Polymer Concepts (601)

Chain Copolymerization

G. Odian:Principles of Polymerization
Ch. 6, 464-543
Judit E. Puskas
Macromolecular Engineering Research Center
(MERC)

Department of Polymer Science

The University of Akron
 What Are Copolymers ?
• Two or more different monomers
• Simultaneously polymerized to form a polymer chain

Type A Type B
• Statistical process Markov order
0 (Bernoullian) Random
1 Terminal model
2 Penultimate model

A copolymer is NOT an alloy of two homopolymers

 Types of Copolymers

Random Copolymer

Alternating Copolymer

Difference between statistical and random?

Types of Copolymers…contd.

Block Copolymer

Graft Copolymer
 Significance of Copolymers
Annual consumption of polystyrene in North America
¾ 10 billion pounds

Styrene homopolymer
Brittle
Low impact resistance
Low solvent resistance

• Only one-third of styrene is used as homopolymer

• Two-thirds are used in copolymers and blends
 Copolymer Composition
• Copolymerization reactions differ substantially from
homopolymerization

– Some monomers are more reactive; others less

– Copolymer behavior cannot be determined from

homopolymer behavior

– Models proposed for copolymerizations

• Terminal Model
• Penultimate Model
 Copolymerization Models

Terminal Model
Reactivity of the growing chain is influenced by the TERMINAL
unit

Penultimate Model
Reactivity of the growing chain is influenced by both the
PENULTIMATE and the TERMINAL units
 Terminal Model

~~M1* + M1 k11 ~~M1*

k12
~~M1* + M2 ~~M2*

~~M2* + M1 k21 ~~M1*

~~M2* + M2 k22 ~~M2*

~: polymer chain
 Mayo-Lewis Equation
differential (instantaneous)
Consumption rates for monomers M1 and M2

• -d[M1]/ dt = k11 [~~M1*][M1]+ k21[~~M2*][M1]

• -d[M2]/ dt = k12 [~~M1*][M2]+ k22 [~~M2* ][M2]

k11 k21 ~~M2* M12 k21 ~~M2* M1

dM1 k12 M2
dM2
= k22~~M2*M2 + k21 ~~M2* M1

For simplicity, [ ] will not be shown but rates are proportional to concentrations in mol/L
 Mayo-Lewis Equation (2)

• Theory of short sequences$

long chain: rate of interconversion is equivalent

k21 ~~M2* M1 = k12 ~~M1* M2

~~M1* = ( k21 ~~M2* M1 ) / ( k12 M2 )

$Harwood/Kelen: not necessary to assume steady state for M1* and M2*
 Mayo-Lewis Equation (3)
• Reactivity ratios
r1 = k11 / k12 r2 = k22 / k21

dm1 M1 ( r1 M1+ M2)

=
dm2 M2 (M1+ r2 M2 )

dm1/dm2 = molar ratio of monomers in copolymer = Y

M1/ M2= molar ratio of monomers in feed/reactor = X

* Mayo, F. R.; Lewis, F. M. J. A. Chem. Soc., 66, 1594 (1944)

Alfrey, T.; Goldfinger, G. J. Chem. Phys., 12, 115, 205, 332 (1944)
 Mayo-Lewis Equation (4)

• f1, f2 : mole fraction of M1 and M2 in feed

f1 = 1-f2 = M1 / ( M1 + M2 )
• F1, F2 : mole fraction of M1 and M2 in copolymer

F1 = 1-F2 = dM1 / ( dM1 +dM2 )

r1f12 + f1f2
F1 =r f 2+2f f +r f 2
1 1 1 2 2 2
 Statistical Derivation
of Copolymerization Equation

n1, n2 number average sequence lengths

R1, R2 polymerization rates (-d[M]/dt)
p probabilities

p11 = R11/(R11 +R12) = r1/(r1 + ([M2]/[M1])

p11 + p12 = 1; p21 + p22 = 1

(N1)x = (p11)(x-1)p12 ~M1M1M1 (p11)2p12

n1 = Σx(N1)x = p12(1+2p11 + 3p112 +4p113 +….)

n1 = p12(1-p11)2 = 1/p12 = (r1 [M1]+[M2])/[M2]
n1 /n2 = d[M1]/d[M2] = {[M1] (r1 [M1]+[M2])}/ {[M2]([M1]+r2[M2])
Methods to Measure Reactivity Ratios
Low conversion copolymerization experiments:

[M1] ≈ [M1]0 ; [M2] ≈ [M2]0

d[M1]/d[M2] copolymer composition analysis - NMR

composition analysis of unreacted
monomer (GC, IR)

Sequence distribution analysis

Methods to Measure Reactivity Ratios
Data evaluation
• Mayo-Lewis (M-L)
r2 = X/[1/Y{1+r1X}-1]
• Fineman-Ross (F-R)
X (Y − 1) X2 G = r1 F – r2
G= F=
Y Y

• Kelen-Tüdös (K-T)  r2  r2
η = r1 + ξ −
η=
G
ξ=
F α = (Fmin ∗ Fmax )  α α
α+F α+F
Extended K-T (high conversion)
• Nonlinear Methods computer programs

K-T and NL can show penultimate effect.

 Polymerization Mechanism
- Composition

1.00
Mole fraction of styrene in copolymer, F1
cationic
0.75

radical
0.50

anionic
0.25
0.00

0.00 0.25 0.50 0.75 1.00

Mole fraction of styrene in comonomer feed, f1

Styrene / Methylmethacrylate
* Pepper, D. C. Quart. Rev. (London), 8, 88 (1954)
Types of Copolymerization Behavior

I. Ideal Copolymerization: (r1 r2 = 1)

r2 = 1/r1
k22 / k21 = k12 / k11

dM1 r1 M1 or F1 r1 f1
=
dM2 = M2 r1 f1+ f2
Types of Copolymerization Behavior

r1 = 1 and r2 =1 Random Copolymer

r1 > 1 and r2 < 1 Almost Random Copolymer

Random Copolymerization ( r1 r2 = 1 )

1.00
Mole fraction of M1 in copolymer F1
0.75 10
5
2
1
0.50

0.5
0.2
0.25

r1 =0.1
0.00

1.00 0.75 0.50 0.25 0.00

Mole fraction of M1 in comonomer feed f1

Walling, C. Free Radicals in Soln., Wiley, Ch.4 (1957)

Types of Copolymerization Behavior

II. Alternating Copolymerization: (r1= r2 = 0)

d[M1]
= 1 or F1 = 0.5
d[M2]

Styrene-maleic anhydride
Types of Copolymerization Behavior

• III. Block Copolymerization: (r1 > 1, r2 > 1)

Most copolymer systems lie between ideal

and alternating behavior
r1 r2 = 1 r1 = r2 = 0

Tendency for Tendency for

randomization alternation
Styrene-butadiene (anionic)
 Theoretical Approaches to Reactivity
Ratios
•Q – e correlates structure with reactivity
P and Q : Reactivity – radical (active species); monomer;
Resonance factor; steric factor is minor
e : Polarity - same for radical (active species) and monomer

•Patterns of reactivity
rs and ν: Reactivity - radical (active species); monomer;
Resonance and steric factors
π and u: Polarity – radical (active species); monomer

•Linear free energy relationships

Hammet/Taft: ρ* and δ: polar and steric factors in monomer-radical reaction
σ* and Es: polar and steric factors due to monomer substituents

Mayr: N and s: nucleophilicity

E: electrophilicity
 Theoretical Approaches
Q-e Scheme

kij = Pi Qj exp(-ei ej)

kij = propagation rate constant; Pi = radical (active species)
reactivity; Qi = monomer reactivity

LEFR

N
OEt

N= -2.63 -1.15 0.78 1.07 1.12 2.39 3.9 5.02

lg k = s ( N + E )
 Q and e Values

Monomer Q e
Acrylamide 0.23 0.54
Butadiene 0.48 1.23
Isobutylene 1.70 -0.50
Isoprene 1.99 -0.55
Styrene 1.00 -0.80
Vinyl Chloride 0.056 0.16

Arbitrary empirical values

 Example: St - BD
Q-e Scheme

kij = Pi Qj exp(-ei ej)

Q1 = 1.00; Q2 = 0.48
e1 = -0.80; e2 = 1.23

r1 = k11 = Q1 exp [ -e1(e1-e2) ]

= 3.4
k12 Q2

r2 = k22 = Q2 exp [ -e2(e2-e1) ] = 6.5

k21 Q1
 Example: St-BD
Finemann-Ross M1 BD

9.000
y = 1.1225x - 0.1065
8.000 2
7.000 R = 0.9924
6.000
5.000
Series1
4.000
F

3.000 Linear (Series1)

2.000
1.000
0.000
-1.0000.000 5.000 10.000
G
 Example: IB-IP
I + LA I*
I* + IB PIB1* Initiation
I* + IP PIP1*
k11
~ PIB* + IB k22
~ PIB*
~ PIP* + IP ~ PIP*
k12 Propagation
~ PIB* + IP ~ PIP*
k21
~ PIP* + IB ~ PIB*

k 11 k 22 Reactivity
r1 ( IB ) = r2 ( IP ) =
k 12 k 21 Ratios

IIR – butyl rubber

 IB-IP Reactivity Ratios
Initiating System Solvent T(0C) r1 r2 Ref
AlCl3 CH3Cl -103 2.5±0.5 0.4±0.1 1944
EtAlCl2 CH3Cl -100 2.17 0.5 1965
AlCl3 CH3Cl -90 2.3 1975
EtAlCl2+Cl2 CH3Cl -35 2.5 1975
AlCl3 EtCl -95 2.26 0.38 1975
EtAlCl2 EtCl -90 2.27 0.44 1975
EtAlCl2 CH3Cl 88%/hexane 12% -80 2.15 1.03 1971
EtAlCl2 CH3Cl 50%/hexane 50% -80 1.9 1.05 1976
EtAlCl2 CH3Cl 12%/hexane 88% -80 1.17 1.08 1976
EtAlCl2 Hexane -80 0.8 1.28 1976
Et2AlCl+EtAlCl2/H20 Hexane -75 1.1 2003
Et2AlCl+EtAlCl2/ MAO Hexane -75 1.0 2003
Et2AlCl+EtAlCl2 Hexane -75 1.54 2003
AlCl3 C5 50%/ CH2Cl2 50% -70 1.56±0.19 0.95±0.17 1971 1984
AlCl3 CH3Cl -80 1.6 1995
BCl3 CH3Cl -30 2.4±0.35 4.5±3.0 1987
(CH3)3Si[B(C6F5)4] Isobutylene/Isoprene -20 1.8 1.5 1998

Low conversion, low IP

 Example: IB-IP
Q-e Scheme

kij = Pi Qj exp(-ei ej)

Q1 = 1.70; Q2 = 1.99
e1 = -0.50; e2 = -0.55

r1 = k11 = Q1 exp [ -e1(e1-e2) ]

=1
k12 Q2

r2 = k22 = Q2 exp [ -e2(e2-e1) ] =1

k21 Q1
 LEFR
lgk = s(N + E)

Mayr, H. NATO Sci. Ser., E 359, Kluver Academic Publishers, 1999, 99

Schimmel, H.; Ofial, A. R.; Mayr, H. Macromolecules 2002, 35, 54

k11 = 5.51*108 L mol-1 s-1; k12 = 4.17*108 L mol-1 s-1

k22 = 1.66*109 L mol-1 s-1; k21 = 2.26*109 L mol-1 s-1
r1 = 1.32; r2 = 0.74
 Experimental: Reactants

Initiator, I (TMPCl)

Lewis Acid, LA

DtBP
Proton Trap
Monomers

CH CH2
Isobutylene (IB) Isoprene (IP)
 Experimental Setup
Data Processing
Computer

Fiber Launch
Module

• MBraun Labmaster 130 Dry Box

• Nitrogen atmosphere
• [O2] < 5 ppm, [H2O] < 1 ppm Spectrophotometer
MCT Detector
• FTS chiller/liquid nitrogen
• Hexane bath -80 oC Probe Heads
• Fiber optic IR probe (ATR, TR)
• FTIR detector module

TR ATR
 Fiber Optic Probes
TR
• IR beam passes through the sample
• More sensitive (10-3 mol / L)
• Signal saturates at higher concentrations
ATR
• IR beam is reflected by the sample
• Less sensitive
• Can be used at higher concentrations
• Can also be used in heterogeneous systems

Mid-IR Optical fiber : primary IR resonances; limited

distance (1 m)
 Experimental Conditions

Run 1 Run 2 Run 3 Run 4

[IB]0 1.78 0.97 1.45 1.80

[IP]0 0.45 0.96 0.55 0.20

[TMPCl]0 0.036 0.037 0.035 0.035

[TiCl4]0 0.69 0.38 0.35 0.35

[DtBP] 0.007 0.007 0.007 0.007

Probe ATR ATR TR TR

[ ] in M; MeCl / Hx 40/60 v/v, T= -80°C

 Copolymer Analysis

Run Wt% IP Time Mn Mw Mz Conv. Comments

in Feed sec g/mol g/mol g/mol %
1 49.80 - - - 89 Gel, I
2 27.50 396 1026 2696 5670 42
525 1282 3381 6812 50
1230 1747 6934 18134 80
1875 1578 12459 45195 92 PI
3 20.25 5598 19298 45976 96 Bimodal;
Cyclization
4 10.00 90 1115 2326 3876 12
240 1409 3104 5041 28
590 1512 3794 6269 56
860 1679 4344 7156 69
1085 1748 4638 7722 78
1410 2345 5012 8160 86 Broad MWD
 1H NMR of IB-IP Copolymer #3

CH3

CH2

tr 1,4-IP
 Real Time FTIR Monitoring
ATR probe 1655 cm-1: C=C 1600 cm-1: C=C 1.4

stretching stretching
1.2
-- IB
1
-- IP
.8

Absorbance
.6

0 .4
200
s)
(s ec

400
.2
600
e
t im

800
1000 0
1900 1850 1800 1750 1700 1650 1600 1550 1500

Wavenumber (cm-1)
Run 2 : [IB]0=0.97 M, [IP]0=0.96 M, [TMPCl]0 = 0.037 M, [TiCl4]0 = 0.38 M,
[DtBP]= 0.007 M, MeCl / Hx 40/60 v/v, T= -80°C
 Real Time FTIR Monitoring
1.6
1655 cm-1: C=C
-- IB TR probe stretching 1.4
1600 cm-1: C=C

-- IP stretching
1.2
1780 cm-1: C-H
1815 cm-1, out of plane 1
wagging, overtone
C-H vibration, overtone
.8

Absorbance
.6

0
.4
s)

200
(s ec

400
.2
e

600
t im

800
1000 0
1850 1800 1750 1700 1650 1600 1550

Wavenumber (cm-1)
Run 3 : [IB]0=1.45 M, [IP]0=0.55 M, [TMPCl]0 = 0.035 M, [TiCl4]0 = 0.35 M,
[DtBP]= 0.007 M, MeCl / MeCHx 60/40 v/v, T= -80°C
 M-L and F-R Methods

• [M1] ≅ [M1]0 ; [M2] ≅ [M2]0 - low conversion

d[M1]/d[M2] copolymer composition analysis
composition analysis of unreacted
monomer (GC)

[ M1]0 d [ M 1 ]t
X= Y= G = X(Y-1) / Y; F = X2 / Y;
[ M 2 ]0 d [ M 2 ]t

M-L: r2 = X/[1/Y{1+r1X}-1]
F-R: G = r1F - r2

Mayo, F. R.; Lewis, F. M. J. Am. Chem. Soc. 1944, 66, 1594

Finemann, M.; Ross, S.D. J.Polym. Sci. 1950, 5, 259
 K-T Method

η = [ r1 + ( r2 / α ) ] ξ - (r2 / α)

η = G / (α + F)
ξ = F / (α + F) η
α = ( Fmin * Fmax )1/2
ξ

Int.= - (r2 / α)

Kelen, T.; Tüdös, F. J. Macromol. Sci.-Chem, 1975, A9(1), 1

 First Order Rate Plots
3.0
-1 2
IB 1780 cm (R =0.99)
-1 2
2.5 IP 1815 cm (R =0.99)

2.0 TR probe
ln [M]0/[M]t

1.5

1.0

0.5

0.0
0 500 1000 1500 2000
time (secs)
Run 3 : [IB]0=1.45 M, [IP]0=0.55 M, [TMPCl]0 = 0.035 M, [TiCl4]0 = 0.35 M,
[DtBP]= 0.007 M, MeCl / MeCHx 40/60 V/V, T= -80°C
 First Order Rate Plots for IB-IP
Copolymerization
3.5
-1
1600 cm , C=C stretch of IP
-1
3.0 1815 cm , C-H overtone of IP
2
Linear Fit (R = 0.998)
2.5
TR probe
2.0
ln [M]0/[M]t

1.5

1.0

0.5

0.0
0 400 800 1200 1600 2000 2400 2800
time (secs)

Run 3 : [IB]0=1.45 M, [IP]0=0.55 M, [TMPCl]0 = 0.035 M, [TiCl4]0 = 0.35 M,

[DtBP]= 0.007 M, MeCl / MeCHx 40/60 V/V, T= -80°C
 New concept
Simultaneous monitoring of: change in feed concentration
differential monomer conversion

f1
0.8
M ole fr ac tion of IP in fe2)e

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
Conversion
Degree of Conv ers ion, 1-M/M0
 Data Analysis
Treating Instantaneous Data as
Separate Low Conversion Experiments

• Between time t and t + δt

d[M1]t = [M1]t+ δt – [M1]t
d[M2]t = [M2]t+ δt – [M2]t

• d[M1]/d[M2] known for any small time interval δt

• Each time interval treated as a separate low conversion
experiment
 Monomer Consumption

 M 10   A10 
ln  = ln  = k1app ⋅ t
 M1   A1 
M0 : initial concentration
M : concentration at time t,
A0 : initial area under IR band,
A : area under IR band at time t
 M 20   A20 
ln  = ln  = k 2 app ⋅ t
 M2   A2 
 Reactivity Ratios: M-L Method

Run IP mol% in Probe r1 r2 No of data

No feed (Std. dev) (Std. dev) points
1 10.00 TR 1.16 0.86 200
(0.0004) (0.0007)
2 20.25 ATR 1.03 0.97 30
(0.0008) (0.0028)
3 27.50 TR 1.17 0.85 200
(0.0012) (0.0007)
4 49.80 ATR 1.08 0.93 70
(0.0017) (0.0013)
 Reactivity Ratios:K-T Method

Run Probe Used r1 r2 No of Data

Points
1 TR 1.15 0.87 200
2 ATR 1.05 0.92 30
3 TR 1.13 0.89 200
4 ATR 1.23 0.81 70
1-4 ATR / TR 1.17 0.98 500
 Reactivity Ratios: K-T Method

1
y = 1.775x - 0.6003
0.8 2
R = 0.9907 TR Probe
0.6
0.4 r1 = 1.17
ATR Probe
0.2 r2 = 0.98
η
0
-0.2 0 0.2 0.4 0.6 0.8 1

-0.4
-0.6
-0.8
ξ
η Vs ξ plot for runs 1,2,3 and 4 combined. Fmin = 0.69, Fmax = 3.82; α = 1.63;
 Contour* Non-Linear Least Square
(NLLS) Algorithm

Input data d [ M 1]t

F1 =
• [M1], [M2], d [ M 1]t + d [ M 2 ]t

• Initial estimates of r1 and r2 [ M 1]t

f1 =
[ M 1]t + [ M 2 ]t

Iteration procedure
* 2
r1 [ f1 ]t + [ f 1 ]t [ f 2 ]t
[F ] =
1
th
t * 2 * 2
r1 [ f 1 ]t + 2[ f1 ]t [ f 2 ]t + r2 [ f 2 ]t

* Van Herk, A. M. J. Chem. Edu., 1995, 72(138)

 Reactivity Ratios by Contour NLLS

Run Probe Used % IP in r1 r2 Data

Feed Points
1 ATR 20.25 1.23±2.96 1.29±10.3 30

2 ATR 49.80 No Convergence 70

1+2 ATR - 1.13±0.03 0.97±0.03 100

3 TR 27.50 1.16±0.06 0.86±0.36 200

4 TR 10.00 1.18±0.05 0.97±0.06 200

3+4 TR - 1.18±0.02 1.00±0.03 400

1-4 ATR / TR - 1.17±0.01 0.99±0.02 500

Reactivity Ratios by Contour NLLS
1.6 95% JCI
NLLS
1.4 Kelen Tudos

1.2
r2 (Isoprene)

1.0

0.8

0.6 95% Joint Confidence

Interval (JCI)
0.4

0.2

1.05 1.10 1.15 1.20 1.25 1.30

r1 (Isobutylene)

TR probe with 200 data points (Run 3)

Reactivity Ratios by Contour NLLS
1.20
1.18
95 % JCI
1.15
NLLS
1.13
Kelen Tudos
1.10
1.08
r2 (Reactivity of IP)

1.05 Increasing the

1.03
number of data
1.00
points considerably
0.98
0.95
reduces the JCI
0.93 boundaries
0.90
0.88
0.85
0.83
0.80
1.10 1.12 1.14 1.16 1.18 1.20 1.22 1.24 1.26 1.28 1.30
r1 (Reactivity of IB)

500 data points (Runs 1-4)

 Styrene-Butadiene Rubber
SBR
HC CH2
Monomers: H2C CH CH CH2

Styrene Butadiene-1,3
Ethenyl benzene
Vinyl benzene
Repeat units:

H H2 H2 H H H2
C C C C C C
n
n

H2
C CH
n
HC CH2

1,2- (vinyl)
 SBR Copolymers

ƒCopolymer of Styrene (@25%) and 1-3 butadiene (@75%)

ƒHas flexibility
ƒBlended with other polymers to improve properties
ƒUses : Belting, hose, molded and extruded goods
 Styrene-Butadiene Rubber
SBR

High vinyl solution SBR with high cis-BR and silica / silane

an excellent balance between wet skid,

rolling resistance and abrasion resistance.

E-SBR and S – SBR with VBR

increased vinyl level. Different microstructures.

 Styrene-Butadiene Rubber
SBR
Properties

good resistance to aging and reversion

high abrasion resistance
good low temperature flexibility and high resilience.

Applications

Used extensively in the production of rubber goods. The main field

of application is tire manufacture, where the product is usually
blended with NR or emulsion SBR.
 Styrene-Butadiene-Isoprene Rubber
SBIR (Aqua tire)
Monomers: HC CH2 H2C CH CH CH2

CH3

H
H2C C C CH2
n
Isoprene; 2-methyl-butadiene-1,2

Repeat units: CH3

H H2 H2 H H H2 H
C C C C C C H2C C C CH2
n n n
CH3
H2 H
C CH H2C C H2C C
n n n
HC CH2 CH CH2 C CH2

CH3
1,2- (vinyl) 1,2- (vinyl) 3,4
 Butadiene-Acrylonitrile Rubber
NBR

Monomers: H2C CH CH CH2 H2C CH C N

acrylonitrile
vinyl cyanide
nitriloethene

Repeat units:

H2 H H H2 H
C C C C H2C C
n n
C N
 Butadiene-Acrylonitrile Rubber
NBR
Properties
Very good resistance to liquid fuels, mineral oils and greases
good resistance to ageing
high resistance to wear and abrasion
low permeability to gases and good physiological properties.

Applications
Seals, sleeves, membranes, bellows, valves, buffers, vibration
dampers, footwear soles, roll covers, printing blocks, printing
blankets, conveyor belting, rubberised fabrics (e.g. for flexible
silos), hoses, cable sheathing, brake and clutch linings, open
and closed cell rubber, punching blocks and gloves.
 SAN Copolymers

ƒRadical polymerization of St with Acrylonitrile (10 to 40%)

ƒImproves solvent resistance, tensile strength
ƒBlended with other polymers to improve properties
ƒUses : House ware (refrigerator shelves and drawers),
packaging (bottle closures, sprayers), electronics (battery cases
, cassette parts ) etc.
 ABS Copolymers

ƒCopolymerization of St and Acrylonitrile in the presence of a

rubber (SBR / NBR / polybutadiene)
ƒCombines properties of SAN with improved impact resistance
ƒUses : Refrigerator doors, sewing machine, business
machines housings (telephone, calculator), recreation (golf
clubs, boat hulls) etc.
 Hydrogenated NBR
HNBR

- H2C - CH - - CH2 - CH2 - CH2 - CH2 -

n m

CH2 – NH2

Saturated structure
 Hydrogenated NBR
HNBR
Properties
Outstanding mechanical properties
very good resistance to abrasion
very good compression set
excellent resistance toweathering, ozone and hot air
very good resistance to technical oils, even in the presence of
hydrogen sulphide and amines.

Applications
Heavily stressed rubber goods used in oil exploration and
production (seal components, hoses, stators, and rubber goods
for drill pipes) High quality gaskets, membranes, V-belts and
timing belts, Cable sheathing, hydraulic hose, special couplings.
 Ethylene-Propylene (Diene)
Rubber EPR/EPDM

Monomers: H2C CH2 H 2C CH CH 3

Ethylene Propylene
Ethene Propene

Repeat unit: H
H2C CH2 H2C C
n n
CH3
Diene: norbornene
 Ethylene-Propylene (Diene)
Rubber EPR/EPDM
Properties
excellent resistance to weathering and ozone
good to very good aging resistance and low temperature
flexibility
low electrical conductivity
satisfactory resistance to polar chemicals.

Applications
Technical moldings of all kinds; extrusion profiles used in the
construction and automotive industries; hoses, sheet, open and
closed cell foamed rubber; roll covers; low voltage cable
insulation.
 Chloroprene Rubber
CR

Monomer: chloroprene Cl
2-chloro-butadiene-1,3
CH2 = C - CH = CH2

Repeat units: Cl

- CH2 - C = CH - CH2 -
n

1,4-
 Chloroprene Rubber
CR
Properties
highly resistant to weathering and ozone
good resistance to ageing, hot air and chemicals
moderately good resistance to oils and petrol
good mechanical and physiological properties
abrasion resistance

Applications
mouldings and extrudates of all types, reinforced hose,
roll covers, belting, cable sheathing and insulation for low
voltage cables, rubber foam (open and closed cell), corrosion-
resistant linings, sheeting, fabric proofings and footwear.
 Effect of Microstructure on Tg
Elastomer Double bonds Tg
cis-1,4 trans-1,4 1,2 C
IR Hevea brasiliensis 100 - - -73
Guttapercha - 100 - -53
BR Ziegler-Natta 96 3 1 -105
Anionic 38 53 9 -95
Radical (E) 10 69 21 -80
NBR 25% ACN 12.5 77.5 10 -26
50% ACN 12.5 77.5 10 -12
CR 100 - - -20
- 100 - -45
 Ethylene-Vinyl Acetate Rubber
EVA
Monomers: ethylene H2C CH2
ethene
O
vinyl acetate
H 2C CH O C
acetoxyethene
CH3

H2C CH H2C CH2

n
n
O
Repeat unit:
C O

CH3
 Ethylene-Vinyl Acetate Rubber
EVA
Properties
very good resistance to weathering, ozone and light
good hot air resistance
very low compression set at high temperatures
good physiological properties.

Applications
Technical moldings and extrudates, lamp seals, cable sheathing
and insulation, cellular rubber goods, footwear soles,
waterproofing sheets, strip, impact modification of PVC and
modification of bituminous compositions.
 Butyl-Halobutyl Rubbers
IIR, BIIR, CIIR
CH3 CH3
Monomers:
H2C C CH3 H2C C CH CH2

isoprene
isobutylene 2-methyl-butadiene-1,3
2-methylpropene

CH3 CH3
Repeat units:
H
H2C C H 2C C C CH2
n n
CH3
Butyl-Halobutyl Rubbers
IIR, BIIR, CIIR

CH3 CH3

H2C C CH2 C C CH2

n m
CH3 X

X = Br, Cl - allylic substitution

m - 1 – 3 mol %
 Halobutyl Rubbers
Exxpro
CH3

H H2
H2C C C C
n m
n
CH3

CH2 - Br

m - 1 – 3 mol %. Needs special curing system

 Butyl-Halobutyl Rubbers
IIR, BIIR, CIIR
Properties
excellent resistance to weathering, ozone and hot air
very good resistance to acidic and basic chemicals
very low permeability to gases and liquids
high damping, good rheological properties.

Applications
tire inner liners,hoses, seals and membranes, curing bags for tires.
pharmaceutical stoppers and rubber articles needing good resistance
to chemicals, weathering and ozone, e.g. tank linings, conveyor
belts and protective clothing.
 Silicone Rubbers
CH3

Monomers: dichloro-dimethylsilane Cl Si Cl + H2 O

CH3

CH3
Repeat unit:
Si O
n
CH3

Crosslinked with peroxides; filled with SiO2

 Silicone Rubbers
CH 3 CH 3 CH 3

( Si O
)(
x
Si O
)(
y
Si O ) z
CH 3 CH

CH 2

Mainly Small amount Small amount

+ SiO 2 (30 microns particles) Filler

Cl Cl

+ Cl C O O C Cl Catalyst

O O

Heat Cl

Products Crosslinked + Cl + CO 2
Silastic