Rubber

Chemistry and Technology of Rubbers
Quingdao
09.05.-15.05.2011
Werner Obrecht
The attached files of my lecture are my personal property.

property. For the exclusive
personal use,
use, an elctronic copy of the files will be made available to the
participants of the lecture.
lecture. It is prohibited to make copies or multiply the files
for commercial use.
use.
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.
High Performance Rubbers

Fluoro Rubber
Silicon Rubber
Hydrogenated Nitrile Rubber
Ethylene/Vinylacetate-Copolymers
6.
Thermoplastic Elastomers
7.
Test Questions
1. Overview on Rubbers, Definitions, Market, Properties,

Production, and Applications
Definition of the Terms Rubber, Elastomer and Thermoplastic

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

(ASTM D 1566 - 98 )
rubber, n-a material that is capable of
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
29C) to twice its length and held for 1
min before release.
30
1 min
25
20
Stress [MPa]
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.
15
rubber
10
5
1 min
0
0
50
Elongation [%]
100
Comparison of Materials According to ASTM D 1566
= residual
Residual Elongation [%]
300
200
TPO
Definition of Rubber
according to
ASTM D 1566 - 98
TPV
100
Thermoplastic
Elastomers
SBS
0
0
100
200
NR/BR based tyre tread

NR gum stock
300
Elongation () [%]
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
unvulcanized (=uncrosslinked) rubber
rubber boot
vulcanized (=crosslinked) rubber
Tgs of Polymers with a Saturated C-C Main Chain
CH3
CH3
O
O
Si
Si
Si
-18C
Polyvinylacetate
+30C
Polystyrene
(ataktisch / amorph)
+100C
Silicon Rubber
-120C
O
O
CH3
Polypropylene
(atactic / amorphous)
CH3
~ -130C
CH3
CH3
CH3
Polyethylene
Si
CH3
Si
Si
Si
Tgs of Polymers with an Unsaturated C=C Main Chain

Polybutadiene
-115C
(100% 1,4-cis)
Polyisoprene
-75C
(100% 1,4-cis)
Polychloroprene
-45C
(100% 1,4-trans)
Nitrile Rubber
-50C bis -5C

(depending on ACN-content)
Cl
Cl
Cl
Cl
CN
CN
Influence of Tg on Rebound of Vulcanized Rubbers

(50 phr carbon black,
black, without plasticizer)
80
Rebound [%]
1,4-cis BR
SBR NBR
NR
60
EPDM
40
IIR
20
0
-75
-50
-25
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
NR (raw rubber)
10000
NR/5 phr DCP

Polystyrene
Shear Modulus [MPa]
1000
100
10
0,1
-150
-100
-50
50
Temperature [C]
100
150
200
Designation of Rubbers (DIN/ISO 1629)

ClassChemical Description
Designation
Examples
Rubbers with fully saturated main chain

(polymethylene type rubbers)
CM, CSM, EAM, ACM,

EPM, EPDM,
Nitrogen containing rubbers
NBR, HNBR
Rubbers with oxygen in the main chain

(Polyether type rubbers)
CO, ECO, GPO
rubbers with a polysiloxane main chain
MQ, MVQ, PMVQ, FMQ
Rubbers with an unsaturated main chain

(double bond containing rubbers)
NR, SBR, BR, NBR,

CR, IIR
Rubbers with sulfur in the main chain

(Polythioether type rubbers)
OT, EOT
Rubbers which contain carbon, nitrogen

and oxygen in the main chain
(polyurethane type rubbers)
AU, EU
Rubbers with phosphorus and oxygen in

the main chain (polyphosphazenes)
FZ
Abbreviations (DIN / ISO 1629) and Examples

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

Annual Consumption [1000 metric tons]
14000
Natural Rubber
12000
Synthetic Rubber (Solid + Latex)
10000
8000
6000
4000
2000
0
1920
1930
1940
1950
1960
1970
1980
1990
2000
2010
2020
Sources:
IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions
Outlook for Elastomers 1996-97 (Wembley 1998)
Rubber World, 21916 (1999) 13-14
European Rubber Journal (Quotation of IISRP Statistics), various editions
LMC International Ltd, Rubber March 2005: Verbrauch 2001-2005
Application Areas of Solid Rubber

(rubber latex not included)
Automotive
15%
Modification
of Plastics
14%
Tyres
45%
Cable and
Wire
Construction
3%
3%
Others
15%
Machine
building
5%
Price and Volume of Rubbers (without Latex)

Volume Shares
FZ
FQ
FKM
HNBR Q
AU/EU EVM
High
Performance
Rubbers
General Purpose Rubbers: 82%
Price
CR (0.3 Mio t)
Special
(0.5 Mio t)Rubbers
NBR (0.32 Mio t)

IIR/X-IIR
Special
Rubbers
17%
High Performance
Rubbers 1%
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: 60%
General
Purpose
Rubbers
High
Performance
Rubbers 10%
Volume
Source: Rubber World, 21916 (1999) 13-14
Special
Rubbers 30%
max. service temperature [C]
Oil and Temperature Resistance of

Vulcanizates According to ASTM D 2000
250
FKM
General
GeneralPurpose
PurposeRubbers
Rubbers
Special
Rubbers
Special Rubbers
High
HighPerformance
PerformanceRubbers
Rubbers
MVQ
225
FMVQ
200
FZ
175
40 % VAc
80 % VAc
EVM
ACM
HNBR
150
CO/ECO 18 %
ACN
NBR
44 %
ACN
125
100
AEM
CM
CSM
(H)IIR
CR
EU
SBR
BR
AU
75
EPDM
NR
50
0
20
40
60
80
100
120
140
Degree of Swelling in ASTM-Oil Nr. 3 [Vol %]
no
requirement
Evaluation of Vulcanizate Properties

1
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
[C]
8
6
10
5
6
5
4
3
3
4
4
5
4
8
4
3
2
8
8
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
Oil Swell
(ASTM 2000-90)
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
Rating
Ozone
Price
Resistance
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
Performance
Index
Rating
[/kg]
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
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
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
FZ
HNBR
MVQ
FKM
ACM
EVM
AU
NBR
AEM
EPDM
ECO
CSM
CM
IIR
CR
Performance Index
35
30
25
NR
BR
SBR
20
FMVQ
15
10
5
0
0,1
10
100
1000
Price of Rubber [/kg]
Ranking of Top 10 Tyre Producers
1
2
3
4
5
6
7
8
9
10
11
Michelin
Bridgestone
Goodyear *
Continental
Sumitomo**
Pirelli
Yokohama
Cooper Tire
Toyo
Kumho
Hankook
Sums:
Total Sales:
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
55.469,2
68.500,0
[%]
95,0
74,0
86,7
49,0
72,7
39,0
71,0
54,0
61,5
60,3
88,9
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
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
Capitalization of Shares
Sales
20
15
10
5
0
Continental
[Mio US $]
Share
of
Tyres
Goodyear
Sales of Tyres
Michelin
Company
Bridgestone
Rank
Source: FAZ 18.08.2003
Ranking of Top 22 Producers of Technical Rubber Products

(without Tyres)
Rank Company
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Company
Site
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
Sales 2001
[Mio US$]
Return on Sales
[%]
2156
2065
2060
1855
1500
1477
1446
1270
1160
1122
1120
987
900
897
812
808
759
750
703
695
670
662
*)
0,8
3,7
5,7
5,7
2
2,9
*)
*)
*)
*)
2,7
*)
1,3
*)
8,6
*)
*)
1,8
*)
1,3
*)
France
Japan
Germany
UK
US
US
Sweden
Germany
US
US
Japan
Japan
Germany
Japan
US
US
Australia
Japan
Japan
US
Japan
Germany
*) not available
Source: European Rubber Journal 184,9 September 2002
Producers of Synthetic Rubber and

Capacities
Lanxess 8.7%
Exxon Mobil 5.7%
Others
30%
Goodyear 5.3%
JSR Corporation 5.2%
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%
Sinopec 5.2%
Sibur 5.1%
Korea Kumho 4.8%
Dow 4.5%
Polimeri 4.2%
Petro-China
3.6%
Source:
R. J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008Globalization of Synthetic Rubber Industry
Chemical and Technological Features of

Rubber Manufacturing Processes
Technological Features
Chemical
Aspects
Emulsion
E-SBR, CR, NBR,
E-BR, ACM, FKM,
EVM
Radical
Polymerization
Solution
Dispersion
EVM
Bulk
Gas-Phase
AEM
EVM
EVM
Ziegler/NattaPolymerization
BR, EPM,
EPDM
Anionic
Polymerization
BR, L-SBR.
IR
Cationic
olymerization
ECO, CO
IIR
Polyaddition and
Polycondensation
AU, EU
EU
AU
Polymer
Modification
CIIR, BIIR,
CM, CSM,
H-NBR, FZ
CM, CSM,
H-NBR*
EPM,
EPDM
G-EPM
G-EPDM
G-BR**
BR*
Q
* Technology not established (only patents for the hydrogenation of NBR-latex)

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

Water
Temperature:
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
Condenser
Settler
AzeotropicDestillation
Waste Water
Flash
Vessel
Condenser
Stripper
Dewatering
screw
Waste Air
Ethene
Propene
Waste
water
Reactor
Hexane
steam
External
cooler
Purification
Oil
PHControl
Purification
Expeller
Antioxydant
Air bed
Dryer
Abwasser
Stripping
aid
Dryer
Baler
Dryer
Modifier
Reactivator
Purification/
Drying
Purification/
Drying
EASC
VOCl3
Hexane
ENB
Wrapper
Evaluation of Rubber Manufacturing Processes

Polymerization Process
Solution
Dispersion
Slurry
Bulk
Gas-Phase
10
10
max. Solids Cont.
Stereoregularitt
10
10
10
Waste Water
10
10
Waste Air
28
27
41
39
45
Aspect
Viscosity
Heat Removal
Sum
Ranking:
Prerequistes:
Emulsion
(Gas-Phase) > Dispersion > Bulk >> Emulsion > Solution

comparable running times
Available Vulcanization Methods for the

Different Types of Rubber
Example
Method of Vulcanization
Sulfur
Peroxide
Resin
Other
X
(X)
X
XX
XX
X
(X)
(X)
(X)
(X)
(X)
XX
XX
(X)
(X)
XX
(X)
(X)
(X)
(X)
XX
R- Rubbers
NR
BR
CR
SBR
NBR
HNBR
IIR
XIIR
XXX
XXX
XX
XXX
XXX
XXX
XX
XX
M-Rubbers
EPDM
EPM
FKM
CM
XX
X
XX
XXX
XX
X
X
X
(X)
XX
X
MVQ
(X)
XX
(X)
XX
Other
Rubbers
Influence of Vulcanization Method and Crosslinking

Density on Tensile Strength (unfilled NR-Vulcanisates)
Tensile Strength [MPa]
30
20
Sx
S1
C C
C C
10
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
C-C
350
C-O
350
C-N
282
C-S-C
272
C-S-S-C
266
-S-S-S-S-
Type of Bond
covalent
TSexpt. = 1/100 - 1/1000 TStheor.
Bond
Energy
[ KJ/Mol]
physical
< 266
Bond
Energy
[KJ/Mol]
260 - 350
10 -
20
Influence of Compound Ingredients on Vulcanizate

Performance
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
Filler
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
-72C
~ 97%
+ 30 C
-25C
~ 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
Naturkautschuk
12
Synthesekautschuk (Fest + Latex)
Mio tons
10
0
1880
1900
1920
1940
1960
1980
2000
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
2020
Source: European Rubber Journal, January/February 2011, 16
NR: Production
Malaysia
Indonesia
Thailand
others
x 1000 metric tons
3500
3000
2500
2000
1500
1000
500
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
Total
Source:
2004
1.934 31,90%
1.530 25,20%
1.070 17,60%
4.534
1997
2.988 34,50%
1.942 22,40%
1.175 13,58%
75% 6.105
70%
India
China
Sri Lanka
Vietnam
2004
570 9,40%
400 6,60%
113 1,90%
741 8,60%
585 6,70%
92 1,10%
110 1,80%
423 4,90%
1.193
20% 1.841
1997
Ivory coast
Philippines
Camerun
Cambodsha
Brasil
Liberia
Burma
Nigeria
21%
Rmpp Lexikon Chemie; Version 1.5; Stuttgart/New York Thieme-Verlag 1998

LMC International Ltd; Rubber April 2005
87 1,40%
60 1,00%
56 0,90%
49
35
25
21
13
0,80%
0,60%
0,40%
0,40%
0,20%
346 5,7%
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
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
BR
9
4
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
NR-Production by smallholders:
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:
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:
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:
Fungal infection:
Spread of fungus:
Euphorbiaceae
Equator + 15
< 300 m
25-30C
> 70%
1800-2000 mm/year
good drainage (not at the bottom of vallleys)
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
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
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 60C/1 week for RSS-production (RSS = Ribbed Smoked Sheet)
Drying in air at 40C/2 months (ADS = Air Dried Sheet)
NR: Range of Grades

Latexconcentration
Acid Coagulation
(factory)
Acid Coagulation
(Plantation/Smallholder
Natural
Coagulation of latex
Sheet-Material
(RSS, ADS)
Cup lump
centrifugation,
creaming,
evaporation of
water
Smallholders
lump
SMR 5
60%
Baled or Crumb
Rubber
Sales latex
(60 wt. % solids)
SMR L
SMR CV 50
SMR CV 60
40%
wet and dry

blending processes
SMR GP
field grades
SMR 10
SMR 20
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
Comminution Process: multi-stage wet blending process with mechanical generation of

crumbs, crumb blending and washing with subsequent crumb drying at 100-120C/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
SMR 5
SMR GP
SMR 10
SMR 20
SMR 50
Strainer Residue [wt.%]

(mesh width: 45 mm)
0,05
0,10
0,10
0,20
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
Impurity Level
Typ
SMR CV
SMR L
SMR 5
SMR 10
SMR 20
Monsanto-Rheometer (160C)
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
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
share
Fraction
Nr.:
bale
1
2
3
4
5
6
Soluble portion
[wt.%]
1,4-trans
content
[%]
Viscosity
(toluene/25C)
[dl/g]
1,2content
[%]
100
24,4
19,7
15,5
8,0
12,9
12,8
6,7
2,2
2,0
2,0
2,0
3,4
4,0
5,0
-
11,5
7,7
3,9
1,9
1,16
0,62
0,3
-
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
100
3
3
1,5
1
1
3
1,6
1
0
[phr]
[phr]
[phr]
[phr]
[phr]
[phr]
[phr]
[phr]
[phr]
[phr]
[phr]
100
3
3
1,5
1
1
3
1,6
1
15
100
3
3
1,5
1
1
3
1,6
1
0
100
3
3
1,5
1
1
3
1,6
1
25
100
50
3
3
1,5
1
1
3
1,6
1
10
OOOO
NNNN
CCCC
OOOO
HHHH
CCCC
HHHH
CCCC
NNNN
NNNN
3333
3333
OOOO
CCCC
NNNN
3333
OOOO
HHHH
CCCC
SSSS
3333
TBBS (Vulkanox NZ)
CCCC
3333
HHHH
HHHH
HHHH
NNNN
SSSS
3333CCCC
NNNN
3333
HHHH
HHHH
CCCC HHHH CCCC
CCCC
HHHH
NNNN
HHHH
NNNN
IPPD (Vulkanox 4010 NA)
100
50
3
3
1,5
1
1
3
1,6
1
0
Desmodur TT (TDI Uretdione)
First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272
NR: Vulcanization with Multifunctional Isocyantes

NR (masticated TSR 5)
Carbon black (Corax N 220)
Desmodur TT
100
0
0
100
0
0
100
0
15
100
0
25
100
50
0
100
50
10
Fmin
Fmax-Fmin
t10
t80
t90
[dNm]
[dNm]
[min]
[min]
[min]
0,30
7,41
4,34
6,21
7,53
0,18
6,30
4,82
6,77
8,24
0,54
24,20
0,74
15,23
17,60
0,96
20,06
0,71
15,56
19,08
1,06
15,94
1,96
4,22
4,99
1,78
36,26
0,34
7,47
9,07
Tensile Strength
Elongation at break
M50
M100
M200
M300
[MPa]
[%]
[MPa]
[MPa]
[MPa]
[MPa]
17,8
605
0,6
0,9
1,4
2,2
15,3
650
0,4
0,6
0,7
1,2
25,7
635
1,5
2,0
2,9
5,0
21,8
565
1,8
2,4
3,7
6,0
27,8
540
1,5
2,7
7,3
13,4
25,2
480
1,9
3,1
8,0
14,4
43
45
40
38
66
-
68
65
66
-
75
-
Shore A Hrte/23C
Shore A Hrte/70C
Rebound/23C
Rebound/70C
[%]
[%]
74
81
69
78
59
-
55
60
DIN-Abrasion
[mm3]
183
327
155
123
102
133
NR contains polymer bound functional groups (-NH2, -COOH, -OH, -CONH2)

which react with isocyanates
Mastication of NR
184 kJ/mol
C*
343 kJ/mol
*C
C*
Degree of Mastication
Pentachlorothiophenol
SH
Cl
*C
2,2'-Dibenzamidodiphenyl-Disulfide
(DBD)
S
NH
HN
Cl
Cl
Cl
O O
Cl
100
Temperature [C]
200
At low temperatures (<120C) mechanical chain

scission prevails
At temperatures >120C thermo-oxidative chain
scission prevails
In the temperature range 100-130C 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 -25C

35
Crystallinity [%]
30
25
20
15
Pale Crepe
pale crepe after acetone extraction
10
5
0
0
10
15
20
25
30
time [h]
The Shore A Hardness of NR increases due to crystallization during storage at low temperatures
NR can only be processed in the uncrystallized state
Decrystallization can be achieved by storage at elevated temperatures (40C-50C)
The decrystallization in the interior of bales needs 2 weeks at 30C
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
40
melting temperature [C]
half time [h]
1000
100
10
30
20
10
0
-10
-20
-30
-40
-50
-30
-10
10
-50
U. Eisele Intorduction to Polymer Physics, Springer-Verlag 1990
-10
10
30
storage temperature [C]
storage temperature [C]
Source:
-30
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
stress [MPa]
25
NR
SBR
20
15
10
5
0
0
200
400
600
800
1000
strain [%]
Dependence of Tack on Testing Temperature

(Unvulcanized NR- and SBR-Compounds)
25
20
NR
Tack-Index
SBR
15
10
0
0
20
40
60
80
temperature [C]
100
120
Chemically Modified NR-Grades
Modification
Application
Hydroxyl amine (CV-Grades)
improved compounding, no mastication

required
Blend with NR-gel (SP-Grades) Improved processability of NR-compounds

Epoxydation (ENR)
Improved oil resistance

Improved wet skid
Improved silica interaction
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
H
H
O
H2 N
- H2 O
H
H
N
Mooney- Increase [MU]
NR: CV-Grades
10
9
8
7
6
5
4
3
2
1
0
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
(100C)
140
130
120
110
100
90
80
before hot air ageing
after hot air ageing
70
60
50
0
0,02
0,04
0,06
0,08
Hexanediamine [mol/kg]
H
H
O
NH2
H2 N
Specification of CV-Grades
H
O
Grade
CV 50
CV 60
CV 70
LV 50
- 2 H2 O
H
H
Ml 1+4 (100C)
Minimum
45
55
65
54
Maximum
55
65
75
55
H
H
H2N
OH
O
- H2O
H
H
C
N
OH
Increase of Mooney Viscosity [%]
NR: CV-Grades
70
60
50
40
30
20
10
0
0
0,05
0,1
0,15
hydroxyl amine [wt. %]
NR CV-Grades (Constant Viscosity) are obtained by the addition

of hydroxylammonium chloride to the latex prior to latex finishing
0,2
ENR: Dependence of Properties on the Degree of Epoxidation

40
20
Epoxidation with
peracids in the
latex stage
Tg [C]
0
-20
-40
O
-60
-80
20
40
60
80
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)
[phr]
[phr]
[phr]
[phr]
100
30
100
30
100
30
Shore A Hrte/23C
M300
Tensile Strength
Elongation at break
Elasticity/23C
Goodrich HBU
CS/24h/70C
[MPa]
[MPa]
[%]
[%]
[C]
[%]
59
7,8
27,1
550
78
44
17
56
6,9
25,9
590
25
60
46
59
8,8
27,8
560
15
52
17
Volume Swell (70h/70C)

ASTM-Oil No. 1
ASTM-Oil No. 2
ASTM Oil No. 3
[%]
[%]
[%]
66
114
191
73
28
108
-5
6
21
27,0
8,0
2,0
Air permeability/23C
[1018 x m4/s.N]
100
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.)
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
-
Sulfur
Sulfur
(Semi EV) (EV)
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
-
Peroxide
Capped
Di-IsoCyanate
100
50,0
3,0
5,0
2,0
2,5
-
100
50,0
3,0
5,0
2,0
6,7
5,0
2,0
2,0
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical
NR: Vulcanization with A Capped Diisocyanate (Novor 924)

O
N N
O
N O
NH
HN
O N
Novor 924: TDI based diisocyanate

Novor 950: MDI based diisocyanate
Thermal Cleavage
Due to health and safety reasons Novor

924 has been replaced by Novor 950
O
N N
N O H
O C N
N C O
Tautomerization
Tautomerization
O N
H O N
H O
O H
O
H
- H2 O
- H2 O
N N
O
NH
HN
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
Shore A Hardness/23C
M100
[MPa]
Tensile Strength
[MPa]
Elongation at break
[%]
Rebound/23C
[%]
Fatigue to Failure
[kZ]
Goodrich HBU
[C]
CS/24h/70C
[%]
TS (7d/100C)
[%]
Sulfur
(konv.)
Sulfur
(Semi EV)
65
2,08
28,8
515
70
223
29
27
73
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
IR
Ti
Li
Nd
93
97
99
no mastication needed
-
2.2. Synthetic Polyisoprene (IR)

Isoprene
Poly-3,4-Isoprene
H 3C
C2
C
C4
Poly-cis-1,4-Isoprene
Type of IR
Catalyst
Trade Name
Cariflex IR-309
Natsyn 200
Vestogrip
IR
3)
Sources:
2)
1)
1)
Poly-trans-1,4-Isoprene
Solvent
Microstructure
cis-1,4 trans-1,4 1,2- 3,4-
Li
unpolar (benzene)
93
Ti
unpolar hydrocarbon
97
Li
Hexane/Additive
Nd
unpolar hydrocarbon
60
99
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
IR: Development of Prices, Producers and Production

Capacities
Price [US $ / kg]
3
2,5
2
1,5
1
0,5
IR
NR (RSS)
0
1980 1985 1990 1995 2000 2005 2010
Company
Plant Location
Capacity [kt]
Goodyear
Beaumont/Texas/USA
90
Kraton Polymers
Rotterdam-Pernis/Nederland
25
Kauchuk Sterlitamak
Nishnekamskneftekhim
Togliattikauchuk
Sterlitamak/Russia
Nishnekamsk /Russia
Togliatti
100
200
130
JSR Corporation
Zeon Corporation
Kashima / Ibaraki Pref.

Mitzushima / Okayama Pref.
36
40
Karbochem
Newcastle / Natal /South Africa
Total Capacity [kt]
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
NR (SMR 5)
High cis-IR/Ti (97%)
Low cis-IR/Li (93%)
Stress [MPa]
7
6
5
4
3
2
1
0
0
100
200
Strain [%]
300
400
500
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
+
+
+
-
+
+
+
-
+
+
+
+
+
Li
IR
Ti
Nd
+
+
+
+
+
Vulcanizate Properties
NR
Modulus
Tensile Strength
Cut growth resistance
Rebound Elastivity
Abrasion resistance
+
+
+
+
+
Poly-3,4-Isoprene: Compound and Vulcanizate Properties

3,4-content (NMR):
ML 1+4 (100C):
Tg
ca. 60 %
65 MU
-8C
Source:
Data sheet of Hls AG
Vestogrip
(3,4-Polyisopren-Kautschuk)
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(100C)
[MU]
t10/150C
[min]
[min]
t90/150C
77
13,8
27,5
Vulcanization (30 min/150C)

Shore A Hrte (22C)
Shore A Hrte (75C)
M 100
[MPa]
M 300
[MPa]
TS [MPa]
b [%]
67
52
2,1
8,4
14,7
510
Cut growth resistance [N/mm]

Residual elongation [%]
25
20
Rebound / 22C
Rebound / 75C
2
44
[%]
[%]
tan /25C
tan /75C
Source: P. Roch (Goodyear) KGK 48,6 (1995) 430-434Compounding for Wet Grip
0,26
0,11
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
Disadvantages:
Waste water
Product impurities (residuals from
emulsifier and coagulants)
no water resistant catalysts
available (Stereospecifity)
Emulsionrubber
Latex
Coagulation
E-SBR
NBR
CR
ACM
FKM
electrolyte
electrolyte
freezing
electrolyte
electrolyte
Application Areas for Rubber Latices:

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

Latex particle
Particle diameter:
concentration:
Monomer containing emulsifier micelle

Diameter:
5-10 nm
concentration:
1021 lw-1
10-500 nm
1017 lw-1
M
M
M
M M
Monomer droplet
Diameter:
concentration:
0,1-10*10 -6 m
1013 lw-1
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
Phase II
Phase III
80
Arbitrary Units
70
Surface tenison
pressure
polymerization rate
60
50
40
30
20
10
0
20
40
60
80
100
Monomer Conversion [%]

Literature:
P. E. Lovell, M. S. El-Aasser, Emulsion Polymerisation, Wiley 1998

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

Phase I:
Phase II:
Phase III:
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
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
Vapour
condensation
Mixer/Settler
Waste water treatment
Mixer/Settler
Brdenkondensation
Stripping
column
Flash
evaporation
Vapour
Short stop
Polymerisa
-tionskessel
Polymerisa
-tionskessel
Abstoppkessel
Polymerisa
-tionskessel
Polymerisa
-tionskessel
Polymerisa
-tionskessel
Wate water
treatment
Latexstorage
Coagulation
tank
Wash water
Flow Diagram of Latex Finishing

(E-SBR, NBR)
Coagulants
Additives (oil, etc)
Puffertank
AO
Latex
Butadiene
Styrene
Aqueous emulsifier solution
Hydroperoxide
Aqueous catalyst solution
Recovered butadiene
Washtank
Mass Balance:
Latex volume :
Rubber
(25%):
Water serum (75%):
Wash water:
Waste water:
Dewatering
screw
400.000 t
100.000 t
300.000 t
100.000 t
400.000 t
dryer
Baler and
packaging
Finishing of CR-Latex
stripped
Latex
dryer
Latex-surge
tank
dewatering rolls
Acidic acid
Freezing
roll
Powdering
Chopper
packaging
Legal Aspects of Water

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

Legislation on the regulation of the water household
of September 23rd, 1986, BGB1. I, S. 1654
Water is a natural ressource. It has to be used in a sustainable
manner for the benefit of the community as well as for the benefit
of individuals. Negative impacts have to be avoided.
Everybody who uses water is obliged under the necessary

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

Germany
Legislation on Charges for the emission of polluted water
of November 6th, 1990, BGB1. I, S. 2432
By law, in 1990 one pollution unit was fixed at 70 DM. According to
this law, one pollution unit was defined to correspond to:
50 kg O2 (COD)
3 kg Phosphorous
25 kg Nitrogen
2 g organic halides
20 g Hg
100 g Cd
500 g Cr
500 g Ni
500 g Pb
1 kg Cu
etc.
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997

1.
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
COD = BOD
COD < BOD
BOD < COD
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
3.1. Emulsion-SBR (E-SBR)

Overview
Microstructure and Property Profile
Market
Application Areas, Market, Products and Important Grades
Producers and Production Capacities
Polymerisation
Polymerization Recipe (Cold Rubber)
Ingredients of a Polymerization Recipe
Sequence of Reaction Steps
Copolymerisation of Styrene und Butadiene
Influence of Chain Modification Agents
Product Properties
Tg
Influence of None Polymeric Residues on Compound and
Microstructure of E-SBR
CH
1 2
HC
HC
CH2
CH2
3
4
C
H2
1,4-cis
CH
CH
CH CH
CH2
1,4-trans
CH2
1
Vinyl
CH
CH2
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)
Application Areas in Western Europe
Negative:
poor ageing resistance
poor resistance to swelling in oils
no variation of microstructure
low / no profits / no R&D-activities
Tyres
72%
Others
2%
Buildings
Shoes Automotive
5%
5%
8%
mechanical
parts
8%
E-SBR: Producers and Production Capacities

Produer
Site
Country Capacity
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
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
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
Altona
Bombay/Bareilly
Omsk/Sterlitamak/Togliatti/Voronezh
Lanzhou/JiLin
Sum
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
3.902.000
Market:
Capacity:
Capacity utilization:
2,0 Mio t
3,9 Mio t
51%
Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.
E-SBR: Producers and Capacities in Europe

(without Latex Capacities):
700
600
Production [t]
500
Company
Site
Country
Capacity
Lanxess France
Dow
Enichem.
Dow (prior owner: Shell)
La Wantzenau
Schkopau
Ravenna
Pernis
France
Germany
Italy
Netherlands
45.000
120.000
295.000
120.000
Sum
400
580.000
415.000
Dwory
Chemopetrol
HIP Petrohemija
Combinatul Petrochimic
Neftochim
300
200
Oswiecim
Kralupy
Zrenjanin
Onesti
Burgas
Poland
Czech Republic
Croatia
Rumania
Bulgaria
104.000
76.000
40.000
100.000
20.000
Sum
340.000
100
0
1990 1992
1994 1996 1998
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
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.%]
ML 1+4
(100C)
[MU]
Antioxydant
Mineral Oil
System
grade loading
[phr]
Carbon Black
grade
loading
[phr]
1500
23,5
50-52
1502
23,5
50-52
NS
1507
23,5
30-35
NS
1509
23,5
30-35
NS
1707
23,5
49-55
NS
NAPH
37,5
1712
1721
23,5
40
49-56
50-55
S
S
HAR
HAR
37,5
37,5
1609
23,5
61-68
HAR
N 110
1808
23,5
48-58
HAR
47,5
N 330
76
S:
staining
NS: none staining
NAPH:
HAR:
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
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
23,2
9,5
wt.%
wt.%
t-DDM
0,07
wt.%
Water
65,4
wt.%
Emulsifier System:
K-salt of disproportionated rosin
Na-salt of methylen-bis-naphthalinsulfonic acid
1,5
0,03
wt.%
wt.%
Initiator-System:
p-Menthylhydroperoxide
FeSO4 * 7 H20
Di-sodium salt of ethylenediaminotetraacetic acid
Na-salt of Formaldehydesulfoxylate
Na3PO4*12 H2O
0,04
0,01
0,02
0,03
0,16
wt.%
wt.%
wt.%
wt.%
wt.%
Modifier:
Reaction medium:
E-SBR: Ingredients of Polymerization Recipe I

(Emulsifiers)
Disproportionation of Abietic Acid
CH3
Na-Salt of Methylene-bis
(Naphthalin-sulfonic Acid)
(Baykanol PQ(R))
H
CH3 COOH
SO3
Na
2 Na +
Abietic Acid
CH2
Pd
CH3
SO3
Na
CH3
CH3
+
H
CH3 COOH
Dehydroabietic Acid
H
CH3 COOH
H
CH3 COOH
Dihydroabietic Acid
Tetrahydroabietic Acid
E-SBR: Ingredients of Polymerization Recipe II

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

Redox Initiation:
R-OOH
Fe3+
R-O*
R-O* + OH- + Fe3+

Fe2+ + oxydized reducing agent
R-O-Mon*
+ Fe2+
+ Reducing agent
+ Monomer
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

175
(ML 1+4 (100C) [ME]
Gel content [wt.%]
100
80
60
40
20
0
140
105
70
35
0
0,2
0,4
Tert-dodecylmercaptane [phm]
0,2
0,4
Tert-dodecylmercaptane [phm]
Styrene Content of Polymer [wt. %]
E-SBR: Styrene/Butadiene-Copolymerization (Differential

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

(Integral Styrene Incorporation)
Integral Styrene Content [wt.%]
100
Copolymerization Parameter:
= 0,78
r1 (Styrene)
r2 (Butadiene) = 1,39
80
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
Probability [%]
E-SBR: Distribution of Styrene Sequences

in E-SBR 1502
Copolymerizationparameter
Styrol = M1
Butadien= M2
r1 = 0,7
r2 = 1,4
80
70
60
50
40
30
20
10
0
1
r1 =
k11
k12
r2 =
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
Source:
The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
E-SBR: Dependence of Tg on Styrene Content

expt. data
Fox-Flory-equation
100
80
Tg of atactic
polystyrene
60
Tg [C]
40
20
0
-20
Fox-Flory-Equation
-40
1
w
w2
= 1 +
Tg2
Tg
Tg1
-60
Tg:
Tg1:
Tg2:
wn:
-80
-100
Tg of
E-BR
20
40
Tg of copolymers in K
Tg of homopolymer 1 in K
Tg of homopolymer 2 in K
weight fraction of copolymers 1 und 2
60
80
100
Styrene Content [Gew.%]

Source: T. G. Fox, P. J. J. Flory; Appl. Sci., 21,581 (1950)

Vulcanizate Properties: Analytical Data
Product
Mw
[g/mol]
Mw/Mn
ML 1+4
(100C)
[ME]
[C]
45
51
52
54
-51
-53
-50
-50
Tg
Krylene 1500
mod. Krylene 1500*
Krylene 1712
mod. Krynol 1712*
424.280
429.210
740.170
716.760
3,46
3,51
3,69
3,74
Product
Ash cont.
(850C)
[wt.%]
Na
Al
chloride
[ppm]
[ppm]
0,33
0,23
0,41
0,20
1105
910
1502
355
655
1
Krylene 1500
mod.* Krylene 1500
Krynol 1712
mod.* Krynol 1712
137,5 phr
of Krynol 1712
contains
37,5 phr oil
==>
27,27 wt.% oil
[ppm]
waterextract
[wt.%]
acetoneextract
[wt.%]
0,110
0,079
0,230
0,045
0,33
0,23
0,41
0,20
6,9
2,4
32,3
30,1
* Modification of latex finishing (coagulation and crumb wash) in order to obtain

a rubber with a reduced content of residues with low molar mass

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
103,13
25,0
-
103,13
25,0
68,75
50
-
68,75
50
Compound-Mooney ML1+4 (100C) [MU]
67,0
71,0
73,5
77,0
Rheometer (160C)
L
F
ts1
t50
t90
[dNm]
[dNm]
[min]
[min]
[min]
8,3
35,3
4,8
7,5
11,2
8,8
38,2
4,3
6,8
9,3
9,1
37,3
4,7
8,2
12,6
10,1
39,2
4,5
7,9
11,1
[MPa]
[%]
[MPa]
[MPa]
17,3
425
2,5
12,6
69
63
25
38
18,5
410
2,7
14,3
71
64
27
42
17,9
480
2,3
10,9
72
64
22
33
18,9
470
2,3
11,8
71
64
25
36
Krylene 1712
Krylene 1500
mod. Krylene 1712*
mod. Krylene 1500*
Vulcanizate Properties:
Tensile Strength
Elongation at break
M100
M300
Rebound/23C
Rebound/70C
[phr]
[phr]
[phr]
[phr[
[%]
[%]
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
Capacity Site
Butadiene Acetylene
Denki Kagaku Kogyo KK
100
Omi/Japan
Lanxess
75
Dormagen/Germany
DuPont
45
Pontchartrin/USA
Tosoh
32
Nanyo/Japan
Chonquin Changshou Chemicals
28
Chongquing/China
Shanxi Syntheic Rubber Co
25
Datong/China
Pidilite
25
India
Showa Denko KK
20
Kawasaki/Japan
Nairit Scientific Industrial
10
Yerewan/Armenia
Total
360
Plant Closures
Stagnant CR-Consumption in WE and USA
Growing Consumption in South-East Asia
Producer
Source: Various Press Releases
Capacity Site
DuPont
30
50
Maydown/N.-Ireland
Louisville/USA
Bayer
25
Houston/USA
Polimeri (BP)
25
Grenoble/France
Monomer Manufacturing Processes

2-Chlorobutadiene-1,3 (Chloroprene)
Acetylene Route (1930)
2 HC
2,3-Dichlorobutadiene 1,3
(DCB)
Butadiene Route
(Gas phase chlorination / 1956)
CH
H 2C
CH CH CH2
Cl
+ Cl2
CuCl/NH4Cl/HCl
Nieuwland
Cl
Cl
H2C
Cl
Cl
+ Cl2
CH2 CH CH CH2+ CH2 CH CH CH2

(ca. 60 %)
(ca. 40 %)
HC
CH CH2
Side products: chlorinated C8-Compounds

Tetrachlorobutane
CuCl
Cl Cl
HCl/CuCl
(30-60C)
H2C
H2C
H 2C
Cl
Cl
Cl
CH
CH2
+ NaOH/85C
- HCl
CH CH CH2
+ NaOH
(85C)
Cl
CH2
CH
- HCl
H2C
Cl
Cl
CH2
Cl
CH CH2 +
2-Chloroprene
DE 1149001; Knapsack AG, Prior.:10.07.1961
Erf.: W. Vogt, K. Kaiser, H. Weiden
HC
CH CH CH2
1-Chloroprene (impurity)
GB 804254; Distillers Co. Ltd. , Prior.:21.03.1956;
Erf.: F. J. Bellringer
Only DuPont, Lanxess und Denki

produce DCB
CR: Grades and Aplication Areas

CR Application Areas (2006)
Rubber
Applications
60%
Latex based
adhesives
5%
Solvent
based
adhesives
30%
Application Areas of Rubber Grades

Profiles
11%
Hoses
44%
Belts
12%
50
Polymerization Temperature [C]
Latex
applications
5%
45
Latex
Grades
40
(Standard Grades,
precrosslinked grades
and sulfur grades)
30
25
20
Adhesive
Grades
15
10
0
DCB-Content of Monomer Feed [phm]
Conveyor
Belts
12%
Cables
21%
Rubber Grades
35
CR: Influence of Polymerization Temperature on

Microstructure
CH2
C
Cl
CH2
Cl
1,4-cis
H
C
Cl
H
CH2 C
CH2
3,4
CH2 C
CH2
Cl
CH2
Microstructure trans-1,4 cis-1,4

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

polymerization temperature and in the 1,4-trans content are an important
factor
80
CR: Basic Features of CR-Polymerization Recipes

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

Dependence of Shore A Hardness
on Crystallization Rate
Mercury dilatometry for the determination

of crystallization rate
(Tc =-5C pretreatment: 30 min at 80C)
He
He-Hi
1/2(He- Hi)
Hi
t1/2
20
Volume [mm3]
Shore A Hardness
10
30
40
50
60
70
80
0,1
10
100 1000 10000
0,1
Storage time [h]

Source: U. Eisele: Internal Bayer-Reporting System
10
Storage time [h]
100
1000
CR: Crystallization Rate and Crystallite Melting Temperature

Dependence of t1/2 on Storage
Temperature
Dependence of Crystallite Melting

Temperatures on Polymerization
Temperature
(Baypren 210; Pretreatment: 1 h / 60C)

30
Crystallite melting temperature [C]
80
25
15
10
5
0
-20
-15
-10
-5
10
15
60
50
40
30
20
lowest figures
highest figures
10
20
0
-60
Storage Temperature [C]
-10
40
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
Polymerizationtemperature [C]
103
45
102
t 1/2 [h]
- 34
Tg [C]
t1/2 [h]
20
70
- 35
35
25
15
101
- 36
100
- 37
- 38
10-1
0
12
15
DCB-Content of Monomer Feed [%]
12
15
DCB-Content of Monomer Feed [%]
Crystalliaztion Rates of Unvulcanized CR, Unvulcanized CRCompounds and CR-Vulcanizates at - 10C

500
lcanizates
300
200
U
nv
ul
ca
ni
ze
d
CR-bases
vu
400
t1/2 [h]
B. 110 VSC
Un
d
ize
n
a
lc
vu
CR
nd
ou
p
m
-c o
CR
Polyetherthioether
Vulkanox DDA
Vulkanox 4010 NA
Stearic acid
Magnesium oxide
Zinc oxide
B. 110
KA 8418
100
B. 112
100,0
75,0
10,0
2,0
0,5
0,5
4,0
5,0
phr
phr
phr
phr
phr
phr
phr
phr
B. 210
0
0
100
200
300
400
500
600
700
800
t1/2 [h] (unvulcanized CR)
Dependence of Crystallization Rate on Blending Ratio of Two

CR-Grades and on Type of Plasticizer
25
Influence of Plasticizers
Unvulcanized ISO- 2475-1975 Compounds;

Measurements at - 10C
CR
Stearic acid
Magnesium oxide
Phenyl-2-Naphthylamin
Zinc oxide (active)
Vulkacit NP
20
100
0,5
0,5
2,0
30
5,0
0,5
(CR-grade: Neoprene W (~ Baypre 210)
phr
phr
phr
phr
phr
phr
phr
300
15
200
t1/2 [h]
t1/2 [h]
Neoprene W + mineral oil
250
150
10
100
Neoprene W + Butyloleate
50
0
100
80
60
40
20
0
Baypren 110 VSC (slowly crystallizing)
-20 -15 -10
-5
10
15
20
Temperature [C]
0
20
40
60
80
Baypren 210 (normally crystallizing)
100 Source:
R. M. Murray, J. D. Detenber Rubber Chem . Technol. 34 (1961)

668-685 First and Second Order Transitions in Neoprene
CS (168 h / variable temperatures)
Dependence of Compression Set (CS) of Different CRGrades on Storage Temperature

100
90
80
DCB-containing rubber grade (Baypren 110)

DCB-free rubber grade
(Baypren 210)
CR Adhesive grade
(Baypren 320)
70
60
50
40
30
20
10
0
-60
-40 -20
20
40
60
80 100 120 140 160 180
Temperature [C]
Bayer-Brouchure: Chloropren-Kautschuk von Bayer: Der vielseitig einsetzbare Werkstoff
Recipe Features which are specific for Different

CR-Rubber Grades
Cl
2 - Chloro - 1,3 - Butadiene
CH2
Standard CR-Grade
CH CH2
Cl
2,3 - Dichloro - 1,3 - Butadiene
CH2
CH2
Sulfur Grade
Cl
Sulfur
S
CH3 O
Precrosslinked CR-Grade
Dimethacrylate
CH2
O
O
CH2 O
n
CH3
CH2
Molar Mass Control by Mercaptanes and by

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

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

Properties
ISO-Compound 2475
CR
100,0 phr
Carbon black N 762
30,0 phr
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
15
M300 [MPa]
14
13
12
11
10
21
20
19
18
30
40
50
60
70
80
ML 1+4 (100C)
90
100 110
10
11
12
13
Modulus M300 [MPa]
14
15
Dynamic Resistance of CR-Standard Grades (Monsanto Test)

Xanthate modified CR-Grade (Baypren 121)
unaged
7 days / 100C
Mercaptane modfied CR-grade (Baypren 110 VSC)
Cycles until failure [kcycles]
250
unaged
7 days / 100C
ISO-Compound 2475
200
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
150
100
Vulcanization: 40 min/150C
50
0
52
54
56
58
60
62
64
68
66
Strain Amplitude[%]
Source: R. Musch presented at the 140th ACS Rubber Division Meeting, Detroit October 8-11, 1991
CR-Sulfur Grades
S
Cl
Cl
NR2 C S ( CH2 C CH CH2 ) S (CH2 C CH CH2 ) x Sy C NR2

u
v w
Application:
Vulcanizates which are based on CR sulfur grades perform particularly well in dynamic
applications. As a consequence, belts which meet the requirements of different applications are
a major application area (conveyor belts, V-belts, poly-v-belts, timing belts)
Production:
CR-Sulfur Grades are obtained by two consecutive production steps (1. Polymerization and 2.
Chemical break down of high molar masses)
In the 1st production step chloroprene and sulfur are copolymerized. The copolymers obtained
have a high molar mass and long sulfur bridges. In the 2nd production step, the molar mass of
the copolymers is reduced by a break down of sulfur bridges (peptization). As a consequence of
the chemical breakt down of the sulfur bridges dithiocarbamate end groups are incorporated.
These end group participate in vulcanization.. As a consequence, the number of dangling chain
ends is reduced and vulcanizate properties are improved.
Compounding and Vulcanization:

During compounding residual sulfur bridges are broken down "Mastication". Sulfur grades
can be vulcanized by the addition of ZnO and/or MgO (without the addition of accelerators).
Critical Aspects:
During storage, the Mooney viscosity of sulfur modified CR can increase or decrease. Heat
resistance of vulcanizates based on sulfur modified CR is inerior to that of standard CR.
Production of CR-Sulfur Grades

1)
Copolymerization of Chloroprene and Sulfur

Cl
CH2 C CH
2)
CH2
S8
Chemical break down of high molar masses by the use of disulfides,

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

and Ageing Performance
80
48
Baypren 610
46
44
42
40
38
36
34
32
30
0
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
10
Change of M100 (7d/100C) [%]
Baypren 510
Incorporated Sulfur
ML 1+4 (100C) [ME]
50
70
60
50
40
30
20
10
0
0
0,2
0,4
0,6
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
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.
C
S
N
S
N
Sx
S
S
H
H
C
N
S
N
Sx
S
N
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.
SH
S
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
Ungelled
(soluble)
CR
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
d0
de
Properties of Precrosslinked CR-Grades

20
50
Die Swell [%]
46
42
38
34
30
18
16
14
12
10
26
0
10
20
30
40
50
60
70
10
Gel content [wt.% %]
Mechanism of CR-Vulcanization
according to Pariser/Du Pont
CH2
CH2
S
CH2
NH
CH2 CH2
CH2
CH2
CH
CH
+ ZnO
- ZnCl +
Cl
NH
CH2
NH
Cl
CH2 CH2
CH2
+
CH
CH2
CH2
CH2
CH
CH2
+ ZnCl +
NR2
S
S
CH
CH2
CH2
CH
S
CH2
Dithiocarbamate end groups are

present in sulfur modified CR
Sx
- ZnCl2
"cyclic Dithiocarbamate"
(Vulkacit(R) CRV)
NH
CH2 CH2
NH
CH3
End groups which participate in

CR-Vulcanization
S
NH
CH2CH2
CH2
CH2
O
NH
CH
CH
Ethylenethiourea
(ETU/Vulkacit(R) NPV)
CH2CH2
S
CH2
CH2
NH
S
CH2 CH2
CH2 CH2
NH
O
NH
NH
60
NH
CH2
50
Chemicals for CR-Vulcanization
Cl
NH
CH2 CH2
CH
40
Vulcanization of CR
CH
+ NH
30
Gel content [wt.% %]
Cl
CH2
20
O
R
Xanthate end groups are present

in in xanthate modified CR
70
Substitution of CR
max. service temperature [C]
250
FKM
MVQ
225
FMVQ
200
FZ
175
Resistance
to high temperatures
80
% VAc
EVM
ACM
AEM to high temperatures, flame resistance

Resistance
HNBR
150
Resistance to dynamic stress
125
NBR
CM
CSM
(H)IIR
Price
CR
100
EU
SBR
BR
AU
75
EPDM
NR
50
0
20
40
60
80
100
120
max. Volume Swell in ASTM-l Nr. 3 [Vol %]
140
no
requirements
Nitrile Rubber (NBR)

Overview
NBR-Microstructure
Basic Features of NBR and Range of NBR Grades
Application Areas of NBR and Market
Range of NBR Grades
Dependence of Properties on Acrylonitrile Content
Polymerisation
Emulsifiers
Initiator systems
Molar mass regulation
Copolymerization
Product groups and Properties

Standard grades
Carboxylated grades
Precrosslinked grades
Vulcanization and Vulcanizate Properties
NBR: Microstructure
N
C
C
N
CH
1 2
HC
HC
3
4
C
H2
1,4-cis
CH2
CH2
CH
CH2
CH
2
CH2
1
1,4-trans
CH
CH
Vinyl
CH
2
CH
2
1
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
Source:
The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
Standard
grades
Basic Features of NBR

Fast curing / Low mould
fouling
(Injection moulding)
slow cure
peroxide cure
Special grades
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 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)
X-NBR
Precrosslinked NBR
NBR/PVC-Blends
NBR-powder grades
liquid NBR
-HO-terminated
-COO-terminated
-NH2-terminated
NBR
mit bound antioxydant
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%
NR
250
200
150
100
SBR
50
CR
NBR
0
14
21
7
time in ASTM-L3 [days]
NBR:Market- und Development

450
400
350
300
250
200
150
100
50
20
10
20
05
20
00
19
95
19
90
19
85
Consumption [j/y]
Volume swell [%]
300
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)
Goodrich
Goodyear
BP
(Copolymer)
Lanxess
La Wantzenau / FR
Leverkusen / DE
Sarnia / CAN
Triunfo / BRA
Polysar
Bayer
Polysar
Petroflex
JSR
Polimeri
Paratec
Korean Kumho
Lucky Gold
President
Eliokem
Yokkaichi / JP
Porto Torres / IT
Altamira / Mexico
Ulsan
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
Total:
45
20
35
28
15
15
100
35
25
30
35
30
25
20
16
15
11
25
10
5
2
Nipol
Nipol
Hycar
Chemigum
Breon
(Nysin)
Perbunan / Krynac
Perbunan
Perbunan / Krynac
Perbunan
JSR NBR
Europrene
Paratec
Kumho NBR
Chemigum (Powder)
Chemigum (bales)
Nitriflex/Nitriclean
424
NBR-Standard Grades
Acrylonitrile content [wt. %]
50
45
40
35
30
25
20
15
20
30
40
50
60
70
80
90
Mooney Viscosity ML 1+ 4 (100C)

without pretreatment (DIN 53523)
100
125
NBR: Dependence of Tg on Acrylonitrile Content

PAN
100
80
60
Tg [C]
40
20
+0
-20
e
ng
a
R
-40
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
-60
*Gordon M., Taylor J. S., J. Appl. Sci., 21, 581 (1950)
-80
E-BR
-100
0
10
20 30
40
50
60
70
80 90
100
Acrylonitrile content [wt.%]
NBR: Dependence of Volume Swelling on

Acrylonitrile Content
90
Expt. Conditions:
14 days
Fuel B and C: 20C
ASTM-Oils: 140C
vvvvvWeight Change[%]
80
70
60
50
40
30
20
Fuel C (Isooctan/Toluene: 50/50)

Fuel B (Isooctan/Toluene: 70/30)
10
ASTM l Nr. 3 (aromatic/naphthenic)

ASTM l Nr. 1 (paraffinic)
0
-10
0
10 15 20 25 30 35 40 45 50
50
80
40
20C
70
60
75C
50
Rebound [%]
90
75C
30
20
20C
10
40
0
0 5
10 15 20 25 30 35 40 45 50
10 15 20 25 30 35 40 45 50
Acrylonitrile [wt.%]
Source: Rubber, 3 Synthetic Ullmann s Encyclopedia of Technical Chemistry, Vol A 23 (1993)
Dependence of Compression Set on Acrylonitrile

Content
50
Compression Set (70 h/100C) [%]
Shore A Hardness
Dependence of Shore A-Hardness and Rebound on

Acrylonitrile Content
40
30
20
10
0
0
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-O* + OH- + Fe3+
Fe2+ + oxydized Reducing agent
R-O-Mon*
+ Fe2+
+ Reducing agent
+ Monomer
R-OOH
Fe3+
R-O*
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
Pd
+
H
CH3 COOH
H
CH3 COOH
Abietic Acid
CH3
CH3
H
CH3 COOH
H
CH3 COOH
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
Sulfates- und Sulfonates (Examples)

Na-Laurylsulfate
Na-Alkylarylsufonate
Na-Alkylsufonate
(Texapon)
(Marlon)
(Mersolat)
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))
CH2
SO3
Na
2 Na +
SO3
Na
Activatator Systems for NBR-Polymerization

Organic Activation System
Inorganic
Activation System
p-Menthylhydroperoxide (p-MHP)
CH2 CH2
CH3 CH
CH3
CH
(NH4)2 S2O8
CH2 CH2
Ammoniumperoxodisulfate
CH3
Na-Formaldehydesulfoxylate
Na-Hydroxymethanesulfinate
O
H
H
Na
CH2
H
Ethylenedinitrilotetraacetic acid (EDTA)
O
O
HO
CH2
N
HO
CH2
OH
CH2
OH
HO
CH2 CH2 N
CH2
CH2 OH
CH2
CH2
CH2
CH2
OH
Triethanolamine
O
Ion-(II) sulfate
Fe SO4
Acrylonitrile content of polymer [wt. %]
Copolymerization Diagram for the Copolymerisation of

Butadiene/ACN- (for incremental conversions)
100
Ideal
Copolymerisation
90
80
70
Azeotropic
Composition
60
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.%
50
40
30
20
r1 =
k11
k12
r2 =
k22
k21
10
0
0
10 20 30
40 50 60 70 80 90 100
Acrylonitrile content of monomer feed [wt.%]

Source: W. Hofmann, Nitrilkautschuk, Berliner Union Verlag
Acrylonitrile Content of Polymer [Gew. %]
NBR: Dependence of Integral Copolymer

Composition on Monomer Conversion
Modellierungsparameter
(ACN = M1; Butadien = M2):
r1 = 0,02; r2 = 0,28
100
90
Acrylonitrile content
of monomer feed:
80
70
60 wt.%
60
50 wt.%
50
40
30
38 wt.%
33 wt.%
28 wt.%
20
20 wt.%
10
10 wt.%
5 wt.%
0
0
10 20 30
40 50 60 70 80 90 100

W. Hofmann, Nitrilkautschuk, Berliner Union Verlag
Acrylnitrilonitrile content of polymer [wt. %]
NBR: Dependence of Incremental and Integral

Acrylonitrile Content on Monomer Conversion
Incorporation of ACN during batch-polymerization
100
Incremental composition
90
80
Integral composition
70
Monomer Feed:
Acrylonitrile: 73,7 wt.%
Butadiene: 26,3 Gew.%
Copolymerizatin parameters:
r1 = 0,023; r2 = 0,30
60
50
40
30
20
10
0
0
10 20 30
40 50 60 70 80 90 100
Monomer conversion [%]
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
NBR: Dependence of Tg on Polymerization Parameters

(Batch-Polymerization)
Sample
Bound Polymerization
ACN
temperature
ACN-addition
during
polymerization
Monomer
Tg
Conversion Lower Tg Upper Tg
[wt.%]
[C]
[%]
38,9
>57
32,8
>57
25,8
>57
44,8
50
>57
[C]
[C]
-19
-22
-61
-33
-13
34
50
>57
29,2
50
>57
-46
-26
-32
28,5
50
>57
-49
-33
-64
23
50
>57
21,1
50
>57
-53
-40
31,4
50
57
-31
Batchwise NBR-Polymerization may result in chemically

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

Molar Mass Regulation
160
Mooney Viscosity
ML1+4 (100C)
140
120
100
TDM / Lanxess
80
TDM / Phillips Chevron
60
40
20
0
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
Amount of TDM [phm]

For NBR-Production C12-Mercaptans are efficient molar mass modifiers
Tert.-Dodecylmercaptane (TDM) is specifically important
TDM by Chevron Phillips is based on propene-tetramers
TDM by Lanxess is based on isobutene-trimers
Molar Mass Regulation by TDM Based on TIB

1. TIB- Production by Isobutene-Oligomerisation
Wagner- MeerweinRearrangement
- H+
+
"Triisobutene (TIB)"
2. TDM-Production by the Addition of H2S to TIB

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

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

Reduction of free (dangling) chain ends / Improvement of mechanical properties
During vulcanization TIB is released which causes odour
Patent No.
Company
Priority
EP 0692496
Zeon
30.03.1993 (Jp)
EP 0779300
Zeon
29.08.1994 (Jp)
EP 0779301
Zeon
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
40
cMg
cNa
24
23
cK
+
ppm
39
Atomic weight
weight
Influence of Ions on Speed of Cure:

accelerating: Na-, K- Ions
retarding:
Mg-, Ca- Ions
Patent No.
Company
Priority
Patent Title
DE 102007024011
DE 102007014010
DE 102007024010
Lanxess
Lanxess
Lanxess
22.05.2007
22.05.2007
22.05.2007
Nitrile Rubber with Specific Ion Number

Dependence of NBR-Properties on Content of

Metal Ions
cCa
Ion-Number
40
cMg
cNa
24
23
cK
+
39
ppm
Atomic Weight
Mooneyscorch MS5 (120C)

[min]
70
60
50
40
30
20
10
0
0,00
20,00
40,00
60,00
Ion-Number (IN)
80,00
100,00
120,00
Dependence of NBR-Properties on Metal Ion

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

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

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

Ingredients
NBR (18 wt.% ACN)* [phr]
Zinc oxide
[phr]
Stearic acid
Vulkanox OCD
TMQ
Vulkanox MB-2
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 (100C)
ts
t90
Shore A
TS
b
M100
M300
[ME]
[min]
[min]
[MPa]
[%]
[MPa]
[MPa]
EV 1
EV 2 EV 3 Peroxide
78
3,2
7,2
87
1,8
2,6
67
3,4
7,0
77
0,6
4,9
71
16,9
310
4,3
16,3
72
19,5
365
4,4
17,3
71
15,8
310
4,7
15,4
70
18,3
260
4,2
13,0
CS (70h/100C)
CS (70h/120C)
CS (70h/125C)
[%]
[%]
[%]
12
-
20
31
16
-
14
Brittleness Point
Tg
CS (24h/-20C)
[C]
[C]
[%]
-60
-49
-
-62
-53,5
17
-62
-60
20
Carboxylated NBR (X-NBR)

C
C
N
COOH
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

CH2
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
CH3
8
CH2
C
COOH
CH2
+ ZnO
- H2O
CH2
CH3
C
CH2
CH3
C
CH2
Vulcanization with metal oxides is used for X-NBR and CSM.

The following metal oxides are used: CaO, MgO, ZnO and ZnO2
For scorch safety ZnO2 is superior over ZnO
Usually, vulcanization with metal oxides is combined with sulfur cure
Dual vulcanization results in a hybride-network-structure
In a hybride network chemical as well as physical networks are present.
Sources: Eisenberg, A. Macromolecules, Vol 3, 2 (1974) 147 Clustering of Ions in Organic Polymers - A Theoretical Approach
Ibarra, L., Alzorriz, M. Polym. Int. 48: 580-586 (1999)
Naskar, N., Debnath, S. C., Basu, D. K.; J. Appl. Pol. Sc., Vol 80, 1725-1736 (2001)
Brown, H. P. Rubber Chemistry and Technol, 30 (1957) 1347 Crosslinking Reactions of Carboxylated Elastomers
Compound- and Vulcanizate Properties of NBR and X-NBR

100,0
X-NBR
NBR
Fmin.
[Nm]
50,0
50,0
100,0
9,0
10,2
8,0
86,3
78,7
60,0
100
50
NBR
50
100
ts
[min]
3,0
2,7
2,8
CB (N 660)
40
40
40
t90
[min]
10,0
7,0
6,8
Dibutylphthalate
t95
[min]
21,5
11,0
8,3
Stearic acid
Shore A
83
80
67
Wingstay 29
M100
[MPa]
5,2
4,5
1,7
0,5
0,5
0,5
M200
[MPa]
11,0
10,0
4,8
18,6
M300
[MPa]
15,5
11,0
TMTD
TS
[MPa]
25,5
21,0
18,2
MBS
430
415
500
Zinc oxide
493
159
73
elongation [%]
- 42
- 35
- 30
CS
34,1
27,1
14,7
X - NBR
Sulfur
Fmax.
b
[%]
Abrasion Index
Ageing at 70h/121C
[%]
Precrosslinked NBR
Properties:
Properties:
Reduction
Reductionofofdie
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
ImprovementofofCS
CS
Reduction
ReductionofofTS
TS
Reduction
Reductionofofelongation
elongationatatbreak
break
Precrosslinked NBR
High Mooney NBR

Krynac 34.80
Precrosslinked NBR-grades provide for high dimensional stability after extrusion which is
only matched by standard NBR-grades with considerably increased Mooney viscosities
Precrosslinked NBR: Compound Study

NBR* (34 Gew.% ACN)
Krynac VP KA 8769
phr
10
20
30
40
NBR (34 Gew.% ACN)
Krynac 34.50
phr
90
80
70
60
Zincoxide
Lanxess
phr
3,0
3,0
3,0
3,0
Stearic acid
Henkel KGaA
phr
1,0
1,0
1,0
1,0
TMQ (Vulkanox HS)
Lanxess
phr
1,5
1,5
1,5
1,5
Zincmethylmercaptobenzimidazol Lanxess
phr
1,5
1,5
1,5
1,5
Carbon black (Corax N 550)
Degussa
phr
30
30
30
30
Vulkanol 81
Lanxess
phr
10
10
10
10
Sulfur
Kali Chemie
phr
0,3
0,3
0,3
0,3
TBBS (Vulkacit NZ)
Lanxess
phr
1,5
1,5
1,5
1,5
TMTD (Vulkacit Thiuram)
Lanxess
phr
1,5
1,5
1,5
1,5
* Precrosslinked NBR
Source: Bayer AG, Marinelli/Welle, KALIS-Nr.: 9588 vom 05. 10. 2000
Precrosslinked NBR: Results of Compound Study

NBR* (34 Gew.% ACN)
NBR (34 Gew.% ACN)
Compound-ML
[ME]
Mooney-Relax.
[%]
Die swell /linear
[%]
Fmin.
[dNm]
[dNm]
Fmax.
[min]
ts1
t90
[min]
t95
[min]
Shore A/23C
Shore A/70C
[MPa]
M100
M200
[MPa]
M300
[MPa]
Tensile Strength
[MPa]
Elongation at break [%]
Rebound/23C
[%]
[%]
Rebound/70C
CS (70h/23C)
[%]
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
solvent
solvent
solvent
solvent
Z/N*
Z/N*
Z/N*
Z/N*
Li-BR
solvent
anionic
L-SBR
EPM/EPDM
solvent
solvent
anionic
Z/N*
CM/CSM
HNBR
solvent
solvent
polymer modif.
polymer modif.
IIR
solvent
cationic
Solution Rubbers
Ti-BR
Ni-BR
Co-BR
Nd-BR
Solution-BR
Catalyst/Process
High-cis1,4-BR
Reaction
Medium
Rubber
* Z/N = Ziegler-Natta Catalysis
Dry Finishing with Extruders (Under Vacuum)

Dry Finishing:
Recovery of rubbers from their solutions by direct evaporation

with extruders without the use of steam
Vent for Devolatilizing Srew press
US 4124306
(French Oil Mill Machinery)
Prior.: 30.11.1977
Inv.: D. K. Bredesen, G. C. Craig,
W. W. Gilius, C. R. Johnson
Dry Finishing with Hot Mills (Under Vacuum)

Dry Finishing:
Recovery of rubbers from their solutions by direct evaporation

under vacuum with heated 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
oil
Steam
Antioxydant
Expander
screw
Steam
PHControl
Waste water
US 2,592,814
(Du Pont)
Prior.: 20.12.1947
Inventor: J. L. Ludlow
Stripping
aid
Process for Precipitating Polymers
US 5266211
Bunawerke Huels GmbH
Prior.: 13.06.19990
Inventor: W. Breuker,
H. Wagner, E. Moeller,
B. Schleimer
Expeller Screw for Mechanical Removal of

Water from Rubbers
After steam stripping a dispersion of rubber crumbs in water is
otained. Before thermal drying water is removed mechanically
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
Source:
US 2003007709 (Bayer AG)
Prior.: 05.07.2001
Inv.: N. Schweigler H.
Goebel, T.-O. Neuner
4.1. Overview on Polybutadiene Rubbers (BR):

CH2
CH
CH2
CH2 CH2
CH CH
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
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
Tyres
71%
Technical
Rubber
Products
5%
Rubber
Toughening
23%
Golf ball cores

1%
BR: Microstuctures and Glass Transition

Temperatures
2
CH2 CH
CH2
CH2
CH2
CH CH
CH CH
CH2
CH
CH2
1,2- bzw. Vinyl
4
1,4-cis
Catalyst
Tg
1,4-trans
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
4,0
5,4
4,6
<1
0,6
0,7
18,1
17,7
17,8
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
* 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
t 1/2 [min]
Raw Rubber
Vulcanizate
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
0
Nd
Ni
Co
Ti
200
t 1/2 (-20C) [min]
Melting temperature of crystallites

[C]
250
150
100
50
0
90
92,5
95
97,5
100
Nd
Ni
Co
Ti
-5
-10
-15
-20
-25
90
92,5
1,4-cis-content [%]
95
97,5
100
1,4-cis-content [%]
BR: Producers and Production Capacities

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

Polimeri, Ravenna, IT
Lanxess, Dormagen, DE
Chemizna Dwory, SA, Kralupy, CZ
Li
Ni
Ti
Co
Nd
Li/Co/Nd
Ni/Nd
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
Capacity [kt]
BR: Application Areas

Application Areas of BR
Technical
Rubber
Goods
5%
HIPS/ABS
23%
not
assigned
7%
Li-BR
7%
Nd-BR
8%
Tyres
71%
Golf balls
1%
Tyre Market (2.2 Mio t)
HIPS/ABS-Market (0,68 Mio t)

Ni-BR
38%
Li-BR
48%
Co-BR
22%
Ti-BR
18%
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
Carcass
NR/BR: 90/10
Rim Cushion
NR/BR: 80/20
Apex
NR/BR: 80/20
Source:
Comparison of BR-Grades for the Application

in Tyres (ASTM-Compound 3189 90)
BR (Nd-, Co-, Ti-, Li-)
Zinc oxide
Sulfur
Stearic acid
Carbon black (NBS 378)
TBBS
Oil (ASTM Type 103)
100,0 phr
3,0 phr
1,5 phr
2,0 phr
60,0 phr
0,9 phr
15,0 phr
Vulcanization:
145C/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
Stress [MPa]
4
3
2
1
Li-BR
Ti-BR
Co-BR
Nd-BR
0
0
250
500
750
1000
Strain [%]
Source:
Tack of Unvulcaniuzed BR-Compounds

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

Source:
Vulcanizate Properties of BR Grades

Nd
BR Grade
Co
Ti
Li
Vulcanizate properties
13,0
400
14,5 13,4
525 510
9,4
8,6
8,1
8,0
65
63
64
66
Tensile Strength
[MPa]
15,3
Elongation at break
[%]
M300
[MPa]
Shore A-Hardness
480
Rebound
[%]
49
47
45
47
DIN-Abrasion
[mm3]
23
27
33
52
Asphalt, dry
85
85
85
89
Asphalt, wet
33
33
33
35
Pendulum -Skid
Dynamic properties
Goodrich-HBU
[C]
27
32
36
18
De-Mattia crack growth
[mm/kc]
1,9
6,0
1,5
5,6
Monsonto-FTF/ =100%
[cycles]
460
50
115
63
Source:
Number of Kilocycles until Failure
Improvement
1,4-cis BR: Dynamic Performance of BRVulcanizates (Monsanto Fatigue to Failure Test)

40
35
30
25
20
15
10
5
0
Ti
Ni
Co
Nd
Source: D. J. Wilson Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes

Makromol. Chem., Macromol. Symp. 66, 273-288 (1993)
1,4-cis BR: Abrasion Resistance of BR-Vulcanizates

(DIN-Abrasion)
50
Ti-BR
Ni-BR
Co-BR
Nd-BR
Abrasion [mm3]
Improvement
45
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
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
Rubber Modified Thermoplastics
Soft
Phase
Hard
Phase
Examples
BR
BR
EPDM
EPM
NBR
SAN
PS
SAN
PP
PP
ABS
HIPS
AES
EPM/PP
NBR/PP
Source:
C. Schade, H.-J Renner, W. Heckmann
(BASF)
Predictive property Adjustment
Kunststoffe international 7/2010, 36-39
Notched impact resistance [kJ/m2]
Influence of Rubber Content on Notched Impact

Resistance of EPM/PP-Blends
52
80
47
33
37
25
60
Rubber content
[wt.%]
40
ho
20
20
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
Viscosity [mPa*s]
100000
10000
1000
100
10
1
HX 565 Mooney: 65
Degree of Branching: 50-55
HX 501 Mooney: 40
HX 530 Mooney: 65
Degree of Branching: ca. 18

Degree of Branching: ca. 10
Solid Contents of BR solution [wt.%]

Source: Rubbers as Impact Modifiers for Plastics Bayer AG Rubber Business Group Order No.: KA 34271e
260
240
Li-BR (commercial grades)

Co-BR (commercial grades)
220
200
180
160
140
120
100
80
60
40
20
0
0
10
L
br in
an ear
ch a
ed nd
BR sli
g
gr htl
ad y
es
Solution Viscosity (5,43 wt.% in toluene) [mPa*s]
Correlation of Solution and Mooney Viscosities of

Different BR-Grades
20
30
Star shaped BR
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
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
Co
Benzene,
Benzene
Toluene
Toluene
(Aliphatics) Hexane
150
120
[min]
[%]
Tendency towards
gel formation
Heat removal
[ppm]
Ti
Nd
Benzene
Toluene
Hexane
Aliphatics
120
100-120
55-80
<85
<95
<100
high
high
low
Very low
partially
adiabatic
14-22
Solids Content
Molar Mass
Control agents
Formation of 4VCH
Transition metal
content
Ni
partially partially
adiabatic adiabatic
15-16
11-12
fully
adiabatic
18-22
yes
yes
no
no
high
high
low
10-50
50-100
Very
high
200-250
100-200
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
1839
1888
1910
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
Capacities of Multi-Purpose Solution Plants*

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

Feature
Technology
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
Firestone/Asahi
Phillips
n-Bu-Li
n-hexane
none
DVB
water
continuous
adiabatic
butadiene
~ 10%
broader
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
Li
Chain growth:
CH2
Li
CH2
+
Transfer reactions:
ideally none
Termination reactions:
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
Molar Mass (Mn) [g/mol]
DP =
nInitiator * f
nMonomer * MWMonomer
Mn =
nInitiator * f
=
Mn
C
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
m *X + C
nInitiator = u
nInitiator = v
n Monomer * MGMonomer
nInitiator * f
nInitiator = w
u<v<w
0,5
Monomer Conversion X
1,0
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)
Costs
for for
Bu-Li
[Pf/kg
rubber]
Costs
BuLi
[[Pf/kg]
Impact of Initiator Concentration on Molar

Masses and on Catalyst Costs
Basis of calculation:
65 DM/kg BuLi (4 DM/mol BuLi; MwBuLi: 61 g/mol)
Ideally Living Polymerization
25
20
15
10
5
0
0
50000
100000 150000 200000 250000 300000 350000 400000
Molar mass [g/mol]
Molar mass [g/mol]
Consequences from the living nature of the polymerization:

Catalyst costs increase with decreasing molar masses.
Star shaped polymers are obtained by the coupling of low molar mass
polymers. Therefore star shaped polymers are bound to be more expensive
than standard rubbers at the same molar mass.
Impact of the Gegenion and of the Solvent

on the Vinyl-Content
Gegenion
Li
Na
K
Cs
Microstructure
(Benzene)
cis-1,4
trans-1,4 1,2[%]
[%]
[%]
35
10
15
6
55
25
40
35
1,4-insertion:
-
10
65
45
59
Hexane
Toluene
THF
Microstructure
cis-1,4
trans-1,4 1,2[%]
[%]
[%]
35
35
0
55
52
9
10
13
91
1,2-insertion:
-
P
Solvent
Li +
Li +
Li
Li
Ether with two coordination sites
Sources:
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
Vinyl-Content [mol%]
80
70
DME
30C
THF
30C
DME
50C
THF
50C
60
50
THF
70C
DME
70C
40
30
Modifier:
DME: Dimethoxyethane
THF:
Tetrahydrofuran
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
VI-BR
-10
-20
Range of commercial
Vinyl-BR grades
-30
Tg [C]
-40
-50
-60
-70
-80
-90
Standard-Li-BR (without modifiers)
-100
0
10
20
30 40
50
60
70 80
90 100
Vinyl-Content [%]
S. L. Aggarwal, T. G. Hargis, R. A. Livigni, H. J. Fabris, L. F. Marker, Advances in
Elastomers & Rubber Elasticity, J. Lal a. J. E. Mark, Eds., Plenum Press, New York, 1986, p. 17
Li-BR: Dependence of Wet Skid and Abrasion Resistance

on Vinyl Content
Vinyl-BR
64
21
15
66
18
16
88
7
5
SBR
1712
18
8
74
Wet Skid Performance (Laboratory)

Portable Test Device*
84
109
104
120
100
Retreaded Tyre
Concrete
Asphalt
70
70
95
90
92
92
93
93
100
100
Abrasion Resistance
140
100
80
Vinyl Content
1,4-cis
1,4-trans
10
40
50
47
26
27
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
CH
Li
CH2 Li
R
n
R
n
Branching by Chain End Coupling

Chain end coupling with SiCl4, SnCl4 etc.:
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.)
SiCl
4
(SnCl4 as alternative)
Coupling with SnCl4:

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)
+ 4 Li Cl
Si
Impact of Chain Branching on Processability

Mooneymeasurement
Com- CalanEx- Injection

Spinpression dering trusion moulding drawing
moulding
Improvement
Improvement
Viscosity
Cold
flow
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
Cold Flow [mg/min]
10
8
Star shaped
polymer with
3 branches
Divinylbenzene
[phm]
0,03
0,06
0
0
20
40
60
80
100
Mooney-Viscosity ML 1+4 (100C) [MU]

Linear BR has an extremely high cold flow which results in the instability of
rubber bales. BR has to be branched in order to improve the stability of bales.
Properties of Linear and Star Branched Li-BR

Li-BR
linear
star branched
Coupling agent
without
SiCl4
Mw
[g/Mol]
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
[%]
256.000
188.000
1,4
16
53
98
64
8,0
16,5
32
77
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
Consumption [t]
700
600
500
400
300
200
100
0
1989
1991
1993
1995
1997
Source: IISRP; Evaluation by Bayer AG (Wachholz/BPO-IIS-BPSC-SP)
1999
2001
Copolymerization of Styrene and Butadiene at

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

The anionic copolymerization of styrene and butadiene in an unpolar
solvent (hexane) yields a block copolymer with the following features:
high chemical homogeinity
narrow molar mass distribution
tapered intermediate sequence
Course of the copolymerization in hexane (full batch process):

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

avoided as they cause high hysteresis losses.
100
90
80
70
60
E-SBR
50
40
ond rs
Ra ize
m
Differential styrene content in the polymer

[wt. %]
Styrene/Butadiene-Copolymerisation
S-SBR
in Hexane
30
20
10
0
0
10 20 30
40 50 60 70 80 90 100
Styrene content in the monomer feed [wt. %]
Impact of Randomizers on the Copolymerization

Behaviour of Styrene and Butadiene
(Styrene = M1; Butadiene = M2)
r1
r2
n-Butyl-Lithium
t-BuOK/n-Buli: 0,067/1
Total Styrene Content of Polymer

[wt.%]
T
[C]
Cyclohexane; 25/75 Styrene/Butadiene

70
60
Benzene
Cyclohexane
Hexane
25
25
25
0,04
0,04
0,03
10,8
15,5
12,5
THF
Diethylether
Triethylamine
Anisol
Diphenylether
25
25
25
25
25
4,0
0,4
0,5
0,3
0,1
0,3
1,7
3,5
3,4
2,8
THF
THF
THF
-78
0
25
11,0
5,3
4,0
0,04
0,2
0,3
t-BuOK/n-Buli: 0,38/1
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
30
20
10
0
10
+10C
Standard Emulsion Technology
Solution technology without

randomizers
Styrene Content [wt. %]
40
+ 0C
- 10C
Solution technology with

randomizers
- 20C
- 30C
- 40C
- 70C
20
30
- 50C
- 60C
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

S-SBR (25% Styrene, 55% Vinyl)
E-SBR 1516 (40% Styrene)
-20
Tg [C]
-40
-60
-80
-100
E-SBR 1500 (23.5% Styrene)

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

preparation of rubber blends is essential in rubber technology. An
alternative to macroscopic blending would be microscopic blending
as with integral rubber.
The Integral Rubber Concept

Li- NR SBR
BR
1500
SBR
1700
tan
10-1
10-2
Integralrubber
10-3
-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
Segment:
Tg [C]
randomizer styrene
Medium-cis BR
-90C
Vinyl-BR
-50C
isoprene
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
+
+
+
t10
t90
t90 - t10
+
0
+
+
Moduli
Tensile Strength
Tear resistance
Abrasion resistance
Heat build up
Rolling resistance
Wet grip
+
+
+
+
+
+*
Black incorporation time

Tack
Green Strength
Vulcanization
In a carbon black loaded compound
there is no real advantage for S-SBR.
Price
Therefore there was no major breakbreakthrough for S-SBR until the green tyre
technology emerged.
emerged.
+
+
+
-
* fully depreciated plants
Green Tyre Technology

CH2
Et-O
Et-O Si CH2 CH2 S
Et-O
S
Si OH
SiO2
Et-O
Et-O Si CH2 CH2 S
Et-O
CH2
Si OH
Performance of the green tyre
Additional costs for the green tyre
Rolling Resistance
150
Carbon black
loaded tread
Green tyre
Rubber
100
Filler
Silane
Additive
50
Raw Materials
Mixing Costs
Ru
Compound
Silica
Compound
E-SBR
Ru
-
L-SBR
NR
BR
Silika
Si 69
DPG
++
++
---
Patents:
Abrasion
Resistance
Wet
Skid
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
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
Li
N
C
91
R2
Li
Si OR
CH2 OR
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
CH2
Li
- 2 Li
Cl
+
Cl
Cl
O
R
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
CH3
N
CH2
CH2
C
CH
CH2
Dimethyl-Aminoisoprene
is incorporated initially at the chain end
it acts as a randomizer during the whole course of the polymerization
the aminoisoprene containing rubber exhibits increased interaction with silica
EP 01165641; Bayer AG, Prior.: 03.02.1999; Erf.: T. Scholl, W. Obrecht, R. Stadler,

R. Morschhuser, G. Mannebach "Kautschukmischungen basierend auf Aminoisopren"
Functionalization of the Living Chain End

with a Polysiloxane Building Block
CH3
H3C
Si
O
R
CH2
+ H3C
Li
Si
Si
O
H3C
CH3
CH3
D3
CH3 CH3 CH3 CH CH3 CH3

3
Si
R
Si
Si
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

H
X
S
X
SH
X: - OH
(US 6252008)
X: - COOH (US 6365668)
Sources:
US 6252008; Bayer AG; Prior.: 18.07.1998; Inv.: T. Scholl, U. Eisele, J. Trimbach, S. Kelbch
WO 02/31028 A1; Bayer AG; Prior.: 10. 10. 2000; Inv.: Th. Scholl, J. Trimbach, W. Nentwig, R. Engehausen
US 6365668; Bayer AG; Prior.: 16.11.1998; Inv.: Th. Scholl, J. Trimbach
4.3. Chemistry and Production Technology of 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
Technical Options for the Control of Molar Mass in Nd-BR-Production
Technically Relevant Catalyst Systems for the

Production of High cis-BR
BR
Li-BR
Co-BR
Ni-BR
Ti-BR
Nd-BR
Catalyst System
Molar
Ratios
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
cis-1,4
Content
36 - 38
97
97
93
98
cis-1,4-Content [%]
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
98
97
96
95
94
93
92
0
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
+ TIBA
+ DIBAC
trans -1,4-BR
cis -1,4-BR
Nd(COOR)3
+ TIBA
Nd(COOR)3
+ DIBAC
trans -1,4-BR
cis -1,4-BR
Nd(COOR)3
Nd(COOR)3
+ Mg (Allyl)2
+ Mg (Allyl)2 + R-Cl
trans -1,4-BR
cis -1,4-BR
Nd(CH2Ph)3
+ TIBA
trans -1,4-BR
cis -1,4-BR
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
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
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
Data from:
US 5134199 Enoxy Chem Ltd.
GB 2161169 (Asahi)
US 4931376 (Asahi)
US 5596053 (Bridgestone/Firestone)*
Tm [C]
80
40
Goodyear
+0
- 40
60
70
90
80
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
M
8
15
Bd
C
C
29
22
M
36
Bd
M
43
54
Bd
M
60
For the achievement of high 1,4-cis contents, a vacant coordination site

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

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

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

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

Polymerization: Influence of Solvents
Contrary to other 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

Polymerization
O
Nd
R1
Cl
Cl
Al Al
Et
Et
Cl
Et
R2
R3
Al
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
Nd ( OOC - R )3 + 3 H Al
Nd (O-CHR- R )3 + 1
Al
Al
Al
Al
O
O
Al
2) Formation of a Nd-Hydrodo Compound (Precursor of Active Nd-Species)

(R-CH2-O)3 Nd + H
Al
(R-CH2-O)2 Nd - H
Nd (O-CH2- R )3 + H Al
(R-CH2-O)2 Nd
RCH2
Al
+ R-CH2-O
Al
CH3
(R-CH2-O)2 Nd
CH2 C
H
CH3
(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

by Nd-Catalysis
3)
Hydride transfer and Formation of a Nd-Allyl Compound

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

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

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

by Nd-Catalysis
6) Control of Molar Mass by Al-Alkyls and by Al-Hydrido Compounds
Nd L
L
H Al
H Nd L
L
+ R
Al
Al
Nd L
L
+ R
Al
R
Nd L
L
R
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:
DIBAH
1. Hexane
2. Butadiene
3. DIBAH
4. Neodymversatate
5. EASC
Polymerization temperature: 60C
2,0; 4,0; 6,0; 10,0 mmol/l

nDIBAH/nNd = 10, 20, 30, 50
Conversion/time-plots
Plot for 1st order monomer consumption
100
80
-1
60
40
nDIBAH/nNd = 10
nDIBAH/nNd = 20
nDIBAH/nNd = 30
nDIBAH/nNd = 50
20
0
ln(1-x)
Addition Sequence:
Solvent n-Hexane
Butadiene 1,85 mol/l
NdV
0,20 mmol/l
EASC
0,13 mmol/l (nCl/nNd = 2/1)
-2
-3
nDIBAH/nNd = 10
nDIBAH/nNd = 20
nDIBAH/nNd = 30
nDIBAH/nNd = 50
-4
-5
50
100
150
time [min]
200
250
50
100
150
200
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
250
300

Dependence of Molar Mass
Distribution on Monomer
Conversion
Dependence of PDI (Mw/Mn)

on Monomer Conversion
c o n v e r s io n / %
nDIBAH/nNd = 10
nDIBAH/nNd = 20
nDIBAH/nNd = 30
nDIBAH/nNd = 50
difference
index Indices
Difference
inof refraction
Refractive
8 2 .5
4,0
6 6 .4
3,5
5 5 .1
4 3 .5
3 5 .6
Mw/Mn
5 0 .0
3 0 .7
2 2 .7
1 2 .2
3,0
2,5
2,0
1,5
1,0
0 10
7 .8
20
4 .8
30
35
30
35
40
40
45
45
50
50
55
55
60
60
30 40 50
60 70 80 90 100

65
65
e lu t io n t im e / m in
Elution time[min]
Source:
L. Friebe: Diploma Thesis at TU Munich, December 2.000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064

Dependence of Mn on
Monomer Conversion
Mn [g . mol-1]
2,0*105
nDIBAH/nNd = 10
nDIBAH/nNd = 20
nDIBAH/nNd = 30
nDIBAH/nNd = 50
1,5*105
1,0*105
0,5*105
0
0 10 20 30 40 50 60 70 80 90 100
Formal Number of Polymer

Chains formed per Nd-Atom
2,5*105
Molar Mass Control

with Al-Component
16
nDIBAH/nNd = 10
nDIBAH/nNd = 20
nDIBAH/nNd = 30
nDIBAH/nNd = 50
14
12
10
8
6
4
2
0
0
10
20
30
nDIBAH/nNd
nDIBAH/nNd = 4,4
Source:
L. Friebe: Diploma Thesis at TU Munich, December 2000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
40
50
Technical Options for the Control of Molar Mass in

Nd-BR Production
Influence of Polymerization Temperature
Nd/Al-ratio
Monomer/Nd-ratio
Monomer Conversion
Polymerization temperature
Molar Mass (Mv)

[kg/mol]
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:
G. Sylvester, B. Stollfuss ACS, Rubber Div. Dallas 1988 Synthesis of

cis-1,4-Polybutadienes by rare earth catalysts
2500
2000
1500
1000
500
0
0
10
20
30
40
50
60
70
80
90
Influence of Butadiene/Nd-ratio
Influence of Monomer Conversion
D. J. Wilson, Polymer 1993, 34,16, 3504-3508
M. Bruzzone ACS Symposium Series No. 3 (1982)

33-55
900
60
ML 1+4 (100C)
Molar Mass (Mv)

[kg/mol]
800
700
600
500
400
300
200
50
40
30
20
10
100
0
0
0
0,05
0,1
0,15
0,2
0,25
0,3
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
Ni
Ti
Nd
Solvents
Benzene
Benzene
Benzene
N-Hexane
Cylcohexane
Hexane
Toluene
120 min
Toluene
Residence time
Toluene
Aliphates
150 min
120 min
100-120 min
55-80 %
< 85%
< 95%
< 100%
high
high
low
Very low
Partially
adiabatic
11-12%
fully
adiabatic
18-22%
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
yes
none
none
high
10-50
high
50-100
very high
200-250
low
100-200
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
EPM
Sulfur
Peroxides
Phenol resins
etc.
(15%)
EPDM
(85%)
Ethene/Propene-Copolymers
Ethene/Propene/Diene-Terpolymers
Major areas of application:
Major areas of application:
Oil additives
Impact modification of thermoplastic
polymers (PP)
(30% of grades are oil extended)
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)
~ 40 : 1
Dicyclopentadiene
(DCPD)
~ 15 : 1
1,4-Hexadiene
(HD)
~5:1
Criteria for the selection of the termonomer:

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

Characteristics
ENB
DCPD
HD
70
ENB
DCPD
1,4-HD
Torque [Nm]
60
50
40
30
20
10
0
0
1,0
2,0
3,0
time [min]
4,0
5,0
6,0
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
Automotive production (world)
200
45
1995
1994
1993
1992
1991
100
40
Automotive Production / Mio.
300
1990
Automotive
Thermoplast Modification
Building
Technikcal Rubber Goods
Electro/Electronics
Oil Additives
50
400
1989
41%
500
1988
6%
1987
16%
9%
55
700 EPDM Consumption (world)

600
1986
13%
15%
EPDM-Consumption / kt
Main Application Areas of EPM/EPDM
Market: 1,050 Mio t (2004)

Growth rate:
3,5 %/a
Source: European Chemical News 10, Mrz 2005, 13
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
EPDM/2% ENB
EPDM/1% ENB
EPM /0% ENB
-47,5
-50
Tg [C]
-52,5
-55
-57,5
-60
Tg(EPDM) = Tg(EPM) + 1,2C/wt.% ENB
-62,5
-65
40
45
50
55
60
65
70
Ethene content [wt.%]

Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001
Dependence of the Cristallinity on the Ethene Content and

on the Polymerization Temperature of V-Catalysed EPM
30
Enthalpy of fusion [J/g]
35-39C
25
40-44C
45-49C
20
50-54C
55-59C
60-64C
15
65-70C
10
5
0
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
Ethene content [wt.%]

Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001
Chemical and Process Aspects in EPM/EPDMManufacturing Technologies

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

Technologies
Source: R. T. Sylvest, J. A. Riedel, J. R. Pillow; GAK 6/1997 (50) 478-483
Process
Solution
Solvent:
Catalyst System
Catalysts:
Cocatalysats:
Reactivators:
Modifier:
Short stos:
Antioxidans:
Stripping aids:
Oil:
Hexane
Slurry
High temperature
solution (Dow)
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.
-
Gas phase
(UCC)
Ziegler/Natta
V(acac)3
Al-Alkyl
CHCl3
H2
?
?
-
Reactivators:
PDCAE
BPCC
Cl
Cl
O
C2H5
Cl
Cl
O
Cl
Cl
Cl
C4H9
Cl
Cl
TCAE
O
O
C 2H 5
Cl
Speculation on the Active Species in the

Vanadium-Catalysed EPDM-Polymerization
+V VOCl3
+IV VCl4
VX3 + R2 AlX
+II
VX2 + R3 Al
{R2VX}
Aktivator
+III
{R2V }
heat
heat
[R2V]
R2AlX
{homogeneously soluble species}
+ R2AlX2
[RVX]
R3Al
[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
total capacity
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
1076
Source: European Chemical News 10, Mrz 2005, 13
EPDM-Solution-Process with Fully Flooded Reactor

Water containing
azeotrope
ENB
Condenser
Boiling point:
Max. exposure limit/MAK:
Smell limit:
Settler
External
cooling
loop
146C
1 ppm
3-5 ppm
Waste water
Condenser
Azeotropic
destillation
Flash
drum
Stripper
Waste air
Propene
dewtering
screwg
Hexane Ethene
destillation
Steam
Polymerization
reactor
Expeller
Settler
Steam
destillation
drier
Waste water
Stripping
aid
drier
Precoller
-32/-35C
Water
Modifier
Reactivator
Drier
Hexane
drier
VNB/ENB
EASC
VOCl3 /VCl 4
3/1
oil
PHControl
drier
Antioxydant
Waste water
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
Packaging
Dows High-Temperature Solution Process

(Source: Dow-Patents, Publications etc.)
Plant location: Plaquemine/Lousiana
Destillation
Solvent
and
monomer
Condenser
Evaporator
Flashdrum
High boiling
residue
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)
Evaporator
(ENB, AO, etc.)
Ta
Antioxidant
(AO)
Polymerization
reactor
baler
Ageing
drum
"Insite-Kat."
Scavenger
Purification
Purification
Ethene
Propene
Temperature:
Ta:
Pressure:
Residence time:
Purification
ENB
packaging
MMAO
40 - 80 C
80C (>130C)
9-15 bar
< 20 Min.
Borane
Metal Content of Commercial EPDM

Activation of Metallocenes
Cl
Alkylation
Zr
Zr
Cl
Activation by MAO
(molar excess of MAO:
10.000 - 10.000 fold)
Activation by
Borane/Borates:
(with molar
B/Zr-ratios)
R
Zr +
Product V Ti Fe
Al Ca Na Sum
Dow-CGC <1 1,0
1,3
1,7
<1
<1
8,0
EPDM # 2 8,0 <1
4,3
31
1,7
1,8
22,3
EPDM #3
1,9 <1
4,3
31
1,7
1,8
48,8
EPDM #4
2,4 <1
2,0
6,7
64
5,7
EPDM #5
5,1 <1
2,8
9,6
160
4,6
82,8
184,1
EPDM#6
4,8 1,9
63
440
64
9,4
584,1
Source: J. G. Pillow (Dow) Ethylene Elastomers made using Constrained Geometry Catalyst Technology
Kautschuk Gummi Kunststoffe 51, 12/98, 855-859
Crystallinity of Metallocene-Based EPDM

30
EBTHI-Cat.
CH2 CH2
CH2
25
Enthalpy of fusion [J/g]
DOW-Insite-Cat.
CH2
ZrCl2
CH2
20
Me2Si
N
CH2
15
CMe3
CH2 CH
2
Ti
X
V-Catalysis
10
5
0
40
42
44
46
48
50
52
54
Ethene Content [wt.%]
56
58
60
62
Impact of Cristallinity on Low-Temperature

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

Flow-Chart:
US 4994534
Plant location: Seadrift/Texas
Filter
Compressor
Temperature:
Pressure:
Residence time:
< 90 C (40C-60C)
9-15 bar
0,5 - 1 h
Cooler
ENB
Fluidizing Aid
Suported Catalyst
Product
EP 1099715
EP 1099473
EP 1086995
EP 1083192
US 6180738
WO 0000333
WO 9965953
Desactivation
Ethene
Purification
Propene
Purification
Modifier
Patents:
Purification
Monomer
degassing
unit
ENB
Boiling point:
Maximum exposure level:
Smell limit
Purification
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
Solution
Slurry
HT-Solution Gas-Phase
V-Catalysis
V-Catalysis
CGC/Dow
V-Catalysis
10
EPM
EPDM
Low Mooney
High Mooney
Oil Extended Grades
10
10
10
5
7
10
10
8
10
10
10
10
10
3
3
10
0
0
10
0
Process Flexibility
42
48
36
20
Overall Process
Performance
46
43
30
Process Economy
53
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 provideaahigher
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)

2.923 Documents
USUS-Patents and EPEP- and WOWO-Patent Applications
200
150
100
50
Bo
re
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
BP
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
ec
Ho
xo
0
Ex
Number of Patents (US) + Pat. - Appl.
250
WPIDS-Recherche Dr. Karjetta vom 29. 09. 2000
Cl
Zr
Alkylation
(BuLi, AlR3 or MAO)
Cl
Alkylation
(BuLi, AlR3 or MAO)
R
Zr
Cl
Activation by MAO
R
Zr
R
Activation by borates and boranes
R
Zr
+ A
Cossee-Mechanism of Metallocene Catalysed

Olefin Insertion
R
Zr
+
CH2 CH2
Zr
+
R
Zr
+
CH2
CH2
CH2
CH2
R
+
Zr
CH2
CH2
Key Patents in Metallocene- und Single-Site-Catalysts

1.1. Bis Cyclopentadienes
X
Zr
X
X
B
Zr
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

1.2. Isoelectronic Bicyclopentadienyl Systems
N
E
X
Zr
B
R
B
Me
B
Y
Cl
Cl
Ph
Ph
Me
Me
P
Zr
Zr
US 5554775
(17.01.1995)
Lyondell
Cl
Cl
X
X
EP 638593
(02.08.1993)
Shell
Zr
E = N, P
Me2Si
Ph
ZrCl2
SiMe3
WO 96/34021 WO 98/01455
(25.04.1995)
(05.07.1996)
Lyondell
Bayer AG
(Ostoja-Starzewski)
WO 98/50392
(08.05.1997)
Nova Chemicals
(Spence)
WO 97/2351
(22.12.1995)
Hoechst AG
(Herberich)
US 5539124
(19.12.1994)
Lyondell
MAO-/Borate- MAO-/BorateActivation
Activation
Polyolefins
HDPE, PP
PE, PP
HDPE, LLDPE, PP,

EPM, EPDM, COC
HDPE, LLDPE,
PP, EPM, EPDM

2. 1. Mono-Cyclopentadienyl Systems
Me2Si
Ti
MeO
MeO
Ti
N
OMe
EP 210615
(29.07.1985)
Idemitsu Kosan
US 5206197
Dow
(04.03.1991)
MAOActivation
S-PS
CMe3
EP 416 815
(31.08.1998)
Dow
EP 420436
(13.09.1989)
Exxon
MAO-/BorateActivation
HDPE
LLDPE
EP(D)M
ES
(IV)
X
X
Ti
Ti
RxE
III
X
X
E= N, O
NR2
X
X
US 5132380
(12.09.1991)
Dow
WO 96/13529
DSM
(Lovocat)
Borate-Activation
MAO_/BorateActivation
HDPE
LLDPE
EPM
PO

2.2. Mono Cyclopentadienyl Systems
F
F
Ti
F
F Ti
N
F
t-Bu
t-Bu
CH3
CH3
CH3
CH3
Ti
N
P
t-Bu
WO 2005/005496
DSM
WO 2008/095687
DSM
US 6063879
(29.10.1997)
Nova
MMAO-Activation
MMAO-Activation
MMAO-Activation
EP(D)M
EP(D)M
PE, LLDPE

3.1. Post Metallocenes
Ar
Ar
Ar
X
X
P
Ar
Ti
Ti
Pd
Ar
O
O
N
Ar
t-Bu
WO 92/12162
(27.12.1990)
Exxon
X
Zr
X
O
N
t-Bu
EP 121965
(05.04.1983)
Shell
JP 5230133
(19.02.1992)
Mitsui Toatsu
EP 606125
(08.01.1993)
Shell
US 5637660
(17. 04. 1995)
Lyondell
Polyacetylens
Polyolefins,
HDPE, PP
Polyacetylens
EP 571945
(29.05.1992)
Sumitomo
Alternating
Polyolefins
Olefin/CO-Copolymers
(Carilon)

3.2. Post Metallocenes
R
R
R
X
N
Cl
M
N
Fe
Cl
Cl
N
Cl
N
Ti
O
M = Ni, Pd
WO 96/23010
(24. 01. 1996)
DuPont
(Brookhart)
DuPont
(Brookhart)
BP
EP 0874005
(24.01.1998)
Mitsui
EP 1881014
(10.05.2006)
Mitsui
polar/unpolar
Copolymers, LDPE
HDPE, (PP)
HDPE(PP)
HDPE, EPM
EPM, EPDM
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)
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
F
R
Zr
R
-R
F
F
F
F
F
F
F F
N+
Ph
Zr +
F
F
Anilinium Borate
F
F
F
Ph
Ph
Me
Me
Borane
Triphenylcarbenium
Borate
B
Ph
For the Activation of metallocenes molar quantities of borane/borates are

required
Polymerizations activated by boranes/borates are very susceptible to impurities
R
R. F. Jordan Turner M. Bochmann

Turner
(1990)
(1986)
1987
1987
Zr
R
-R
M. D. Rausch,
J. C. W. Chien
(1991)
Ag
N+
BPh4
Ph
Me
+R
Ph
CH3CN
Me A
+R
- RH
Ph
B
F5
+R
R
Zr +
+ Ph
T. J. Marks (1991;
JACS 113, 3623)
F5
+R
N
Ph
Me
A :
F
F
F
F
- F
F
F
Ph
Ph
- F5
F5
Ph
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)
FF
F5
Me
R
Ag+1/2 R2 + BPh4
F5
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
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
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
Activation of metallocenes
by borates (Exxon/Turner)
EP 418044; Prior.: 14.09.89 [Cp1MXn]+ [BR4]-
Activation by borates (Dow/Stevens)
Activation by boranes (Fina/Ewen) EP 427 697; Prior.: 10. 10. 1989
1990
CGC-Activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993
CGC/Diene-activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993

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

F
F
F
F
F
F
F
F
F
F
B
F
F
F
F
F
F
F
F
F
F
F
F
FF
F
F
FF
F
Si
F
F
FF
F
F
F
F
F F F
FF
F
F
F
F F
F
F
F
F
F
F
F
F
F
F
F
- F
FF
4
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 1066296
(Bayer AG)
Prior.:
24.03.1998
Inv.: Becke, Denninger,
Mager, Windisch
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 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
[EUR/100 kg] 2,25
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
MAO-activation
MAO-activationof
ofmetallocenes
metallocenesisisnot
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
CH2 C
CH3
CH CH2 CH2 C
CH2 C
CH3
CH3
CH3
20
CH3
Butyl Rubber (IIR)

CH
2
35
CH3
CH2 C
CH3
CH3
CH2 C
CH3
CH3
CH2
CH2 C
CH CH2 CH2 C
CH2 C
CH3
CH3
CH3
CH2 C
CH2 CH CH2 CH CH2 C
CH3 n
CH3
CH2Br
CH3
123
CH
2
21
16
15
29
30
CH3
CH2
CH3
C27
CH
2
26
H3C
CH
28
45
CH
C
2
23
H3C
Standard Angle: 109,5
Basic Features:
Isoprene content:
0,5 - 2,5 Mol%
Incorporation of Isoprene: random 1,4-trans
Tg:
ca. -72C
Mw/Mn:
3-5
CH3
Brominated Isobutene-co-p-Methylstyrene Rubber (BIMS)

Isobutene-Terpolymers
19
CH3
CH3
X = Cl: Chloro Butyl Rubber (CIIR)

X = Br: Bromo Butyl Rubber (BIIR)
CH3
38
39
CH3
Butyl- and Halo Butyl Rubber (X)IIR: Property Profile and

Areas of Application
Property Profile
Positive:
Tyres
Others
Chewing gum
5%

high resistance to heat and vapour
high resistance to chemicals
good insulation properties
good covulcanization (XIIR))
product purity
(grades without antioxydants)
Pharmaceutical
Adhesives
Automotive
4%
3% 1%1%
Negative:
low elasticity /highly damping
Areas of Applications:
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
86%
Source:
CHEManager 20/2006, Seite 8 (GIT Verlag Darmstadt)
Butyl and Halobutyl Rubber (X)IIR: Grades

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

X2 (Cl2 / Br2)
CH3
CH2 C
CH3
CH2 C
CH3
CH3
CH3
CH2
CH2 C
n
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)
Rebound
Temperature [C]
(50 phr SRF, without plasticizer)

70
60
50
100
Rebound Elasticity [%]
1,4-cis BR
60
Luftdurchlssigkeit(Q x 10exp8)
80
SBR
NBR
NR
EPDM
40
IIR
20
0
-75
-50
-25
0
25
50
Temperature [C]
75
1,4-cis-BR
NR
EPDM
10
SBR
NBR/28 ACN
NBR/33 ACN
NBR/38 ACN
IIR
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:
- 2,3 %/ p.a.
+ 2,3 % p.a.
+ 1,2 % p.a.
(90%:
XIIR:
IIR:
IIR:
Tyres and Tyre Production)

Inner liners
Truck tyre tubes
heating bladders
Pricing (1996):
700
Company
400
300
200
100
0
20
00
19
97
19
94
19
91
19
88
19
85
Butyl Halo- Total

butyl [kt]
Exxon
414
Lanxess
252
Nizhnekamsk
180
Togliatti
Sinopec
(X)
45
Japan Butyl Co.
80
Total Capacity
19
82
ca. 1,80 /kg

ca. 2 /kg
ca. 3,5 /kg
Production capacities (2008)
500
19
79
Consumption [kt]
600
IIR:
XIIR:
BIMS:
IIR
XIIR
Sum
50
1.041
Range of Commercial IIR and XIIR Grades
100
100
90
90
80
80
70
60
50
40
30
70
60
50
40
30
20
20
10
10
Ch
Br lorb
om uty
bu l
tyl
Range of XIIR Grades
Mooney Viscosity
ML (1+8) 125C
Mooney Viscosity
ML (1+8) 125C
Range of Standard Butyl Grades
0
0
10
Content of double bonds [Mol%]
10
Halogen Content [Mol%]
IIR: Flow Chart of Slurry Polymerization

(Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)
compressor
CH3Cl
AlCl3solution
drum
dryer
compressor
Al2O3
Cond
enser
catalyst cocatalyst
drum
H2O
slop isoprene
H2O
Storage tank
for
mixed feed
Storage
units for
IIR-slurry
in water
NH3EtheneHeat exchangers
Isobutene- Isoprene
drying unit
Reactor
Steam- Flashunit
Strippingunit
Features of IIR Production Technology

Process:
Catalyst:
Cocatalysts:
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
Ethylene
(gas)
Ethylene
(liquid)
Inlet and Drain

for light
hydrocarbon
wash
catalyst
Sources:
mixed feed
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
HCl
AlCl3
H2O
+
H + AlCl4
+ AlCl3OH
CH3
Initiation of Polymerization:
CH3
CH3
Chain Propagation (Growth) Reaction:

CH3
CH3
n
CH2 C
CH3
CH3
CH3
CH3
+
C + CH3 C AlCl4
CH3
CH3
CH2 C Cl + AlCl3
CH2 C
n
CH3
CH3
CH
CH2 C
CH3
CH3
CH3
CH3
CH3
CH2 C AlCl4
CH2 C
CH3
CH3
Termination Reaction:
CH3
CH3
H
+
CH2 C AlCl4
CH2 C
CH3
CH2 C AlCl4 +CH2 C
CH2 C
CH3
CH3
CH3
CH3
Transfer Reaction:
CH3
CH3
H
AlCl4
CH3 C
CH3
+
H + AlCl4 + CH2 C
+
CH3 C AlCl4 +
CH3
CH3
IIR: Living Cationic Polymerization

Generation of Carbo Cation:
R - Cl + MX n
+ MX n+1
Initiation:
CH3
CH3
R
+ CH2 C
Propagation:
CH3
CH2 C MX n+1
CH2 C
CH3
Reversible Termination:
CH3
CH3
R
CH2 C
CH2 C
CH3
CH2 C
CH2 C
n
CH3
CH3
CH3
MXn (Metal halides) and R-Cl used for the preparation

of Isobutylene based blockcopolymers:
Cl
BCl3 and TiCl4
MX n+1
CH3
CH3
MX n+1
CH2 C
CH2 C
CH3
CH3
CH3
CH3
CH3
MX n+1
CH2 C
CH3
CH3
R
Cl
MX n
CH3
Cl
Cl
Cl
Cl
Influence of Polymerization Temperature on Molar Mass

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

Storage tank
Halogenation reactor
Neutralization reactor
Br2 bzw. Cl2

IIR-solution
in hexane
Addition of AO
Hexane
water
X-IIRSlurry
in water
Antiagglo- steam
merants
Caustic
soda
Source: Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)
XIIR: Mechanism of IIR-Halogenation
CH3
CH2 C
CH3
CH2 C
CH3
CH3
CH3
CH3
CH2 C
CH2 C
CH3
CH3
CH2 C
CH3
CH3
CH3
CH3
CH CH2 CH2 C
CH2 C
n
X2
CH3
CH3 H
X
CH3
CH2 C
n
CH3
CH2 CH2 C
CH3
CH3
CH2 C
CH3 H
CH2 C
n
CH3
CH2 C
CH3
CH2 C
CH3
CH3
CH3
CH3
CH2 C
CH3
CH2 C
CH3
CH3 X
Source:
CH3
Kirk-Othmer Encyclopedia of Chemical Technology,

Fourth Edition, Volume 8, 1993
CH CH2 CH2 C
- HX
CH2 X
CH2 C
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
CH2 C
Solvent:
IIR-solids
Ratio of Halogen/Isoprene:
Reaction temperature :
Residence time:
Stripping-Vapour :
Antioxydants / stabilizers:
CH2 CH2 C
- HX
CH3
Reaction Conditions:
CH3
CH3
CH CH2 CH2 C
CH3
Patents:
US 2631984; US 3099644; US 4288575; US 4554326;
US 4632963; US 4681921; US 4650831; US 4384072;
US 4513116; US 5681901
Crosslinking Efficiencies in Vulcanization by

Peroxides (Dicumyl Peroxide)
Rubbber
O O
2
C
(R*)
efficiency
(98% Vinyl)
Number of crosslinks
Type of Rubber
~ 100 1)
Vi-BR
+ 2 R-H
X-linking efficiency =
X-linking
SBR
12,5
cis 1,4-BR
10,5
EPDM
1,5
EPM
0,4 - 0,7
NBR
1,0
Theoretical Cross-
IR
1,0
linking efficiencies
CR
0,5
Peroxide Functions
M - Rubbers
IIR
<<1
R - Rubbers
>1
PE
1,0
Degradating polymers
<1
PP
<<1
1)
Dissertation Th. Frh, TU Hannover 1995
Properties of Sulfur- and Peroxide Cured IIR and XLIIR

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

Bismaleic Imide
CH3
CH3
CH2 C
CH3
CH3
CH2 C
CH3
CH2 C
CH3
CH2
CH2 C
CH CH2 CH2 C
CH3
CH2 C
CH3
CH3
CH2 C
CH3
CH2
CH3
CH3
CH3
+ ZnO
- ZnOHX
CH3
CH CH CH2 C
O
CH3
CH2
O
CH2 C
CH3
CH2 C
CH3
CH2 C
CH CH CH2 C
CH3
C
CH3
CH2 C
CH3
CH2 C
CH3
CH2
CH2 C
CH3
O
CH3
CH CH CH2 C
CH3
IIR and XIIR: Methods of Vulcanization and

IIR (Lanxess Butyl 301)
XIIR (Bromo butyl
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
-
100
50
5
1,0
-
1,5
0,5
180
4
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]
Vulcanization
Compound Properties
ML 1+4 (100C)
[MU]
MS5 (125C)
[min]
MS5 (135C)
[min]
Physical Properties
Shore A Hardnes
[MPa]
M100
M300
[MPa]
CS (70h/150C)
[%]
100
100
100
100
100
100
100
50
50
50
50
50
50
50
S/MBT
Chinon
Resin
ZnO
DCP
DCP/BMI
ZnO/BMI
91
94
82
83
88
88
89
17
>30
16
12
14
16
66
64
64
48
40
54
58
2,5
2,1
1,9
0,9
0,5
0,12
0,19
5,2
1,8
9,5
10,2
16,6
12,8
15,8
12,4
8,9
10,5
13,6
530
400
590
580
680
325
360
68
68
12
58
53
28
13
Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92
J. Rogers, W. H. Waddell (Exxon) Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturbersicht, GAK 9/1999-Jahrgang 52, 670-682
Influence of Oil Loading on Properties of BIIRVulcanizates
BIIR
Polysar Brombutyl 2030
100
100
Carbon black
N 660
60
60
Paraffin Oil
Sunpar/Sunoco Inc.
Resin
Pentalyn A / Hercules
1,3
1,3
Zinc oxide
Sulfur
0,5
0,5
Stearic Acid
MBTS
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
-
BIIR
7
72
5,1
2,3
62
5,5
2,2
10,5
650
0,9
1,7
5,4
60
47
9
30
2,3
8,9
670
0,8
1,1
4,0
58
40
9
29
3,0
Influence of Carbon Black Loading on BIIR

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

BIIR (Butyl rubber 2030)
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]
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
100
40
100
30
100
20
100
0
72
5,1
62
7,4
56
7,6
51
7,8
40
7,2
2,3
2,9
6,2
7,9
1,7
3,3
6,8
5,5
1,4
1,3
7,1
4,3
1,2
3,3
7,8
3,4
0,8
3,3
6,8
2,2
11,8
730
0,9
1,3
5,4
55
43
10
32
2,14
0,647
0,251
13,1
865
0,7
0,9
2,4
46
33
10,7
39
2,27
0,809
0,215
13,7
975
0,7
0,8
1,8
39
27
11,9
42
2,39
0,863
0,190
13,5
1055
0,6
0,7
1,2
33
23
12,2
44
2,58
0,900
0,178
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
100
CIIR
100
NR
60
40
80
60
40
20
20
40
40
60
60
60
60
60
60
60
60
60
60
Paraffin oil
Pentalyn A*
Stearic acid
Zinc oxide
MBTS
1,0
1,0
1,0
1,0
1,0
1,0
1,0
1,0
Sulfur
0,5
0,5
0,5
0,5
0,5
0,5
0,5
0,5
80
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]
Aged (168h/100C)
M300
[MPa]
Tensile Strength
[MPa]
Air permeation at
50psi/65C (Q x 10-8]
Adhesion at 100C
Self adhesion / tack [kN/m]
Adhesion to NR
[kN/m]
Fatigue to failure after
ageing at 168h/120C [kcycles]
40
60
100 100
-
80
20
4,2 3,7
9,3 9,9
740 770
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
6,8
10,0
550
2,9
7,6
9,8
420
5,4
5,5
10,9
640
2,9
16,8 4,4
7,5 1,3
80
20
7,9
11,0
465
5,7
14,7 4,7
10,0 1,6
61,8 72,7 23,6 3,9
60
40
8,4
9,3
320
9,2
60
40
7,7
9,2
365
7,5
15,2 9,1
14,7 1,9
0,3
0,1
40
60
6,7
8,8
370
13,8
3,6
5,8
475
13,2
15,4 5,2
20,8 2,9
0,0
0,0
5. Rubber Specialities:
Performance Profiles of Vulcanizates
Maximal Service Temperature

100
80
Processability
60
Low Temperature Performance
40
20
0
Silicon Rubber
Hydrogenated Nitrile Rubber
Fluoro Rubber
Ethylene-Vinylacetate-Copolymers
Ozone Resistance
Oil Swelling
5.1. Fluoro Rubber (FKM / FPM)

Bond
Bond
energy
[J/mol]
Radius
of atoms
[A]
C-H
413
0,37
C-F
485
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:

60 %
10 %
10 %
Positive:
Excellent resistance to ozone, UV- and weather
High service temperature
Low oil swell
High resistance to chemicals and acids
High flame resistancy
20 %
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:
Automotive (75% in Europe)

Aviation and Aerospace
Chemical planty s (Fume treatment
of incineration and power plants)
rest
30-40 %
30-40 %
10-15 %
~5%
4.5 %
10 %
O-Rings and seals

crank shaft seals
hoses and profiles
Modification of polyolefins
pipes and tubings
rest
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

World Market
Market:
2002: ca. 15.000 t
Prices:
Top price:
20 - 50 EUR/kg
(correlated with F-content)
~ 500 /kg (Kalrez)
Growth:
8 - 10% p. a.
Return on Sales: 20 - 25%
Asia
22%
USA
45%
WEurope
33%
Source: Kunststof En Rubber; 11 November 2003
Producer
Trade
names
Market
Share [%]
Site
Capacity*
[kt]
Du Pont
Viton/Kalrez
43
3,0
1,0
1,0
Dyneon
Fluorel
22
Deepwater, NJ
Dordrecht, NL
Utsonomiya, Jp
Kawasaki, Jp
Decatur, AL
Solvay
(Ausimont)
Daikin Kogyo
Asahimont
Asahi Glass
Unimatec
Tecnoflon
15
Daiel
10
Aflas
Noxtite
5
5
DuPont-Showa
Zwijndrecht, BE
Gendorf, DE
Spinetta, I
Osaka, Jp
Chiba, Jp
Chiba, Jp
Jp
Estimated total capacity: 20 kt; capacity utilization: 80-100%
2,0
2,1
2,0
1,0
2,0
1,0
1,0
FKM: Composition of Standard Grades

HFP
Fluorine containing monomers
[w
.t%
]
40
60
HF
P
VDF
F
C
TFE
F
F
F
CF3
C
80
20
F
C
60
40
us
ho s
orp er
Am olymbers)
P
b
(ru
]
.%
wt
F[
VD
20
80
HFP
F
Y
Copolymers
[wt.%]
TFE
80
60
40
TFE [wt.%]
VDF
[%]
33
55
22
X
Y
Z
Soures:
fluorine cont.
TFE
[%]
33
23
12
20
VDF
HFP
[%]
33
22
65
TFE/P
54
VDF/HFP
65
VDF/HFP/TFE
67
VDF/HFP/TFE/CSM*
69
TFE/PMVE/CSM*
71
*Cure Site Monomer
A. L. Logothetis Chemistry of Fluorocarbon Elastomers Prog. Polym. Sci., Vol. 14, 251-296 (1989)
FKM: Performance of Standard Grades

Copolymers
Fluorine Cont.
Volume swell
[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
-
-18
-8
-5
-19
-2 (0)
Storage in motor oil which contains amines (163C)
180
Benzene/21C
160
reduction of elongation at
break [%]
Volume Swell [%]
Tg [C]
Gear Oil/121C
140
120
100
80
60
40
20
0
60
65
70
Fluorine Content [wt.%]
75
10
0
-10
-20
-30
HNBR
FKM (68% F)
-40
-50
-60
-70
-80
0
200
400
600
time [h]
800
1000
FKM: Glass Transition Temperatures

F
Glass transition temperature [C]
TFE/VDF/PMVE
TFE/VDF/HFP
-5
-10
CF3
VDF Vinylidene fluoride

(59% fluorine)
HFP Hexafluoropropene
(76% fluorine)
-15
-20
-25
-30
CH3
-35
0
0,5
1,5
TFE Tetrafluoroethylene
(76% fluorine)
CF3
PMVE Perfluoromethylvinyl ether

(69% fluorine)
P
Propen
Hydrogen content [wt.%]
Source: J. Scheirs Modern Fluoropolymers High Performance Polymers for Diverse Applications John Wiley & Sons
Ageing Resistance in Media with Basic Additives
Range of FKM-Grades and Vulcanization
Vulcanization with
Peroxides
peroxidisch
Vulcanization with
Bisphenols
Vulcanization
with Diamines
Aflas
Viton A
PVDF
55
Viton B, GF
Viton GLT
Kalrez PTFE
65
Fluorine Content [wt. %]
75
FKM: Vulcanization with Diamines
1. Elimination of HF by MgO, CaO und PbO.

CF3
CF2
CF3
- HF
CF2
CH2 CF2 CH2 CF2
CF3
- HF
CH CF2 CH2 CF2
CH CF CH CF2
CF2
2. Crosslinking by Diamines, which are used in "capped form" (such as carbamates) in

order to increase scorch resistance
CF
CF
3
CH CF CH2 CF2
CF2
CF3
CF2
CH CF CH CF2
CF2
CH CF CH CF2
H2N
CF2
CH
N
NH
NH2
- 2HF
R
N
NH
CF3
CF2
CH2 CF2
CF2
CH CF CH2 CF2
CF3
CH
CH2 CF2
CF3
Diamine cure yields crosslinks which are liable to hydrolysis (not steam resistant)
CF3
CF3
CF2
CH
CF2
CH2 CF2
CH
O
H2O
CH
O
CH2 CF2
CF2
CF3
Sources:
NH2
R
N
CF2
CH2 CF2
CH
NH2
CH2 CF2
CF3
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
CF3
- HF
CF2
CH2 CF2 CH2 CF2
CF3
- HF
CH CF2 CH2 CF2
CF2
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
OH +
HO
CH2 P
Cl
CF3
- HCl
CH2 P
HO
CF3
CF3
n
n
CF3
CF2
CH CF CH CF2
CF3
CH CF CH2 CF2
O
HO
CH CF CH CF2
CF2
CF2
CF3
CF3
Sources:
CF3
CF3
CF3
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
CF2
CF2
CF2
CF
CF2
CF2
CF
CF2
CF2
CF2
Br
CF2
CF2
Br/J-Content:
0,5-1 wt.%
C H2J2
C F2J2
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
CFBr
CF2
CHBr
CF
Br
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:
5.2. Silicon Rubber (Q)

CH3
CH3
(
Si
CH3
CH3
CH3
CH3
Si
Grade
Si
)
n
MQ
)
n
VMQ
Si
)
n
PVMQ
CH
CH3
CH2
CH3
(
Si
Positive:
Negative:
CH3
Si
CH2 CH2
CF3
Si
)
n
Low reistance against acids, bases, vapour and

hydrocarbons (significant improvement with
FMVQ)
Mechanical properties
RTV: poor HTV: better / DVR !
High gas permeability
Bond energies
Si-O
C-O
C-C
C-S
S-S
FMQ
CH3
CH3
- 45
- 45
- 70
Low temperature performance

High temperature resistance
Low dependence of properties on temperature
changes
Ozone-, UV- and Weather resistance
Hydrophopic character
Physiological inertness
CH2
Tm [C]
- 120
- 120
- 120
- 69
Vulcanizate Properties:
Si
CH
CH3
Tg [C]
MQ
VMQ
PVMQ
FMQ
[kJ / mol]
444
339
348
272
266
Silicon Rubber: Properties and Application Areas

Application Areas:
Haushalt
20%
Medical
Applications
25%
Automotive
industry
40%
Machine building
15%
Pharmaceutical- and medical rubber

goods
Rubber goods with food contact
Cable insulation
Adhesives
Temperature [C]
duration
90
121
150
200
250
315
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)
Sources:
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
Dow Corning
Momentive
(formerly: GE + Bayer)
SiloxaneCapacity
[kt]
Silicone
RubberBrand Name
Carollton, USA
260.000
Silastic
Barry, GB
110.000
Waterford,
USA
110.000
Ohta, Japan
40.000
Leverkusen,
DE
65.000
Silopren
Shin-Etsu
Isobe, Japan
95.000
KE, Sylon
Wacker
Burghausen,
DE
90.000
Elastosil
Nnchritz, DE
30.000
Rousillon, FR
60.000
Rhodia
S Western World (2000)
Rhodorsil
850.000
*Evonik and Crompton are active in this market without proprietary siloxane production
Japan
25%
Nordamerika
44% Year
1995
Consumption
/t:
Growth rate 2005:
2005
~ 110.000
~ 200.000
ca. 3,5 % / a;
LSR ca. 10 % / a
Europe
31%
Source:
Winnacker/Kchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Silicon Rubber: Production

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

H3C
O
H3C Si
O
Si
H3C
H3C
CH3
CH3
Si
CH3
85 %
O
O
CH3
CH3
Si
OH
15 %
Si
Si
CH3
CH3
CH3
bliche Temperaturen:
KOH
140C
NaOH
170C
Katalysatoren:
Suren, Lewis Suren, Saure Silikate,
Basen
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.%)
CH2
HC
O
H3C Si
O
H3 C
Si
CF3
CH2
CH
Si CH3
O
O
Si
CH
CH3
CH
CH2
CH2
CH3
H3C
Si
Si
H2C
O
H3C Si
Si
O
O
H3 C
CF3
Si
H3C
CH3
CH2
CH3
Si
O
Si
CH2
CF3
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

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

(RTV)
Silanol containing
Silicon rubbers
Platinum catalyzed hydrosilylation

at low or elevated temperature
(RT to 80C, LSR: 110-200C)
Silicon rubbers with

silanol and vinyl
groups
High temperature-Vulcanization
with peroxides (HTV: 120-180C)
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
OH
HO
OR
RO
Si
- 4 ROH
O
Si
OR
OH
Si
Si
Si
OR
Si
HO
Si
Si
Si
R
Typical mulftifunctional alkoxysilanes are:
RO
OR
OR
Si OR
RO
Si OR
RO
O ( Si
Si
OR
OR
OR
OR
O
)
n
R = Me, Et
OR
Metal carboxylates are often used for catalysis :

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

(1K- und 2K-Systems)
1b)
Condensation of polysiloxanes which contain capped silanol groups by

multifunctional alkoxysilanes
R
Si
O
CH3
CH3
RO
OR
Si
R
Si
R
O
O
RO
CH3
Si
O
CH3
Si
Si
Si
+ H 2O
- CH3COOH
Si
R
OR
Si
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
OH
Si
Si
- H2
R
Si
HO
Si
Si
Si
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 (50-150C)

CH3
(
Si
CH3
O ) Si
n
CH3
CH
CH3
Si
CH3
O ) Si
n
CH3
O
CH2
(
Pt-Compounds as
H2PtCl6 (ca. 10 ppm)
Si
CH3
CH2
CH3
CH2
( Si
CH3
CH3
Inhibitors:
CH3
O ) Si
n
O ) Si
n
CH3
Si
HT-Vulcanization of Silicon Rubber

3) Peroxide Cure (120-180C)
Temperature F
Typical Peroxides
(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
R
Si
Si
Si
Si
Si
Si
R*
Si
R
Si
R
Si
Si
R*
Si
Si
Si
R
Si
- 2 H*
R
Si
Peroxide
R
O
Si
R
Si
R
Si
R
Impact of Vulcanization Method on Cost of Articles

Comparison of PeroxidePeroxide- (HTV) and platinum catalysed LTVLTV-Cure
Cost Factor
HTV
LTV
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 [%]
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
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
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
C
N
CH2
CH
H3C
CH2
Butylidene-Moiety
H
CH CH
C
C
H2
H2
Ethylidene-Moiety
CH
2
CH
2
1
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

Blow Out Preventer
Expansion
Joints
15%
45%
25%
7%
Ship Couplings
4%
4%
Riemen
Schluche
Dichtungen
Kabel
lfrderung
Sonstige
Rotor/Stator- Pumps
Roll Covers
Oil well Packers
Catalytic Hydrogenation of NBR

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:
Selective Hydrogenation of C=C bonds
(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)
C
N
H2/Catalyst
Heterogenous(Supported) Catalyst Systems:

C
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
C N
- NH3
HNBR Grades with Low Mooney Viscosities
R
C
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.
C
N
Catalyst
R
CH 2 H C
C
N
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.
Catalysts without Activity in NBR-Metathesis *

PCy3
PPh 3
Cl
Cl
Ru
Ru
Ph
Cl
Cl
PCy3
PPh 3
BH 3
2Ph
Ciba-Catalyst
Cl
Ru
Cl
Grubbs-I-Catalyst
Ru
Cl
P
PCy3
BF 4
Cl
R1
Cl
PCy3
R3
Ph
Catalyst from Prof. Berke' s

group (University of Zurich)
Ph
Frstner-(I)-Nolan-Catalyst (Umicore)
2-
SnCl3
BH 3
Ph
Ru
Cl
Cl
Ph
Ph
Ru
SnCl 3
Ph
Cl
SnCl3
2-
SnCl 3
Ph
P
Ph
2
2
Catalyst from Prof. Berke' s group (University of Zurich)
Catalyst from Prof. Berke' s group (University of Zurich)
*Source: Julia-Maria Mller, Dissertation TU Mnchen
Catalysts which are Active in NBR-Metathesis*

(Number of Catalytic Steps (TON))
Mes
CF 3 COO
Mes
Mes
Mes
Mes
Mes
Cl
Cl
Ru
Ru
Cl
CF 3COO
R1
P
Ru
Cl
PCy 3
R2
R3
Buchmeiser-Nuyken-Catalyst
TON = 8 / 23C
Mes
Piers-II-Catalyst
TON=12 / 55C
Grubbs-II-Catalyst
TON=40 / 23C
Mes
Mes
Mes
Mes
Mes
Cl
Cl
Ru
R2
Piers-Catalyst
Cl
Ph
PCy3
Cl
2 K
Ru
Cl
Cl
Ru
Cl
Cl
O
O
NO 2
Grubbs-Hoveyda-Catalst
TON=53 / 23C
Grela-Catalyst
TON=78 / 23C
Ru
N
Br
Grubbs-III-Catalyst
TON=120 / 23C
*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
Br
Sequence of Process Steps in NBR and HNBRProduction

NBR-Production: Sequence of Process Steps:
Removal of
residual
monomers
Emulsionspolymerization
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
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
Capacity [t]
Zeon
Takaoka
Houston
Japan
USA
2.800
2.000
Lanxess
Leverkusen
Orange
Germany
USA
3.000
3.600
11.400
Total
Markt- und Marktentwicklung

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

(Increase of Mooney Viscosity ML 1+4/100
1+4/100C))
+1
NBR Hydriergrad: 0 %
HNBR Hydriergrad: 96 %
HNBR Hydriergrad: 99,5 %
+0
-1
-2
ln Vbr
-3
-4
-5
-6
-7
-8
2,0
2,4
2,6
2,8
3,0
3,2
1/T *103 [K-1]

T [C]
180
160
140
120
100
80
60
40
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
Tg of HNBR and NBR

E/ACN-Copolymers
HNBR (fully hydrogenated)
100
100
NBR
80
80
60
60
40
20
Tg [C]
40
20
-20
-40
-60
-20
-80
-40
-100
20
40
60
80
Acrylonitrile Cont. [wt.%]
100
20
40
60
80
Acrylonitrile Cont. [wt.%]
Data for Ethene/Acrylonitrile-Copolymers from: R. E. Uschold, I. B. Finlay, Appl. Polym. Symp. 25 (1974) 205
100
Tg of Ethene/Vinylacetate- und Ethene/Vinylchloride-Copolymers

Ethene/Vinylacetate-Copolymers
100
Ethene/Vinylchloride-Copolymers
80
80
Levapren
Nielsen et al.*
60
Tg [C]
100
60
40
40
20
20
-20
-20
-40
-40
0
20
40
60
80
100
40
60
80
100
Vinylchloride Cont. [wt.%]
Vinylacetate Cont. [wt.%]

Source:
20
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
Crystallinity [%]
1. DSC-Aufheizung
12
2. DSC-Aufheizung
10
8
6
4
2
0
0
10
20
30
40
Acrylonitrile Content [wt. %]
50
60
Tgs of Ethylene-Copolymers
100
50
Tg [C]
-50
EPM
HNBR
EVC
EVM
-100
-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
HNBR (fully hydrogenated)

NBR
-100
-150
0
10
20
30
40
50
60
70
Acrylonitrile Content [wt. %]
80
90
100
Dependence of Tg on Degree of NBR-Hydrogenation (ACNCont.: 34 wt. %)

-20
dyn. mech. (11 Hz)
-22
DSC
-24
Tg [C]
-26
-28
-30
-32
-34
0
20
40
60
80
100
Degree of Hydrogenation [%]

Source:
U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) Correlation Between
Network Structure and Properties of Sulfur- and Peroxide-Cured HNBR Vulcanizates
Influence of Residual Double Bond Content on Stress/StrainProperties of HNBR-based Vulcanizates

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

38,5 wt .% ACN)
10000
E' and tan [MPa]
1000
E'
E''
100
10
0,1
-200
-150
-100
-50
50
100
Temperature [C]
NBR and HNBR: Impact of ACN-Content on

Stress/Strain-Properties of Unvulcanized Raw Rubbers
0,8
50
HNBR
NBR
45
0,7
40
0,6
18,9 wt.%
28 wt.%
33,9 wt.%
38,5 wt.%
48,3 wt.%
0,5
0,4
19,2 wt.%
28 wt.%
34,2 wt.%
39,1 wt.%
49 wt.%
0,3
0,2
0,1
stress [MPa]
Stress [MPa]
35
30
25
20
15
10
5
1000
2000
elongation [%]
3000
4000
500
1000
elongation [%]
1500
Influence of ACN-Content of Unvulcanized NBR and HNBR on

Maximum Stress (Yield-Stress) on True Tensile Strength
"True" Tensile Strength [MPa]
300
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
120
160
48,3 %
= bleibend
140
permanent elongation [%]
permanent elongation [%]
280%
120
100
18,8 %
ASTM D 1566 - 98
Kautschukdefinition
80
60
39,0 %
28,2 %
40
34,9 %
100
80
200%
60
40
120%
20
80%
20
0
0
0
100
200
elongation [%]
300
400
20
40
ACN-content [wt.%]
60
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
Vulcanization time: 20 min

temperature:
160C
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
Temperature:
180C
Annealing:
6h/150C
Perkadox 1440
Bis(t-butylperoxyisopropylbenzol 40%ig
1706 S
HNBR-Grade (Therban)
33,7
ACN-content
[wt.%]
4,3
RDB-content
[Mol.%]
60
ML 1+4(100C)
[MU]
Compound Properties
64
Compound Mooney/ ML 1+4(100C)
12,5
Mooney-Scorch (120C)
[min.]
56,4
Fmax [N]
Vulcanizate-Properties
72
Shore A Hardness(23C)
69
Shore A Hardness (70C)
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/-10C
[%]
70h/23C
[%]
73
70h/100C
[%]
70h/150C
[%]
Hot air ageing
55
D/D0 (150C/ 5 d)
[%]
D/D0 (150C/24 d)
[%]
Degree fo vol. swelling in fuel
100*(V/ V0-1) (48h/50C)
[%] 75
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(100C) [ME]
60
Compound Properties
Compound Mooney [ML 1+4(100C)]64
Mooney-Scorch (120C) [min.]
12,5
Fmax [N]
56,4
Sulfur Core
(Press 160C/20`)
Peroxide Cure (Press 180C/15`)
Shore A Hrte (23C)
72
Shore A Hrte (70C)
69
M 100 [MPa]
3,4
M 200 [MPa]
8,8
M 300 [MPa]
14,7
27
Elongation [%]
510
Rebound [%]
38
Compression Set
70h/-10C [%]
73
70h/23C [%]
70h/100C [%]
73
70h/150C [%]
Hot Air Ageing
D/D0 (150C/ 5 d) [%]
55
D/D0 (150C/24 d) [%]
Degree of Vol. Swelling in Fuel
100*(V/V0 -1) (48h/50C) [%]
75
1706 S
33,7
4,3
60
1706
34,5
0,4
63
66
14
51,2
74
16
52
72
70
5,6
17,8
26
295
36
73
71
6,9
17,7
24
280
34
68
10
27
12
28
54
59
65
70
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
Performance of HNBR in Power Transmission Belts
Leather
SBR
200
10.000
log t/h for b = 50%
Materials used for

power transmission
belts
180
160
140
120
100 [C]
HNBR / peroxide cured
1.000
CR
HNBR / sulfur cured

100
CR
10
2,1
2,2
2,3
2,4
2,6 10 -3 (
2,5
-1
1
-1
K )
T
HNBR
(Sulfur cured)
HNBR
(Peroxide cured)
rate of crack growth
1000
CR
HNBR
100
Tear-Analyzer-Test / Exp. Conditions
10
Frequency:
Strain Ampli tude:
Attenuation mode:
Rate of crack growth:
4 Hz
20%
sinuoidal
1/co (dc/dn)
0,1
-20
20
40
Temperature [C]
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
5.4. EVM: Profile of Properties and Applications

O
O
CH3
CH3
CH3
O

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
VAc-content: 40-90 wt.%

radical polymerization in solution
Random monomer incorporation
Low molar masses
Significant degree of short chain branches
Application Araeas:
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
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
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

Producer Process
10000
Products
Exxon, BP, High pressure Escorene

Mitsui ctc.
High pressure bulk process
750-3000 bar
120-300C
pressure [bar]
1000
Du Pont
USI
High pressure Elvax

High pressure Vynathene
Lanxess
Mitsui
Solution
Solution
Solution process
100-500 bar
50-120C
100
Levapren
High pressure process:

Preferred mprocess for EVA
(thermoplastic polymers with
VAc-content <40 wt.%)
Monomer conversion: < 20%
Molar mases decrease with
increasing VAc-content
Emulsion process
10-100 bar
30-70C
10
Solution process:
EVM-Rubbers
Preferred process for EVM-r

rubbers (VAc-cont. 40-90%)
Monomer conversion: 60- 70%
Solvents: t-Butanol; Methanol
1
0
20
40
60
Vinylacetate content [wt.%]
80
100
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
Rubber
Enthalpy of fusion
(DH)[J/g]
Glass Transition
Temperature (Tg) [C]
100
80
60
40
20
0
-20
Temperature of Fusion
(Fp)[C]
-40
0
20
40
60
Vinyl acetate content [wt.%.]
80
100
20
40
60
Vinyl acetate content [wt.%]
80
100
100
80
60
40
20
0
-20
-40
EVM: Maximum Service Tempeature

0
CH3
- HAc
O
O
CH3
O
CH3
O
weight loss [wt.%]
-10
-20
-30
-40
350 C
-50
-60
-70
-80
-90
-100
200
N C N
OCN
NCO
106
Stabaxol P 200
n n = ca. 4
O
H3C O
nO
O
N
H
N C N
135
400
500
600
Temperature [C]
N O
H
O nCH3
n
n = ca. 4
The addition of acid scavengers

such as carbodiimides and
isocyanates does not improve hot
air performance
time till elongation becomes <50 % in h
Elastostab H 02
300
100000
20000 h
10000
1000
1000 h
> 170C
100
200
190
180
170
160
150
137C
140
temperature in C
130
120
110
EVM: Dependence of Oil Swell and LOI (Limiting

Oxygen Index) on Vinyl Acetate Content
Storage time in SAE-oil SAE 90 (3 d/125C)
LOI according to ASTM-D 2863
80
60
Delta F/F0 x 100 [%]
Al2O3: 190 phr
Delta D/D0 x 100 [%]
Limiting Oxygen Index (LOI) [%]
Change of Properties [%]
60
Delta V/ V0 x 100 [%]
40
20
-20
50
Al2O3:
0 phr
40
30
20
10
-40
20
40
60
80
100
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
100,0 phr
MgO
2,0 phr
Stearic acid
1,0 phr
Carbon black/N 550

Vulkanox DDA 1)
Plasticizer DOS 2)
Plasticizer ODTM
PE-Wax
65,0 phr
1,0 phr
7,5 phr
7,5 phr
2,0 phr
Aktiplast PP
2,0 phr
TAIC
1,5 phr
Peroxide (40%ig) 3)
6,0 phr
Vulkanization time:
10 min
Temperature:
180C
no post vulcanization storage

in hot air
1)
Styrenated Diphenyl amine (SDPA)

Dioctylsebacate (DOS)
3) 1,3-Bis(tert.-butylperoxyisopropyl)benzene (Perkadox 14/40)
2)
Source:
E. Rohde
DKG-Bezirksgruppentagung
NRW in Bad Honnef
07.-08. Mai 1992
40
45
50
60
70
80
Compound properties
Mooney ML 1+4(100C)
[min]
t10/180C
t90/180C
[min]
[N]
FH-FL/180C
20
1,2
7,2
17
24
1,2
6,6
20
23
1,2
6,6
19
25
1,2
6,2
21
20
1,3
6,9
19
20
1,3
6,1
17
Vulcanised properties
(ISO-Stab Nr. 2, 2mm)
Shore A Hrte (23C)
S 100
MPa]
Tenjsile Strength
[MPa]
75
5,0
295
11,7
74
5,7
275
13,6
68
4,4
285
12,6
71
5,4
280
12,8
68
4,2
300
11,5
72
4,7
300
10,5
Compression Set
70h/100C
70h/125C
70h/150C
23
25
41
20
23
38
20
25
41
22
26
40
21
24
46
27
31
51
Hot air ageing (14d/150C)

[%]
F/F0 x100
[%]
D/D0 x100
H/H0 x100
[%]
-3
-2
10
-12
-2
9
-10
2
11
-11
-2
12
10
-7
15
-8
-15
14
Storage in SAE Oil90

(3d/150C)
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)
Temperature:
177C
Anealing:
16 h
1)
Carbodiimide
Vulcup 40 KE
Therban 1707
Levapren 500
Rhenogran P 50
100
-
75
25
1,5
50
50
3
25
75
4,5
100
6
Compounc properties
Relative compound price
ML 1+4(100C)
[ME]
[min]
t2/177C
t90/177C
[min]
100
123
1,5
11,7
80
99
1,6
11,0
60
58
1,5
10,2
40
40
1,6
10,2
20
32
1,6
9,5
Vulcanized properties
Shore A Hrte (23C)
S 100
[MPa]
Tensile Strength
[MPa]
78
10,7
240
26
80
13,1
190
24
80
12,6
170
22,5
81
12,0
145
18,8
77
8,3
165
18,5
12
20
27
12
17
27
12
17
25,5
14
14
20
14
9
15
Hot air ageing(14d/150C)

[%]
F/F0 x100
[%]
D/D0 x100
[%]
H/H0 x100
-2,3
-37
+6
-3,8
-26
+5
-10
-29
+4
-7,5
-21
+3
-1,6
-12
+2
Storage in ASTM oil Nr. 3

(7d/150C)
F/F0 x100
[%]
D/D0 x100
[%]
[%]
V/V0 x100
-10
-4
+24
-17
-11
+34
-36
-29
+49
-50
-34
+67
-56
-45
+83
Compression Set
70h/23C
70h/150C
70h/175C
Source:
Test Report WR 26/83
(Mobay, Chem. Corp.)
[%]
[%]
[%]
EVM: Influence of Post Cure on Physicals
Stress [MPa]
15
10
th
wi
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
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
torque [dNm]
8
7
6
5
= 75 % of
total cure
Sources:
cycle time
for IM
2
1
0
20
40
60
80 100 120 140 160 180 200 220 240
time [sec ]
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
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
CH
Zn
2+
Levapren grade
Levapren
TMQ
N 762
ZnO
ZMB-2
Ficon 153 1)
Saret SR 633 2)
Vul-CUP 40 KE
500HV
100
1,0
35
10
1,0
20
6,5
500HV
100
1,0
35
10
1,0
20
6,5
9,9
26,8
77
72
13,5
80
6,6
43
62
77
73
20,8
175
4,2
10,5
46
61
-10
2
11
1
-8
6
-5
-29
8
-8
-4
31
-13
-6
13,7
-22
-29
12,1
500
100
3)
1) 1,2-BR
(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
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)
Compound properties
Mooney ML 1+4(100C)
[MU]
Vulcanized properties
Shore A Hrte (23C)
Shore A Hrte (150C)
Tensile strength
Elongation at break
M 50
M100
Rebound/23C
Rebound/100C
68
[MPa] 12,6
[%]
285
[MPa]
[MPa] 4,4
[%]
[%]
-

[%]
F/F0 x100
[%]
D/D0 x100
H/H0 x100
[%]
Storage in SAE-oil 90 (3d/150C)
F/F0 x100
[%]
[%]
D/D0 x100
[%]
V/V0 x100
23
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
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
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)
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
Negative:
High permanent set after (tension set, compression set)
Poor mechanical properties at elevated temperatures (tensile strength, compression set)
Deterioratioon of mechanical properties in appropriate solvents
High heat-build-up in dynamic applications
Limited range of grades (particularly no soft grades available)
Anisotropic properties of injection moulded articles (particularly for TPEs with uncrosslinked rubber phase)
Nomenclature and Range of Available TPEs

Examples
TPE-O
mechanical and
reactor-blends
(unvulcanized)
EPM / PP
EPDM / PP
Olefin TPE-V
EPDM / PP
NBR/ PP
PVC based blends
NBR / PVC
EVM / PVC
ACM / PVC
Thermoplastic
Polyolefins
(dynamically vulcanized)
Polyblends1
(without dynamic vulcanization)
High Performance
TPE-V
(without polyolefines
(dynamically vulcanized)
Thermoplastic
Elastomers
HNBR / PA
HNBR / PBT
NBR / PA
EVM / PA
EVM / PBT
TPE-S
SBC
(SBS, SIS, SEBS, SIBS)
TPE-U
Polyester-Urethanes,
Polyether-Urethanes
TPE-E
COPE based on aromatic

Polyesters (Terephthalates)
PBT/ PTHF; PET / PTHF
Styrenic Block-Copolymers
Polyurethane Block Copolymers
Multi-BlockCopolymers2
Copolyester Block Copolymers
TPE-A
Polyamide Block Copolymers
PEBA based on
PA 6 and PA 12
1 Consists of an elastomer finely dispersed in a thermoplastic matrix

2 Rubber and thermoplastic segments are chemically bonded by block- or graft copolymerization
Sources: SRI Elastomers Overview 2008; Stratley Consultants
Selection of Commercially Available TPEs, Producers

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

TPE-S
SBS, SIS, SEBS
Glassy hardening
(vitrification)
Zeon
Shell
BASF
Firestone, Polimeri
Dow
Kaneka
Boston Scientific
Innovia
Bayer
BASF
Goodrich
DuPont
Toyobo
Atochem
Dow
Du Pont
?
Kraton
Styrolux
SIBS
TPE-U
Hydrogen bonds /
Crystallization
TPE-E
Crystallization
TPE-A
Hydrogen bonds /
Crystallization
Ionomer
Sibstar
Taxus
SIBS
Desmopan/Texin
Elastollan
Estane
Hytrel
Pelprene
Pebax
Estamid
Surlyne
TPE: Market, Application Areas and Range of Prices

WO-TPE-Market: 1,5 Mio t
SBC
TPO-V
TPU
COPE
PEBA
Rest
Areas of Application
IRP
18%
Hoses
5%
Shoe
15%
Cables
3%
Medical
Appl.
3%
TPOBlends
Asphalt
Mod.
12%
Adhesives
12%
Automotive
32%
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
226
172
59
79
30
10
3
5
10,5
5
8
5
455,5
576
4,5
Price [/kg]
PP/EPM-Reactor Blends
PP/EPM-TPE-V
SBC
SBS
SIS
SEBS
0,90-1,20
2,00-2,50
1,00-3,30
1,30-1,50
1,50-1,70
2,60-3,30
TPE-U (TPU)
TPE-E (COPE)
TPE-A (PEBA)
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
Shear Modulus [MPa]
104
103
Tempeature
of Use
Temperature of
Processability
Temperature
Softening
Temperature of
Thermoplast Phase
102
101
100
10-1
Tg of
Rubber
Phase
Dependence of Modulus on
Temperature: Target and Reality
Shear Modulus [MPa]
104
103
102
Target
101
Reality
100
10-1
-100
- 50
0
50
100
Temperature [C]
150
200
Schematic Presentation of the Dependence of the Shear

Modulus on Temperature for Different Engineering Polymers
Shear Modulus [MPa]
104
103
102
100
150
6
101
100
10-1
- 100
8
- 50
50
Temperature
200
Dependence of Shear Modulus on Temperature for Different

Engineering Polymers
104
(Polycarbonate, PP.PA)
2. Thermoplastic
(Polystyrene, PMMA)
102
3. Rubber Modified
Thermoplastic
4. Elastomer (crosslinked)
101
5. TPE
7
100
6. TPE
7. Elastomer (crosslinked)
10-1
- 100
8. Unvulcanized Rubber
8
- 50
50
100
150
200
Temperature
Schematic Presentation of Stress/Strain Diagrams

of Block Copoymers
elongation
A-B-A, (A-B)n und (A-B)xBlock Copoymers
stress [MPa]
Shear Modulus [MPa]
1. Thermoplastic Polymer
103
Residual elongation
A-B Block Copolymers
strain [%]
residual elongation (
Residual ) [%]
Dependence of Residual Elongation on Original

Elongation for Different Engineering Polymers
residual = original
300
200
TPE-O (EPDM / PP: 60/40)
ASTM D 1566 - 98
Definition of Rubber
100
TPE-V (EPDM / PP: 78/22)
SBS with 27 wt.% styrene

NR/BR-tyre tread (with filler)
vulcanized gum stock
(unfilled NR)
0
0
100
200
original elongation (
original )
300
[%]
Compression - Set
h1
ho
CS =
ho
ho- h1
h2
h1
ho- h2
h2
ho- h2
ho- h1
x 100
[%]
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
Cla ssica l
E la stome rs
S BS
S IS
S hore A
10 to 80
71
52
S hore D
P rope rtie s
T e nsile S tre ngth [MP a ]
10 to 35
E longa tion a t bre a k [% ] 300 to 800

CS (22h/ 70C)
CS (24h/ 70C)
CS (22h/ 100C)
5 to 30
5 to 40
5 to 40
CS (70h/ 150C)
30 (H N BR , FKM)
T P E -U
T P E -A
S E BS E ste r E the r
75
T P E -E
92
93
44
42
25
40
63
32
54
79
36
51
15,4
32
20
34
45
40
880
1200
500
450
380
60
60
715 485 380
62
21
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
72
75
47
12
5,5
8,5
880
660
650
350
490
75
60
38
90
53
88
44
Technologische Eigenschaften von TPEs

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

7
180
TPE-V
(EPDM / PP-blend,
highly crosslinked)
160
Performance [arbitrary units]
Melting temperature [C]
140
120
100
80
60
PP-Properties:
PP-Properties:
Low Price
40
Low Price
High
HighSoftening
SofteningTemperaure
Temperaure
Good
Ageing
Good AgeingResistance
Resistance
20
TPE/SEBSBlends
TPE-V
(EPDM/PP partially
cross-linked)
TPE-O
(mechanical
blends)
TPE-O
(ReactorBlends)
(Residual Catalyst Content)

(Residual Catalyst Content)
0
20
40
60
80
100
0,5
1,5
Price [$/kg]
Isotacticity [%]
Source: T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced
Technologies 4, pp. 406-414 New Polymers from New
Catalysts
Source: Robert Eller Associates, Inc. 1996
TPE-O and TPE-V: Basic Properties

Properties
TPE-O
TPE-V
(Mechanical PP/EPDM
Blend)
(PP/EPDM-Blend with
partially crosslinked
EPDM-phase)
TPE-V
(PP/EPDM-Blend with
highly crosslinked
EPDM-Phase)
Shore A-Hardness
78
72
75
12
5,5
20
650
350
490
75
60
38
soluble
90
50
Compression Set
(22 h /70C) [%]
Volume Swell in ASTMOil Nr. 3 [Vol%]
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
no. of recycles
1
M100 [psi]
650
630
620
600
Tensile Strength [psi]
1530
1520
1500
1590
495
500
505
535
20
Shore D
Hardness: 50
Shore A
Hardness: 87
35
30
1,0-1,5
Particle diameter [ m]
25
Stress [MPa]
15
5,4
20
17
15
72
10
10
Shore A
Hardness: 64
39
0
5
0
0
0
400
200
100
Filter
Filter
ventilator
PE*
PP**
UCC
BASF
BP
Hoechst
Exxon
Amoco
Montell
Montell
Fina
Phillips
Solvay
UCC
BASF
Amoco/Chisso
Sumitomo
* Ind Eng. Res. 33 (1994) 449-479

** Chem. Systems (April 1992)
"Polypropylene"
Cooler
Product
outlet
Supported
catalyst
Cooler
Ethylene
500
Gas Phase Technology
Sources:
Propylene
400
Elongation [%]
600
TPE-O: PP/EPM-Reactor-Blends
ventilator
300
200
Removal
of
residual
monomer
purification
purification
Temperature:
Pressure:
Residence time per reactor:
< 90 C (40C-60C)
9-15 bar
0,5 - 1 h
Source: T. W. Klimek (Quantum Chemical Corp.) ANTEC `91, 1382-1384
packaging
Properties of PP/EPM- Reactor-Blends

1000
Catalyst Fragmentation
during Polymerization
900
E-Modulus [MPa]
800
Catalyst System A
700
600
Catalyst System B
500
400
300
20
30
40
50
60
Rubber Content [wt.%]

Source:
H. Schwager (BASF); Kunststoffe 82, 499 (1992)
T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 New Polymers from New Catalysts
Preparation of TPE-Vs by Reactive Processing

Blending
Definitions:
1)
Reactive Processing stands for a chemical reaction in the course of which

polymers are modified without the use of solvents.
2)
Dynamic Blending stands for the solvent free blending process during which
a chemical reaction occurs.
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
3)
4)
5)
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- 190C

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

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

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

EPDM/PP blend with Phenol Resin
2) Addition of PP und EPDM with subsequent vulcanization of the EPDM-Phase
OH
PP
CH2
EPDM
CH2
1) Addition of EPDM and PP at 185- 190C (5 Min.)

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

Dynamic Vulcanization of PP/NBR-Blends
185-190C
5 min.
2 min.
0
0
0
185-190C
Polypropylene
5 min.
NBR +
Aminino terminated NBR
Dimethylolphenol resin + 5 min.
SnCl2 . 2 H2O
Tensile Strength
M100
E-Modulus
Elongation at break
Permanent elongation
Polypropylene
Dimethylolphenol resin
SnCl2 . 2 H2O
[MPa]
[MPa]
[MPa]
[%]
[%]
50
2
0,4
50
2
0,4
50
2
0,4
50
50
0
0
0
0
50
0
0
0
0
50
0
1,67
0
0
45
5
5
0,5
7,2
0
149
36
0
10,1
0
170
66
10,1
0
157
170
15,3
10,2
107
390
54
Compatibilising Effect of Dimethylolphenol Resins in

Dynamic Vulcanization of PP/NBR-Blends
185-190C
Polypropylene
5 min
Dimethylolphenol resin
2 min
SnCl2 . 2 H2O
25
1
0,2
37,5
1,5
0,3
50
2
0,4
62,5
2,5
0,5
75
3
0,6
5 min
Polypropylene
5 min
NBR +
Aminino terminated NBR
Dimethylolphenol resin +
SnCl2 . 2 H2O
5 min
67,5
7,5
9,38
1,13
1,13
56,25
6,25
7,81
0,78
0,94
45
5
6,25
0,5
0,75
33,75
3,75
4,69
0,28
0,56
22,5
2,5
3,13
0,13
0,38
Tensile Strength
M100
E-Modulus
Elongation at break
Permanent elongation
17,0
15,8
33
330
20
19,6
15,7
92
400
33
23,0
15,2
221
500
50
22,7
16,2
320
490
63
21,5
17,1
456
480
70
[MPa]
[MPa]
[MPa]
[%]
[%]
Reactive Blending von EPDM/SAN: Results
elongation at break
[%]
SAN
EPDM
Reactive Processing
2 wt.% PF-Harz/0,2 wt.% Catalyst/130C
(without fillers/without oils)
EPDM-grade: EP T 2370 (Lanxess)
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
ataktisches
Polymer
R2
Zr
622
595
R1
R
Isotaktisches
Polymer
R2
Zr
R1
R
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"
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
Cl
Cl
B
Zr
Et
Et
Cl
Cl
Cl
Temperature
B
Zr
Cl
Cl
P
Et
Et
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
4
Schubmodul (MPa)
Komplex modulus (G*) [MPa]
10
Elastomeric PP
G'
3
10
10
G''
1
10
10
-120
-80
-40
40
-80
-40
40
tan
10
-1
10
-2
10
-160
-120
Temperatur[(C)
Temperature
C]
Sample from Prof. Aladyshev
PP-Based TPE
6
2
2] ]
Spannung
[N/mm
stress [N/mm
Elast.PP
Probenform: S1-Stab
Anlieferzustand: Platte
Medatum: 05.06.02
Dateiname: S14308sd (Graph 1)
0
0
200
400
600
800
Dehnung
[%]
strain () [%]
Sample from Prof. Aladyshev
Abb.
PP-Based TPE
Komplex
modulus (G*) [MPa]
komplexer Schubmodul [MPa]
10
G'
G'
G" HAIFA 1
G" HAIFA 2
10
10
10
10
-1
10
10
-120
-80
-120
-80
-40
40
80
-40
40
80
-1
tan()
10
-2
10
-3
10
-160
120
Temperatur [C]
Temperature [C]
Sample from Prof. Eisen/Haifa
PP-Based TPE
6
2] ]
Spannung
[N/mm
stress [N/mm
HAIFA-1
HAIFA-2
0
0
100
200
300
400
500
Dehnung
[%]
strain [%]
Sample from Prof. Eisen/Haifa
600
700
800
900
TPEs from the Viewpoint of a Producer of Technical

Rubber Goods
Reduction of Manufacturing Costs
Reduction in number of raw materials and associated costs for logistics (ordering,
transportation and storage,)
Reduction/elimination of compounding costs including energy savings
Significant reduction of cycle time and increase of output (seconds instead of minutes)
Cost reduction by recycling of waste (no costs for incineration and land fill)
New Technology for Rubber Processors

Installation of equipment for the processing of thermoplastic materials
Know-how in thermoplastics and their processing not available
Know-how for the compounding and processing of rubbers becomes abundant
TPE- Range of Products and Proeprties
Limited availability of soft grades with Shore A Hardness < 50

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

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

Rubbers?
Nr.
Rubber
Abbreviation
Polybutadiene
Polychloroprene
Chlorinated Polyethylene
Chlorosulfonated Polyethylene
Ethene/Propene/Diene-Terpolymers
Ethene/Propene-Copolymers
Epoxydized Natural rubber
Fluororubber
Acrylic Rubber
10
11
Isobutene/Isoprene-Copolymers
12
Styrene/Butadiene-Copolymers
13
Natural Rubber
14
Silicon Rubber with Viny Groups
15
Butadiene/Acrylonitrile-Copolymers
16
Brominated Isobuylen/Isoprene-Copolymers
17
Vinylmethylsilicon Rubber, which also contains fluorine
18
Polyphosphazene modified with perfluorinated alcohols
19
Standardized NR from Vietnam
20
Smoked Sheets based on NR
Family Name
Given Name
Please Assign the following Rubbers to the

Correct Position in the Matrix:
ACM, BIIR, BR, CM, CSM, EVM, FKM, HNBR, IIR, SBR
Process Features
Chemical
Features
Emulsion
Solution
Dispersion
(slurry)
Mass or
Bulk
GasPhase
Radical
Polymerization
anionic
Polymerization
Cationic
Polymerization
Polyaddition und
Polycondensation
Polymermodification
Family Name
3
Given Name
Residual Elongation [%]
Which of the Curves Matches the Performance of the

Materials Mentioned Below ?
300
200
100
4
5
6
0
100
200
300
elongation [%]
Nr.: Questions
1
2
3
4
5
6
7
8
9
10
Answers
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
Family Name
4
Given Name
Natural Rubber
Please Mark RIGHT or WRONG
Nr.: Frage
1
2
3
4
5
6
7
8
9
10
Right Wrong
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
Family Name
Given Name
5
Natural Rubber
Nr.: Frage
1
2
3
4
5
6
7
8
9
10
Right Wrong
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
Family Name
Given Name
6
Nr.: Question
1
2
3
4
5
6
7
8
9
10
RIGHT WRONG
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
Family Name
Given Name
7
Emulsion Rubbers
Nr.: Question
Right Wrong
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
10
The addition of electrolytes increases latex stability
Family Name
Given Name
Pollution of Water and Air:

Nr.
Question
Right Wrong
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
10
Emulsion rubbers cause air pollution
Family Name
Given Name
Crystallization of Rubbers
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
Family Name
Given Name
10
Crystallization of Rubbers
Nr.: Question
1
2
3
4
5
6
7
8
9
10
Right Wrong
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
Family Name
Given Name
11
NBR
Nr.: Frage
1
2
3
4
5
6
7
8
9
10
Right Wrong
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
Family Name
Given Name
12
NBR
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
Family Name
Given Name
13
NBR
In the literature you find the following Tgs for polybutadiene (BR) and
polyacrylonitrile (PAN:
BR (Li-catalysis)
-90C
BR (Ti-catalysis)
-100C
BR (Nd-catalysis)
-110C
BR (emulsion polymerization)
PAN
-80C
+100C
Please select the relevant Tgs and calculate the Tg of an NBR grade
which contains 50 wt.% acrylonitrile.
acrylonitrile.
The calculated Tg is:
is:
..
C
..
Family Name
Given Name
14
NBR:

Nr.: Frage
Right Wrong
1
2
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
Family Name
Given Name
15
CR
Nr. Question
Right Wrong
1
2
3
4
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
Family Name
Given Name
16
HNBR:
Nr.: Question
1
2
3
4
5
6
7
8
9
10
Right Wrong
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
Family Name
Given Name
17
HNBR:
Nr.: Question
1
2
3
4
5
6
7
8
9
10
Right Wrong
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
Family Name
Given Name
18
IIR, CIIR and BIIR:

Nr.: Question
Right Wrong
1
2
3
4
5
6
7
8
9
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
Family Name
Given Name
19
Thermoplastic Elastomers:
Nr. Question
Right Wrong
1
2
3
4
5
6
7
8
9
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
Family Name
Given Name
20
Please assign the Curves

Schubmodul [MPa]
104
1
103
4
102
6
7
101
8
9
100
10-1
-100
-50
0
50
100
Temperatur
150
200
Nr.: Frage
1
2
3
4
5
6
7
8
9
10
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
-
100
-
100
Carbon black (N 220) [phr]
30
30
30
Rubber A
59
8,8
27,8
560
15
52
17
Rubber B
Modulus300
[MPa]
Tensile Strength
[MPa]
Rebound/23C
[%]
Goodrich HBU
[C]
CS (24h/70C)
[%]
Volume swell (70h/70C)
ASTM-oil Nr. 1
[%]
ASTM-oil Nr. 2
[%]
ASTM oil Nr. 3
[%]
59
56
7,8
6,9
27,1 25,9
550 590
78
25
44
60
17
46
Rubber C
modification
Family Name
66
114
191
73
28
108
-5
6
21
Air permeation/23C [1018 x m4/s.N] 27,0
8,0
1,98
Given Name
22
Which Metal is used for the production of BR in order to

obtain the Properties below ?
2
CH2 CH
CH2
CH2
CH2
CH CH
CH CH
CH2
CH
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
-107
98
1
<1
<1
0,6
0,7
-109
12,9
68,3
18,8
18,1
17,7
17,8
-80
23
Please Assign Rubber A and Rubber B

Rubber A
Rubber B
100
-
75
25
50
50
25
75
100
Compound Properties
ML 1+4(100C)
[MU]
[min]
t2/177C
[min]
t90/177C
123
1,5
11,7
99
1,6
11,0
58
1,5
10,2
40
1,6
10,2
32
1,6
9,5
Shore A Hrte (23C)
Modulus 100
[MPa]
Tensile Strength
[MPa]
78
10,7
240
26
80
13,1
190
24
80
12,6
170
22,5
81
12,0
145
18,8
77
8,3
165
18,5
12
20
27
12
17
27
12
17
25,5
14
14
20
14
9
15
-2,3
-37
+6
-3,8
-26
+5
-10
-29
+4
-7,5
-21
+3
-1,6
-12
+2
Compression Set
70h/23C
70h/150C
70h/175C
[%]
[%]
[%]
Heat ageing (14d/150C)

[%]
F/F0 x100
[%]
D/D0 x100
[%]
H/H0 x100
Oil swelling (7d/150C)
ASTM-l Nr. 3
F/F0 x100
[%]
[%]
D/D0 x100
V/V0 x100
[%]
Rubber A
Rubber B
Family Name
-10
-4
+24
-17
-11
+34
-36
-29
+49
-50
-34
+67
-56
-45
+83
Given Name
24

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

scheme below applies
Hard phase
(coherent phase or matrix)
Soft phase
(dispersed phase)
Nr.:
Hard phase
Soft phase
1
2
3
4
5
Family Name
Given Name
26
Which Series of Rubbers Yields the Properties Given in

the Table Below?
Rubber
Compound properties
Mooney ML 1+4(100C)
[min]
t10/180C
[min]
t90/180C
FH-FL/180C
[N]
20
1,2
7,2
17
24
1,2
6,6
20
23
1,2
6,6
19
25
1,2
6,2
21
20
1,3
6,9
19
20
1,3
6,1
17
Variation
Vulcanised properties
Shore A Hrte (23C)
S 100
MPa]
Tenjsile Strength
[MPa]
75
5,0
295
11,7
Compression Set
70h/100C
70h/125C
70h/150C
74
5,7
275
13,6
68
4,4
285
12,6
71
5,4
280
12,8
68
4,2
300
11,5
72
4,7
300
10,5
23
25
41
20
23
38
20
25
41
22
26
40
21
24
46
27
31
51

[%]
F/F0 x100
[%]
D/D0 x100
H/H0 x100
[%]
-3
-2
10
-12
-2
9
-10
2
11
-11
-2
12
10
-7
15
-8
-15
14
Storage in SAE Oil90

(3d/150C)
[%]
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
Family Name
Given Name

Rubber A
[phr]
Rubber B
[phr]
Unaged:
[MPa]
M300
Tensile Strength
[MPa]
Aged (168h/100C)
M300
[MPa]
Tensile Strength
[MPa]
Air permeation at
50psi/65C (Q x 10-8]
Adhesion at 100C
Self adhesion / tack [kN/m]
Adhesion to NR
[kN/m]
Fatigue to failure after
ageing at 168h/120C [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
Rubber B
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
28
Please Assign Rubber A

Family Name
Rubber A
Given Name
Rubber A
[phr]
Carb. black (N 774) [phr]
100
50
100
50
100
50
100
50
Vulcanization
Compound Properties
ML 1+4 (100C)
[MU]
MS5 (125C)
[min]
ZnO
DCP
DCP/BMI
ZnO/BMI
83
-
88
-
88
-
89
-
16
12
14
16
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
MS5 (135C)
[min]
Physical Properties
Shore A Hardnes
M100
[MPa]
[MPa]
M300
CS (70h/150C)
[%]
29

Rubber

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Chemistry and Technology of Rubbers

The attached files of my lecture are my personal property.

Chemistry and Technology of Rubbers

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

2.1. Natural Rubber

Overview on Emulsion Rubbers

High Performance Rubbers

1. Overview on Rubbers, Definitions, Market, Properties,

Definition of the Terms Rubber, Elastomer and Thermoplastic

Standard Terminology Relating to Rubber

recovering from large deformations

Comparison of Materials According to ASTM D 1566

Residual Elongation [%]

NR/BR based tyre tread

My personal Definition of Unvulcanized Rubber,

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

unvulcanized (=uncrosslinked) rubber

vulcanized (=crosslinked) rubber

Tgs of Polymers with a Saturated C-C Main Chain

Tgs of Polymers with an Unsaturated C=C Main Chain

-50C bis -5C

Influence of Tg on Rebound of Vulcanized Rubbers

Schematic Presentation of the Dependence of the

NR/5 phr DCP

Shear Modulus [MPa]

Designation of Rubbers (DIN/ISO 1629)

Rubbers with fully saturated main chain

CM, CSM, EAM, ACM,

Nitrogen containing rubbers

Rubbers with oxygen in the main chain

CO, ECO, GPO

rubbers with a polysiloxane main chain

MQ, MVQ, PMVQ, FMQ

Rubbers with an unsaturated main chain

NR, SBR, BR, NBR,

Rubbers with sulfur in the main chain

Rubbers which contain carbon, nitrogen

Rubbers with phosphorus and oxygen in

Abbreviations (DIN / ISO 1629) and Examples

Epoxidised Natural 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

Synthetic Rubber (Solid + Latex)

Application Areas of Solid Rubber

Price and Volume of Rubbers (without Latex)

General Purpose Rubbers: 82%

NBR (0.32 Mio t)

EPM/EPDM (0.9 Mio t)

General Purpose Rubbers: 60%

max. service temperature [C]

Oil and Temperature Resistance of

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

Evaluation of Vulcanizate Properties

Evaluation of Vulcanizate Performance*

Correlation of Rubber Price and Vulcanizate

Price of Rubber [/kg]

Ranking of Top 10 Tyre Producers

* Dunlop is not included

Source: FAZ 18.08.2003

Ranking of Top 22 Producers of Technical Rubber Products

Producers of Synthetic Rubber and

Chemical and Technological Features of