH 2 CH 2 1
1,4-cis
1,4-trans
Vinyl
Acrylonitrile
Dependence of the Microstructure of Incorporated Butadiene Moieties on Polymerization Temperature
Polymerizationtemperature [C] -20 5 50 100
Microstructure of Butadiene Sequences 1,4-cis 1,4-trans Vinyl [%] [%] [%] 0,8 7,7 14,8 27,6 79,6 71,5 62,0 51,4 19,6 20,8 23,2 21,0
Standard grades
Basic Features of NBR

Fast curing / Low mould fouling (Injection moulding) slow cure peroxide cure
Special grades
X-NBR Precrosslinked NBR NBR/PVC-Blends NBR-powder grades liquid NBR -HO-terminated -COO-terminated -NH2-terminated NBR mit bound antioxydant
Positive:
Low degree of swelling in oil, fuels, greases and fats High kevel of mechanical properties High abrasion resistance especiall for carboxalated grades Broad range of grades Low gas permeability Low price level / high competition
Negative:
Maximal service temperature: < 110 C (Criterium: 1000 h / b=0,5*b0) Standard grades are not applicable for outdoor use (contrary to NBR/PVC-Blends)
NBR-Application Areas in Western Europe

Automotive 35% Rubber Goods (without automotive) 34% Rubber modification of Thermoplastic and duroplastic polymers 11%
Adhesives 1% Others 4% Cable and shoes 5% wiring 5%
building 5%
300
Volume swell [%]
250 200 150 100 50 0
NR
SBR CR NBR
0 14 21 7 time in ASTM-L3 [days]
NBR:Market- und Development

450 400 350
Consumption [j/y]
300 250 200 150 100 50 0
19 85
19 90
19 95
20 00
20 05
20 10
NBR: Production Capacities

(European Rubber Journal 181, no no 4, April, S. 10 1999; updated in July 2010)
Zeon Tokuyama / JP Kawasaki /JP Louisville / USA Houston / USA Barry/Wales / GB (Baton Rouge / USA) La Wantzenau / FR Leverkusen / DE Sarnia / CAN Triunfo / BRA Yokkaichi / JP Porto Torres / IT Altamira / Mexico Ulsan Goodrich Goodyear BP (Copolymer) Polysar Bayer Polysar Petroflex
Lanxess
JSR Polimeri Paratec Korean Kumho Lucky Gold President Eliokem Nitriflex PASA S&C Sibur
Negromex/Uniroyal
Hyundai Kaoshing / Taiwan Sandouville / FR Goodyear Valia /Gujarat - Indien Goodyear Duque de Caxais / BRA Santa Fe Bareilly Omsk
45 20 35 28 15 15 100 35 25 30 35 30 25 20 16 15 11 25 10 5 2 424
Nipol Nipol Hycar Chemigum Breon (Nysin) Perbunan / Krynac Perbunan Perbunan / Krynac Perbunan JSR NBR Europrene Paratec Kumho NBR Chemigum (Powder) Chemigum (bales) Nitriflex/Nitriclean
Total:
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 (100C)

without pretreatment (DIN 53523)
NBR: Dependence of Tg on Acrylonitrile Content

100 80 60 PAN
Tg [C]
40 20 +0 -20 -40 -60 -80 -100 0 10 20 30 E-BR

e ng a R o om C f er m
s de a gr l a ci
Gordon-Taylor-Equation* TgCopolymer = w1*Tg1 + w2*Tg2

TgE-BR = - 80C TgPAN = + 100C *Gordon M., Taylor J. S., J. Appl. Sci., 21, 581 (1950)
40
50
60
70
80 90
100
Acrylonitrile content [wt.%]
NBR: Dependence of Volume Swelling on Acrylonitrile Content

90 80 Expt. Conditions: 14 days Fuel B and C: 20C ASTM-Oils: 140C
vvvvvWeight Change[%]
70 60 50 40 30 20 10 0 -10 0 5
Fuel C (Isooctan/Toluene: 50/50) Fuel B (Isooctan/Toluene: 70/30) ASTM l Nr. 3 (aromatic/naphthenic) ASTM l Nr. 1 (paraffinic)
10 15 20 25 30 35 40 45 50
Dependence of Shore A-Hardness and Rebound on Acrylonitrile Content
90 80 Shore A Hardness 70 60 50 40 0 5 10 15 20 25 30 35 40 45 50 75C
50 40 75C
Rebound [%]
20C
30 20 10 0 0 5 10 15 20 25 30 35 40 45 50 Acrylonitrile [wt.%] 20C
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/100C) [%]
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 Fe3+ R-O* + Fe2+ + Reducing agent + Monomer R-O* + OH- + Fe3+ Fe2+ + oxydized Reducing agent R-O-Mon*
Growth reaction:
R-O-Mon* + n Monomer P*
Molar Mass Regulation by Mercaptanes:

P* + HS - R R - S* + n Monomer R - S - Mn* + HS - R P- H R - S - Mn* R - S - Mn - H + R - S* + 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 CH3 COOH H CH3 COOH
+
H CH3 COOH
+
H CH3 COOH
Abietic Acid
Dehydro abietic acid
Dihydro abietic acid
Tetrahydro abietic acid
Partially hydrogenated tallow fatty acids

Producer Brand name
BAX Holm Oleon Unichema Cognis AG IS/1 THT 1618W Radiacid 40 Prifac 5910 Edenor C1618
C14 ges. C14 ges. C18 ges. C18 unges.

3,1 0,4 3,5 2,6 1,2 32,5 27,5 35,1 37,7 40,3 33,5 34,8 24,8 31,5 26,4 31 37,3 36,6 28,3 32,1
Methylen-Bis (Naphthalinsulfonsure), Na-Salz (Baykanol PQ(R))

SO3 Na 2 Na + SO3 Na
Sulfates- und Sulfonates (Examples)

Na-Laurylsulfate Na-Alkylarylsufonate Na-Alkylsufonate (Texapon) (Marlon) (Mersolat)
CH2
Activatator Systems for NBR-Polymerization

Organic Activation System
p-Menthylhydroperoxide (p-MHP) CH2 CH2 CH3 CH CH CH3 O O H
Inorganic Activation System

(NH4)2 S2O8 Ammoniumperoxodisulfate
CH3 Na-Formaldehydesulfoxylate Na-Hydroxymethanesulfinate H H O O S O Na

+
CH2 CH2
CH2 N CH2 HO CH2
CH2 OH
H Ethylenedinitrilotetraacetic acid (EDTA) O O HO HO O Ion-(II) sulfate Fe SO4 CH2 N CH2 CH2 CH2 N CH2 O OH CH2 OH
CH2 CH2 OH
Triethanolamine
Copolymerization Diagram for the Copolymerisation of Butadiene/ACN- (for incremental conversions)

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

Source: W. Hofmann, Nitrilkautschuk, Berliner Union Verlag
NBR: Dependence of Integral Copolymer Composition on Monomer Conversion

Acrylonitrile Content of Polymer [Gew. %] 100 90 80 70 60 50 40 30 20 10 0 0 10 20 30
Modellierungsparameter (ACN = M1; Butadien = M2): r1 = 0,02; r2 = 0,28
Acrylonitrile content of monomer feed:

60 wt.% 50 wt.% 38 wt.% 33 wt.% 28 wt.% 20 wt.% 10 wt.% 5 wt.%
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 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100
Incremental composition
Integral composition
Monomer Feed: Acrylonitrile: 73,7 wt.% Butadiene: 26,3 Gew.% Copolymerizatin parameters: r1 = 0,023; r2 = 0,30
For the production of a NBR-grade with a high chemical homogenity one or both of the two monomers (ACN respectively butadiene) have to be incrementally added during the course of the polymerization in order to compensate for changes in the composition of the monomer feed, unless polymerization is performed in the azeotropic monomer composition
Monomer conversion [%]
NBR: Dependence of Tg on Polymerization Parameters (Batch-Polymerization)

Sample Bound Polymerization ACN temperature [wt.%]
A B C D E F G H I K 38,9 32,8 25,8 44,8 34 29,2 28,5 23 21,1 31,4
ACN-addition during polymerization + -
Monomer Tg Conversion Lower Tg Upper Tg [%]

>57 >57 >57 >57 >57 >57 >57 >57 >57 57 -46 -49 -64 -61
[C]
5 5 5 50 50 50 50 50 50 50
[C]
[C]
-19 -22 -33 -13 -26 -32 -33 -40 -53 -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 ML1+4 (100C)
120 100 TDM / Lanxess 80 60 40 20 0 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 TDM / Phillips Chevron
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
2 + + Wagner- MeerweinRearrangement +
- H+ + "Triisobutene (TIB)"
2. TDM-Production by the Addition of H2S to TIB

H2S / Cat. + "Triisobutene (TIB)" 2,2',4,6,6'-Pentmethylheptanthiol-4 SH
Patent No.
Jp 07 316 126 Jp 07 316 127 Jp 07 316 128 DE 102007024009
Company
Zeon Zeon Zeon Lanxess
Priority
27.12.1994 27.12.1994 27.12.1994 22.05.2007
Patent Title
Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol TDM-Mischung: Herstellung und Anwendung
Reaction of Incorporated TDM-End Groups During Vulcanization

3. Thermal Decomposition of TDM-End Groups
CH3 H3C C CH2 CH2 CH CH CH2 S C CH2 H3C C CH3 CH3 H3C CH3 CH3 C CH3 CH2 C CH3 CH3 CH C CH3 CH3 CH3 Vulcanization CH2 CH CH + CH2 SH
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 Patent No.
EP 0692496 EP 0779300 EP 0779301
Company
Zeon Zeon Zeon
Priority
30.03.1993 (Jp) 29.08.1994 (Jp) 29.08.1994 (Jp)
Patent Title
Unsatuarated Nitrile/Conjugated Diene copolymer, process for Producing the same, and Rubber Composition
Dependence of NBR-Properties on Content of Metal Ions

cCa Ion-Number = 3 40 + cMg 24 cNa 23 + cK 39
ppm Atomic weight weight
Influence of Ions on Speed of Cure: accelerating: Na-, K- Ions retarding: Mg-, Ca- Ions
Patent No.
DE 102007024011 DE 102007014010 DE 102007024010
Company
Lanxess Lanxess Lanxess
Priority
22.05.2007 22.05.2007 22.05.2007
Patent Title
Nitrile Rubber with Specific Ion Number Nitrile Rubber with Specific Ion Number Nitrile Rubber with Specific Ion Number
Dependence of NBR-Properties on Content of Metal Ions

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

Rubber
O O 2
C
O (R*)
NBR
Crosslinking efficiency 1,0
O
C C
+ 2 R-H
Avoidance of phenoland amine based antioxydants (=radical scavengers)

H O
X-linking efficiency =
Number of x-links PeroxidePeroxide-functions Theoretical X-linking efficiency 1 >1 <1
H O
H O
Type of Rubber M - Rubber R - Rubber Degradating rubbers
H O S
H O
Vulcanization of NBR: Compound Study

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

Vulcanization System ML1+4 (100 C) ts t90 Shore A TS b M100 M300 [ME] [min] [min] EV 1 78 3,2 7,2 71 16,9 310 4,3 16,3 12 -60 -49 EV 2 EV 3 Peroxide 87 1,8 2,6 72 19,5 365 4,4 17,3 20 31 -62 -53,5 17 67 3,4 7,0 71 15,8 310 4,7 15,4 16 -62 -60 20 77 0,6 4,9 70 18,3 260 4,2 13,0 14 -
[MPa] [%] [MPa] [MPa] [%] [%] [%] [ C] [ C] [%]
CS (70h/100C) CS (70h/120C) CS (70h/125C) Brittleness Point Tg CS (24h/-20 C)
Carboxylated NBR (X-NBR)

C C N COOH N
Carboxl-containing monomers: Methacrylic acid Itaconic acid Maleic Acid
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 stators / Pump pump stators / Pumpseals seals belts belts Hydraulic Hydraulichoses hoses
Chemistry of Vulcanization with Metal oxides

C CH3 CH3 _ _ OOC _ _ C OOC COO 2+ COO Zn + ZnOH 2+ ZnO CH3 Zn_ 2+ ZnO Zn _ _ + C COO _ OOC ZnOH COO CH3 _ _ CH2 H3C OOC C C CH2 CH2 CH3 C CH2 CH2 CH3 C CH2 CH3 C CH2
CH3 8 CH2 C COOH
CH2
+ ZnO - H2O
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 NBR Fmin. X - NBR NBR CB (N 660) Dibutylphthalate Stearic acid Wingstay 29 Sulfur TMTD MBS Zinc oxide 100 0 40 5 2 1 0,5 2 1 5 50 50 40 5 2 1 0,5 2 1 5 0 100 40 5 2 1 0,5 2 1 5 Fmax. ts t90 t95 Shore A M100 M200 M300 TS [MPa] [MPa] [MPa] [MPa] [min] [min] [min] [Nm] 100,0 0 9,0 86,3 3,0 10,0 21,5 83 5,2 11,0 18,6 25,5 430 493 - 42 34,1 50,0 50,0 10,2 78,7 2,7 7,0 11,0 80 4,5 10,0 15,5 21,0 415 159 - 35 27,1 0 100,0 8,0 60,0 2,8 6,8 8,3 67 1,7 4,8 11,0 18,2 500 73 - 30 14,7
b [%] Abrasion Index Ageing at 70h/121 C
elongation [%]
CS [%]
Precrosslinked NBR
Properties: Properties:
Reduction Reductionof ofdie dieswell swell Increased dimension Increased dimensionstability stabilityafter afterextrusion extrusion Improvement of surface quality of extruded/calendered Improvement of surface quality of extruded/calenderedarticles articles Increase of Moduli Increase of Moduli Improvement Improvementof ofCS CS Reduction Reductionof ofTS TS Reduction Reductionof ofelongation elongationat atbreak 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) NBR (34 Gew.% ACN) Zincoxide Stearic acid TMQ (Vulkanox HS) Carbon black (Corax N 550) Vulkanol 81 Sulfur TBBS (Vulkacit NZ) TMTD (Vulkacit Thiuram)
* Precrosslinked NBR
Krynac VP KA 8769 Krynac 34.50 Lanxess Henkel KGaA Lanxess Degussa Lanxess Kali Chemie Lanxess Lanxess
phr phr phr phr phr phr phr phr phr phr phr
10 90 3,0 1,0 1,5 1,5 30 10 0,3 1,5 1,5
20 80 3,0 1,0 1,5 1,5 30 10 0,3 1,5 1,5
30 70 3,0 1,0 1,5 1,5 30 10 0,3 1,5 1,5
40 60 3,0 1,0 1,5 1,5 30 10 0,3 1,5 1,5
Zincmethylmercaptobenzimidazol Lanxess
Source: Bayer AG, Marinelli/Welle, KALIS-Nr.: 9588 vom 05. 10. 2000
Precrosslinked NBR: Results of Compound Study

NBR* (34 Gew.% ACN) NBR (34 Gew.% ACN) Compound-ML [ME] Mooney-Relax. [%] Die swell /linear [%] Fmin. [dNm] [dNm] Fmax. [min] ts1 t90 [min] t95 [min] Shore A/23 C Shore A/70 C [MPa] M100 M200 [MPa] M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23 C [%] [%] Rebound/70 C CS (70h/23 C) [%] CS (70h/100C) [%] 10 90 42 5,8 42,9 0,77 10,63 1,85 5,31 6,61 51 49 1,2 2,4 4,5 19,8 677 40 54 13 34 20 30 80 70 44 47 5,6 5,5 31,7 31,2 0,95 1,15 11,31 12,1 1,77 1,68 4,76 4,58 5,84 5,57 53 55 50 52 1,4 1,5 2,9 3,2 5,2 5,8 16,4 15,5 563 560 39 39 56 57 13 13 32 30 40 60 51 5,7 16,8 1,44 13 1,64 4,5 5,48 57 54 1,7 3,6 6,4 14,1 488 39 61 12 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
Ti-BR Ni-BR Co-BR Nd-BR Li-BR L-SBR EPM/EPDM CM/CSM HNBR IIR
Reaction Medium
solvent solvent solvent solvent solvent solvent solvent solvent solvent solvent
Catalyst/Process
Z/N* Z/N* Z/N* Z/N* anionic anionic Z/N* polymer modif. polymer modif. cationic * Z/N = Ziegler-Natta Catalysis Solution-BR
High-cis1,4-BR
Solution Rubbers
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 millswithout 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 Steam PHControl Stripping aid
oil Antioxydant Expander screw US 2,592,814 (Du Pont) Prior.: 20.12.1947 Inventor: J. L. Ludlow
Waste water
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 otained. Before thermal drying water is removed mechanically
Source:
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 CH2 CH CH CH CH2 CH2 CH CH CH CH CH2 CH2 1,4-cis 1,4-trans CH2 CH CH2 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 Rubber Products 5% Rubber Toughening 23% Tyres 71%
Golf ball cores 1%
BR: Microstuctures and Glass Transition Temperatures

1 1
CH2
4
CH2 CH
1 3 3
CH2
2
CH2
CH CH
4
CH
4
CH CH
3
CH2
1,4-cis
1,4-trans
CH2 1,2- bzw. Vinyl
Catalyst Tg
Li* -93
Co -106
Ni -107
Ti -103
Nd -109
E-BR** -80
Microstructure (according to manufacturers product specifications) [%]

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

Vinyl/1H-NMR*** Vinyl/FT-IR*** Vinyl/Metathese*** 10,4 11,4 10,7 1,9 1,0 1,7 4,0 5,4 4,6 <1 0,6 0,7 18,1 17,7 17,8
* aliphatic, cycloaliphatic aromatic solvents without polar additives ** Polymer Handbook/Polymerisation temperature: 25C
*** 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 t 1/2 [min]

10
0,1 -100
-80
-60
-40
-20
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 [ C]
200
t 1/2 (-20 C) [min]
Nd Ni Co Ti
-5
Nd Ni Co Ti
150
-10
100
-15
50
-20
0 90 92,5 95 97,5 100
-25 90 92,5 95 97,5 100
1,4-cis-content [%]
1,4-cis-content [%]
BR: Producers and Production Capacities

500 450 400 350
Capacity [kt]
300 250 200 150 100 50 0

iz D hn ow ek T am ha ila sk nd ne fte ch im La nx es G oo s dy ea r M ic he lin Si no pe c B S/ FS K um ho er i ol im sa hi Ze on ot he rs ib ur be U C TS R S JS R A
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 Ube, Chiba, JP Nizhnekamskneftechim Michelin, Bassens, FR Dow, Schkopau, DE Petroflex, Cabo, BR Lanxess, Port Jrme, FR 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
Li Ni Ti Co Nd Li/Co/Nd Ni/Nd
Capacity [kt]
BR: Application Areas

Application Areas of BR
Technical Rubber Goods 5% HIPS/ABS 23% Tyres 71%
Golf balls 1%
not assigned 7% Li-BR 7% Nd-BR 8%
Tyre Market (2.2 Mio t)

Ni-BR 38%
HIPS/ABS-Market (0,68 Mio t)
Li-BR 48%
Ti-BR 18%
Co-BR 22%
Co-BR 52%
Anatomy of a Passenger Tire and Use of BR
Tread SBR/BR: 70/30 Sub Tread NR/BR: 80/20
Sidewall NR/BR: 60/40 Rim Cushion NR/BR: 80/20
Carcass NR/BR: 90/10
Apex NR/BR: 80/20
Source:
Comparison of BR-Grades for the Application in Tyres (ASTM-Compound 3189 90)

BR (Nd-, Co-, Ti-, Li-) Zinc oxide Sulfur Stearic acid Carbon black (NBS 378) TBBS Oil (ASTM Type 103) Vulcanization: 100,0 phr 3,0 phr 1,5 phr 2,0 phr 60,0 phr 0,9 phr 15,0 phr 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

5 4 3 2 1 0 0 250 500 750 1000
Stress [MPa]
Li-BR
Ti-BR
Co-BR
Nd-BR
Strain [%]
Source: Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Tack of Unvulcaniuzed BR-Compounds

350 Li-BR
time until separation [sec]
300 250 200 150 100 50 0 100
Ti-BR Co-BR Nd-BR
Improvement
1000
10000
critical load for separation [g]

Source:
Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Vulcanizate Properties of BR Grades

BR Grade Vulcanizate properties Tensile Strength Elongation at break M300 Shore A-Hardness Rebound DIN-Abrasion Pendulum -Skid Asphalt, dry Asphalt, wet Dynamic properties Goodrich-HBU De-Mattia crack growth Monsonto-FTF/ =100%
Source:
Nd [MPa] [%] [MPa] [%] [mm3] 15,3 400 9,4 65 49 23 85 33 [ C] [mm/kc] [cycles] 27 1,9 460
Co
Ti
Li 13,0 480 8,0 66 47 52 89 35 18 5,6 63
14,5 13,4 525 510 8,6 63 47 27 85 33 32 6,0 50 8,1 64 45 33 85 33 36 1,5 115
Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
1,4-cis BR: Dynamic Performance of BRVulcanizates (Monsanto Fatigue to Failure Test)

Number of Kilocycles until Failure 40 35 30 25 20 15 10 5 0
Improvement
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 45 Ti-BR Ni-BR Co-BR Nd-BR
Improvement
Abrasion [mm3]
40 35 30 25 20 0
Source:
5 10 Modulus at 300% elongation [MPa]
15
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

Grafted Shell Compatibilizer Hard Phase (coherent phase or matrix) Soft (dispersed) Phase
Rubber Modified Thermoplastics
Soft Phase
BR BR EPDM EPM NBR
Hard Phase
SAN PS SAN PP PP
Examples
ABS HIPS AES EPM/PP NBR/PP
The impact resistance of hard and brittle thermoplastic and duroplastic polymers is improved by rubber particles Prerequisites for an efficient impact modification are: 1) good dispersion of the rubber phase in the matrix 2) good mechanical bonding across the phase boundaries 3) x-linking of the rubber phase
Source:
C. Schade, H.-J Renner, W. Heckmann (BASF) Predictive property Adjustment Kunststoffe international 7/2010, 36-39
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 20
ho he
-40
-20
20
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 1000 100 10 1
HX 565 Mooney: 65 HX 501 Mooney: 40 HX 530 Mooney: 65 Degree of Branching: 50-55 Degree of Branching: ca. 18 Degree of Branching: ca. 10
Viscosity [mPa*s]
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

Solution Viscosity (5,43 wt.% in toluene) [mPa*s] 260 240 220 200 180 160 140 120 100 80
L br in an ear ch a ed nd BR sli g gr htl ad y es
Li-BR (commercial grades) Co-BR (commercial grades)
60 40 20 0 0 10
Star shaped BR
20
30
40
50
60
70
80
Mooney-Viscosity (ML1+4/100C) [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
Solvent Residence time Conversion Tendency towards gel formation Heat removal Solids Content Molar Mass Control agents Formation of 4VCH Transition metal content
Co
Ni
Ti
Benzene Toluene 120 <95 low
Nd
Hexane Aliphatics 100-120 <100 Very low fully adiabatic 18-22 no low 100-200
Benzene, Benzene Toluene Toluene (Aliphatics) Hexane 150 120 [min] [%] 55-80 high partially adiabatic 14-22 yes high [ppm] 10-50 <85 high
partially partially adiabatic adiabatic 15-16 11-12 yes high 50-100 no Very high 200-250
Positive 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

Charles Goodyear discovers the vulcanization by sulfur John Dunlop patents pneumatic tire 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
1839 1888 1910
Capacities of Multi-Purpose Solution Plants*

(BR/S-SBR-SBS-TPEs)
Capacity [kt]
100.000 80.000 120.000 85.000 80.000 80.000 60.000 110.000 180.000 125.000 30.000 360.000 35.000 30.000 10.000 48.000 296.500 30.000 145.000 210.000 30.000 incl. TPEs
Plant Location
Western Europe
EniChem Bayer Michelin Repsol Qimica Fina Polymers Dow Ravenna Grangemouth Lillebonne Bassens Santander Antwerp Schkopau Louisville, Ky Lake Charles Orange Orange Beaumont, Tx Cabo Salamanca Altamira Oita Tokuyama Yokkaichi Yeochon Kaohsiung Newcastle
Remarks Origin of basic technology

Firestone/Asahi Phillips-Petroleum technology origin not assigned
incl. TPEs incl. TPEs
Americas
ASR Bridgestone/Firestone Bayer Goodyear Petroflex Negromex incl. TPEs incl. TPEs
Japan
Asahi Japan Elastomer Nippon Zeon JSR incl. TPEs incl. E-SBR incl. Hydrogenated polymers incl. TPEs
Others
Korean Kumho Taiwan Synthetic Dow (Carbochem)
Total Capacity
* Source: IISRP Worldwide Rubber Statistics 2001
2.274.500
Origin of S-SBR-Technologies and Basic Features

Feature
Initiator Solvent Randomizer branching agent/chain end coupling short stop process temperature control sequential monomer addition Vinyl content of BR-moieties molar mass distribution of base polymer n-Bu-Li n-hexane none DVB water continuous adiabatic butadiene ~ 10% broader
Technology Firestone/Asahi Phillips

sec.-Bu-Li cyclohexane glymes DVB, SiCl4, SnCl4 stearic acid discontinuous, batch isotherm one shot > 20% narrower
Until today, the technologies have merged and there are only small differencies in the technologies of the leading companies
Basic Patents:
Firestone: Phillips: Bridgestone:
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 US 3458490, US 3438952, US 3502746 JP 75-015271
Mechanism of the Anionic Polymerization

Initiation: R Li
+
CH2 R
Li
Chain growth: CH2 R Transfer reactions: Termination reactions: Li

+
CH2
+
n ideally none ideally none
Li
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 =
Molar Mass (Mn) [g/mol]
nInitiator * f
nMonomer * MWMonomer Mn = Mn C m = = = 0 n Monomer * MGMonomer nInitiator * f nInitiator * f m *X + C X
DP: degree of po0lymerization number average of molar mass Mn: X: monomer conversion nMonomer : amount of monomer [moles] MWMonomer: molar mass of monomer amount of initiator [moles] nInitiator : f: functionality of initiator u, v, w: amounts of initiator
nInitiator = u nInitiator = v nInitiator = w u<v<w

1,0
0,5 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

Costs for for Bu-Li [Pf/kg rubber] Costs BuLi [[Pf/kg]
25 20 15 10 5 0 0 50000 100000 150000 200000 250000 300000 350000 400000
Basis of calculation: 65 DM/kg BuLi (4 DM/mol BuLi; MwBuLi: 61 g/mol) Ideally Living Polymerization
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

Gegenion Microstructure (Benzene) cis-1,4 trans-1,4 1,2[%] [%] [%] 35 10 15 6 55 25 40 35 10 65 45 59
1,4-insertion:
P
Li + Li + P
Li Na K Cs
1,2-insertion:
P
Li X X X X
+
Li X X
Solvent
Microstructure cis-1,4 trans-1,4 1,2[%] [%] [%] 35 35 0 55 52 9 10 13 91
Hexane Toluene THF Sources:
Ether with two coordination sites
R. Casper in Ullmanns Encyclopedia of Technical Chemistry G. Sylvester u. P. Mller 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 30C DME 50C DME 70C THF 30C THF 50C THF 70C Modifier: DME: Dimethoxyethane THF: Tetrahydrofuran
Vinyl-Content [mol%]
70 60 50 40 30 20 10 0 0,1
1,0
10
100
Ether [mol/mol Li]

Source: Ullmanns Encyclopedia of Technical Chemistry
Impact of the Vinyl Content of Li-BR on Tg

+0 -10 -20 -30 -40 VI-BR
Range of commercial Vinyl-BR grades
Tg [ C]
-50 -60 -70 -80 -90 -100 0 10 20 30 40 50 60 70 80 90 100 Standard-Li-BR (without modifiers)
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 Vinyl Content 1,4-cis 1,4-trans 10 40 50 47 26 27 64 21 15 66 18 16 88 7 5 SBR 1712 18 8 74
Wet Skid Performance (Laboratory) Portable Test Device* 84 Retreaded Tyre Concrete Asphalt Abrasion Resistance
109
104
120
100
70 70 140
95 90 100
92 92 80
93 93
100 100 100
* Road Research Laboratory Instrument, on wet Syenite-Glass Surface
Branching by the Copolymerization with Divinylbenzene

Copolymerization with multifunctional monomers (DVB):
CH2 Li
CH
Li
R
n
CH2 Li
R
n
CH
Li
Branching by Chain End Coupling

Chain end coupling with SiCl4, SnCl4 etc.: 4 SiCl C Li
+
Coupling with SiCl4:

Reduction of Cold-Flow low viscosity of BR-solutions Application for HIPS and Bulk-ABS Highly filler loaded rubber compounds with good processability and high ShoreA Hardness (roll covers, tyre beads etc.)
4 (SnCl4 as alternative)
Coupling with SnCl4:

+
Si
+ 4 Li Cl
exclusive se is for tyres; during compound preparation the Sn-C bonds seems to break and the bound rubber content is increased. 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 flow
Improvement
Mooneymeasurement
Com- CalanEx- Injection Spinpression dering trusion moulding drawing moulding
Viscosity
Improvement
Narrow molar mass distribution Highly branched (Star shaped) 100 101 102 103 Broad molar mass distribution 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 6 4 2 0 0 20 40 60 80 100

Star shaped polymer with 3 branches
Divinylbenzene [phm] 0,03 0,06
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 Coupling agent Mw [g/Mol] Mn [g/Mol] Mw/Mn Cold flow [mg/min] ML 1+4(100C) Compound-Mooney ML 1+4 (100C) Shore A Hardness S300 [Mpa] Tensile Strength [Mpa] heat-build-up [C] Rebound [%] linear without 256.000 188.000 1,4 16 53 98 64 8,0 16,5 32 77 star branched SiCl4 310.000 158.000 2,0 0 54 80 61 8,1 16,2 40 71
Compound Preparation: BR: 100 phr, Ru (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
700 600 500 400 300 200 100 0 1989 1991 1993 1995 1997 1999 2001
Consumption [t]
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 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100
Parameters of copolymerization (styrene = M1; butadiene = M2) Radical copolymerization (emulsion) r1 = 0,7 r2 = 1,4 Anionic colymerisation in hexane (Bu-Li/no randomizers/50C) r1 = 0,04 r2 = 11,8
E-SBR S-SBR in hexane
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 [wt. %]
100 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100
E-SBR
ond rs Ra ize m
S-SBR in Hexane
Styrene content in the monomer feed [wt. %]
Impact of Randomizers on the Copolymerization Behaviour of Styrene and Butadiene

(Styrene = M1; Butadiene = M2)
Total Styrene Content of Polymer [wt.%]
Cyclohexane; 25/75 Styrene/Butadiene
T [C]
Benzene Cyclohexane Hexane THF Diethylether Triethylamine Anisol Diphenylether THF THF THF 25 25 25 25 25 25 25 25 -78 0 25
r1
0,04 0,04 0,03 4,0 0,4 0,5 0,3 0,1 11,0 5,3 4,0
r2
10,8 15,5 12,5 0,3 1,7 3,5 3,4 2,8 0,04 0,2 0,3
70
n-Butyl-Lithium t-BuOK/n-Buli: 0,067/1 t-BuOK/n-Buli: 0,38/1
60
50
40
30
20
10
0 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
Styrene Content [wt. %]
Standard Emulsion Technology
+10 C + 0 C - 10 C
30 20 10 0
Solution technology without randomizers
Solution technology with randomizers
- 20 C - 30 C - 40 C
- 70 C
- 60 C
- 50 C
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 -40 S-SBR (25% Styrene, 55% Vinyl) E-SBR 1516 (40% Styrene) S-SBR (34% Styrene, 32% Vinyl) E-SBR 1500 (23.5% Styrene) E-SBR (15% Styrene) S-SBR (18% Styrene, 10% Vinyl) Emulsion BR Li-BR high cis Nd-BR
Decrease of Rolling Resistance and Abrasion Increase of Heat Build Up and Wet Skid Resistance
Tg [C]
-60 -80 -100
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 BR 1500
1 10-1
SBR 1700
tan
10-2 10-3
Integralrubber
-100 -80 -60 -40 -20
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: Tg [C]
Vinyl-BR -90C
S-SBR -20C
3,4-IR ~ 0C
Integral-Rubber 2 based on butadiene, styrene and isoprene

(batch process with sequential monomer- and modifier addition) butadiene randomizer styrene isoprene
Segment: Tg [C]
Medium-cis BR -90C
Vinyl-BR -50C
S-SBR -20C
3,4-IR ~ 0C
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 + + + + 0 + + + + + +* + + + + + In a carbon black loaded compound there is no real advantage for S-SBR. Therefore there was no major breakbreakthrough for S-SBR until the green tyre technology emerged. emerged.
Vulcanization
t10 t90 t90 - t10
Mechanical Properties
Moduli Tensile Strength Tear resistance Abrasion resistance Heat build up Rolling resistance Wet grip
Price
* fully depreciated plants
Green Tyre Technology

SiO2
Si OH Si OH CH2 Et-O Et-O Si CH2 CH2 S Et-O S Et-O Et-O Si CH2 CH2 S Et-O CH2 S
Performance of the green tyre

Rolling Resistance
Additional costs for the green tyre

Ru Compound Rubber Filler Silane Additive Raw Materials Mixing Costs Patents:
DE 2447614; Degussa, Prior.: 05.10.1974; Erf.: K. Burmester, S. Wolf, E. Kltzer, 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. DE 3813678; Bridgestone; Prior.: 23.04.1987; Erf.: M. Takeshita et al. EP 501 227; Michelin, Prior.: 25. 02. 1991; Erf.: R. Rauline EP 447066; Bridgestone; Prior.: 27.02.1991; Erf.: T. Hamada
150
Carbon black loaded tread Green tyre
Silica Compound L-SBR NR BR Silika Si 69 DPG ---
100 50 0
E-SBR Ru ++ ++
Abrasion Resistance
Wet Skid
Recent Developments in S-SBR Technology Towards Improving Tyre Performance
Functionalisation of SS-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 R
n
N C
91
Li
Si OR CH2 OR
R2
Li
OR Si OR N C CH2 OR R1 R2
80
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
n
CH2
Li
Cl
+
Cl
- 2 Li
Cl
O R
n n nR
DE 10057508; Bayer AG, Prior.: 21.11.2000; Erf.: T. Scholl, W. Obrecht, Braubach, E. Giebeler, Grn, A. Mller, M. Graf Polyether/Diolefin-Kautschuke enthaltende Kautschukmischung
Incorporation of Aminoisoprene
CH3 N CH2 CH2 C CH CH2 CH3
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. Morschhuser, G. Mannebach "Kautschukmischungen basierend auf Aminoisopren"
Functionalization of the Living Chain End with a Polysiloxane Building Block

H3C Si O R n CH2 Li
+
CH3 O Si O D3 CH3 CH3
+ H3C H3C
Si
CH3 CH3 CH3 CH CH3 CH3 3 Si R n O Si O Si O Li

+
Source: EP 0778 311; Michelin, Prior.: 07.11.1995; Erf.: J.-L. Cabioch Composition de caoutchouc base de silice et de polymre dinique fonctionnalis ayant une fonction silanol terminale
Modification of S-SBR with Hydroxyl-Moieties

X S X SH H
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 Highcis-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 Ratios cis-1,4 Content
36 - 38 97 97 93 98
Li-BR Co-BR Ni-BR Ti-BR Nd-BR
nBu-Li Co(II)Octanoate / DEAC / H20 1 / 7 0-80 / 20-30 Ni(II)Naphthenate /Bu2O.HF/TIBA 1 / 100 / 40 TiJ3(OEt) / TiCl4 / TEA 1 / 0,7 / 5 Nd(III)Versatate / DIBAH / EASC 1 / 10-15 / 3
Abbreviations:
nBu-Li DEAC TIBA TEA DIBAH EASC n-Butyl-Lithium Diethyl Aluminum Chloride Triisobutyl Aluminum Triethyl Aluminum Diisobutyl Aluminum Chloride Ethylaluminum Sesquichloride
Influence of Halides on 1,4-cis-Content

Metal Component of Halide Catalyst System Ti Co Ni Nd
F Cl Br J 35 75 87 93 93 98 91 50 98 85 80 10 95,7 96,2 96,8 96,7
cis-1,4-Content [%]
98 97 96 95 94 93 92 0 1 2 3 4
Molar Cl/Nd - Ratio

Source: Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian; J. Pol. Sci., Chem. Ed. 18 (1980) 3345-3357 Sources: Lars Friebe: Diploma Thesis TU Munich 2000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Role of Halides and Electron Donors on Microstructure

Nd(OR)3 Nd(OR)3 Nd(COOR)3 Nd(COOR)3 Nd(COOR)3 Nd(COOR)3 Nd(CH2Ph)3 + TIBA + DIBAC + TIBA + DIBAC + Mg (Allyl)2 + Mg (Allyl)2 + R-Cl + TIBA trans -1,4-BR cis -1,4-BR trans -1,4-BR cis -1,4-BR trans -1,4-BR cis -1,4-BR trans -1,4-BR cis -1,4-BR
For the achievement of high 1,4-cis contents the presence of a halide source is essential
Source: Shiro Kobayashi; Transition in Precision Polymerization (1997) Part 1. H. Watanabe, T. Masuda, Diene Polymerization, pages 55-66
Nd(CH2Ph)Cl2 + TIBA
Co(Oct)2 + AlR2Cl + H2O Co(Oct)2 + AlR2Cl + H2O + PPh3 Co(Oct)2 + AlR3 + CS2 Ni(Oct)2 + BF3 - OEt2 + AlR3 Ni(Oct)2 + BF3 - OEt2 + AlR3 + PPh3
cis - 1,4-BR s - 1,2 - BR s - 1,2 - BR cis - 1,4 - BR trans - 1,4 - BR
The coordination of electron donors to vacant catalyst sites results in a significant reduction of 1,4-cis contents. As a consequence, syndiotactic BR or trans-1,4 BR are obtained.
Trans 1,4-BR: Dependence of Melting Temperature on 1,4-trans Content

160 120 80
Data from: US 5134199 Enoxy Chem Ltd. GB 2161169 (Asahi) US 4931376 (Asahi) US 5596053 (Bridgestone/Firestone)*
Tm [ C]
40 +0 - 40 60 70 80 90
Goodyear
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
8
M
15
C C
`
29
C
22
Bd
M
36
M
43
M
54
Bd
60
M
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 90 80 70
Only rare earth metals in the oxydation state +III show polymerization activity Al-alkyls reduce Pm, Sm and Eu salts to the oxydation stage +II
U m satz [% ]
60 50 40 30 20 10 0 La Ce Pr Nd Pm Sm Eu Gd Tb Dy
Ho
Er
Tm
Yb
Source: Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian J. Pol. Sci., Chem. Ed. 18 (1980)3345-3357
Mechanism of Neodymium Catalyzed Butadiene Polymerization: Influence of Solvents
Contrary to other ZieglerCatalysts, aromatic solvents have a negative impact 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
Lu
Mechanism of Neodymium Catalyzed Butadiene Polymerization

O Nd O R3 R1 R2
3
Al
Cl Cl Al Al Et Et Cl Et
NdV 1
DIBAH 10 - 15
EASC 3
Literature: http://dx.doi.org/10.1007/12_094 Neodymium-Based Ziegler/Natta Catalysts and their Application in Diene Polymerization
1) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner; Adv. Polym. Sci. (2006) 204, 1-154 (Review); 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
Al O Al
Nd ( OOC - R )3 + 3 H Al
Nd (O-CHR- R )3 + 1
Al O
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
Nd (O-CH2- R )3 + H Al
CH3 (R-CH2-O)2 Nd CH2 C H CH3
(R-CH2-O)2 Nd
+ R-CH2-O
Al
(R-CH2-O)2 Nd - H
CH3 + H2C CH3
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

3) Hydride transfer and Formation of a Nd-Allyl Compound
CH3 (R-CH2 - O)2 Nd - H + AlR 3 (R-CH2 - O)2 Nd
4)
Halogenation of the Nd-Allyl Compound

CH3 (R-CH2 - O)2 Nd Al2Et3Cl3 Cl2 Nd CH3
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

5) Formation of polymerization active Nd species (cationic Nd allyl complex) and first butadiene insertion
AlR3 Cl Nd Cl R AlR3 Nd Cl Cl R AlR3
+ Nd
ClAlR3 Cl R
AlR3
ClAlR3
+ Nd
+ Nd
ClAlR3 Cl
+ Nd
ClAlR3 Cl R
Cl R AlR3 R
AlR3
AlR3
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

6) Control of Molar Mass by Al-Alkyls and by Al-Hydrido Compounds
Nd L L R Nd L L R
H Al
H Nd L L
+ R
Al
Al
Nd L L
+ R
Al
Active living polymer chain (attached to Nd)
inactive dormant polymer chain (attached to Al)
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht, Journal of Macromol. Sci.

Experimental Conditions:
Solvent n-Hexane Butadiene 1,85 mol/l NdV 0,20 mmol/l EASC 0,13 mmol/l (nCl/nNd = 2/1) DIBAH 2,0; 4,0; 6,0; 10,0 mmol/l nDIBAH/nNd = 10, 20, 30, 50
Addition Sequence:
1. Hexane 2. Butadiene 3. DIBAH 4. Neodymversatate 5. EASC Polymerization temperature: 60C
Conversion/time-plots Monomer Conversion [%]

100 80 0 -1
Plot for 1st order monomer consumption
40 20 0 0 50 100 150 200 250 nDIBAH/nNd = 10 nDIBAH/nNd = 20 nDIBAH/nNd = 30 nDIBAH/nNd = 50
ln(1-x)
60
-2 -3 -4 -5 0 50 100 150 200 250 300 nDIBAH/nNd = 10 nDIBAH/nNd = 20 nDIBAH/nNd = 30 nDIBAH/nNd = 50
time [min]
Time [min]
Sources: Lars Friebe: Diplomarbeit and der TU Mnchen, Dezember 2.000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

Dependence of Molar Mass Distribution on Monomer Conversion
c o n v e r s io n / %
8 2 .5
Dependence of PDI (Mw/Mn) on Monomer Conversion

nDIBAH/nNd = 10 nDIBAH/nNd = 20 nDIBAH/nNd = 30 nDIBAH/nNd = 50
difference of refraction index Indices Difference in Refractive
6 6 .4
4,0 3,5 Mw/Mn 3,0 2,5 2,0 1,5 1,0

0 10
5 5 .1
5 0 .0
4 3 .5
3 5 .6
3 0 .7
2 2 .7
1 2 .2
7 .8
20
30 40 50
60 70 80 90 100
4 .8

65 65
30
30
35
35
40
40
45
45
50
50
55
55
60
60
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
e lu t io n t im e / m in

Dependence of Mn on Monomer Conversion
Formal Number of Polymer Chains formed per Nd-Atom
2,5*105 2,0*105 nDIBAH/nNd = 10 nDIBAH/nNd = 20 nDIBAH/nNd = 30 nDIBAH/nNd = 50 16 14 12 10 8 6 4 2 0 0 10 20 30 40 50 nDIBAH/nNd = 10 nDIBAH/nNd = 20 nDIBAH/nNd = 30 nDIBAH/nNd = 50
Molar Mass Control with Al-Component
Mn [g . mol-1]
1,5*105 1,0*105 0,5*105 0 0 10 20 30 40 50 60 70 80 90 100
Monomer Conversion [%] nDIBAH/nNd = 4,4
nDIBAH/nNd
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
Contrary to Catalysts based on Co, Ni and Ti, for Nd-based catalysts there is no agents for the control of molar mass available. Therefore in Nd-BR technology molar mass has to be controlled by:
Nd/Al-ratio Monomer/Nd-ratio Monomer Conversion Polymerization temperature
G. Sylvester, B. Stollfuss ACS, Rubber Div. Dallas 1988 Synthesis of cis-1,4-Polybutadienes by rare earth catalysts 2500
Molar Mass (Mv) [kg/mol]
2000 1500 1000 500 0 0 10 20 30 40 50 60 70 80 90
Polymerization Temperature [ C]
Influence of Butadiene/Nd-ratio
D. J. Wilson, Polymer 1993, 34,16, 3504-3508 900 800
Influence of Monomer Conversion

60
M. Bruzzone ACS Symposium Series No. 3 (1982) 33-55
Molar Mass (Mv) [kg/mol]
ML 1+4 (100C)
0 0,05 0,1 0,15 0,2 0,25 0,3
700 600 500 400 300 200 100 0
50 40 30 20 10 0 0 20 40 60 80 100
Nd (mmol/100 wt.-parts of butadiene]
Comparison of Technologies for the Production of High cis-1,4-BR

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

Ethene/Propene/Diene-Terpolymers
(30% of grades are oil extended)
Oil additives Impact modification of thermoplastic polymers (PP)
Major areas of application:

Technical rubber goods Cables and wires TPEs
EPDM-Termonomers
Relative polymerization rates of termonomer double bonds in Vanadium catalysed polymerizations
5-Ethyliden-2-norbornene (ENB) Dicyclopentadiene (DCPD)
~ 40 : 1
~ 15 : 1
1,4-Hexadiene (HD) Criteria for the selection of the termonomer:
~5:1
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 60 Torque [Nm] 50 40 30 20 10 0 0 1,0 2,0 3,0 4,0 5,0 6,0 time [min]
ENB DCPD 1,4-HD
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

6%
15%
EPDM-Consumption / kt
13%
9%
500 400 300 200 100 1987 1988 1991 1986 1989 1990 1992 1993 1994 1995 0 Automotive production (world)
50
16%
41%
45
Automotive Thermoplast Modification Building Technikcal Rubber Goods Electro/Electronics Oil Additives
40
Market: 1,050 Mio t (2004) Growth rate: 3,5 %/a
Source: European Chemical News 10, Mrz 2005, 13
Automotive Production / Mio.
700 EPDM Consumption (world) 600
55
Range of EP(D)M-Grades
Ethene Content
[wt.%]
50 - 75
1,7 - 3 4-7 ENB-Content: [wt.%] 0 8 - 12 Mooney Viscosity: [MU] 16 - 20 20 - 60 60 - 90 [ML 1+4 (125C)] Oil Content: [phr] 0, 25, 30, 50, 100
Dependence of Tg on the Ethene- and the ENB-Content

(V-catalysed commercial products) products)
-45 -47,5 -50 -52,5
EPDM/2% ENB EPDM/1% ENB EPM /0% ENB
Tg [C]
-55 -57,5 -60 -62,5 -65 40 45 50 55 60 65 70
Tg(EPDM) = Tg(EPM) + 1,2C/wt.% ENB
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 35-39C 25 20 15 10 5 0 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64
Enthalpy of fusion [J/g]
40-44C 45-49C 50-54C 55-59C 60-64C 65-70C
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/EPDMManufacturing Technologies

Chemical Aspects
free radical Polymerization Ziegler/NattaPolymerization anionionic Polymerization cationic Polymerization Polyaddition und Polycondensation Polymermodification
Process Features
Emulsion
E-SBR, CR, NBR, E-BR, ACM,FKM, EVM
Solution
EVM
Dispersion
EVM
Bulk
AEM, EVM, (ENM)
Gas-Phase
BR
(G-BR)
EPM/EPDM
BR, LSBR. IR ECO, CO IIR
EPM/EPDM
Q Q
(G-EPM/EPDM)
AU, EU CIIR, BIIR, CM, CSM, H-NBR, FZ
EU CM, CSM, (H-NBR)
AU, Q
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 solution (Dow)
Gas phase (UCC)

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

+V VOCl3 +IV VCl4 +III VX3 + R2 AlX {R2VX}
Aktivator heat
{R2V }
heat
+ R2AlX2
+II
VX2 + R3 Al
[R2V] R2AlX
[RVX] 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

Exxon DSM DPDE Lanxess Lion Copolymer Polimeri Mitsui JSR Sumitomo Kumho Petro China Nizhnekamsk Herdillia Baton Rouge, Louisiana Notre Dame de Gravenchon Geleen, Niederlande Triunfo, Brasilien Plaquemine, Louisiana Seadrift, Texas Marl, Deutschland Orange, Texas Geismar, Louisiana Ferrara, Italien Chiba, Japan Kashima, Japan Yokkaichi, Japan Chiba, Japan Yeochon, Sdkorea Jilin, China Nizhnekamsk, Russland Maharashtra, Indien 180 85 135 35 100 90 60 55 91 85 60 25 45 40 40 30 30 10 Vistalon Keltan Nitriflex EP Nordel-IP Elastoflo (UCC) Buna EP G Buna EP T Royalene / Trilene Dutral Mitsui EPT JSR EP Esprene KEP
total capacity
1076
Source: European Chemical News 10, Mrz 2005, 13
EPDM-Solution-Process with Fully Flooded Reactor

Water containing azeotrope Condenser Settler External cooling loop
ENB
Boiling point: Max. exposure limit/MAK: Smell limit: 146C 1 ppm 3-5 ppm
Waste water
Azeotropic destillation Condenser Flash drum Stripper Waste air dewtering screwg
Propene
Hexane Ethene
destillation
Polymerization reactor
Steam Settler Steam oil drier Antioxydant PHControl Expeller
destillation
drier Waste water
Stripping aid
Waste water
drier
Precoller -32/-35C
Water Modifier Reactivator
Process Features
Propene precooling: Temperature: Pressure: Residence time: Soldis conc.: H2 O: -32C/-35C 20-65C 5-10 bar 6-15 Min. 3 -7 Gew.% < 3 ppm
baling
Drier
drier
EASC VOCl3 /VCl 4 3/1
Packaging
Hexane
VNB/ENB
Dows High-Temperature Solution Process

(Source: Dow-Patents, Publications etc.)
Plant location: Plaquemine/Lousiana
Destillation
Solvent and monomer

High boiling residue (ENB, AO, etc.)
Condenser
In the Dow-HT-Process low amounts of CGC- catalyst are required. The catalyst is not washed out and no steam stripping is applied (leave-in-catalyst)
Flashdrum
Evaporator
Evaporator
Ta Antioxidant (AO)
Polymerization reactor
baler
Ageing drum
Scavenger
"Insite-Kat."
packaging
Purification
Purification
Purification
Temperature: Ta: Pressure: Residence time: MMAO Borane
40 - 80 C 80C (>130C) 9-15 bar < 20 Min.
Ethene
Propene
ENB
Metal Content of Commercial EPDM

Activation of Metallocenes
Cl Zr Cl
Alkylation
R Zr R
Product V Ti Fe
Dow-CGC <1 1,0 EPDM # 2 8,0 <1 EPDM #3 EPDM #4 EPDM #5 1,9 <1 2,4 <1 5,1 <1 4,8 1,9 1,3 4,3 4,3 2,0 2,8 63
Al Ca Na Sum
1,7 31 31 6,7 9,6 440 <1 1,7 1,7 64 160 64 <1 1,8 1,8 5,7 4,6 9,4 8,0 22,3 48,8 82,8 184,1 584,1
Activation by MAO
(molar excess of MAO: 10.000 - 10.000 fold)
Activation by Borane/Borates:
(with molar B/Zr-ratios)
R
Zr +
EPDM#6
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 25 Enthalpy of fusion [J/g] 20 15 10 5 0 40 42 44 46 48 50 52 54 Ethene Content [wt.%] 56 58 60 62
CH2 CH2 CH2 CH 2
ZrCl2
EBTHI-Cat.
CH2 CH2 CH2 CH2
DOW-Insite-Cat.
Me2Si N
Ti X
X
V-Catalysis
CMe3
Impact of Cristallinity on Low-Temperature Compression Set of EPDM-Based Vulcanizates

DOW-Insite-Cat.
Low-Temperature-Compression-Set [%]
100 90 80 70 60 50 40 30 20 10 0
8, 5 10 ,0 0 37 ,5 0 32 ,5 37 ,5 47 ,5 18 8, 5 21 12 35 0 3 5 7 7
Me2Si N CMe3 Ti X X
EPDM/V-Cat. EPDM/CGC (Dow)
Enthalpy of Fusion [J/g]
UCCs EPDM-Gas-Phase-Process (now Dow)

Flow-Chart:
US 4994534 Filter Compressor
Plant location: Seadrift/Texas

Temperature: Pressure: Residence time: < 90 C (40C-60C) 9-15 bar 0,5 - 1 h
Cooler ENB Fluidizing Aid Suported Catalyst

Purification Desactivation Monomer degassing unit
Patents:
Product EP 1099715 EP 1099473 EP 1086995 EP 1083192 US 6180738 WO 0000333 WO 9965953
Ethene Propene Modifier
Purification Purification Purification
ENB
Boiling point: Maximum exposure level: Smell limit 146C 1 ppm 3-5 ppm
Baling of Product etc.
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 Process Economy
EPM EPDM Low Mooney High Mooney Oil Extended Grades
Solution
V-Catalysis
Slurry
V-Catalysis
HT-Solution Gas-Phase
CGC/Dow V-Catalysis
4
10 10 10 5 7
5
10 10 8 10 10
7
10 10 10 3 3
10
10 0 0 10 0
Process Flexibility Overall Process Performance
42 46
48 53
36 43
20 30
The Thewell wellestablished establishedvanadium vanadiumbased basedsolution solutionand andslurry slurryprocesses processes are inferior in investment and operation costs, but provide are inferior in investment and operation costs, but providea ahigher higher flexibility. flexibility. The TheHT-solution HT-solutionand andthe thegas-phase gas-phasetechnology technologyare arelow lowcostcosttechnologies, which are superior in the production of specific technologies, which are superior in the production of specificgrades grades
Metallocene-Patents 1980-2000 (Oct. 2000)

250
Number of Patents (US) + Pat. - Appl.
2.923 Documents
USUS-Patents and EPEP- and WOWO-Patent Applications
200
150
100
50
0
hs t Do w BA S Ph F il l i ps T ar Mi go ts ui r Pe tr o l Sh el l UC C M on Mi ts t el ui Ch l em Id em . i ts u DS M al i s Fi na EN Mo I b il Du P Ci b a on t Ge i Al b e gy m Nr . 2 ar l e 2B ay er xo ec Ex re Bo BP n Ho
WPIDS-Recherche Dr. Karjetta vom 29. 09. 2000
Cl Zr Cl
Alkylation (BuLi, AlR3 or MAO)
R Zr Cl
Alkylation (BuLi, AlR3 or MAO)
R Zr R
Activation by MAO
Activation by borates and boranes
R
Zr + A
Cossee-Mechanism of Metallocene Catalysed Olefin Insertion

R
Zr +
CH2 CH2
R
Zr +
CH2 CH2
R
Zr +
CH2 CH2
R
+ Zr
CH2 CH2
Key Patents in Metallocene- und Single-Site-Catalysts 1.1. Bis Cyclopentadienes
X Zr X
B Zr
X X
Me2C
ZrCl2
Me2Si
ZrCl2
B = Bridge
EP 35242 EP 129368 EP 468537 (29.12.1980) (06.06.1983) (30.01.1987) BASF Exxon Exxon (Turner) (Kaminsky) (Ewen) EP 69951 (09.07.1981) Hoechst (Kaminsky) MAOMAOBorateActivation Activation* Activation HDPE, LLDPE, a-PP HDPE, LLDPE, i-PP, EP(D)M
EP 351392 (15.07.1988) Fina (Ewen, Razavi)
EP 4858821 (12.11.1990) Hoechst (Spaleck)
MAO-Activation 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
Key Patents in Metallocene- und Single-Site-Catalysts 1.2. Isoelectronic Bicyclopentadienyl Systems

E X Zr X E E = N, P
N B R B R Zr
R X X
Y B X Zr X B Y
Cl Cl B Zr P Ph Ph Cl SiMe3 Cl
Me P Me2Si Ph
Me Me ZrCl2
EP 638593 (02.08.1993) Shell US 5539124 (19.12.1994) Lyondell
US 5554775 (17.01.1995) Lyondell
WO 96/34021 WO 98/01455 (25.04.1995) (05.07.1996) Lyondell Bayer AG (Ostoja-Starzewski) WO 97/2351 (22.12.1995) Hoechst AG (Herberich)
WO 98/50392 (08.05.1997) Nova Chemicals (Spence)
MAO-/Borate- MAO-/BorateActivation Activation Polyolefins HDPE, PP PE, PP HDPE, LLDPE, PP, EPM, EPDM, COC HDPE, LLDPE, PP, EPM, EPDM
Key Patents in Metallocene- und Single-Site-Catalysts 2. 1. Mono-Cyclopentadienyl Systems
Ti MeO MeO OMe
Me2Si N
Ti CMe3
(IV)
X X
Ti RxE X X E= N, O
Ti NR2
III
X X
EP 210615 (29.07.1985) Idemitsu Kosan US 5206197 Dow (04.03.1991) MAOActivation S-PS
EP 416 815 (31.08.1998) Dow EP 420436 (13.09.1989) Exxon MAO-/BorateActivation HDPE LLDPE EP(D)M ES
US 5132380 (12.09.1991) Dow
WO 96/13529 DSM (Lovocat)
Borate-Activation PO
MAO_/BorateActivation HDPE LLDPE EPM
Key Patents in Metallocene- und Single-Site-Catalysts 2.2. Mono Cyclopentadienyl Systems
F F F F t-Bu t-Bu P t-Bu F Ti N CH3 CH3

N C N N Ti
CH3 CH3
O Ti N P X
WO 2005/005496 DSM MMAO-Activation EP(D)M
WO 2008/095687 DSM MMAO-Activation EP(D)M
US 6063879 (29.10.1997) Nova MMAO-Activation PE, LLDPE
Key Patents in Metallocene- und Single-Site-Catalysts 3.1. Post Metallocenes

Ar P Pd P Ar Ar X N Ar Ar N X Ti X
t-Bu t-Bu
Ar
S
X
X
Ti O O
N O O N X Zr X
EP 121965 (05.04.1983) Shell
WO 92/12162 (27.12.1990) Exxon EP 571945 (29.05.1992) Sumitomo
JP 5230133 (19.02.1992) Mitsui Toatsu
EP 606125 (08.01.1993) Shell
US 5637660 (17. 04. 1995) Lyondell
Alternating Polyolefins Olefin/CO-Copolymers (Carilon)
Polyacetylens
Polyolefins, HDPE, PP Polyacetylens
Key Patents in Metallocene- und Single-Site-Catalysts 3.2. Post Metallocenes
R R N M R R N X R R X
N Cl N N Fe Cl
N O Cl Ti O Cl N
M = Ni, Pd
WO 96/23010 (24. 01. 1996) DuPont (Brookhart) polar/unpolar Copolymers, LDPE DuPont (Brookhart) BP EP 0874005 (24.01.1998) Mitsui HDPE, EPM EP 1881014 (10.05.2006) Mitsui EPM, EPDM
HDPE, (PP)
HDPE(PP)
Features of the Activation by MAO

Chemical Structure of Methylalumoxane (MAO):
(CH3)2 Al - [O - Al - CH3]n- O - Al(CH3)2 (CH3) Al - [O - Al - CH3]n- O - Al(CH3) O
n :
6 - 20
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
Zr
F F F F F F H Ph F F F
Borane
F F F F _
R
-R -
B
F F
F F
N+
Me Me
B
F F F F
Anilinium Borate
4 _
R
Zr +
Ph
+
Ph
Ph
B
F F
F 4
Triphenylcarbenium Borate
For the Activation of metallocenes molar quantities of borane/borates are required Polymerizations activated by boranes/borates are very susceptible to impurities
R
Zr
R. F. Jordan Turner M. Bochmann Turner (1990) (1986)
1987 1987
M. D. Rausch, J. C. W. Chien (1991) Ph
T. J. Marks (1991; JACS 113, 3623) F5
R
-R -
Ag
BPh4
H Ph Me N+ Me A
+ Ph A
Ph +R
B F5 F5 +R
+R
CH3CN
+R - RH
F5
R
Zr +
Ag+1/2 R2 + BPh4 N Ph Me
F F F F F F F F B F F F F F F F
R Me
Ph Ph
Ph
- F5
A :
F F
- F
EP (Exxon) EP468 468537 537 (Exxon) Prioritt: Prioritt:1987 1987 EP 561 479 (Exxon) Prioritt: EP 561 479 (Exxon) Prioritt:1987 1987 Nicht Nicht oder oderschwach schwachkoordinierende koordinierendeAnionen Anionen "NCA"oder "NCA"oder"WCA" "WCA" (insbesondere: (insbesondere:Tetrakis(Pentafluorophenylborat) Tetrakis(Pentafluorophenylborat) US Prioritt: US5599761 5599761(Exxon) (Exxon) Prioritt:04.02.1987 04.02.1987 Erfinder: H. W. Turner Erfinder: H. W. Turner Ionic IonicMetallocene MetalloceneCatalyst CatalystCompositions Compositions
F5
FF
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 by borates (Exxon/Turner) EP 468 537; Prior.: 30.01.87 [Cp2MX]+ [BR4] EP 561 479; Prior. 30. 01. 1987 US 559 976; Prior. 04. 02. 1987 Ionic metallocene catalyst comosition EP 418044; Prior.: 14.09.89 [Cp1MXn]+ [BR4]-
Activation by borates (Dow/Stevens) 1990
Activation by boranes (Fina/Ewen) EP 427 697; Prior.: 10. 10. 1989 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 F FF F FF F F F F F F F F F F F F F F F F F FF F F F
F F F F F F F F F F B F F
F
F F F F F F F F F F F F F F F F F F
B B
F
F - F F F F
F F F
Si
F
F F
FF
B B
F FF F F F F F F
F F F
F F
F F
FF
F F F F
EP 468537 (Exxon) WO 01/08691 (Bayer AG) Prior.: 30.01.1987 Prior.: 18.08.2000 Inv.: Turner, Hlatky Inv.: Becke, Kahlert, Denninger, Windisch, Obrecht EP 561479 (Exxon) WO 01/10124 (Bayer AG) Prior.: 30.01.1987 Prior.: 11.09.2000 Inv.: Turner, Hlatky Inv.: Becke, Denninger, Kahlert, Obrecht, Schmid, Windisch,
EP 1066296 (Bayer AG) Prior.: 24.03.1998 Inv.: Becke, Denninger, Mager, Windisch EP 111927 (Bayer AG) Prior.: 23.06.1999 Inv.: Becke, Mager, Zahalka
Comparison of Catalyst Costs

Example
Plant 1 [EUR/kg] Plant 2 [EUR/kg] Exxon- Pat. [EUR/kg] Exxon- Pat.
Catalyst [EUR/100 kg]

VOCl3 0,50 V(acac)3 1,25 Et(Ind)2ZrCl2 13,00 Et(Ind)2ZrMe2
Cocat. Reactivator Total Cat-Costs [EUR/100 kg] [EUR/100 kg] [EUR/100 kg]
EASC 3,75 DEAC 1,30 MAO 151,00 Borate 3,45 DCPEE 2,00 TEA 0,65 6,25 3,20 164,00 5,70
[EUR/100 kg] 2,25
MAO-activation MAO-activationof ofmetallocenes metallocenesis isnot noteconomical economicalin inaasolution solutionprocess process Borate-activation results in catalyst costs which are comparable Borate-activation results in catalyst costs which are comparablewith with Vanadium-systems Vanadium-systems For Foran animprovement improvementin inoverall-economy overall-economymetallocene-technology metallocene-technologyhas hasto tobe 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: Bromo Butyl Rubber: Chloro Butyl Rubber: Brominated Isobutene Paramethylstyrene Rubber: IIR-Terpolymer (mainly with Divinyl benzene): IIR BIIR CIIR BIMS 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 CH2 C CH3 CH3 CH2 C CH3 CH3 CH2 C
n
CH3 CH CH2 CH2 C CH3

20
CH3 C
19
39
CH3 C
29
30
H3C CH C 2 23 H3C
45
CH3 C 27 CH 28
CH2
Butyl Rubber (IIR)

CH 2 35
n
123
15
CH3 CH CH2 CH2 C X CH3
38
CH3
CH 2 21
16
CH3
CH 2 26
Standard Angle: 109,5
X = Cl: Chloro Butyl Rubber (CIIR) X = Br: Bromo Butyl Rubber (BIIR)
CH3 CH2 C CH3
CH3 CH2 C
CH3 CH2 CH CH2 CH CH2 C CH3
CH3 n
Basic Features: Isoprene content: 0,5 - 2,5 Mol% Incorporation of Isoprene: random 1,4-trans Tg: ca. -72C 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:
Tyres Others Chewing gum 4% Pharmaceutical Adhesives Automotive 3% 1% 1%
5%
Low gas permeability high resistance to heat and vapour high resistance to chemicals good insulation properties good covulcanization (XIIR)) product purity (grades without antioxydants)
Negative:
low elasticity /highly damping
Areas of Applications:
86%
Source:
CHEManager 20/2006, Seite 8 (GIT Verlag Darmstadt)
XIIR based Innerliners (passenger tyres) IIR b ased tubes (truck tyres) bladders (IIR) ABC-protection clothes Cable and wiring Pharmaceutical stoppers Adhesives and sealants absorbers for noise and fenders chewing gum
Butyl and Halobutyl Rubber (X)IIR: Grades

n
CH3 CH CH2 CH2 C CH3
Butyl Rubber (IIR)

X2 (Cl2 / Br2) CH3 CH2 C CH3 CH3 CH2 C CH3 CH2 CH2 C
n
CH3 CH CH2 CH2 C X CH3
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)
Temperature [ C] 70
100
(50 phr SRF, without plasticizer)

80 Rebound Elasticity [%] SBR NBR NR EPDM 40 IIR 20
Luftdurchlssigkeit(Q x 10exp8)
Rebound
60
50
1,4-cis BR 60
1,4-cis-BR NR EPDM
10
SBR NBR/28 ACN NBR/33 ACN NBR/38 ACN IIR
0 -75 -50 -25 0 25 50 Temperature [ C] 75 100
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):

IIR: XIIR: Sum:
700 600
IIR XIIR Sum
- 2,3 %/ p.a. + 2,3 % p.a. + 1,2 % p.a.
(90%: XIIR: IIR: IIR: IIR: XIIR: BIMS:
Tyres and Tyre Production) Inner liners Truck tyre tubes heating bladders ca. 1,80 /kg ca. 2 /kg ca. 3,5 /kg
Pricing (1996):
Consumption [kt]
500 400
Production capacities (2008)

Company
Exxon
Butyl Halo- Total butyl [kt]

X X X X X X (X) X X X X 414 252 180 50 45 80
300 200 100 0

19 79 19 82 19 85 19 88 19 91 19 94 19 97 20 00
Lanxess Nizhnekamsk Togliatti Sinopec Japan Butyl Co.
Total Capacity
1.041
Range of Commercial IIR and XIIR Grades

Range of Standard Butyl Grades
100 90 80 Mooney Viscosity ML (1+8) 125C Mooney Viscosity ML (1+8) 125C 70 60 50 40 30 20 10 0 0 2 4 6 8 10 Content of double bonds [Mol%] 100 90 80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 Halogen Content [Mol%]
Range of XIIR Grades
IIR: Flow Chart of Slurry Polymerization

(Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993) CH3Cl compressor dryer compressor
AlCl3solution drum
Ch Br lorb om uty bu l tyl

Al2O3 Cond enser H2O
catalyst cocatalyst drum H2O slop isoprene Storage tank for mixed feed Storage units for IIR-slurry in water Reactor Steam- Flashunit Strippingunit
NH3EtheneHeat exchangers Isobutene- Isoprene drying unit
Features of IIR Production Technology

Slurry polymerization AlCl3 HCl (Exxon) H2O (Lanxess) 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) 0,4 - 1,0 wt.% Antioxydants: 0,02-0,15 wt.% -discolouring: alkylated Phenylene Diamines -None discolouring: phenolic AO (+ alk. Phenyl phsophites) -chewing gum: without AO catalyst Sources: mixed feed Process: Catalyst: Cocatalysts: Ethylene (gas)
Ethylene (liquid)
Inlet and Drain for light hydrocarbon wash catalyst
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 AlCl3 + + HCl H2O
+ H + AlCl4
+ AlCl3OH CH3
Initiation of Polymerization: CH3

+ H + AlCl4 + CH2 C
CH3 C CH3
AlCl4
CH3 CH3 CH2 C CH3

n
Chain Propagation (Growth) Reaction: CH3 CH3

+ CH3 C AlCl4 +
CH3
+ CH2 C AlCl4
CH2 C CH3
CH3 Transfer Reaction: CH3 CH3 H CH2 C CH3

n +
CH3 CH3 CH3 CH

n
CH2 C AlCl4 +CH2 C CH3 CH3
CH3 H
CH3
CH2 C CH3 CH3
+ C + CH3 C AlCl4
CH3
CH3
Termination Reaction: CH3 CH3 H CH2 C CH3

n
CH3 CH2 C Cl + AlCl3
CH2 C AlCl4 CH3
CH2 C CH3
n
CH3
IIR: Living Cationic Polymerization

Generation of Carbo Cation: R - Cl + MX n Initiation: CH3 R
+
+ MX n+1 CH3
+ CH2 C CH3 CH3 +

n
CH2 C
MX n+1
Propagation: CH3 R
CH3 CH3 R CH3 CH2 C CH3

n
CH3 CH2 C
+
CH2 C MX n+1 CH3
CH2 C
MX n+1
CH3 CH3 CH2 C

n
Reversible Termination: CH3 CH3 R CH2 C CH3

n
CH3
CH2 C
MX n+1
CH2 C CH3
Cl
MX n
CH3
CH3
MXn (Metal halides) and R-Cl used for the preparation of Isobutylene based blockcopolymers: BCl3 and TiCl4 Cl Cl
Cl
Cl
Cl
Influence of Polymerization Temperature on Molar Mass (Polyisobutylene / without Isoprene)

13 107 -25 -50 -75 -90 -106 -120 -143 EtAlCl2/H2O AlCl3/H2O
-Strahlung
Mn [g/mol] 106
105
Molar Masses:
BF3/H2O 104 3,5 4,0 4,5 5,0 5,5 3 1/T *10 [K-1] 6,0 6,5 7,0
-Strahlung > EtAlCl2 > BF3 > AlCl3
Source: J. Kennedy, P. D. Trivedi, Adv. Pol. Sci. (1978) 28, 113-151
XIIR: Flow Chart of IIR-Halogenation

Storage tank Halogenation reactor Br2 bzw. Cl2 IIR-solution in hexane Neutralization reactor
Addition of AO Hexane
water X-IIRSlurry in water Antiagglo- steam merants Caustic soda
Source: Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)
CH3 CH2 C CH3 CH3 CH2 C CH3
XIIR: Mechanism of IIR-Halogenation

CH3 CH3 CH3 CH2 C CH3 CH3 CH2 C CH3 CH2 C
n
CH CH2 CH2 C X2 CH3 CH3
Reaction Conditions:
Solvent: IIR-solids Ratio of Halogen/Isoprene: Reaction temperature : Residence time: Stripping-Vapour : Antioxydants / stabilizers: Hexane 20 - 25 wt.%: 1:1 Mol/Mol 40 60 C lh 2 - 2 kg/ kg XIIR Ca-Stearate, Epoxydized Soy bean oil (ESB)
CH3 H X CH2 C
n
+ X
CH2 CH2 C CH3
CH3 CH2 C CH3
CH3 CH2 C CH3
CH3 H CH2 C
n
CH3
+ X
CH2 CH2 C CH3
- HX CH3 CH2 C CH3 CH3 CH2 C CH3 CH3 CH2 C CH3 CH3 CH2 C CH3 CH3 X CH2 C
n
Source:
CH3
Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993
CH CH2 CH2 C - HX CH3 CH3
Patents:
US 2631984; US 3099644; US 4288575; US 4554326; US 4632963; US 4681921; US 4650831; US 4384072; US 4513116; US 5681901
CH2 X CH2 C
n
CH CH2 CH2 C CH3
Crosslinking Efficiencies in Vulcanization by Peroxides (Dicumyl Peroxide)

Rubbber
O O
2 C O + C O (R*)
X-linking efficiency ~ 100 1) 12,5 10,5 1,5 0,4 - 0,7 1,0 1,0 0,5 <<1 1,0 <<1
+ 2 R-H
Vi-BR (98% Vinyl) SBR cis 1,4-BR
C C
X-linking efficiency =
Number of crosslinks Peroxide Functions Theoretical Crosslinking efficiencies 1 >1 <1
EPDM EPM NBR IR CR IIR PE PP

1)
Type of Rubber M - Rubbers R - Rubbers Degradating polymers
Dissertation Th. Frh, TU Hannover 1995
Properties of Sulfur- and Peroxide Cured IIR and XLIIR

IIR IIR -Terpolymer* N 762 Hard Clay Polarite 102R/EEC Int Pb3O4 Stearic acid Bis(t-butylperoxy-isopropyl)benzene Trimethylolpropanetrimethacrylate Dibenzoyl chinone dioxime Dibenzo thiazyldisulfide Polysar Butyl 402 Polysar Butyl XL 10000 Carbon black Silicate Silanised calcinated Clay Perkadox 14-40 B/Akzo Sartomer 350/Sartomer Actor DQ/Kawaguchi Vulkacit DM / Lanxess 6 1 100 50 130 10 1 100 50 20 80 1 1,5 1,5 -
* 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 Compound Properties Compound Mooney (ML 1+4/100C) Mooney-Scorch (125C) [min.] Vulkanizate Properties (160C/12 min.) Shore A Hrte (23C) S100 [MPa] Elongationat break [%] Tensile Strength [MPa] Compression Set (70h/105C [%]) Hot air ageing (100C/96h) Shore A Hrte (23C) S100 [MPa] Elongation at break [%] Tensile Strength [MPa] Electrolyte permeability (g*mm/day*m2) Ethylenglycol g-Butyrolactone Dimethyl formamide IIR 105 4,0 81 6,0 155 6,8 75 83 7,8 110 8,0 0,38 1,0 7,8 XLIIR 98 6,2 76 6,5 105 7,5 15 78 95 8,2 0,21 0,8 1,8
Vulcanization of BIIR by Peroxides
CH3 CH2 C CH3
CH3 CH2 C CH3
CH2 CH2 C
n
CH3 CH CH2 CH2 C
CH3 CH2 C
CH3 CH2 C CH3 CH3 CH2 C CH3
CH2 CH2 C
n
CH3 CH CH2 CH2 C CH3 CH3
CH3
+ DCP - 2 X*
CH3 CH2 C CH3 CH3 CH2 C CH3 CH2 C
n
CH3 CH3 CH2 C CH3
X
CH2
CH3
CH2 C
n
CH CH2 CH2 C CH3
CH CH2 CH2 C CH3
CH2
Vulcanization of BIIR by ZnO/NN-m-Phenylene Bismaleic Imide

CH3
n
CH3 CH2 C CH3 CH2 C

n
CH3 CH CH CH2 C CH3 C C O

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

n
O CH3
CH CH CH2 C CH3
IIR and XIIR: Methods of Vulcanization and Vulcanizate Properties

IIR (Lanxess Butyl 301) XIIR (Bromo butyl Carbon black (N 330) Carbon black (N 774) Zinc oxide Lead Oxide (Pb3O4) Stearic Acid Sulfur MBT Benzochinondioxim PF-Resin (Amberol) CR (Baypren 110) Dicumyl peroxide Zinc oxide Dicumyl peroxide BMI (HVA 2) temperature time [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [ C] [min] 100 50 5 1,0 1,25 1,5 160 25 100 50 5 10 1,0 6 150 12 100 50 5 6 1,0 10 5 190 30 100 50 1,0 1,5 180 15 100 50 5 1,0 5 180 3 100 50 5 1,0 1,5 0,5 180 4 100 50 5 1,0 1,5 180 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 Literaturbersicht, GAK 9/1999-Jahrgang 52, 670-682
IIR und XIIR: Methods of Vulcanization and Vulcanizate Properties

IIR XIIR Carb. black (N 330) Carb. black (N 774) [phr] [phr] [phr] [phr] 100 50 S/MBT 91 17 66 2,5 16,6 530 68 100 50 Chinon 94 7 64 2,1 12,8 400 68 100 50 Resin 82 >30 64 1,9 15,8 590 12 100 50 ZnO 83 16 48 0,9 5,2 12,4 580 58 100 50 DCP 88 12 40 0,5 1,8 8,9 680 53 100 50 DCP/BMI 88 14 54 0,12 9,5 10,5 325 28 100 50 ZnO/BMI 89 16 58 0,19 10,2 13,6 360 13
Vulcanization Compound Properties ML 1+4 (100 C) [MU] MS5 (125 C) [min] MS5 (135 C) [min] Physical Properties Shore A Hardnes [MPa] M100 M300 [MPa] Tensile Strength [MPa] Elongation at break [%] CS (70h/150 C) [%]
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 Literaturbersicht, GAK 9/1999-Jahrgang 52, 670-682
Influence of Oil Loading on Properties of BIIRVulcanizates
BIIR Carbon black Paraffin Oil Resin Stearic Acid MBTS Zinc oxide Sulfur
Polysar Brombutyl 2030 N 660 Sunpar/Sunoco Inc. Pentalyn A / Hercules Vulkacit DM / Lanxess
100 60 4 1 1,3 3 0,5
100 60 7 4 1 1,3 3 0,5
Influence of Oil Loading on Properties of BIIRVulcanizates

Butylkautschuk-Typ Paraffinl Mischungseigenschaften Compound-Mooney (ML 1+4/100C) Mooney-Relaxation (MR30) [%] Monsanto-Tack [N] Vulkanisateigenschaften (160C/12 min.) Zugfestigkeit [MPa] Bruchdehnung [%] S 50 [MPa] S 100 [MPa] S 300 [MPa] Shore A Hrte/23C Shore A Hrte/70C Rckprallelastizitt/23C [%] Rckprallelastizitt/70C [%] Luftdurchlssigkeit/70C (DIN 53536) [m2/s*Pa]) BIIR 72 5,1 2,3 10,5 650 0,9 1,7 5,4 60 47 9 30 2,3 BIIR 7 62 5,5 2,2 8,9 670 0,8 1,1 4,0 58 40 9 29 3,0
Influence of Carbon Black Loading on BIIR Vulcanizates

BIIR Carbon Black Paraffin Oil Resin Stearic Acid MBTS Zinc Oxide Sulfur Vulkacit DM / Lanxess Polysar Brombutyl 2030 N 660 Sunpar/Sunoco Inc. Pentalyn A / Hercules 100 60 4 1 1,3 3 0,5 100 40 4 1 1,3 3 0,5 100 30 4 1 1,3 3 0,5 100 20 4 1 1,3 3 0,5 100 0 4 1 1,3 3 0,5
Influence of Carbon Black Loading on BIIR Vulcanizates

BIIR (Butyl rubber 2030) Carbon black (N 660) Compound Properties Compound-Mooney (ML 1+4/100C) [%] Mooney-Relaxation (MR30) Monsanto Rheometer MDR 165C minimal torque [Nm] [min] t50 t90 [min] Maximal torque [Nm] Vulcanizate properties (160C/12 min.) Tensile Strength [MPa] Elongation at break [%] M50 [MPa] [MPa] M100 M300 [MPa] Shore A Hardness/23C Shore A Hardness/70C Rebound at 23C [%] Rebound at 70C [%] Air permeation at 70C/E+17 [m2/s*Pa]) tan / 0C (Roelig-test) tan /70C (Roelig-test) 100 60 72 5,1 2,3 2,9 6,2 7,9 11,8 730 0,9 1,3 5,4 55 43 10 32 2,14 0,647 0,251 100 40 62 7,4 1,7 3,3 6,8 5,5 13,1 865 0,7 0,9 2,4 46 33 10,7 39 2,27 0,809 0,215 100 30 56 7,6 1,4 1,3 7,1 4,3 13,7 975 0,7 0,8 1,8 39 27 11,9 42 2,39 0,863 0,190 100 20 51 7,8 1,2 3,3 7,8 3,4 13,5 1055 0,6 0,7 1,2 33 23 12,2 44 2,58 0,900 0,178 100 0 40 7,2 0,8 3,3 6,8 2,2 7,3 1100 0,4 0,5 0,6 22 17 13,8 49 2,78 0,945 0,151
Influence of (X)IIR/NR-Blend Ratio on Vulcanizate Properties

BIIR CIIR NR Carbon black (N 660) Paraffin oil Pentalyn A* Stearic acid Zinc oxide MBTS Sulfur 100 0 0 60 7 4 1 3 1,0 0,5 100 0 60 7 4 1 3 1,0 0,5 80 0 20 60 7 4 1 3 1,0 0,5 80 20 60 7 4 1 3 1,0 0,5 60 0 40 60 7 4 1 3 1,0 0,5 60 40 60 7 4 1 3 1,0 0,5 40 0 60 60 7 4 1 3 1,0 0,5 40 60 60 7 4 1 3 1,0 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] CIIR [phr] NR [phr] Unaged: M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Aged (168h/100 C) M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Air permeation at 50psi/65 C (Q x 10-8] Adhesion at 100 C Self adhesion / tack [kN/m] Adhesion to NR [kN/m] Fatigue to failure after ageing at 168h/120 C [kcycles] 100 100 4,2 3,7 9,3 9,9 740 770 6,8 10,0 550 2,9 5,5 10,9 640 2,9 80 20 80 20 60 40 60 40 40 60 40 60
5,7 5,1 7,1 5,7 8,9 4,3 10,0 10,7 12,8 10,3 14,7 9,7 620 620 560 560 490 580 7,6 9,8 420 5,4 7,9 11,0 465 5,7 8,4 9,3 320 9,2 7,7 9,2 365 7,5 6,7 8,8 370 13,8 3,6 5,8 475 13,2
16,8 4,4 7,5 1,3
14,7 4,7 10,0 1,6
15,2 9,1 14,7 1,9 0,3 0,1
15,4 5,2 20,8 2,9 0,0 0,0
61,8 72,7 23,6 3,9
5. Rubber Specialities: Performance Profiles of Vulcanizates
Maximal Service Temperature 100 80 Processability 60 40 20 0 Low Temperature Performance
Mechanical Properties
Ozone Resistance
Silicon Rubber Hydrogenated Nitrile Rubber Fluoro Rubber Ethylene-Vinylacetate-Copolymers
Oil Swelling
5.1. Fluoro Rubber (FKM / FPM)

Bond C-H C-F Bond energy [J/mol] 413 485 Radius of atoms [A] 0,37 0,72 Maximum Service Temperature: 3.000 h 1.000 h 240 h 48 h 232C 260C 288C 316C
Properties of FKM-Vulcanizates: Areas of Application:

Positive:
Excellent resistance to ozone, UV- and weather High service temperature Low oil swell High resistance to chemicals and acids High flame resistancy 60 % 10 % 10 % 20 % 30-40 % 30-40 % 10-15 % ~5% 4.5 % 10 % Automotive (75% in Europe) Aviation and Aerospace Chemical planty s (Fume treatment of incineration and power plants) rest O-Rings and seals crank shaft seals hoses and profiles Modification of polyolefins pipes and tubings rest
Rubber goods:
Negative:
High price Poor low temperature flexibility (except Kalrez) Poor resistance to amines and bases Poor compounding Necessity to oven ageing after vulcanization
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

Market: Prices: 2002: ca. 15.000 t 20 - 50 EUR/kg (correlated with F-content) ~ 500 /kg (Kalrez) 8 - 10% p. a.
World Market
Asia 22%
USA 45%
Top price:
Growth:
Return on Sales: 20 - 25%
WEurope 33%
Source: Kunststof En Rubber; 11 November 2003
Producer
Du Pont DuPont-Showa
Trade names
Viton/Kalrez
Market Share [%]

43
Site
Deepwater, NJ Dordrecht, NL Utsonomiya, Jp Kawasaki, Jp Decatur, AL
Capacity* [kt]
3,0 1,0 1,0
Dyneon Solvay (Ausimont) Daikin Kogyo Asahimont Asahi Glass Unimatec
Fluorel Tecnoflon Daiel Aflas Noxtite
22 15 10 5 5
Zwijndrecht, BE Gendorf, DE Spinetta, I Osaka, Jp Chiba, Jp Chiba, Jp Jp
2,0 2,1 2,0 1,0 2,0 1,0 1,0
Estimated total capacity: 20 kt; capacity utilization: 80-100%
FKM: Composition of Standard Grades

HFP
] .% wt F[ VD 20
Fluorine containing monomers H F C H F C F F C F C F C F CF3 C F F
80
VDF
[w .t% ] 40 60
40 us ho s orp er s) r Am olym P bbe (ru
TFE
HF P
60
HFP
80
20
Y Copolymers fluorine cont. [wt.%] 54 65 67 69 71
TFE
80
60 40 TFE [wt.%]
VDF [%] 33 55 22 TFE [%] 33 23 12
20
VDF
TFE/P VDF/HFP VDF/HFP/TFE VDF/HFP/TFE/CSM* TFE/PMVE/CSM*

*Cure Site Monomer
X Y Z Soures:
HFP [%] 33 22 65
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

Fluorine Cont. Volume swell [wt.%] benzene gear oil 21C 121C VDF/HFP 65 20 171 VDF/HFP/TFE 67 15 127 VDF/HFP/TFE/CSM* 69 7 45 TFE/PMVE/CSM* 71 3 10 TFE/P 54 180
Copolymers
Tg [C]
-18 -8 -5 -19 -2 (0)
Storage in motor oil which contains amines (163C)

Benzene/21 C Gear Oil/121 C
Volume Swell [%]
160 140 120 100 80 60 40 20 0 60 65

d
reduction of elongation at break [%]
10 0 -10 -20 -30 -40 -50 -60 -70 -80 0 200 400 HNBR FKM (68% F)
70
75
600
800
1000
Fluorine Content [wt.%]
time [h]
FKM: Glass Transition Temperatures

H F F CF3 F F F O F CH3 H CF3
Glass transition temperature [ C]
0 -5 -10 -15 -20 -25 -30 -35 0 0,5
TFE/VDF/PMVE TFE/VDF/HFP
H F F F F F F H
VDF Vinylidene fluoride (59% fluorine)
HFP Hexafluoropropene (76% fluorine) TFE Tetrafluoroethylene (76% fluorine)
PMVE Perfluoromethylvinyl ether (69% fluorine) P Propen
1,5
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
peroxidisch
Vulcanization with Bisphenols Vulcanization with Diamines
Aflas
Viton A PVDF
Viton B, GF
Viton GLT Kalrez PTFE 75
55
65 Fluorine Content [wt. %]
1. Elimination of HF by MgO, CaO und PbO.

CF3 CF2 F CH2 CF2 CH2 CF2 - HF CF2
FKM: Vulcanization with Diamines

CF3 CH CF2 CH2 CF2 - HF CF3 CF2 CH CF CH CF2
2. Crosslinking by Diamines, which are used in "capped form" (such as carbamates) in order to increase scorch resistance CF CF
3 3
CF3 CF2 CF2 CF3 CH CF CH CF2 CH CF CH CF2 H2N R NH2
CF2
CH CF CH2 CF2 NH R NH - 2HF
CF2
CH N R N
CH2 CF2
CF2 CF3
CH CF CH2 CF2
CF2 CF3
CH
CH2 CF2
Diamine cure yields crosslinks which are liable to hydrolysis (not steam resistant)
CF3 CF2 CH N R N CF2 CF3 CH CH2 CF2 CF2 CF3 CH CH2 CF2 H2O O CF3 CF2 CH O CH2 CF2 NH2 R NH2 CH2 CF2
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 CF2 F CH2 CF2 CH2 CF2 - HF CF2 CF3 CH CF2 CH2 CF2 - HF CF2 CF3 CH CF CH CF2
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 HO CF3 n CF3 CF3 HO CH CF CH CF2 CF3 O CF2 CH CF CH2 CF2 O OH + CH2 P
+
Cl
- HCl HO
CF3 O CF3 n CH2 P

+
CF3 CF2
CF2 CF3
CH CF CH CF2
CF3
CF3
Sources:
T. L. Smith, W. H. Chu, J. Polym. Sci A-2, 10, 133 (1972) O A. W. Fogiel, J. Polym. Sci., Symp., 53, 333 (1975) 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 Peroxides CF

CF3 CF CF2 CF2
3
CF2
CF2 CF2
CF2 CF2
n
CF CF2
CF2
Br
J
C H2J2 C F2J2
CF2
Br/J-Content: 0,5-1 wt.%
J-( C F 2 ) - J 4 -6
Type of bond C-F C-H C-Br C-J
Bond energy [kJ/mol] 480 405 270 200
CF2 CF2 CF2 Br CF O
CFBr CHBr CF2 CF2 Br
CF2 CF2 Br
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 ( Si CH3 O CH3 Si CH3 CH3 O Si CH CH2 O ) n VMQ O ) n MQ
Grade
MQ VMQ PVMQ FMQ
Tg [ C]
- 120 - 120 - 120 - 69
Tm [ C]
- 45 - 45 - 70
CH3 ( Si CH3
Vulcanizate Properties:
Positive:
Low temperature performance High temperature resistance Low dependence of properties on temperature changes Ozone-, UV- and Weather resistance Hydrophopic character Physiological inertness Low reistance against acids, bases, vapour and hydrocarbons (significant improvement with FMVQ) Mechanical properties RTV: poor HTV: better / DVR ! High gas permeability
CH3 ( Si CH3 O Si CH CH2 O ) n PVMQ
Negative:
CH3 ( Si CH3 O
CH2 CH2 Si CH3 O
CF3 ) n FMQ
Bond energies
Si-O C-O C-C C-S S-S
[kJ / mol]
444 339 348 272 266
Silicon Rubber: Properties and Application Areas

Haushalt 20%
Application Areas:
Automotive industry 40%
Pharmaceutical- and medical rubber goods Rubber goods with food contact
Medical Applications 25%
Machine building 15%
Cable insulation Adhesives
Temperature [C]
90 121 150 200 250 315
Sources:
duration
40 years 10-20 years 5-10 years 2-5 years 3 months 2 months
Moulded articles Hoses, sealants (Automotive, Machine building and E&E)
K. Polmanteer, Rubber Chemistry Technology, Vol 61: 471-502Silicon 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/Kchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Producers Capacities and Silicon Rubber Market

Manufacturer* Site SiloxaneCapacity [kt]
260.000 110.000 110.000 40.000 65.000 95.000 90.000 30.000 60.000 Rhodorsil Silopren KE, Sylon Elastosil
Silicone RubberBrand Name

Silastic
Dow Corning
Carollton, USA Barry, GB
Momentive (formerly: GE + Bayer)
Waterford, USA Ohta, Japan Leverkusen, DE
Shin-Etsu Wacker
Isobe, Japan Burghausen, DE Nnchritz, DE
Rhodia
Rousillon, FR
S Western World (2000)
850.000
*Evonik and Crompton are active in this market without proprietary siloxane production
Japan 25%
Nordamerika 44% Year
1995 /t: ~ 110.000 ca. 3,5 % / a;
2005 ~ 200.000 LSR ca. 10 % / a
Consumption
Europe 31%
Growth rate 2005:
Source: Winnacker/Kchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Silicon Rubber: Production

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

H3C O H3C Si O Si H3C H3C O Si O Si CH3 CH3 15 % CH3 CH3 85 % O CH3 Si CH3 O
n
CH3 Si CH3 OH
Katalysatoren: Suren, Lewis Suren, Saure Silikate, Basen
bliche Temperaturen: KOH 140 C 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 H3C Si O Si H3 C O O CH3 Si O Si CH3 CF3 H3C H2C O H3C Si O Si CH2 O CF3 CH2 CH3
CH2 HC O H3C Si O H3 C Si CH CH2 O
CH2 CH Si CH3 O Si CH3 CH CH2
Si O Si
CH3 C H2
CF3
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
Chain length [nSi] Viscosity processing 10.000 Greasy/Highly viscous Transfer moulding Extrusion Transfer Moulding predominantly 1C- und 2C-systems 110 -300 C
Liquid Rubber
1.000 Highly viscous Transfer moulding
RTV-Rubber
200 liquid / pourable
Crosslinking method Peroxides Addition Cure temperature
predominantly 2C-Systeme 110 - 200 C
RTV-1: Condensation RTV-2: Addition 25 - 150 C
Vulcanization Method
Condensation at room temperature (RTV) Platinum catalyzed hydrosilylation at low or elevated temperature C) (RT to 80 C, LSR: 110-200 High temperature-Vulcanization with peroxides (HTV: 120-180 C)
Products
Silanol containing Silicon rubbers Silicon rubbers with silanol and vinyl groups MQ, PVMQ, MVQ, FVMQ
RT-Vulcanization of Silicon Rubber (2K-System)

1a) Condensation of polysiloxanes which contain silanol groups by multifunctional alkoxysilanes
R
R Si R R Si R OH OH RO OR Si OR HO OR HO R Si R R Si R
R Si O Si O Si R R R
Si
- 4 ROH
R R Si
O O R
Typical mulftifunctional alkoxysilanes are:

OR RO Si OR OR RO R Si OR OR RO OR Si OR OR O ( Si OR O
)
n
R = Me, Et
Metal carboxylates are often used for catalysis : Metals: Carboxylates: Pb, Zn, Zr, Sb, Fe Sn Ba, Ca 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 Si R O
O C CH3 RO Si RO CH3 OR OR CH3 CH3
O C O
R Si R + H 2O - CH3COOH R R Si
R O Si O Si R
R Si O O Si R R R
R Si R O
O C
O C O
R Si 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 Si R R OH H
O Si O Si O H HO R R Si R - H2
R Si R R O
O Si O Si O O R R Si 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 ( Si CH3 CH3 ( Si CH3 CH3 O ) Si n CH H O ) Si n CH3 CH2 O O Pt-Compounds as H2PtCl6 (ca. 10 ppm) (
CH3 Si CH3 CH3 ( Si CH3
CH3 O ) Si n CH2 CH2 O ) Si n CH3 O O
Inhibitors:
HT-Vulcanization of Silicon Rubber

3) Peroxide Cure (120-180C) Typical Peroxides Temperature F
(t1/2) = 1 min.) 234 Bis(2,4-dichlorobenzoyl)Peroxide 271 Di-Benzoylperoxide 340 Di-Cumylperoxide 2,5-Dimethyl-2,5-bis(t-butyl peroxy) hexane 354 379 Di-t-Butylperoxide
R Si R O R Si R O R Si R Peroxide - 2 H* R Si R O R Si R O R Si R R Si R O R* Si R O R Si Si R R O R Si R O R Si R* O R R Si Si R R R R R Si R O R R Si R O Si O R R Si
Impact of Vulcanization Method on Cost of Articles

Comparison of PeroxidePeroxide- (HTV) and platinum catalysed LTVLTV-Cure
Cost Factor
Raw materials [$/pound] Vulcanization time [sec] Overhead-Costs [$/h] salaries [$/h] Hours per shift Shifts per week Number of nests per mould Weight per article + 10% loss Number of articles per week Material consumption per week Raw material costs per week [$] Total cost per week [$] Cost per article [$] Savings per article [%] Financial result per year [$] Increase of financial result [%]
HTV
3,50 120 60,00 12,00 10 8 3 59,5 7200 885 3.097,31 8.857,31 1,23 0 44.286,55 0
LTV
5,00 60 60,00 12,00 10 8 3 59,5 14.400 1.770 8.849,45 14.609,45 1,01 21,25 230.563,76 420,62
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
CH2 CH H3C CH2
H CH CH C C H2 H2
C CH 2 CH 2 1
Butylidene-Moiety
Ethylidene-Moiety
Nitrilo-EhylideneMoiety
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 < 155C High Tg >-30C Bad incorporation of softeners High price (~ 20/kg)
HNBR: Application Areas and Articles

Expansion Joints
45%
Blow Out Preventer

15%
25%
Ship Couplings
Riemen Kabel
7%
4%
4%
Dichtungen Sonstige
Schluche lfrderung
Rotor/Stator- Pumps Roll Covers Oil well Packers
Catalytic Hydrogenation of NBR

Selective Hydrogenation of C=C bonds
C C N H2/Catalyst C C N
Requirements for Hydrogention Catalyst: 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 Homogenous Catalyst Systems:
(PPh3)3 RhI Cl and (PPh3)4RhI H
(US 3700637, DE 2539132, EP 134023, DE 3541689, DE 3540918, EP 298386, DE 3529252, DE 3433 392, US 4,464,515, US 4,503,196, DE 3921264, US 6084033)
Heterogenous(Supported) Catalyst Systems:

N
Pd/SiO2; Pd/C; Pd/CaCO3; Pd/BaSO4
(DE 3229871, US 4337329, US 4384081, US 4510293, DE 3227650, DE 3046008, EP 0298386)
Relative prices of noble metals [/g]: Rh (150) > Ru (75) > Pd (12,50)
Unselective Hydrogenation of Nitrile-Groups Results in Gel Formation

H C NH2 + HN - NH3 C N
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 the range of standard HNBR viscosities was limited to >60 MU until recently. Cross-metathesis of NBR with olefins allows for the production of NBR with Mooney viscosities < 30 MU. In-situ hydrogenation of theseNBR-feedstocks yields HNBR-grades with Mooney viscosities < 60 MU. As a consequnece of low TONs, large amounts of catalysts are required for the cross-metathesis of NBR. Metathesis catalysts which are robust towards nitrile groups are protected by patents. Their use implies the payment of licence fees.
R C C N
Catalyst
R CH 2 H C C N
Catalysts without Activity in NBR-Metathesis *

PPh 3 Cl
PCy3 Cl Cl PCy3 Ciba-Catalyst S

Cl Cl
Ru
Ph
Ru
PPh 3
BH 3 P Ru P
2Ph
Cl
2 K
Ph
Grubbs-I-Catalyst
Cl
Ru P
+
BF 4
R1
PCy3 Cl Ru PCy3
Ph
BH 3
Cl
PCy3 Piers-Catalyst
SnCl3 Cl
Cl
Ph
R2 R3
Catalyst from Prof. Berke' s group (University of Zurich)
Frstner-(I)-Nolan-Catalyst (Umicore)
2Ph P N Ph Ph P Ph Ph
+
Cl
SnCl 3
2-
Ru
SnCl3
Cl
Ph
Ru
SnCl 3
Cl
2
2
*Source: Julia-Maria Mller, Dissertation TU Mnchen
Catalysts which are Active in NBR-Metathesis* (Number of Catalytic Steps (TON))

Mes N N Mes Mes N N Mes Mes N N Mes
CF 3 COO
Ru
Cl
Cl
Ru Cl R1 P
+
Cl
Ru PCy 3
CF 3COO O
R2 R3
Buchmeiser-Nuyken-Catalyst TON = 8 / 23C
Piers-II-Catalyst TON=12 / 55C
Grubbs-II-Catalyst TON=40 / 23C
Mes
Mes Mes N N Mes
Mes
N
Cl
Mes
Cl
Ru
Cl
Cl Cl O
Ru
N Cl
Ru N
O NO 2
Br
Grubbs-Hoveyda-Catalst TON=53 / 23C
Grela-Catalyst TON=78 / 23C
Grubbs-III-Catalyst TON=120 / 23C
Br
*Sources: Julia-Maria Mller, Dissertation TU Mnchen; M. Schneider, Dissertation TU Mnchen, M. Kellner, MSc-Thesis TU Mnchen; K. Langfeld, MSc-Thesis TU Mnchen; C. Gantner, MSc-Thesis TU Mnchen
Sequence of Process Steps in NBR and HNBRProduction NBR-Production: Sequence of Process Steps:
Emulsionspolymerization Removal of residual monomers Latexcoagulation + crumb wash Mechanical dewatering Thermal drying Bale pressing Bale wrapping Packaging and storage
HNBR-Production: Sequence of Process Steps

Make-up of Hydrogenation catalyst solution Catalyst recovery
Bale cutting
Cemement preparation-
Removal of oxygen and hydrogenation
dilution
Catalyst recovery
Solvent removal by evaporation
Wet solvent stripping
Mechanical dewatering of crumbs
Thermal crumbdrying
Bale pressing
Bale wrapping Packaging and storage
HNBR-Producers and Capacities

Producers and Capacities Company Site
Zeon Lanxess Total Takaoka Houston Leverkusen Orange Japan USA Germany USA
Capacity [t]
2.800 2.000 3.000 3.600 11.400
Markt- und Marktentwicklung

14000 12000 10000 Consumption capacity 8000 6000 4000 2000 0 1992
Volume [t]
1994
1996
1998
2000
2002
2004
Ageing of Unvulcanized NBR and HNBR

(Increase of Mooney Viscosity ML 1+4/100 C)) 1+4/100
+1 +0 -1 -2 -3 ln Vbr -4 -5 -6 -7 -8 2,0 180 2,4 160 140 2,6 120 2,8 100 80 3,0 60 3,2 40 1/T *103 [K-1] T [ C]
Source: W. Obrecht, H. Buding, U. Eisele, Z. Szentivani, J. Thrmer, Angew. Makromol Chem. 145/146 (1986) 161-179 (2373)
Hydrierter Nitrilkautschuk: Ein Werkstoff mit neuen Eigenschaften
NBR Hydriergrad: 0 % HNBR Hydriergrad: 96 % HNBR Hydriergrad: 99,5 %
Tg of HNBR and NBR

100 80 60 40
E/ACN-Copolymers HNBR (fully hydrogenated)
100 80 60 40 20 0
NBR
Tg [C]
20 0 -20
-20 -40 -60 -80
-40 0 20 40 60 80 100
-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 80 60 40
Ethene/Vinylacetate-Copolymers
Levapren Nielsen et al.*
100 80 60 40 20 0 -20 -40
Ethene/Vinylchloride-Copolymers
Tg [ C]
20 0 -20 -40 0 20 40 60 80
100
20
40
60
80
100
Vinylacetate Cont. [wt.%]

Source:
Vinylchloride Cont. [wt.%]
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
Crystallinity [%]
12 10 8 6 4 2 0 0 10 20 30
2. DSC-Aufheizung
40
50
60
Acrylonitrile Content [wt. %]
Tgs of Ethylene-Copolymers
100 50
Tg [C]
-50
-100
EPM 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
Tg [C]
-50
-100
?
0 10 20 30 40 50 60
HNBR (fully hydrogenated) NBR
-150 70 80 90 100
Acrylonitrile Content [wt. %]
Dependence of Tg on Degree of NBR-Hydrogenation (ACNCont.: 34 wt. %)

-20 dyn. mech. (11 Hz) -22 DSC -24 -26 -28 -30 -32 -34 0 20 40 60 80 100
Tg [C]
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/StrainProperties of HNBR-based Vulcanizates (34 wt.% ACN; unfilled; sulfur vulcanized)
12 10 stress [MPa] 8 6 4 2 0 0
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 100 phr HNBR 0,07 phr Schwefel 2,63 phr TMTD 2,07 phr DTDC* * Dithiodicaprolactam
11,0% 7,9% 4,0% 1,9% 0,5%
100
200
300
400
500
600
700
strain [%]
Dependence of E and E on Temperature (HNBR with 38,5 wt .% ACN)

10000
1000
E' and tan [MPa]
100
E' E''
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
0,7 0,6
HNBR
45 40 35 18,9 wt.% 28 wt.% 33,9 wt.% 38,5 wt.% 48,3 wt.%
Stress [MPa]
stress [MPa]
4000
0,5 0,4 0,3 0,2 0,1 0 0 1000 2000 3000 19,2 wt.% 28 wt.% 34,2 wt.% 39,1 wt.% 49 wt.%
30 25 20 15 10 5 0 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
Yield-Strength [MPa]
1 0,8 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
160 140 120 100 80 60
120
280%
permanent elongation [%]
permanent elongation [%]
= bleibend
48,3 %
100 80
200%
ASTM D 1566 - 98 Kautschukdefinition
18,8 %
60 40 20 0
39,0 %
40 20 0 0 100 200 300 400
120% 80%
28,2 % 34,9 %
20
40
60
elongation [%]
ACN-content [wt.%]
Influence of Sulfur- and Peroxide Vulcanization on Properties of Partially Hydrogenated HNBR

H-NBR Sulfur Stearic acid ZnO MgO OCD ZMB-2 N 550 TMTD CBS 100,0 phr 0,5 phr 1,0 phr 2,0 phr 2,0 phr 1,0 phr 0,4 phr 45,0 phr 2,0 phr 0,5 phr
1706 S HNBR-Grade (Therban) 33,7 ACN-content [wt.%] 4,3 RDB-content [Mol.%] 60 ML 1+4(100 C) [MU] Compound Properties 64 Compound Mooney/ ML 1+4(100 C) 12,5 Mooney-Scorch (120 C) [min.] 56,4 Fmax [N] Vulcanizate-Properties 72 Shore A Hardness(23 C) 69 Shore A Hardness (70 C) 3,4 M 100 [MPa] 8,8 M 200 [MPa] 14,7 M 300 [MPa] 27 TS [MPa] 510 elongation [%] 38 Rebound [%] Compression Set 73 70h/-10 C [%] 70h/23 C [%] 73 70h/100 C [%] 70h/150 C [%] Hot air ageing 55 D/D0 (150 C/ 5 d) [%] D/D0 (150 C/24 d) [%] Degree fo vol. swelling in fuel 100*(V/ V0-1) (48h/50 C) [%] 75 1706 S 33,7 4,3 60 66 14 51,2 72 70 5,6 17,8 26 295 36 68 10 27 54 65
Vulcanization time: 20 min temperature: 160 C H-NBR 100,0 phr ZnO 2,0 phr MgO 2,0 phr DDA 1,0 phr ZMB-2 0,4 phr N 550 45,0 phr TAIC 1,5 phr Perkadox 1440* 7,0 phr Vulcanization time: 15 min Temperature: 180 C Annealing: 6h/150 C
Perkadox 1440 Bis(t-butylperoxyisopropylbenzol 40%ig
Vulcanizate Properties of Sulfur- and Peroxide Cured HNBR (Partially and Fully Hydrogenated)
HNBR-Grade (Therban) 1706 S ACN-content [wt.%] 33,7 Residual double bond cont. [Mol.%]4,3 ML 1+4(100 C) [ME] 60 Compound Properties Compound Mooney [ML 1+4(100 C)] 64 Mooney-Scorch (120 C) [min.] 12,5 Fmax [N] 56,4 Vulcanizate Properties Sulfur Core (Press 160 C/20`) Peroxide Cure (Press 180 C/15`) Shore A Hrte (23 C) 72 Shore A Hrte (70 C) 69 M 100 [MPa] 3,4 M 200 [MPa] 8,8 M 300 [MPa] 14,7 Tensile Strength [MPa] 27 Elongation [%] 510 Rebound [%] 38 Compression Set 70h/-10 C [%] 73 70h/23 C [%] 70h/100 C [%] 73 70h/150 C [%] Hot Air Ageing D/D0 (150 C/ 5 d) [%] 55 C/24 d) [%] D/D0 (150 Degree of Vol. Swelling in Fuel 100*(V/V0 -1) (48h/50 C) [%] 75 1706 S 33,7 4,3 60 66 14 51,2 1706 34,5 0,4 63 74 16 52
72 70 5,6 17,8 26 295 36 68 10 27 54 65
73 71 6,9 17,7 24 280 34 12 28 59 70
Performance of HNBR in Power Transmission Belts

log t/h for b = 50%
Materials used for power transmission belts Leather SBR CR
10.000
200
180
160
140
120
100 [ C]
HNBR / peroxide cured HNBR / sulfur cured 100 CR
1.000
10 2,1
-1
2,2
2,3
2,4
2,5
2,6 10 -3 (
1 -1 K ) T
1000
rate of crack growth
HNBR (Sulfur cured) HNBR (Peroxide cured)
CR
100 10
HNBR
Tear-Analyzer-Test / Exp. Conditions
Frequency: Strain Ampli tude: Attenuation mode: Rate of crack growth: 4 Hz 20% sinuoidal 1/co (dc/dn)
0,1 -20 0 20 40 60 80 100
Source: M. Mezger; D. Achten Therban: The high performance elastomer in power transmission systems 9. Tagung Zahnriemengetriebe am Institut fr Feinwerktechnik und Elektronik-Design der TU Dresden
Temperature [ C]
5.4. EVM: Profile of Properties and Applications

O O C CH3 O O C CH3 O C CH3 O
VAc-content: 40-90 wt.% radical polymerization in solution Random monomer incorporation Low molar masses Significant degree of short chain branches
Positive:
Ozone-, UV-, and weather resistance Maximum service temperature 175C High filler loadability FRNC-applicability (Flame resistant non corrosive) Resistance to water/glycole Braod range of grades No necessity for post cure in oven
Application Araeas:
Automotive- and engineering: seals and membrandes Hoses in high temperature environment FRNC-products: cables and floorings Sound protection FRNC Conveyor belts Hot Melt and pressure sensitive adhesives Protecting foils Blending component for HNBR, EPDM, CM, NBR) Rubber modification of thermoplasts (PVC, TPU, SAN, PC etc.) Oil additive Shoe soles
Negative:
fair mechanical properties Low temperature flexibility (depending on VAccontent) Fair oil resistance Range of products limited to ML 1+4 = 20 - 35 Vulcanization only peroxides
Source: H. Bartl, J. Peter, ber thylen/Vinylacetat-Copolymerisate und ihre Vernetzung; Kautschuk und Gummi, Jahrgang 14, 2 (1961) WT 23-32
Production Routes Towards EVM and EVA

10000
Producer Process
High pressure bulk process 750-3000 bar 120-300C
Products
Exxon, BP, High pressure Escorene Mitsui ctc. Du Pont USI Lanxess Mitsui High pressure Elvax High pressure Vynathene Solution Solution Levapren
1000
pressure [bar]
100
Solution process 100-500 bar 50-120C Emulsion process 10-100 bar 30-70C
High pressure process:

Preferred mprocess for EVA (thermoplastic polymers with VAc-content <40 wt.%) Monomer conversion: < 20% Molar mases decrease with increasing VAc-content
10
Solution process: EVM-Rubbers

1 0 20 40 60 80 100
Preferred process for EVM-r rubbers (VAc-cont. 40-90%) Monomer conversion: 60- 70% Solvents: t-Butanol; Methanol
Vinylacetate content [wt.%]
Emulsion Process:
Preferred process for latices with high gel content (paints) Monomer conversion: ~ 100%
High Pressure Bulk Process: 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
100
Rubber
Enthalpy of fusion (DH)[J/g]
Glass Transition Temperature (Tg) [C]
80 60 40 20 0 -20 -40 0 20 40 60 Vinyl acetate content [wt.%.] 80 100
Temperature of Fusion (Fp)[ C]
100 80 60 40 20 0 -20 -40 0 20 40 60 Vinyl acetate content [wt.%] 80 100
EVM: Maximum Service Tempeature

0 -10 -20 -30 -40 -50 -60 -70 -80 -90 -100 200 300 400 500 600
O O O O
CH3 - HAc CH3
O O
CH3
weight loss [wt.%]
350 C
time till elongation becomes <50 % in h
Elastostab H 02 Stabaxol P 200

O H3C O O n N H
OCN
N C N
106
Temperature [C]
NCO
n n = ca. 4
100000
O N C N
135
N O H
n n = ca. 4
O nCH3
10000
20000 h
1000
1000 h
The addition of acid scavengers such as carbodiimides and isocyanates does not improve hot air performance
100 200 190 180 170
> 170 C 160 150 140
137 C 130 120 110
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/125C)
80
Delta F/F0 x 100 [%]
LOI according to ASTM-D 2863

60
Al2O3: 190 phr
Limiting Oxygen Index (LOI) [%]
60 Change of Properties [%]
Delta D/D0 x 100 [%] Delta V/ V0 x 100 [%]
50
Al2O3:
0 phr
40
40
20
30
20
-20
10
-40 0 20 40 60 80 100 Vinyl acetate content [wt.%]
0 0 20 40 60 80 100
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 MgO Stearic acid Carbon black/N 550 Vulkanox DDA 1) Plasticizer DOS 2) Plasticizer ODTM PE-Wax Aktiplast PP TAIC Peroxide (40%ig) 3) Vulkanization time: Temperature: 100,0 phr 2,0 phr 1,0 phr 65,0 phr 1,0 phr 7,5 phr 7,5 phr 2,0 phr 2,0 phr 1,5 phr 6,0 phr 10 min 180 C
Vinyl acetate content [wt.%] Compound properties Mooney ML 1+4(100 C) C [min] t10/180 t90/180 C [min] C [N] FH-FL/180 Vulcanised properties (ISO-Stab Nr. 2, 2mm) Shore A Hrte (23 C) S 100 MPa] Elongation at break [%] Tenjsile Strength [MPa] Compression Set 70h/100 C 70h/125 C 70h/150 C [%] [%] [%]
40 20 1,2 7,2 17
45 24 1,2 6,6 20
50 23 1,2 6,6 19
60 25 1,2 6,2 21
70 20 1,3 6,9 19
80 20 1,3 6,1 17
75 5,0 295 11,7 23 25 41 -3 -2 10
74 5,7 275 13,6 20 23 38 -12 -2 9
68 4,4 285 12,6 20 25 41 -10 2 11
71 5,4 280 12,8 22 26 40 -11 -2 12
68 4,2 300 11,5 21 24 46 10 -7 15
72 4,7 300 10,5 27 31 51 -8 -15 14
no post vulcanization storage in hot air

1) 2)
Styrenated Diphenyl amine (SDPA) Dioctylsebacate (DOS) 3) 1,3-Bis(tert.-butylperoxyisopropyl)benzene (Perkadox 14/40) Source: E. Rohde DKG-Bezirksgruppentagung NRW in Bad Honnef 07.-08. Mai 1992
Hot air ageing (14d/150 C) [%] F/F0 x100 [%] D/D0 x100 H/H0 x100 [%] Storage in SAE Oil90 (3d/150 C) F/F0 x100 [%] D/D0 x100 [%] V/V0 x100 [%]
-26 -19 69
-12 -4 47
-8 -4 31
8 2 13
6 8 3
10 -12 -4
EVM/HNBR-Blends
EVM/HNBR 100,0 phr 1) Rhenogran P 50 var. Carbon black/N 550 50,0 phr Carnuba Wax 2,0 phr MgO 10,0 phr ZnO 2,0 phr TAIC 1,75 phr 7,0 phr Peroxide (40%ig) 2) Vulcanization time: 15 min Temperature: 177 C Anealing: 16 h
1) 2
Therban 1707 Levapren 500 Rhenogran P 50 Compounc properties Relative compound price ML 1+4(100 C) [ME] C [min] t2/177 t90/177 C [min] Vulcanized properties Shore A Hrte (23 C) S 100 [MPa] Elongation at break [%] Tensile Strength [MPa] Compression Set 70h/23 C 70h/150 C 70h/175 C [%] [%] [%]
100 100 123 1,5 11,7 78 10,7 240 26 12 20 27 -2,3 -37 +6
75 25 1,5 80 99 1,6 11,0 80 13,1 190 24 12 17 27 -3,8 -26 +5
50 50 3 60 58 1,5 10,2 80 12,6 170 22,5 12 17 25,5 -10 -29 +4
25 75 4,5 40 40 1,6 10,2 81 12,0 145 18,8 14 14 20 -7,5 -21 +3
100 6 20 32 1,6 9,5 77 8,3 165 18,5 14 9 15 -1,6 -12 +2
Carbodiimide Vulcup 40 KE
Hot air ageing(14d/150 C) [%] F/F0 x100 [%] D/D0 x100 [%] H/H0 x100
Source: Test Report WR 26/83 (Mobay, Chem. Corp.)
Storage in ASTM oil Nr. 3 (7d/150 C) F/F0 x100 [%] D/D0 x100 [%] [%] V/V0 x100
-10 -4 +24
-17 -11 +34
-36 -29 +49
-50 -34 +67
-56 -45 +83
EVM: Influence of Post Cure on Physicals

15 10
Stress [MPa]
th wi
5
e ur tc s o
t ou th i w
r cu st o p
O-Ring: Mechanical properties without post with post cure cure Tensile Strength [MPa] 10,4 11,8 [%] 285 230 b M100 [MPa] 1,8 3,1 CS 72 h / 150C [%] 63 31 CS 168 h / 150C [%] 71 50
0 0 50 100 150 200 250 300
strain [%]
10 9 8
torque [dNm]
7 6 5 4 3 2 1 0
= 75 % of total cure
Sources:
cycle time for IM
H. Meisenheimer, Kautschuk Gummi Kunststoffe, 52 (1999) 724 P. J- Pazur, L. Ferrari, H. Meisenheimer, ACS Rubber Div. 165th Spring Meeting, Grand Rapids, Michigan H. Magg, A. Welle, Nordic Rubber Conf. 2005, Kge, Denmark
20
40
60
80 100 120 140 160 180 200 220 240
time [sec ]
EVM: Acrylate Reinforcing Technology (ART)

Z in c d ia c ryla te S a re t 6 3 3 S a rto m e r 7 0 5 O H2C
1) 1,2-BR
CH
O
2
Zn
2+
Levapren grade Levapren TMQ N 762 ZnO ZMB-2 Ficon 153 1) Saret SR 633 2) Vul-CUP 40 KE Compound properties Mooney ML 1+4(100 C) Vulcanized properties (ISO-Stab Nr. 2, 2mm) Shore A Hrte (23 C) Shore A Hrte (150 C) Tensile strength Elongation at break M 50 M100 Rebound/23 C Rebound/100 C [MU]
500 100
3)
500HV 100 1,0 35 10 1,0 20 6,5 9,9
500HV 100 1,0 35 10 1,0 20 6,5 26,8
(liequid rubber) 2) Zn diacrylate 3) For further ompound ingredients see Stuey on variation of vinyl acetate content Source: T. A. Brown, Polysar Rubber Corporation, Technical Report TR 552.92,17 vom 22.05.92
23
Acrylate-Reinforcing is used for golf ball cores based on high

ART based Golf-Ball-Core-Patents
EP 0496947, Prior.: 29.01.1991 (Bridgestone) US 6426387, Prior.: 04.08.2000 (Taylor Made Golf Co. EP 1227121, Prior.: 24.01.2001 (JSR) US 6525141, Prior.: 02.04.2001 (Bridgestone) US 6270428, Prior.: 07.08.2001 US 6517451, Prior.: 11.02.2003 (Titleist)
68 [MPa] 12,6 [%] 285 [MPa] [MPa] 4,4 [%] [%] -10 2 11
77 72 13,5 80 6,6 43 62 1 -8 6
77 73 20,8 175 4,2 10,5 46 61 -5 -29 8
Hot air ageing (14d/150 C) [%] F/F0 x100 [%] D/D0 x100 H/H0 x100 [%] Storage in SAE-oil 90 (3d/150 C) F/F0 x100 [%] [%] D/D0 x100 [%] V/V0 x100
-8 -4 31
-13 -6 13,7
-22 -29 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 Soft Segment Hard Segment
Scheme of the Phase Morphology of A-B-A, (A-B)n and (A-B)xMultiblock Copolymers
Examples for physical crosslinks

Hydrogen bonds /Crystallization Dipol/Dipol - Interaction Glassy Hardening (vitrification) Ionomers Type of bond covalent physical Bond energy [kJ / Mol] 260 - 350 10 - 20
Positve:
Good vulcanizate properties at low / moderate temperatures No compounding and vulcanization know-how necessary Short cycle times no time consuming vulcanization Recycling of waste (due to thermo labile/reversible crosslinks)
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
mechanical and reactor-blends (unvulcanized)
TPE-O
EPM / PP EPDM / PP EPDM / PP NBR/ PP NBR / PVC EVM / PVC ACM / PVC HNBR / PA HNBR / PBT NBR / PA EVM / PA EVM / PBT SBC (SBS, SIS, SEBS, SIBS) Polyester-Urethanes, Polyether-Urethanes COPE based on aromatic Polyesters (Terephthalates) PBT/ PTHF; PET / PTHF PEBA based on PA 6 and PA 12
Thermoplastic Polyolefins
(dynamically vulcanized)
Olefin TPE-V
Polyblends1
PVC based blends

(without dynamic vulcanization)
High Performance TPE-V Thermoplastic Elastomers

(without polyolefines (dynamically vulcanized)
Styrenic Block-Copolymers
TPE-S
Multi-BlockCopolymers2
Polyurethane Block Copolymers
TPE-U
Copolyester Block Copolymers
TPE-E
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
TPE-A
Sources: SRI Elastomers Overview 2008; Stratley Consultants
Selection of Commercially Available TPEs, Producers and Brand Names

Type of TPE
TPE-O (reactor blends) TPE-V PVC-based blends High performance TPE-V TPE-S SBS, SIS, SEBS SIBS TPE-U TPE-E TPE-A Hydrogen bonds / Crystallization Crystallization Hydrogen bonds / Crystallization Ionomer
Crosslinking Principle
Crystallization Crystallization Dipol/Dipol
Producer
UCC Bassell Exxon AES (Advanced Elastomer Systems) AES (Advanced Elastomer Systems) Denki KK Zeon Shell BASF Firestone, Polimeri Dow Kaneka Boston Scientific Innovia Bayer BASF Goodrich DuPont Toyobo Atochem Dow Du Pont
Brand Name
Flexomer Spherilene Exxtral Santoprene Geolast Denka LS ? Kraton Styrolux Sibstar Taxus SIBS Desmopan/Texin Elastollan Estane Hytrel Pelprene Pebax Estamid Surlyne
Glassy hardening (vitrification)
TPE: Market, Application Areas and Range of Prices

WO-TPE-Market: 1,5 Mio t
SBC
Areas of Application
Hoses 5% Cables 3% Medical Appl. 3% Adhesives 12% Automotive 32% IRP 18% Shoe 15%
TPO-V
TPU COPE PEBA Rest
TPOBlends
Asphalt Mod. 12%
W.-Europe:: 576a t (2001)

TPE
Type SBC's TPO's TPV's TPU's COPE's COPA's Sonstige Sum Source: 2.000 2.005 Growth [%] 195 135 36 62 20 7,5 455,5 226 172 59 79 30 10 576 3 5 10,5 5 8 5 4,5
PP/EPM-Reactor Blends PP/EPM-TPE-V SBC SBS SIS SEBS TPE-U (TPU) TPE-E (COPE) TPE-A (PEBA)
Price [/kg]
0,90-1,20 2,00-2,50 1,00-3,30 1,30-1,50 1,50-1,70 2,60-3,30 3,00-4,00 3,50-4,40 3,60-7,00
European Rubber Journal 184,no.1 (January 2002)
Schematic Presentation of the Dependence of the Shear Modulus on Temperature

104 103 102 101 100 10-1 Tg of Rubber Phase Temperature
Softening Temperature of Thermoplast Phase
Shear Modulus [MPa]
Tempeature of Use
Temperature of Processability
Dependence of Modulus on Temperature: Target and Reality

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

elongation
A-B-A, (A-B)n und (A-B)xBlock Copoymers
stress [MPa]
Residual elongation
A-B Block Copolymers
strain [%]
Dependence of Residual Elongation on Original Elongation for Different Engineering Polymers
Residual ) [%]
300
residual = original
200
residual elongation (
TPE-O (EPDM / PP: 60/40)
100
ASTM D 1566 - 98 Definition of Rubber
TPE-V (EPDM / PP: 78/22)
0 0 100 original elongation ( 200
300 [%]
SBS with 27 wt.% styrene NR/BR-tyre tread (with filler) vulcanized gum stock (unfilled NR)
original )
Compression - Set
ho
h1
h2
CS = ho- h1 h2 h1 ho- h2
ho- h2 ho- h1
x 100
[%]
ho
In compression set (CS) measurements ho , h1, compression, exposition time, and 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 P rope rtie s Cla ssica l E la stome rs S BS S IS T P E -U S E BS E ste r E the r T P E -A T P E -E T PO me ch. T PV T PV E P D M/ P P E P D M/ P P E P D M/ P P ble nd (pa rtia lly (highly x-linke d) x-linke d) 78 25 79 40 36 63 51 32 15,4 880 54 47 660 12 650 75 60 60 62 21 5 90 53 88 44 5,5 350 60 8,5 490 38 72 75
S hore A S hore D T e nsile S tre ngth [MP a ]
10 to 80 10 to 35
71
52
75
92 44
93 42 40 380
32 880
20 1200
34 500
45 450
E longa tion a t bre a k [% ] 300 to 800 CS (22h/ 70 C) CS (24h/ 70 C) CS (22h/ 100 C) CS (70h/ 150 C) 5 to 30 5 to 40 5 to 40 30 (H N BR , FKM)
715 485 380
Technologische Eigenschaften von TPEs und von Hauptvalenzelastomeren

klassische Elastomere PEBA TPO 100 TPU COPE SBC 0
200 Gebrauchstemperatur [ C]
-100 0 50 Shore A Hrte 80 30 100 40 50 60 70 Shore D Hrte 80
PP-Performance and Price of EPDM/PP-Blends

180
TPE-V
(EPDM / PP-blend, highly crosslinked)
160
Performance [arbitrary units]
140
Melting temperature [C]
120
TPE/SEBSBlends
100
TPE-V
3
80
(EPDM/PP partially cross-linked)
60
TPE-O
(mechanical blends)
40
PP-Properties: PP-Properties: Low Price
20
Low Price High Softening Temperaure High Softening Temperaure Good Ageing Resistance Good Ageing Resistance
(Residual Catalyst Content) (Residual Catalyst Content)
TPE-O
(ReactorBlends)
0 20 40 60 80 100
0 0 0,5 1 1,5 2
Isotacticity [%]
Source: T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 New Polymers from New Catalysts
Price [$/kg]
Source: Robert Eller Associates, Inc. 1996
TPE-O and TPE-V: Basic Properties

Properties TPE-O
(Mechanical PP/EPDM Blend) 78 12 650 75
TPE-V
(PP/EPDM-Blend with partially crosslinked EPDM-phase) 72 5,5 350 60
TPE-V
(PP/EPDM-Blend with highly crosslinked EPDM-Phase) 75 20 490 38
Shore A-Hardness Tensile Strength [MPa] Elongation at break [%] Compression Set (22 h /70 C) [%] Volume Swell in ASTMOil Nr. 3 [Vol%]
soluble
90
50
Uncrosslinked rubber phase
Crosslinked rubber phase
n ctio e r i w D Flo of
n ctio e r i w D Flo of
TPE-O and TPE-V: Mechanical Properties

Properties
1
no. of recycles
2 3 5
M100 [psi] Tensile Strength [psi] Elongation at break [%]
650 1530 495
630 1520 500
620 1500 505
600 1590 535
20 Shore D Hardness: 50 15 Shore A Hardness: 87 10
35 30 25 20 15 10 5 0
0
Particle diameter [ m] 5,4 17 72 39
1,0-1,5
Stress [MPa]
Shore A Hardness: 64
0 400 200 Elongation at break [%] 600
100
200
300
400
500
Elongation [%]
TPE-O: PP/EPM-Reactor-Blends
Gas Phase Technology PE*

UCC BASF BP Hoechst Exxon Amoco Montell
PP**
Montell Fina Phillips Solvay UCC BASF Amoco/Chisso Sumitomo
ventilator
Filter
Filter
ventilator
Cooler
* Ind Eng. Res. 33 (1994) 449-479 ** Chem. Systems (April 1992) "Polypropylene"
Sources:
Supported catalyst
Product outlet Cooler

Removal of residual monomer
Propylene Ethylene
purification purification
Temperature: Pressure: Residence time per reactor:
< 90 C (40C-60C) 9-15 bar 0,5 - 1 h
packaging
Source: T. W. Klimek (Quantum Chemical Corp.) ANTEC `91, 1382-1384
Properties of PP/EPM- Reactor-Blends

1000 900 800 E-Modulus [MPa] 700 600 500 400 300 20 30 40 50 60
Catalyst Fragmentation during Polymerization
Catalyst System A
Catalyst System B
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) 2) 3) 4) 5) Reactive Processing stands for a chemical reaction in the course of which polymers are modified without the use of solvents. Dynamic Blending stands for the solvent free blending process during which a chemical reaction occurs. Dynamic Vulcanization is used for vulcanization reactions (without solvent) with simultaneous shearing. Every vulcanization method can be performed dynamically 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
PP
HOCH 2
CH2 OH
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
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
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 PP Phase
CH2
OH CH2
EPDMEPDM 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 Dimethylolphenol resin SnCl2 . 2 H2O 185-190 C 5 min. 2 min. 0 0 0 50 50 0 0 0 7,2 0 149 36 0 50 2 0,4 0 50 0 0 0 10,1 0 170 66 50 2 0,4 0 50 0 1,67 0 10,1 0 157 170 50 2 0,4 0 45 5 5 0,5 15,3 10,2 107 390 54
185-190 C Polypropylene 5 min. NBR + Aminino terminated NBR Dimethylolphenol resin + 5 min. SnCl2 . 2 H2O Tensile Strength M100 E-Modulus Elongation at break Permanent elongation [MPa] [MPa] [MPa] [%] [%]
Compatibilising Effect of Dimethylolphenol Resins in Dynamic Vulcanization of PP/NBR-Blends

185-190C Polypropylene 5 min Dimethylolphenol resin 2 min SnCl2 . 2 H2O 5 min Polypropylene 5 min NBR + Aminino terminated NBR Dimethylolphenol resin + SnCl2 . 2 H2O 5 min Tensile Strength M100 E-Modulus Elongation at break Permanent elongation [MPa] [MPa] [MPa] [%] [%] 25 1 0,2 67,5 7,5 9,38 1,13 1,13 17,0 15,8 33 330 20 37,5 1,5 0,3 56,25 6,25 7,81 0,78 0,94 19,6 15,7 92 400 33 50 2 0,4 45 5 6,25 0,5 0,75 23,0 15,2 221 500 50 62,5 2,5 0,5 33,75 3,75 4,69 0,28 0,56 22,7 16,2 320 490 63 75 3 0,6 22,5 2,5 3,13 0,13 0,38 21,5 17,1 456 480 70
Reactive Blending von EPDM/SAN: Results SAN EPDM

Reactive Processing 2 wt.% PF-Harz/0,2 wt.% Catalyst/130C (without fillers/without oils) EPDM-grade: EP T 2370 (Lanxess)
elongation at break [%]

1000
100
10
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, 209-218Blend Preparation by Reactive Processing
Advanced technologies for the production of PPbased TPEs

608
R R2
Zr
R1
ataktisches Polymer
622
Preparation of PP-Blockcopolymers by the use of the Waymouth-Catalyst The length of building blocks is determined by the ratio of propagation rates versus Rotation rate
Source:
R. Waymouth, J. Coates, A-L. Mogstad, K. Stein, D. Fischer, S. Borkowsky Stepol `94; Milano June 6-10, 1994 "Stereospecific Polymerization and Copolymerization of Functionalized Olefins"
595
R R2
Zr
R1 R
Isotaktisches Polymer
BP/Amoco started to manufacture PPPP-based multimulti-block copolymers in the pilotpilot-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; 9494-99 HeatHeat-resistant, resistant, flexible olefins meet tough medical demands demands-SingleSingle-Site metallocene catalysts yield autoclavable, autoclavable, highhigh-clarity elastomers with cost/performance benefits of flexible PVC.
Advanced technologies for the production of PPbased TPEs

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

Preparation of PPPP-based multiblock copolymers by the use of Donor/Acceptor Metallocenes (Ostoja Starzewski) Starzewski)
PP-Based TPE
10
4
Komplex modulus (G*) [MPa]
G'
10
3
Elastomeric PP
Schubmodul (MPa)
10
G''
10
1
10
-120 10
0
-80
-40
40
tan
10
-1
10
-2
-160
-120
-80
-40
40
Temperatur[ (C) Temperature C]
Sample from Prof. Aladyshev
PP-Based TPE
6 Elast.PP
2 2] ] Spannung [N/mm stress [N/mm
Probenform: S1-Stab Anlieferzustand: Platte Medatum: 05.06.02 Dateiname: S14308sd (Graph 1)
0 0 200 400 600 800

Abb.
Dehnung [%] strain ( ) [%]

Sample from Prof. Aladyshev
PP-Based TPE
Komplex modulus (G*) [MPa] komplexer Schubmodul [MPa]
10
4
G' G'
G" HAIFA 1 G" HAIFA 2
10
10
10
10
10
-1
10
-120
-80
-40
40
80
10
-1
tan()
10
-2
10
-3
-160
-120
-80
-40
40
80
120
Sample from Prof. Eisen/Haifa
Temperature [ C]
Temperatur [C]
PP-Based TPE
6
HAIFA-1 HAIFA-2
2] ] Spannung [N/mm [N/mm stress
0 0 100 200 300 400 500 600 700 800 900
Dehnung [%] [%] strain

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.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Rubber
Polybutadiene Polychloroprene Chlorinated Polyethylene Chlorosulfonated Polyethylene Ethene/Propene/Diene-Terpolymers Ethene/Propene-Copolymers Epoxydized Natural rubber Fluororubber Acrylic Rubber Synthetic Polyisoprene Isobutene/Isoprene-Copolymers Styrene/Butadiene-Copolymers Natural Rubber Silicon Rubber with Viny Groups Butadiene/Acrylonitrile-Copolymers Brominated Isobuylen/Isoprene-Copolymers Vinylmethylsilicon Rubber, which also contains fluorine Polyphosphazene modified with perfluorinated alcohols Standardized NR from Vietnam Smoked Sheets based on NR
Abbreviation
Family Name Given Name

2
Please Assign the following Rubbers to the Correct Position in the Matrix:
ACM, BIIR, BR, CM, CSM, EVM, FKM, HNBR, IIR, SBR
Chemical Features
Radical Polymerization Ziegler/NattaPolymerization anionic Polymerization Cationic Polymerization Polyaddition und Polycondensation Polymermodification Family Name Given Name
3
Process Features
Emulsion Solution Dispersion (slurry) Mass or Bulk GasPhase
Which of the Curves Matches the Performance of the Materials Mentioned Below ?
300
Residual Elongation [%]
200
2 3 4 5 6
0 100 200 300
100
elongation [%]
Nr.: Questions
1 2 3 4 5 6 7 8 9 10 Thermoplastic Polymer ? Unvulcanized HNBR at 20C ? Unvulcanized HNBR at 120C? Unvulcanized BR with Mn = 10 kg/mol at 50C ? Unvulcanized BR with Mn = 500 kg/mol at 20C? SBS at 20C? SBS at 120C TPU at 20C NR (unfilled and vulcanized) at 60C NR (filled and vulcanized) at 60C
Answers
Family Name
4
Given Name
Natural Rubber Please Mark RIGHT or WRONG
Nr.: Frage
1 2 3 4 5 6 7 8 9 10 Unvulcanized NR does not crystallize Today, Malaysia is NR-Producer No. 1 For NR plantations China is ideal. For NR plantations Brasil is ideal. A smallholder earns ~ 10000 /a SMR 20 is a NR-grade with high purity SMR CV vulcanizes faster than SMR 10 NR has to be masticated before use IR has to be masticated before use For the mastication of NR, mastication aids have to be used
Right Wrong

5
Natural Rubber Please Mark RIGHT or WRONG

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

6
Synthetic Polyisoprene Please Mark RIGHT or WRONG

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

7
Emulsion Rubbers Please Mark RIGHT or WRONG

Nr.: Question
1 2 3 4 5 6 7 8 9 10 The term "emulsion" is used for a dispersion of polymer particles in water The term "latex" is used for a dispersion of rubber particles in water Polymer dispersions are obtained by slurry (precipitation) polymerization Latices are obtained by emulsion poymerization Latices with a solids content > 50 wt. % can not be made The addition of emulsifier increases the stability of latices The addition of emulsifier increases the stability of emulsions At freezing temperatures latex stability is higher than at 23C At elevated temperatures (>100C) latex stability is higher than at 23C The addition of electrolytes increases latex stability
Right Wrong

8
Pollution of Water and Air:

Please Mark RIGHT or WRONG
Nr.
1 2 3 4 5 6 7 8 9 10
Question
COD = 0 BOD = 0 BOD = COD COD < BOD BOD < COD There are no biodegradable emulsifiers Emulsion rubbers yield considerable amounts of water water Dry finishing of solution rubbers does not cause water pollution Rubber recovery from a solution by steam stripping causes waste water Emulsion rubbers cause air pollution
Right Wrong

9
Crystallization of Rubbers Please Mark RIGHT or WRONG

Nr.: 1 2 3 4 5 6 7 8 9 Frage Additives can increas the rate of crystallization Additives can reduce the rate of crystallization SBR is a crystallizing rubber NBR is a crystallizing rubber NR is a crystallizing rubber Rubber compounds crystallize slower than raw rubbers Vulcanizate crystallize faster then the respective rubber compounds Strain induced crystallization is a wanted property 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 Right Wrong

10
Crystallization of Rubbers Please Mark RIGHT or WRONG

Nr.: Question
1 2 3 4 5 6 7 8 9 10 SBR exhibits spontaneous crystallization NBR is a crystallizing rubber CR is a crystallizing rubber The rate of CR crystallization depends on polymerization temperature NR is a crystallizing rubber Spontaneous crystallization is a wanted property Strain induced crystallization provides high abrasion resistance The rcrystallization rate of CR depends on temperature The crystallization rate of rubbers shows a temperature maximum The crystallization rate of rubbers shows a temperature minimum The rate of crystallite nucleation increases with increasing temperature The rate of crstallite growth decreases with increasing temperature The rate of crystallization of vulcanizates can be monitored by Shore A measurements
Right Wrong
11
NBR
Nr.: Frage
1 2 3 4 5 6 7 8 9 10 NBR which is polymerized under azeotropic conditions has 2 Tgs NBR which is polymerized under azeotropic conditions has 1 Tg A batch polymerization with incremental monomer addition can result in 2 Tgs Low monomer conversions result in NBR with chemical heterogenity High amounts of emulsifier improve chemical homogenity High amounts of modifier improve chemical homogenity Rebound of NBR increases with the content of acrylonitrile The degree of oil swelling increases with acrylonitrile content Shore A hardness of NBR vulcanizates dempend on acrylonitrile content The compression set of NBR vulcaniaztes depend on acrylonitrile content
Right Wrong

12
NBR Please Mark RIGHT or WRONG

Nr.: Frage
1 2
3 4 5 6 7 8 9 10
Right Wrong
The properties of NBR depend on the emulsifier used for polymerization The properties of NBR depend on the electrolytes used for latex coagulation The tendency to gelling increases with increasing polymerization temperature The tendency to gelling decreases with increasing polymerization temperature Molar masses increase with increasing monomer conversion Molar masses do not depend on monomer conversion Molar masses do not depend on modifier level Molar masses decrease with increasing amounts of modifier Molar masses increase with increasing amounts of modifier The properties of NBR depend on the modifier used

13
NBR
In the literature you find the following Tgs for polybutadiene (BR) and polyacrylonitrile (PAN:
BR (Li-catalysis) BR (Ti-catalysis) BR (Nd-catalysis) BR (emulsion polymerization) PAN -90 C -100C -110C -80 C +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 ..

14
NBR:

Nr.: Frage
The compatability of NBR and PVC depends on acrylonitrile content 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 1 2
Right Wrong
Family Name Given Name 15
CR Please Mark RIGHT or WRONG

Nr. Question
The properties of CR do not depend on the temperature of polymerization Vulcanization with ETU* results in crosslinks which contain 1 sulfur atom CR-based adhesive grades contain 2-3-Dichlorobutadiene-1,3 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 1 2 3 4
Right Wrong
16
HNBR: Please Mark RIGHT or WRONG
Nr.: Question
1 2 3 4 5 6 7 8 9 10 Tg of HNBR does depend on the degree of hydrogenation The rebound of HNBR vulcanizates depends on ACN content HNBR and EVM are fully compatible at all copolymer compositions The compatibility of PVC and HNBR depends on the acrylonitrile content of HNBR Compatibility of HNBR and EVM depends on the vinyl acetate content of EVM The crystallinity of HNBR depends on acrylonitrile content Ethene sequences are prone to crystallization Tg of amorphous PE is at -200C Tg of amorphous PE ist at + 0C Unvulcanized HNBR with a low acrylonitrile content performs like a TPE
Right Wrong
Family Name Given Name 17
HNBR: Please Mark RIGHT or WRONG
Nr.: Question
1 2 3 4 5 6 7 8 9 10 Pd-Catalysats can be used for the selective hydrognation of C=C bonds in NBR Raney-Nickel can be used for the selective hydrogenation of C=C bonds in NBR Li[AlH4] can be used for the selctive hydrogenation of C=C bonds in NBR NN=NH can be used for the selective hydrogenation of C=C bonds in NBR Supported catalaysts can be recovered by centrifugation Supported catalaysts are not quantitatively recovered after hydrogenation Homogeneous catalysts can be recovered by filtration Ethene and acrylonitrile can be radically copolymerized Metallocenene-based catalysts readily copolymerize ethene and propene In the hydrogenation on NBR, gel formation is a major problem
Right Wrong
18
IIR, CIIR and BIIR: Please Mark RIGHT or WRONG

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

Nr. Question
The hard phase is not crosslinked The hard phase is crosslinked The soft phase can be polar The soft phase can be crsslinked Tg of soft phase > Tg of hard phase Tg of soft phase < Tg of hard phase Hard- and soft phase have to be mechanically coupled Hard- and soft phase have to be compatible Dynamic vulcanization can be performed in a twin screw extruder 10 Dynamic vulcanization can be performed on a mixing mill 1 2 3 4 5 6 7 8 9
Right Wrong
20
Please assign the Curves

104
Schubmodul [MPa]
103
4 3 2
1 5 6 7 8 9
102 101 100 10-1
-100
Nr.: Frage
1 2 3 4 5 6 7 8 9 10
-50
0 50 100 Temperatur
150
200
Number of curve(s)
Which curve(s) matches the performance of unvulcanized NR ? Which curve(s) matches the performance of unvulcanized SBR ? Which curve(s) matches the performance of vulcanized SBR ? Which curve(s) matches the performance of unvulcanized NBR ? Which curve(s) matches the performance of vulcanized NBR ? Which curve(s) matches the performance of isotactic Polypropylene? Which curve(s) matches the performance of Polycarbonate? Which curve(s) matches the performance of atactic Polytyrene? Which curve(s) matches the performance of ABS with 30 wt.% BR ? Which of the curve(s) matches the performance of SBS ?
21
Which series of modified rubbers and which modification results in the following properties
Rubber A Rubber B Rubber C [phr [phr] [phr] 100 30 100 30 100 30 59 8,8 27,8 560 15 52 17 -5 6 21 1,98
22
Carbon black (N 220) [phr] Shore A Hardness/23C Modulus300 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23C [%] Goodrich HBU [C] CS (24h/70C) [%] Volume swell (70h/70C) ASTM-oil Nr. 1 [%] ASTM-oil Nr. 2 [%] ASTM oil Nr. 3 [%]
Rubber A Rubber B Rubber C modification
59 56 7,8 6,9 27,1 25,9 550 590 78 25 44 60 17 46 66 114 191 73 28 108 8,0
Air permeation/23C [1018 x m4/s.N] 27,0
Which Metal is used for the production of BR in order to obtain the Properties below ?
1
CH2
4
CH2 CH
1 3 3
CH2
2
CH2
CH CH
4
CH
4
CH CH
3
CH2
CH2
Metal
Microstructure [%] 1,4-cis 36-38 1,4-trans 52 Vinyl 10-11 1 Vinyl/ H-NMR*** 10,4 Vinyl/FT-IR*** 11,4 Vinyl/Metathese*** 10,7 Tg -93 97 1 2 1,9 1,0 1,7 -106 97 2 1 93 3 3-4 4,0 5,4 4,6 -103 98 1 <1 <1 0,6 0,7 -109 12,9 68,3 18,8 18,1 17,7 17,8 -80
-107
23
Please Assign Rubber A and Rubber B

Rubber A Rubber B Compound Properties ML 1+4(100 C) [MU] C [min] t2/177 C [min] t90/177 Vulcanizate Properties Shore A Hrte (23 C) Modulus 100 [MPa] Elongation at break [%] Tensile Strength [MPa] Compression Set 70h/23 C 70h/150 C 70h/175 C [%] [%] [%] 100 123 1,5 11,7 78 10,7 240 26 12 20 27 -2,3 -37 +6 75 25 99 1,6 11,0 80 13,1 190 24 12 17 27 -3,8 -26 +5 50 50 58 1,5 10,2 80 12,6 170 22,5 12 17 25,5 -10 -29 +4 25 75 40 1,6 10,2 81 12,0 145 18,8 14 14 20 -7,5 -21 +3 100 32 1,6 9,5 77 8,3 165 18,5 14 9 15 -1,6 -12 +2
Rubber A Rubber B
Heat ageing (14d/150 C) [%] F/F0 x100 [%] D/D0 x100 [%] H/H0 x100 Oil swelling (7d/150 C) ASTM-l Nr. 3 F/F0 x100 [%] [%] D/D0 x100 V/V0 x100 [%]
Family Name
-10 -4 +24 -17 -11 +34 -36 -29 +49 -50 -34 +67 -56 -45 +83
Given Name
24

Rubber A Rubber B Fmin. Fmax. ts t90 t95 Shore A Modulus100 Modulus200 Modulu300 Tensile Strength Abrasion Index Ageing at 70h/121 C [MPa] [MPa] [MPa] [MPa] [min] [min] [min] [Nm] 100,0 0 9,0 86,3 3,0 10,0 21,5 83 5,2 11,0 18,6 25,5 430 493 [%] [%] - 42 34,1 50,0 50,0 10,2 78,7 2,7 7,0 11,0 80 4,5 10,0 15,5 21,0 415 159 - 35 27,1 0 100,0 8,0 60,0 2,8 6,8 8,3 67 1,7 4,8 11,0 18,2 500 73 - 30 14,7
25
Rubber A Rubber B
Elongation at break [%]
Dehnung
CS (70 h/121C)
Please assign 5 polymer blends for which the scheme below applies
Hard phase (coherent phase or matrix) Soft phase (dispersed phase)
Nr.:
1 2 3 4 5
Hard phase
Soft phase

26
Which Series of Rubbers Yields the Properties Given in the Table Below?
Rubber Compound properties Mooney ML 1+4(100 C) C [min] t10/180 C [min] t90/180 FH-FL/180 C [N] Vulcanised properties (ISO-Stab Nr. 2, 2mm) Shore A Hrte (23 C) S 100 MPa] Elongation at break [%] Tenjsile Strength [MPa] Compression Set 70h/100 C 70h/125 C 70h/150 C [%] [%] [%] A 20 1,2 7,2 17 B 24 1,2 6,6 20 C 23 1,2 6,6 19 D 25 1,2 6,2 21 E 20 1,3 6,9 19 F 20 1,3 6,1 17
Rubber Variation
75 5,0 295 11,7 23 25 41 -3 -2 10
74 5,7 275 13,6 20 23 38 -12 -2 9
68 4,4 285 12,6 20 25 41 -10 2 11
71 5,4 280 12,8 22 26 40 -11 -2 12
68 4,2 300 11,5 21 24 46 10 -7 15
72 4,7 300 10,5 27 31 51 -8 -15 14
C) Hot air ageing (14d/150 [%] F/F0 x100 [%] D/D0 x100 H/H0 x100 [%] Storage in SAE Oil90 (3d/150 C) [%] F/F0 x100 D/D0 x100 [%] [%] V/V0 x100
-26 -19 69
-12 -4 47
-8 -4 31
8 2 13
6 8 3
10 -12 -4

Rubber A [phr] Rubber B [phr] Unaged: [MPa] M300 Tensile Strength [MPa] Elongation at break [%] Aged (168h/100 C) M300 [MPa] Tensile Strength [MPa] Elongation at break [%] Air permeation at 50psi/65 C (Q x 10-8] Adhesion at 100 C Self adhesion / tack [kN/m] Adhesion to NR [kN/m] Fatigue to failure after ageing at 168h/120 C [kcycles] 100 80 20 60 40 40 60 Rubber A 4,2 5,7 7,1 8,9 9,3 10,0 12,8 14,7 740 620 560 490 6,8 10,0 550 2,9 7,6 9,8 420 5,4 8,4 9,3 320 9,2 6,7 8,8 370 13,8 Family Name 16,8 14,7 15,2 15,4 7,5 10,0 14,7 20,8 61,8 23,6 0,3 0,0 Given Name Rubber B
28
Please Assign Rubber A

Family Name Rubber A Given Name
100 50 ZnO 83 16 100 50 DCP 88 12 100 50 DCP/BMI 88 14 100 50 ZnO/BMI 89 16
Rubber A [phr] Carb. black (N 774) [phr] Vulcanization Compound Properties ML 1+4 (100 C) [MU] MS5 (125 C) [min] MS5 (135 C) [min]
Physical Properties Shore A Hardnes M100 [MPa] [MPa] M300 Tensile Strength [MPa] Elongation at break [%] CS (70h/150 C) [%]
48 0,9 5,2 12,4 580 58
40 0,5 1,8 8,9 680 53
54 0,12 9,5 10,5 325 28
58 0,19 10,2 13,6 360 13

29

Chemistry and Technology of Rubber

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Chemistry and Technology of Rubber

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Chemistry and Technology of Rubbers

Chemistry and Technology of Rubbers

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

Standard Terminology Relating to Rubber (ASTM D 1566 - 98 )

Comparison of Materials According to ASTM D 1566

300 Residual Elongation [%]

200 Definition of Rubber according to ASTM D 1566 - 98 100

TPO Thermoplastic Elastomers

0 0 100 200 Elongation () [%]

NR/BR based tyre tread NR gum stock 300

My personal Definition of Unvulcanized Rubber, Vulcanized Rubber, Elastomer, and TPE

Tgs of Polymers with a Saturated C-C Main Chain

Polystyrene (ataktisch / amorph)

Tgs of Polymers with an Unsaturated C=C Main Chain

-75 C (100% 1,4-cis)

-45 C (100% 1,4-trans)

-50 C bis -5 C (depending on ACN-content)

0 -75 -50 -25 0 25 50 75 100

Schematic Presentation of the Dependence of the Shear Modulus on Temperature

NR (raw rubber) NR/5 phr DCP Polystyrene

Shear Modulus [MPa]

0,1 -150 -100 -50 0 50 100 150 200

Designation of Rubbers (DIN/ISO 1629)

Abbreviations (DIN / ISO 1629) and Examples

Annual Consumption of NR and Synthetic Rubber

Annual Consumption [1000 metric tons]

Synthetic Rubber (Solid + Latex)

Application Areas of Solid Rubber (rubber latex not included)

Cable and Wire Construction 3% 3%

Others 15% Machine building 5%

Price and Volume of Rubbers (without Latex)

High Performance Rubbers

General Purpose Rubbers: 82%

NBR (0.32 Mio t) IIR/X-IIR

Special (0.5 Mio t)Rubbers

High Performance Rubbers 1%

Special Rubbers 17%

EPM/EPDM (0.9 Mio t) Shares in Turnover

BR (2,8 Mio t) SBR (2,7 Mio t) NR (6.7 Mio t)

General Purpose Rubbers

General Purpose Rubbers: 60%

Source: Rubber World, 21916 (1999) 13-14

High Performance Rubbers 10%

Special Rubbers 30%

Oil and Temperature Resistance of Vulcanizates According to ASTM D 2000

max. service temperature [ C]

175 150 125 100 75 50 0

EVM AEM CO/ECO 18 % ACN NBR CM CSM (H)IIR EPDM

Degree of Swelling in ASTM-Oil Nr. 3 [Vol %]

Evaluation of Vulcanizate Properties

Evaluation of Vulcanizate Performance*

Correlation of Rubber Price and Vulcanizate Performance

Price of Rubber [/kg]

Ranking of Top 10 Tyre Producers

Return Market on Shares Sales in [%] Tyres [%] [%]

Capitalization of Shares Sales

Sums: Total Sales:

Source: FAZ 18.08.2003

Ranking of Top 22 Producers of Technical Rubber Products (without Tyres)

Sales 2001 [Mio US$]

Return on Sales [%]

*) not available Source: European Rubber Journal 184,9 September 2002

Producers of Synthetic Rubber and Capacities

Total: 12,097 KMT