ORIGIN OF POLYMERS

4 Billion years
EARTH

C, H, O, N etc. combined
to form PROTEINS

LIFE

NATURAL POLYMERS
WOOD, COTTON, CELLULOSE,
STARCH ETC.
CLOTHING
ANIMAL SKIN
NATURAL FIBRES
SYNTHETIC FIBRES

POLYMER
CLASSIFICATION
a) NATURAL / SYNTHETIC
b)ORGANIC / INORGANIC
c) THERMOPLASTIC /
THERMOSETTING

WHAT ARE POLYMERS?

COMPLEX GIANT MOLECULEDIFFERENT FROM LOW MOL. WT.
COMPOUNDS
Eg.1) Nacl - MOL.WT. 58.5
Eg. 2) BUTADINE- MOL.WT. 54

POLY BUTADIENE (* 4000 units)

- MOL. WT. 2,00, 000

1)BIFUNCTIONALITY
RESULTS IN LINEAR
POLYMERS

2) POLY FUNCTIONALITY
RESULTS IN X-LINKED OR
BRANCHED POLYMERS

POLYMERIZATION
MECHANISMS
a) FREE RADICAL b) IONIC
FREE RADICAL INITIATORS
a) AZO COMPOUNDS
b) PEROXIDES
c) HYDROPEROXIDES
d) PERACIDS

IONIC POLYMERIZATION
a) CATIONIC b) ANIONIC
CATIONIC POLYMERIZATION CATALYST
BF3/HOH

(F3BOH)- H+

ANIONIC POLYMERIZATION CATALYST

Eg. BUTYL LITHIUM
LIVING POLYMERIZATION
APPLICATION- MANUFACTURE OF BLOCK
COPOLYMERS

COORDINATION POLYMERIZATION
Eg. ORGANOMETALIC COMPOUND/DIENES
RCH2Mt+BUTADIENE
CATALYST- ZIEGLER NATTA- TRIALKYL
ALUMINIUM & TiCl3

STEP POLYMERIZATION
Eg.1) POLYHYDRIC ALCOHOL+ADIPIC
ACID- RESULTS IN POLYESTER
2) POLYHYDRIC ALCOHOLS- RESULTS IN
POLY ETHERS
3) DICARBOXYLIC ACID+ DIAMINESRESULTS IN POLYAMIDE

TYPES OF POLYMERS
a) RUBBERS
b) PLASTIC
c) FIBRES

CHRISTOPHER COLUMBUS- 15th

CENTURY OBSERVED IN SOUTH
AMERICA CHILDREN PLAY WITH
BALLS MADE OF NATURAL RUBBER

21 st CENTURY- RUBBER IS A
MULTIBILLION DOLLAR INDUSTRY

SYNTHETIC RUBBERS

General purpose

Resistance to chemicals
Solvents
Fire
Temperature

Special purpose

Oil resistance
Chemical resistance
Extreme temperature service

General purpose
Styrene butadiene rubber (SBR)
Poly butadiene rubber (BR)
Ethylene propylene rubber (EPM)
Ethylene propylene diene rubber (EPDM)
Poly isoprene rubber (IR)
Iso butylene isoprene Rubber (IIR)

SBR
SBR elastomer is principally manufactured by the
emulsion-polymerization process or by the
solution-polymerization process. Although the
emulsion process is dominant worldwide, SBR
producers are moving toward the solution
technology because it yields an elastomer of
superior properties. In the emulsion processes,
a major portion of the SBR elastomer is
manufactured via the cold-emulsion
polymerization method; globally, cold emulsion
accounts for more than 90% of emulsion SBR.

Styrene - Butadiene Rubber (SBR)

SBR is the largest tonnage synthetic rubber being made all over the
world. It accounts for about 60% of the synthetic rubber production
and more than 30% of all the rubber consumed. It is a copolymer of
butadiene and styrene. The most common SBR is having
approximately 25% styrene and 75% butadiene with a random
distribution of monomers. There are about 500 grades of this rubber
including a large proportion of oil-extended forms and
masterbatches of SBR with carbon black. SBR exhibits good abrasion
resistance and hence its major application is in tyre sector,
especially in passenger car tyres. Other important applications
include soles and heels for the footwear, floorings, mats and other
domestic items, conveyor belting, hose, rollers, cycle tyres, buffers,
gaskets and a large number of other industrial components. About
90% of the SBR produced is by emulsion polymerisation and the rest
by solution polymerisation. In addition, about 10% of all the SBR
produced is marketed in latex form and is used for applications such
as carpet backing, paper coating and latex foam. There is also a
small but growing quantity used in adhesives such as butadiene
styrene vinyl pyridine for making tyre

Styrene Butadiene Rubber (SBR)

-CH=CH2

CH2=CHCH=CH2

Styrene (30%)

Butadiene ( 70%)
4 0C

40 C
0

- CH2-CH=CH-CH2CH2
CH
Cold SBR

Hot SBR

Styrene butadiene rubber

Butadiene

CH2=CHCH=CH2

Petroleum cracking
Dehydrogenation of butanes/butenes

Styrene
-CH=CH2

Dehydrogenation of ethyl benzene

Ingredient

Hot polymer

Cold polymer

Butadiene
Styrene
Water
Fatty acid
KCL electrolyte
t-dodecyl mercaptan (modifier)
K2S2O8 (initiator)
P-methane hydroperoxide
FeSO4. H2O (activator) EDTA
Sodium formaldehyde sulphoxylate-

75
25
180
4.5
0.28
0.30
-

Temperature
Conversion
Short stop

42
72
hydroquinone

72
28
180
4.5
0.3
0.20
0.063
0.010
0.05
0.05
4
60
N-N, dimethyl
dithio carbanmate

Different Grades of SBR

Number

Type

SBR 1000
SBR 1100

Hot polymers
Hot balck filled SBR (14% oil)

SBR 1500
SBR 1600
SBR 1700
SBR 1800
SBR 1900

Cold polymer
Cold black filled SBR (14% oil)
Cold oil master batch
Cold black filled SBR (>14% oil)
Miscellaneous dry polymer

SBR 2000
SBR 2100

Lattices hot
lattices cold

Properties of SBR

SBR is inferior to NR

SBR is superior to NR

Processing
Tensile strength
Tear strength
Tack
Heat build-up
Permeability
Ageing
Resistant to heat and wear
Reinforcement by carbon black
Low viscosity
Premastication not required
Less scorch

Compounding and Processing

SBR is slower curing than NR
Requires lower less sulphur & more accelerator
Scorch problems are less with SBR
ZnO
3 4
Diethylene glycol
1.5 2
(Triethanol amine)
Stearic acid
1.5 2
Process oil
5 7
Filler
20 30
Antioxidant
1 - 3
Accelertor (sulphenamide) 1.5 2
Sulphur
1.5 - 2

Applications
Passenger car tyres
Wires
Cables
Shoe soles
Extruded goods
SBR lattices are used in carpet back coatings

Polybutadiene Rubber (BR)

Polybutadiene can be produced by both emulsion and solution
polymerisation. Emulsion polymers are of random nature in
stereospecificity. Solution polymers can be manufactured into
stereospecifically tailor-made forms. It is achieved with the
use of different catalysts such as anionic or ziegleratta type.
BR has excellent resilience, abrasion resistance, and low
temperature flexibility. BR can have higher filler loading and
oil extension without property deterioration. Tear strength
and resistance to cut growth are relatively poor for BR and
hence is used as a blend with other rubbers. About 90% of
BR is used in tyres, blended in various proportions with SBR,
NR etc. Other application of BR is as an additive in rigid
plastics such as polystyrene for impact modification. Other
engineering applications such as V-belts, conveyor belting,
solid rubber tyres, antivibration mounting roller covering and
flexible heavy duty suction and discharge hoses.

Butadiene Rubber
n

CH2=CHCH=CH2
Butadiene

Production
Emulsion BR
Solution BR

-CH2-CH=CH-CH2cis-Poly butadiene

Solution/emulsion polymerisation
Low mol.wt and shows cold flow
High mol.wt and difficult to process

Properties of BR

Very good low temperature properties

Low heat build-up
High resilience
Better flex resistance
Good heat stability
Very high air permeability
Poor tack
Poor road grip
Poor tear and tensile strength

Processing
Highly resistant to break down and poor mill banding
Rough extrusion appearance
Tight nip and low mixing temperature preferred
Used along with NR or SBR

Applications
Truck tyre treads
Modifier to plastics

Ethylene Propylene Rubber (EPM / EPDM)

Raw materials
Ethylene
Propylene
Catalysts

Amount of unsaturation in EPDM is 0.6 to 1,0 %

Properties
Resistance to ozone and weathering
Resistance to heat ageing and compression set
Chemical resistance
Low temperature flexibility
Low polymer specific gravity
Good physical properties in highly filled stocks
Fast mixing, moulding and extrusion characteristics
Excellent electrical properties

Applications
Electrical insulation and jacketing
Automotive seals
Automobile hoses

Polyisoprene Rubber (IR)

This rubber can be considered as a synthetic replica
of natural rubber (NR). Special catalysts that could
produce Cis-1, 4-Polyisoprene, the chemical
analogue of NR was invented by the middle of the
20th century. Synthetic material is purer than NR,
as the latter contains protein, wood resins and
other non-rubber constituents. Applications include
tyres, extruded gaskets, sheeting, footwear, sponge
rubber and springs. Gutta-percha, the trans isomer
of polyisoprene can also be made synthetically. It
finds application as insulating material in deep sea
cables and gall ball covers.

Poly Isoprene Rubber (IR)

Solution polymerisation techniques
Stereo isomeric purity
Molecular weight and molecular weight distribution
Presence of functional groups attached to the polymer chain
Impurities

Processing
Little tendency of storage hardening
Initial banding is rapid
Avoid over mastication
Care for good dispersion

Applications
Areas where NR is used
Production of Chlorinated and isomerised rubbers
Pharmaceutical industry

CH3

CH3

CH2=CCH=CH2

- CH2-C=CH- CH2 -

1soprene(C5H8)

CH3

Cis-1,4-poly 1soprene
CH3

CH3

H
C

H
C

CH2

CH2

CH2

CH2

CH2

CH2

CH3

CH2

CH2

CH3

C
CH2

CH2

C
CH3

C
CH2

CH2

CH3

CH3

H
C

C
CH2

CH2

CH3

CH2

H
C

CH2

CH2

CH2

CH3

Cis-1,4 Polyisoprene (Natural Rubber)

CH3

CH2

H
C

C
CH2

CH2

CH2
C

C
CH3

trans-1,4 Polyisoprene (Guttapurcha)

CH2

CH2

Butyl Rubber (IIR)

Butyl Rubber is a solution copolymer of isobutylene with a small
proportion (from 1 to 4%) of isoprene. Polyisobutylene by itself is fully
saturated, and the isoprene is included to provide sufficient double
bonds to allow vulcanisation with sulphur. Its outstanding property is
the very low permeability to air and other gases. Low resilience, very
good resistance to sunlight, ozone and aging, and relatively good
resistance to high temperature are the other specialities. Butyl tends to
be incompatible with other rubbers, but this difficulty can be overcome
by modifying the polymer with chlorine and bromine to give chlorobutyl
and bromobutyl rubbers.
The main application for all forms of butyl rubber is to make inner tubes
for tyres, and more recently is being used as linings for tubeless
industries. Its high heat resistance has lead to its utilization for
applications such as steam hose and the curing bags used in tyre
vulcanisation. Sunlight and weather resistance of butyl is exploited in
roofing membranes and reservoir sheeting. Its chemical resistance is
made use of in anticorrosion linings.

Iso Butylene Isoprene Rubber (IIR)

Co-polymerisation of isobutylene with isoprene
at very low temperature ( - 65oC)

Properties
Low rates of gas permeability
Thermal stability
Ozone and weathering resistance
Vibration damping and higher coefficients of friction
Chemical and moisture resistance

Butyl rubbers are characterized by

Mooney viscosity (ML=100oC(1+8) -- 41 to 49
Degree of unsaturation---- 0.7 to 2.2 mole %
Type of antioxidant---- non staining antioxidant
Production by Exxon Butyl (USA)
Polysar Butyl (Canada)

Processing
Mastication low level of unsaturation, difficult to degrade,
use of plasticizer is recommended (DCP)
Mixing
- Low mooney grade, cold tight mill, high mooney higher
temperature is preferred
Extrusion --Extruded surfaces has smooth surfaces and finish, filler
is added to reduce the nerve, Extrusion temperature
200-270 oC
Building good green strength, good for building purposes
Vulcanization: Free of scorch, reversion ec, accelerated sulphur
vulcanization, crosslnking with dioxime and related
nitroso compound and polymethylol-phenol resin
Softeners:

Paraffinic oils

Synthetic Rubber Production in India

Sl
No.

Product

SBR

Manufacturer

Capacity

Synthetics &
Chemicals Ltd.
Apar Ltd.

41,000
5,000

BR

IPCL

50,000

NBR

Apar Ltd.

8,000

EPDM

Herdillia Ltd.

10,000

VP
Latex

Apcotex

1,000
(D.WT)
1,000
(D.WT)

ENPRO

USA

EUROPE

FAR EAST

Dexco
polymers

Dow Europe

Asahi Kasei,
Japan

Lion
copolymers

Dynasol,
Elastomers,
spain

Kabushiki,
Japan

Dupont
performance
elastomers

Exxon
chemical,
Europe

JSR
Corporation,
Japan

Exon mobil

Michelin,
France

Kumho,
Korea

Firestone
polymers

Polimeri,
Europa

LG Chem,
Korea

Goodyear
Tyre and
Rubber Co.

Petrochina,
China
Reliance
Industries,
India

Nitrile Rubber (NBR)

Copolymer of butadiene and acrylonitrile by emulsion
process
CH2=CHCH=CH2
Butadiene ( 70%)

CH2=CH
CN
Acrylonitrile

-CH2-CH=CH-CH2

-CH2=CHCN

Acrylonitrile butadiene rubber

Properties
Good resistance to a wide variety of
non-polar Oils, fats and solvents

Acrylonitrile content (20-50%)

Low
Medium
High

---25%
35-50%
---35-50

Hot NBR----- 30 oC (Trans 52 %)

Cold NBR--- 7 oC (higher)