General Introduction to

Synthetic Rubbers

Prof. Kinsuk Naskar

Rubber Technology Centre
IIT Kharagpur
Content
History

Types of Polymers – Comparison of Properties

Rubbers – Ways to Influence the Properties

Production of Synthetic Rubber

History

• End of 19th century:

growing demand for Natural Rubber due to rapidly
increasing transportation

• 1903: Prof. Harries discovered structure of NR based

on isoprene units

• 1906: Initiative from Bayer to find a technical synthesis

for synthetic rubber
History

• 1909 Fritz Hofmann

(Bayer) polymerization
of isoprene

• First patent:
Process of producing
artificial rubber
History

1920’s – 1930’s

Discovery of

• BUNA : BUtadiene + NAtrium (sodium)

• Styrene – butadiene copolymer, SBR

• Acrylonitrile – butadiene copolymer, NBR

• Polychloroprene , CR
History
• Development of Synthetic rubber based on
arduous and systematic research – not on
coincident

• Basic science of macromolecules (Hermann

Staudinger!) not well established, yet

• Industry had big labs for basic research &

they committed resources

• Basic experiments with reaction times of

several weeks (!)
- not promising for industrial application
History

World War II

• GRS program in USA and Canada

• Government rubber styrene

• Rubber was regarded as strategic war

commodity

• Large production on SBR in several plants

History of industrial rubber research
1950’s – 1970’s

• Development of new rubber families

• Ziegler-Natta catalyst opens way for EPDM

• Development of ethylene-vinylacetat rubber EVM,

Fluoro rubber, Acrylate rubber,…

• Polymers : new products from new monomers

• Later: Modification Halo-Butyl, Hydrogenation of NBR

Content
History

Types of Polymers – Comparison of Properties

- What is a Polymer?
- Characteristics of Polymers
- Comparison of different polymers:
Rubber, Thermoplastic, Thermoset and TPE

Rubbers – Ways to Influence the Properties

Production of Synthetic Rubber

From Monomer to Polymer
Monomer Polymer

... ...

Types of reaction:

Polymerisation: all main rubber

- double bonds

Polyaddition: e.g. Polyurethane

- functional groups with hetero atoms, e.g. N, O

Polycondensation: e.g. Polyester, Polyamide

- small molecules as side reaction, e.g. H²0
Polymers

Molecular weight (correlates with number of monomers)

Molecular weight distribution (MWD),

e.g.: Broad or narrow distribution:

narrow

broad
Polymer structures

Linear:

Branched:

Statistical copolymers: AB BABAABAAABAB B B

Alternating copolymers: A B A B A B A B A B A B A B A B

Block copolymers: AAAB B BAAAAB B B B

Polymers

Hydrocarbons:

- Only C Carbon and H Hydrogen (non-polar)

- Very limited interactions between polymer chains

Polymers containing heteroatoms:

- Containing C Carbon and H Hydrogen and

atoms such as O Oxygen, N Nitrogen (polar)

- Effect on oil resistance

- Interaction between chains, e.g. via O---H or N---H

 Polymers
Polymer Polymer Chain Service Temperature
Thermoplastics:linear, below melting point
non-crosslinked below Tg
Thermosets: highly crosslinked -
Elastomers: crosslinked after above Tg
vulcanisation
TPE: physical crosslinks below melting point of hard phase
above Tg of soft phase

Melting Point: crystalline areas melt

Glass transition temperature, amorphous areas freeze
Tg:
Temperature dependence of shear moduli
6
10

5
10
Steel
4
10

3
10 Thermoset
2
10

1 Thermoplastic
10

0
10
-80 -40 0 +40 +80 +120 +160 +200 +240

Temperature (°C)
Thermoplastic elastomer
Elastomer
E-Moduli of different materials [GPa]

Iron 211 LDPE 0,2-0,5

Copper 130 i-PP 1,1-1,3

Aluminium 70 Polycarbonate 2,1-2,4

Tungsten 411 Polyester resin 10-35

Glass 80 Rubber:

Quarz 73  filled 0,01-0,05

 unfilled 0,001-0,005
Siliconcarbid 470

Diamond 965
Mechanical properties of different polymers

modulus elongation at
Polymer
[MPa] break [%]

Elastomer 1 1000

Thermoplastic 100 200

Thermosets 1000 1
Cycled stress-strain experiments

NR-BR Elastomer
Stress [MPa]

Thermoplastic Elastomer, EPDM/PP

Thermoplast, Polypropylen

Strain [%]
Content
History
Types of Polymers – Comparison of Properties

Rubbers – Ways to Influence the Properties

- Nomenclature

- Difference between General Purpure Rubber & Specialities

- Temperature and Oil Resistance

- Comparison of the most important Rubbers

Production of Synthetic Rubber

Rubber names

type: Backbone of rubber contains of: Examples:

R double bonds CR, SBR, NR
M saturated hydrocarbon EPDM, EVM
(methylen-type)
Q siloxane-group MQ
O oxygen ECO
U urethane-group AU, EU

Monomers:
B butadiene, S styrene, N acrylonitrile, E ethylene, P propene, F
fluorine
2.1 (Synthetic) (R) rubber overview
Natural rubber (NR)/isoprene rubber (IR)
simplified
structures
Butadiene rubber (BR)

Styrene-butadiene rubber (SBR)

Acrylonitrile-butadiene rubber (NBR)

Hydrogenated NBR (hNBR)

Chloroprene rubber (CR)

Butyl rubber (IIR) R: unsaturation in polymer

main chain
M: no unsaturation in
Chlorinated/brominated IIR (C/BIIR)
polymer main chain

12
2.2 (Synthetic) (M) rubber overview (ctd.)

Ethylene-propylene(-diene)
rubber [EP(D)M]
Ethylene-vinyl acetate rubber (EVM)

Ethylene-acrylate rubber (EAM)

Acrylate rubber (ACM)

Fluoro elastomer (FKM)

Silicone rubber (QM)

13
2.3 Elastomer properties vary between rubber types and
determine the applications
poor fair excellent

non polar polar

oil resistance

ozone and ageing

resistance

thermal stability (°C) 80 150 80 130 100 130 170 110 220 130 125 160 80 250

mechanical properties

low temperature -72 -60 -120 -60 -40 -25 -35 -39 -120 -50 -40 -26 -30 -20
properties (Tg / °C)

elastomer NR EPDM BR IIR SBR CM/ EVM CR QM ECO NBR hNBR AU FKM
CSM /CO
Production and net sales of rubbers
General Purpose Rubbers
NR: natural rubber
SBR: styrene-butadiene
Production Sales rubber
BR: butadiene rubber
IR: isoprene rubber
85% 68%

Special Purpose Rubbers

CR: chloroprene rubber
IIR: butyl rubber
EPDM: ethylene-propylene
rubber
NBR: acrylonitrile-
butadiene rubber
Speciality Rubbers
ACM: acrylate rubber
FKM: fluorocarbon rubber
EVM: ethyene/vinyl
acetate rubber
13% 2% 19% 13%
Q: silicone rubber
HNBR: hydrogenated nitrile
rubber
Relationship: price and performance of rubbers
Performance [arbitrary units]

Speciality
HNBR, FKM, ACM

Special Purpose
CR, EPDM, NBR, EVM

General Purpose
NR, BR, SBR

price [arbitrary units]

Elastomer properties - requirements
Under the bonnet liquids and their operating temperatures

Surrounding Temperature
engine oil engine:

automatic gearbox oil 150°C

gearbox oil

hydraulic oil
engine block:
air conditioning fluids air
130°C
brake fluid

grease

radiator coolant engine surroundings:

110°C
fuel
Classification of elastomers (based on ASTM-D 200 / SAE J 200 )

H 250 FKM
G 225

F 200 MVFQ

E 175 EVM EPDM

heat resistance

D 150 HNBR CM
IIR
CSM
C 125
NBR
B 100 CR SBR
A 75 BR
NR

10 20 30 40 60 80 100 120 140 no demand

type K J H G F E D C B A
oil resistance
Classification of elastomers (based on ASTM-D 200 / SAE J 200 )

H 250 FKM
G 225

F 200 MVFQ
80% VA 40% VA
E 175 EVM EPDM
heat resistance

D 150 HNBR CM
IIR
CSM
C 125
NBR 18% ACN
48% ACN
Hydrocarbons
B 100 CR SBR
A 75 BR
NR

10 20 30 40 60 80 100 120 140 no demand

type K J H G F E D C B A
oil resistance
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  
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  

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     
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  

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Oil and petrol resistance

Similia similibus solventur

(Compounds are soluble in fluids of the same kind)
Rubber with polar groups are resistant towards oil and
petrol (non-polar hydrocarbons) e.g. Acrylonitrile-
Butadiene-Rubber (NBR)

Non-polar rubber are non-resistant towards polar

compounds (brake fluid) e.g. Styrene-Butadiene-Rubber
(SBR), EPDM
Special purpose rubber / Specialities
General purpose rubber:
„Working Horse“, main use in tyres

Special purpose rubber:

good ozone resistance
good oil and petrol resistance
flame resistance

Specialities:
ageing stability (saturated backbone, hetero atoms)
excellent oil and petrol resistance (polar groups)

Just to mention a few:

NR, BR, SBR, IIR, HIIR, CR, EPDM, EVM,
NBR, HNBR, FKM…
Natural Rubber (NR)
( CH2 CH2 )
 cis-1,4-Polyisoprene
C C

CH3 H
Properties:
• Excellent mechanical properties, e.g. tear resistance
• Good dynamic properites (low heat-build-up)
• Low temperature properties
• But: Reversion
Applications:
 Tyres (esp. truck, bus), technical goods (conveyor
belts, engine mounts,…)
Polybutadiene (BR)
( CH2 CH2 )
 High-cis 1,4-Polybutadiene
Nd, Co, Ni, Ti-catalysts C C

 Also on the market: H H

Vinyl-BR, Li-Catalyst
Properties:
• Good mechanical properties
• Good low temperature properites
• Abrasion resistance
• Elasticity
Applications:
 Tyres, golf balls, technical goods,…
Styrene-Butadiene-Rubber (SBR)

styrene 1,2-vinyl 1,4-trans 1,4-cis

Properties:
• Good mechanical properties
• Good processability
• SBR: E (Emulsion) and S (Solution)
• S-SBR important for Silica tyres

Applications:
 Tyres, technical goods
 Butyl-Rubber (IIR) CH3

Copolymer: Isobutylene + 1-5% Isoprene CH2-C

Properties: CH3

• Excellent low gas permeability

• Good resistance towards chemicals and ozone
• Low elasticity
• But:
- Slow vulcanisation
- Minor compatibility with other rubbers Halo Butyl

Applications:
 Tubes, pharma stopper, bubble gum,…
Halo Butyl (BIIR, CIIR)

• Halogenation of „Regular“-Butyl:
- Chloro Butyl
- Bromo Butyl
Properties:
• Faster vulcanisation, due to increased reactivity
• Blends with other rubbers possible
 Better tack
Applications:
 Tyre innerliner
 Application for Rubber: Tyre (typical values for compound in phr)

Tread: SBR, BR, NR

Steel belt compound: NR

Carcass: NR,
up to 20 phr BR (Reversion protection)
Sidewall 50 phr BR
50 phr NR
Innerliner BIIR (CIIR)

Chafer 75 phr BR Apex 25 phr BR, 75 phr NR

25 phr NR

phr: per hundred (parts of) rubber

Polychloroprene (CR)
Cl Cl Cl Cl

Properties: n

• Good mechanical resistance

• High ozone/weather resistance
• Good chemical resistance
• Favourable flame resistance
• Good low-temperature resistance
• Medium oil and fuel resistance
Applications: Surf- and diving suits, wiper blades,
profiles, tubes, conveyor belts,…
 EPDM

CH2=CH2 + CH2=CH-CH3 +

Ethylene Propylene Diene (ENB)

• Diene with two double bonds
- one for polymerisation n
- one for vulcanisation

45-65% Ethylene: amorphous grades

65-80% Ethylene: semi-crystalline
EPDM
Properties:
 Very good resistance to ozone, weathering, heat,
oxidation
 Good chemical resistance towards water, chemicals,
polar solvents
 Good low temperature flexibility (depends on ethylene
content)
 Good electrical insulation

Applications:
 Profiles, Cables, Gaskets, Roofing membranes, …
Ethylene Vinylacetat Rubber (EVM)
CH2=CH2 + CH =CH2 -CH2-CH2 - CH-CH2 -
O O
C=O C=O
CH3 CH3
Properties:
• High heat resistance, good weathering and ozone
resistance
• Low swelling in oil
• No formation of HCl and halogen containing chemicals
in case of fire
Applications:
• Cables, Seals, Profiles
Nitrile Rubber (NBR) *
n
*
C
Copolymer: Acrylonitrile + Butadiene N

Properties:
• Exellent resistance to oils, grease, fuels, lubricants,…
• Good mechanical properties
• Low permanent set
• Good abrasion and wear resistance
Applications:
• Seals, Hoses, Shoe soles, Roll covers, …
Hydrogenated Nitrile Rubber (HNBR)

Made from NBR by Hydrogenation reaction

Properties:
• Exellent resistance to lubricant oils with chemically
agressive additives
• Very good hot air resistance, good mechanical
properties at elevated temperatures
• High strength and abrasion resistance
• Good low temperature properites
Applications:
• Belts, dynamic applic., seals, hoses, cables,…
Hydrogenated Nitrile Rubber (HNBR)
C
N
N
C

C C

N N

H H H H
H H H H
H H
H H H
H H H H
H H H H
H
H
H C H
C H 2
H H H
H H
H CH H H
H H
N H 3

Pendant nitrile group Residual double bond Pendant ethyl group Polyethylene sequence

Oil resistance Cross linking Low temperature properties Strain crystallization

Heat resistance
Fluoro-rubber (FKM)
CF2=CH2 + CF =CF2 -CF2-CH2 - CF-CF2 - CF2-CF2
+ CF3 CF3
CF2=CF2

Properties:
• Extremly good heat resistance
• Very low oil swelling
• High resistance towards acids
Applications:
• O rings (heat + oil + long life), ventil stem valve,
oil hose innerliner, static applications…
Application for Rubber: Hose

Outer Cover: Inner Tube:

Resistance Depending on
against applications:
weather, Resistance
water, ozone against
hydrocarbons
For special or polar liquids
applications:
resistance
against oil,
chemicals
Abrasion
resistance
Content

History

Types of Polymers – Comparison of Properties

Rubbers – Ways to Influence the Properties

Production of Synthetic Rubber

- Comparison of different polymerisation reactions
- Overview of production processes
Comparison of different polymerisation reactions

Radical
Polymerisation

Anionic
Polymerisation

Monomer
Cationic
Polymerisation

Orgometallic
Polymerisation
Radical polymerisation

starter:
Initiation: I* + M IM*
AIBN, KPS, Peroxide

Propagation: M* + nM Mn+1*=P*

Pi* + Pj* Pi+j Combination

Termination:
Pi* + Pj* Pi + Pj Disproportionation
Ionic polymerisation
cationic:
Initiation _____________________
K(+) + M K - M(+) starter: e.g. AlCl3 BF3,
Propagation________________ C2H5AlCl2
K - M(+) + nM K - M n+1(+)
anionic:
Initiation _____________________
A(-) + M A - M(-) starter: alkoholates,
alkaline earth
Propagation ________________ alkyles, Li-Butyl
A - M(-) + nM A - Mn+1(-)
Ziegler – Natta polymerisation

Organometalic catalyst system:

Reaction products of metal salts, e.g. based on
titanium, vanadium, neodymium, nickel und cobalt, with
organometallic compounds, e.g. aluminiumalkyls and
aluminium halides
Polymerisation of isobutene
radical
polymerisation back reaction

CH3 H anionic methyl groups

polymerisation destabilise
C=C
cationic
CH3 H polymer
polymerisation

organometallic monomer too

polymerisation bulky
Polymerisation of propene
radical
dimer
polymerisation

H H
ionic no propagation
C=C
polymerisation reaction

CH3 H

organometallic polymer
polymerisation (Ziegler-Natta)
Polymerisation of vinyl chloride
radical
polymer
polymerisation

Cl H
ionic side
C=C
polymerisation reactions
H H

monomer
organometallic
catalyst
polymerisation
poison
Overview of different production processes

Natural
Rubber

Emulsion
Process

Processes
Solution
Process

Polymer
Modification
Natural Rubber (NR)

• NR-Latex from Hevea-tree

• Precipitation of Rubber by additon of formic
acid (Ameisensäure)
• Washing of rubber
• Drying of rubber "Sheets" by smoke
• The smoke contains phenolic components,
which acts like antioxidants
Emulsion Process, e.g. NBR polymerisation

short stop

Emulsifier Initiator
Butadiene,
MW
Acrylonitrile stopper
Reg.

water continuous
polymerisation
monomer recovery

latex to latex stripping

steam
coagulation
Emulsion Process, e.g. NBR coagulation and finishing

coagulant

mixing tank washing washing

store coagulation

packaging drying dewatering

Solution-Process, e.g. Solution SBR
to momomer and
solvent recovery

monomers a

dissolved
b b c c
rubber

product
d e f
solvent
recycling a
short stop

catalyst antioxidant steam

a - purification towers c - stripping vessels e - drying oven

b - polymerisation reactors d - extruder f - packaging

Polymer Modification

• Reaction after polymerisation to improve

properties for special applications:

• Butyl rubber  Halogenation  Halobutyl

• NBR  Hydrogenation  HNBR

H2
* *
n * n
*
C C
N N
Main rubber production processes
Slurry/
Emulsion Solution
Dispersion
radical E-SBR, CR, EVM EVM
polymerisation NBR, ACM,
EVM
Ziegler-Natta BR, EPM, EPDM EPM, EPDM
Polymerisation

anionic BR, S-SBR, IR

polymerisation

cationic IIR
polymerisation

polymer CIIR, BIIR, HNBR

modification
Rubber production process advantages and disadvantages

+ -
viscosity,
microstructure
solid content,
emulsion MW,
, waste water,
emusifier
cooling
solvent,
microstructure waste water,
solution , block viscosity,
structure solids content
Elastomer map of properties
Each polymer is used in specific applications

non polar polar

oil resistance

ozone and ageing

resistance

thermal stability (°C) 80 150 80 130 100 130 170 110 220 130 125 160 80 250

mechanical properties

low temperature -55 -60 -40 -25 -35 -39 -50 -35 -30 -30 -20
-72 -109 -120
properties (Tg / °C)

elastomer NR EPDM BR IIR SBR CM/ EVM CR MVQ ECO NBR HNBR AU FKM
CSM /CO

Source: Company estimates

5 GlobalLyon,
Webinar, Recent Advances
2nd Non-Metallic in Elastomers
Symposium, and Composites,
December 17-18, 2019 June 25, 2021
Influencing the rubber properties

Type of monomer (ethylene/diene; polar/nonpolar; Tg)

Composition (content of co-/termonomer; Tg)

Structure (MW, MWD; microstructure; crystallinity)

Production process (Emulsion, solution,…)

For each application a different rubber

grade is best – choose the right one