Documente Academic
Documente Profesional
Documente Cultură
Quingdao
09.05.-15.05.2011
Werner Obrecht
4.
Overview on Solution Rubbers
4.1. Overview on Polybutadiene
4.2. Li-Polybutadiene and Solution-Styrene/Butadiene-Rubber with an Emphasis on
Integral Rubber
4.3. Chemistry and Production Technology of High cis-1,4-BR with a Special Emphasis on
Nd-BR
4.4. Ethylene/Propene-Co- und Terpolymers
4.5. Butyl- and Halobutyl Rubber
5.
5.1.
5.2.
5.3.
5.4.
6.
Thermoplastic Elastomers
7.
Test Questions
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]
15
rubber
10
5
1 min
0
0
50
Elongation [%]
100
= residual
300
200
TPO
Definition of Rubber
according to
ASTM D 1566 - 98
TPV
100
Thermoplastic
Elastomers
SBS
0
0
100
200
Elongation () [%]
rubber boot
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
-115C
(100% 1,4-cis)
Polyisoprene
-75C
(100% 1,4-cis)
Polychloroprene
-45C
(100% 1,4-trans)
Nitrile Rubber
Cl
Cl
Cl
Cl
CN
CN
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
10000
1000
100
10
0,1
-150
-100
-50
50
Temperature [C]
100
150
200
Examples
NBR, HNBR
OT, EOT
AU, EU
FZ
Butadiene-Rubber
CR
Chloroprene Rubber
CM
Chlorinated Polyethylene
CSM
Chlorosufonated Polyethylene
EPM
Ethylene/Propylene-Rubber
EPDM
Ethylene/Propylene/Diene-Rubber
ENR
IR
Synthetic Polyisoprene
IIR
Butyl rubber
NR
Natural Rubber
NBR
Nitrile-Butadiene-Rubber
SBR
FPM
FKM
14000
Natural Rubber
12000
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
Tyres
45%
Cable and
Wire
Construction
3%
3%
Others
15%
Machine
building
5%
FZ
FQ
FKM
HNBR Q
AU/EU EVM
High
Performance
Rubbers
Price
CR (0.3 Mio t)
Special
(0.5 Mio t)Rubbers
Special
Rubbers
17%
High Performance
Rubbers 1%
BR (2,8 Mio t)
SBR (2,7 Mio t)
NR (6.7 Mio t)
General
Purpose
Rubbers
High
Performance
Rubbers 10%
Volume
Source: Rubber World, 21916 (1999) 13-14
Special
Rubbers 30%
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
no
requirement
10
Improvement
Criteria of Evaluation:
Maximal Service Temperature
Low Temperature Flexibility
Oil Swell
Mechanical Properties
Ozone Resistance
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
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
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
Capitalization of Shares
Sales
20
15
10
5
0
Continental
[Mio US $]
Share
of
Tyres
Goodyear
Sales of Tyres
Michelin
Company
Bridgestone
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Company
Site
Hutchinson SA
Bridgestone Corp.
Freudenberg Group
Tomkins plc.
Parker Hannifin
Cooper Tire & Rubber
Trelleborg AB
Continental AG
Federal Mogul Corp.
Goodyear Tire & Rubber
NOK Inc.
Tokai Rubber Industries Ltd.
Metzeler Automotive Profile Syst.
Toyoda Gosei Co. Ltd.
Mark IV Automotive
GenCorp. Inc.
Ansell Ltd.
Sumitomo Rubber Ind.
Yokohama Rubber Co Ltd.
Dana Corp.
Toyo Tire Rubber Co. Ltd.
Phoenix AG
Sales 2001
[Mio US$]
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
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
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
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
Dispersion
Slurry
Bulk
Gas-Phase
10
10
Stereoregularitt
10
10
10
Waste Water
10
10
Waste Air
28
27
41
39
45
Aspect
Viscosity
Heat Removal
Sum
Ranking:
Prerequistes:
Emulsion
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
30
20
Sx
S1
C C
C C
10
0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
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
Bond
Energy
[ KJ/Mol]
physical
< 266
Bond
Energy
[KJ/Mol]
260 - 350
10 -
20
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
NR-Production
NR-Latex and Latex Finishing
General Features of NR and Hevea brasiliensis
NR Grades and Specifications
Vulcanization of NR
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 %
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
Naturkautschuk
12
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
NR: Production
Malaysia
Indonesia
Thailand
others
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%
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%
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
Tread [wt.%]
NR
45
60
77
86
86
100
SBR
21
12
7
5
5
BR
34
28
16
9
9
SBR
37
19
6
BR
15
37
36
38
25
40
Carcass [wt.%]
NR
71
84
100
100
100
100
SBR
20
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
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: http://www.therubbereconomist.com
NR-Production by smallholders:
1,25 ha;
625 trees in total; 520 trees under tap
180/a
95.000 tappings for 625 trees/a
850 kg/a
ca. 250 /a
(0,30 /kg)
1020 /a
(1,2 /kg)
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)
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer, Encyclopedia of Chemical
Technology, vol 21, 4th ed., 562-591
Features of NR-Latex
Total solids concentration:(25) 30-40 wt. % (dependent on many parameters)
Rubber content:
90 - 95 wt. % of total solids
Particle diameter:
150-3000 nm (dependent on many parameters)
Gel content:
dependent on many parameters (latex age, finishing method)
Molar mass:
105-107 g/mol (not constant, dependent on many parmaters)
Latex stability
without the addition of additives (NH3, formaldehyde, boric acid,
phenolates, Na2SO3 (0,05 Gew.%), etc.) latex coagulation occurs
as a consequence of encymatic decay
Latex Finishing
Dilution of the latex to 15-20 wt. % solids
Removal of heavy impurities such as sand by sedimentation
Removal of impurities such as wood, leafs, insects, etc. by filtration
Latex fractionation for the removal of carotinoids for L (light = colourless) grades
Addition of:
Na2SO3 (0,15 wt.%) for pale-crepe-grades
[HONH3]2 SO4 for CV- grades (Constant Viscosity)
Discontinuous latex coagulation with formic or acetic acid (5 wt. %) in pH-range 5,0 - 5,2
Completion of coagulation by maturing for 12-16 h
Mechanical water removal by riffle mills (6-9 passes)
Drying in smoke at 60C/1 week for RSS-production (RSS = Ribbed Smoked Sheet)
Drying in air at 40C/2 months (ADS = Air Dried Sheet)
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%
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
NR Grade
SMR 5
SMR GP
SMR 10
SMR 20
SMR 50
0,05
0,10
0,10
0,20
0,50
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
ACS 1- Compound
NR
Stearic Acid
ZnO
Sulfur:
MBT
100 phr
0,5 phr
6,0 phr
3,5 phr
0,5 phr
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
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
-
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
CCCC
3333
HHHH
HHHH
HHHH
NNNN
SSSS
3333CCCC
NNNN
3333
HHHH
HHHH
CCCC HHHH CCCC
CCCC
HHHH
NNNN
HHHH
NNNN
100
50
3
3
1,5
1
1
3
1,6
1
0
First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272
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
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
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)
1000
100
10
30
20
10
0
-10
-20
-30
-40
-50
-30
-10
10
-50
-10
10
30
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
30
stress [MPa]
25
NR
SBR
20
15
10
5
0
0
200
400
600
800
1000
strain [%]
20
NR
Tack-Index
SBR
15
10
0
0
20
40
60
80
temperature [C]
100
120
Modification
Application
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
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
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
NR: CV-Grades
70
60
50
40
30
20
10
0
0
0,05
0,1
0,15
0,2
Epoxidation with
peracids in the
latex stage
Tg [C]
0
-20
-40
O
-60
-80
20
40
60
80
[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
[%]
[%]
[%]
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
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
Technology, vol 21, 4th ed., 562-591
N O
NH
HN
O N
Thermal Cleavage
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
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
98
yes
yes
yes
IR
Ti
Li
Nd
93
97
99
no mastication needed
-
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
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
36
40
Karbochem
3
624
Source: R.J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008 Globalization of Synthetic Rubber Industry
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
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
+
+
+
+
+
ca. 60 %
65 MU
-8C
Source:
Data sheet of Hls AG
Vestogrip
(3,4-Polyisopren-Kautschuk)
Compound Properties
ML 1+4(100C)
[MU]
t10/150C
[min]
[min]
t90/150C
77
13,8
27,5
67
52
2,1
8,4
14,7
510
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
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
Emulsifier
Initiator
Monomer
Polymerization
Wasser
Monomer emulsion
Polymer dispersion
(Latex or rubber latex)
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
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
Phase III:
x = 0,4; y = 0,6
[n]= 0,5
Mixer/Settler
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
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
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
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
COD = 0
BOD = 0
COD = BOD
COD < BOD
BOD < COD
COD = BOD
COD < BOD
BOD < COD
Polymerisation
Polymerization Recipe (Cold Rubber)
Ingredients of a Polymerization Recipe
Sequence of Reaction Steps
Copolymerisation of Styrene und Butadiene
Influence of Chain Modification Agents
Product Properties
Tg
Influence of None Polymeric Residues on Compound and
Vulcanizate Properties
Microstructure of E-SBR
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
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%
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.
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
2000 2002
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.
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)
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:
naphthenic oil
highly aromatic
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
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:
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
CH2 CH2
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
+ Fe2+
+ Reducing agent
+ Monomer
Growth Reaction:
R-O-Mon* + n Monomer
P*
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
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]
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
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 [%]
80
70
60
50
40
30
20
10
0
1
r1 =
k11
k12
r2 =
k22
k21
9 10 11 12
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)
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
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
[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
103,13
25,0
68,75
50
-
68,75
50
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
Shore A Hardness/23C
Shore A Hardness/70C
Rebound/23C
Rebound/70C
[phr]
[phr]
[phr]
[phr[
[%]
[%]
Manufacturing
CR-Microstructure
Monomer Manufacturing Processes
Basic Features of Polymerization Recipes
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
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:
Capacity Site
Butadiene Acetylene
100
Omi/Japan
Lanxess
75
Dormagen/Germany
DuPont
45
Pontchartrin/USA
Tosoh
32
Nanyo/Japan
28
Chongquing/China
25
Datong/China
Pidilite
25
India
Showa Denko KK
20
Kawasaki/Japan
10
Yerewan/Armenia
Total
360
Plant Closures
Stagnant CR-Consumption in WE and USA
Growing Consumption in South-East Asia
Producer
Capacity Site
DuPont
30
50
Maydown/N.-Ireland
Louisville/USA
Bayer
25
Houston/USA
Polimeri (BP)
25
Grenoble/France
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
(ca. 40 %)
HC
CH CH2
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
Latex based
adhesives
5%
Solvent
based
adhesives
30%
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
Conveyor
Belts
12%
Cables
21%
Rubber Grades
35
Cl
CH2
Cl
1,4-cis
H
C
Cl
H
CH2 C
CH2
3,4
CH2 C
CH2
Cl
CH2
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
50
60
70
20
40
30
Polymerization Temperature [C]
80
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
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
5 - 20
20-50
30-50
30-50
30-50
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)
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
0,1
10
100
1000
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
-10
40
- 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
12
15
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
Carbon black (N 762)
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
Influence of Plasticizers
20
100
0,5
0,5
2,0
30
5,0
0,5
phr
phr
phr
phr
phr
phr
phr
300
15
200
t1/2 [h]
t1/2 [h]
250
150
10
100
Neoprene W + Butyloleate
50
0
100
80
60
40
20
0
Baypren 110 VSC (slowly crystallizing)
-5
10
15
20
Temperature [C]
0
20
40
60
80
100 Source:
70
60
50
40
30
20
10
0
-60
-40 -20
20
40
60
Temperature [C]
Bayer-Brouchure: Chloropren-Kautschuk von Bayer: Der vielseitig einsetzbare Werkstoff
CH2
Standard CR-Grade
CH CH2
Cl
CH2
CH2
Sulfur Grade
Cl
Sulfur
S
CH3 O
Precrosslinked CR-Grade
Dimethacrylate
CH2
O
O
CH2 O
n
CH3
CH2
+ HS - R
P- H
+ R - S*
R - S*
+ nM
R - S - M n*
R - S - Mn*
+ HS - R
R - S - Mn - H
+ R - S*
+ (RO - CS - S -)2
P - S - CS - OR
RO - CS - S*
+ Mn
RO - CS - S - Mn*
+ 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
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
14
15
unaged
7 days / 100C
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
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.
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.
2)
CH2
S8
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
48
Baypren 610
46
44
42
40
38
36
34
32
30
0
200 x 400 mm
1:1,2
20 min-1
1,2 mm
600 mg
10
Baypren 510
Incorporated Sulfur
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
C
S
N
S
N
Sx
S
S
H
H
C
N
S
N
Sx
S
N
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
50
46
42
38
34
30
18
16
14
12
10
26
0
10
20
30
40
50
60
70
10
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
Sx
- ZnCl2
"cyclic Dithiocarbamate"
(Vulkacit(R) CRV)
NH
CH2 CH2
NH
CH3
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
Cl
NH
CH2 CH2
CH
40
Vulcanization of CR
CH
+ NH
30
Cl
CH2
20
O
R
70
Substitution of CR
max. service temperature [C]
250
FKM
MVQ
225
FMVQ
200
FZ
175
Resistance
to high temperatures
80
% VAc
EVM
ACM
HNBR
150
125
NBR
CM
CSM
(H)IIR
Price
CR
100
EU
SBR
BR
AU
75
EPDM
NR
50
0
20
40
60
80
100
120
140
no
requirements
NBR-Microstructure
Basic Features of NBR and Range of NBR Grades
Application Areas of NBR and Market
Producers and Production Capacities
Range of NBR Grades
Dependence of Properties on Acrylonitrile Content
Polymerisation
Emulsifiers
Initiator systems
Molar mass regulation
Copolymerization
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
Polymerizationtemperature
[C]
-20
5
50
100
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
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 gas permeability
Low price level / high competition
Negative:
Maximal service temperature: < 110 C
(Criterium: 1000 h / b=0,5*b0)
Standard grades are not applicable for outdoor use
(contrary to NBR/PVC-Blends)
X-NBR
Precrosslinked NBR
NBR/PVC-Blends
NBR-powder grades
liquid NBR
-HO-terminated
-COO-terminated
-NH2-terminated
NBR
mit bound antioxydant
Rubber Goods
(without
automotive)
34%
Rubber
modification of
Thermoplastic
and
duroplastic
polymers
11%
Adhesives
1%
Others
4%
building
5%
NR
250
200
150
100
SBR
50
CR
NBR
0
14
21
7
time in ASTM-L3 [days]
20
10
20
05
20
00
19
95
19
90
19
85
Consumption [j/y]
300
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
100
125
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
-80
E-BR
-100
0
10
20 30
40
50
60
70
80 90
100
Expt. Conditions:
14 days
Fuel B and C: 20C
ASTM-Oils: 140C
vvvvvWeight Change[%]
80
70
60
50
40
30
20
10
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.%]
Shore A Hardness
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)
+ Fe2+
+ Reducing agent
+ Monomer
R-OOH
Fe3+
R-O*
Growth reaction:
R-O-Mon* + n Monomer
P*
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
CH3
CH3
Pd
+
H
CH3 COOH
H
CH3 COOH
Abietic Acid
CH3
CH3
H
CH3 COOH
H
CH3 COOH
AG IS/1
THT 1618W
Radiacid 40
Prifac 5910
Edenor C1618
32,5
27,5
35,1
37,7
40,3
(Texapon)
(Marlon)
(Mersolat)
33,5
34,8
24,8
31,5
26,4
31
37,3
36,6
28,3
32,1
CH2
SO3
Na
2 Na +
SO3
Na
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
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
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
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
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
Mooney Viscosity
ML1+4 (100C)
140
120
100
TDM / Lanxess
80
60
40
20
0
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
- H+
+
"Triisobutene (TIB)"
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
Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol
Jp 07 316 128
Zeon
27.12.1994
Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol
DE 102007024009
Lanxess
22.05.2007
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
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
40
cMg
cNa
24
23
cK
+
ppm
39
Atomic weight
weight
Patent No.
Company
Priority
Patent Title
DE 102007024011
DE 102007014010
DE 102007024010
Lanxess
Lanxess
Lanxess
22.05.2007
22.05.2007
22.05.2007
40
cMg
cNa
24
23
cK
+
39
ppm
Atomic Weight
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
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)
O (R*)
2
C
+ 2 R-H
Crosslinking
efficiency
1,0
NBR
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
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
[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
C
N
COOH
Carboxl-containing monomers:
Methacrylic acid
Itaconic acid
Maleic Acid
Advantages:
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
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
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
Precrosslinked NBR-grades provide for high dimensional stability after extrusion which is
only matched by standard NBR-grades with considerably increased Mooney viscosities
Krynac VP KA 8769
phr
10
20
30
40
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
Lanxess
phr
1,5
1,5
1,5
1,5
Zincmethylmercaptobenzimidazol Lanxess
phr
1,5
1,5
1,5
1,5
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
Lanxess
phr
1,5
1,5
1,5
1,5
Lanxess
phr
1,5
1,5
1,5
1,5
* Precrosslinked NBR
Source: Bayer AG, Marinelli/Welle, KALIS-Nr.: 9588 vom 05. 10. 2000
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
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)
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
US 4124306
(French Oil Mill Machinery)
Prior.: 30.11.1977
Inv.: D. K. Bredesen, G. C. Craig,
W. W. Gilius, C. R. Johnson
Source:
DE 4032598 (Bayer AG)
Prior.: 16.04.1992
Inv.: B. von der Linden, K. Goth
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
US 5266211
Bunawerke Huels GmbH
Prior.: 13.06.19990
Inventor: W. Breuker,
H. Wagner, E. Moeller,
B. Schleimer
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
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
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%
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
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
10,4
11,4
10,7
1,9
1,0
1,7
t 1/2 [min]
Raw Rubber
Vulcanizate
10
0,1
-100
-80
-60
-40
-20
Temperature [C]
Nd
Ni
Co
Ti
200
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 [%]
Capacity [kt]
350
300
250
200
150
100
50
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
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]
not
assigned
7%
Li-BR
7%
Nd-BR
8%
Tyres
71%
Golf balls
1%
Li-BR
48%
Co-BR
22%
Ti-BR
18%
Co-BR
52%
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:
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
Stress [MPa]
4
3
2
1
Li-BR
Ti-BR
Co-BR
Nd-BR
0
0
250
500
750
1000
Strain [%]
Source:
Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Improvement
Li-BR
300
Ti-BR
Co-BR
250
Nd-BR
200
150
100
50
0
100
1000
10000
Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
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
[mm/kc]
1,9
6,0
1,5
5,6
Monsonto-FTF/ =100%
[cycles]
460
50
115
63
Source:
Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Improvement
Ti
Ni
Co
Nd
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)
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
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
Viscosity [mPa*s]
100000
10000
1000
100
10
1
HX 565 Mooney: 65
HX 501 Mooney: 40
HX 530 Mooney: 65
260
240
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
20
30
Star shaped BR
40
50
60
70
80
Performance Requirements
for tyres
for HIPS/ABS
Tg
as low as possible
as low as possible
Vinyl content
> 1 Mol%
Gel content
not crical
<500 ppm
Solution viscosity
<21 mPas (5,2% / toluene)
colour
colourless
Tack
yes
Green strength
yes
Strain induced crystallization
yes
dynamic resistance
yes
Abrasion resistance
yes
-
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
Plant Location
Capacity [kt]
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
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:
Li
CH2
Li
Chain growth:
CH2
Li
CH2
+
Transfer reactions:
ideally none
Termination reactions:
ideally none
Li
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]
25
20
15
10
5
0
0
50000
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
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
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
VI-BR
-10
-20
Range of commercial
Vinyl-BR grades
-30
Tg [C]
-40
-50
-60
-70
-80
-90
-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
66
18
16
88
7
5
SBR
1712
18
8
74
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
CH2 Li
CH
Li
CH
Li
CH2 Li
R
n
R
n
Li
SiCl
4
(SnCl4 as alternative)
+ 4 Li Cl
Si
Improvement
Improvement
Viscosity
Cold
flow
Narrow molar
mass distribution
Highly branched
(Star shaped)
100
101
102
103
105
106
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
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
Consumption [t]
700
600
500
400
300
200
100
0
1989
1991
1993
1995
1997
1999
2001
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
tapered sequence
styrene block
100
90
80
70
60
E-SBR
50
40
ond rs
Ra ize
m
Styrene/Butadiene-Copolymerisation
S-SBR
in Hexane
30
20
10
0
0
10 20 30
40 50 60 70 80 90 100
r1
r2
n-Butyl-Lithium
t-BuOK/n-Buli: 0,067/1
T
[C]
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)
30
20
10
0
10
+10C
40
+ 0C
- 10C
- 20C
- 30C
- 40C
- 70C
20
30
- 50C
- 60C
40
50
60
Vinyl [%]
-20
Tg [C]
-40
-60
-80
-100
SBR
1700
tan
10-1
10-2
Integralrubber
10-3
20
40
60
80
100
Temperature [C]
Segment:
Tg [C]
Vinyl-BR
-90C
S-SBR
-20C
3,4-IR
~ 0C
Segment:
Tg [C]
randomizer styrene
Medium-cis BR
-90C
Vinyl-BR
-50C
isoprene
S-SBR
-20C
3,4-IR
~ 0C
t10
t90
t90 - t10
+
0
+
+
Moduli
Tensile Strength
Tear resistance
Abrasion resistance
Heat build up
Rolling resistance
Wet grip
+
+
+
+
+
+*
Vulcanization
In a carbon black loaded compound
there is no real advantage for S-SBR.
Mechanical Properties
Price
Therefore there was no major breakbreakthrough for S-SBR until the green tyre
technology emerged.
emerged.
+
+
+
-
Si OH
SiO2
Et-O
Et-O Si CH2 CH2 S
Et-O
CH2
Si OH
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
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
Li
N
C
91
R2
Li
Si OR
CH2 OR
OR
Si OR
N
C
CH2 OR
R1
R2
80
CH2
Li
- 2 Li
Cl
+
Cl
Cl
O
R
nR
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
H3C
Si
O
R
CH2
+ H3C
Li
Si
Si
O
H3C
CH3
CH3
D3
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
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
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 [%]
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
Sources:
Lars Friebe: Diploma Thesis TU Munich 2000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;
Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
+ 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
cis - 1,4-BR
s - 1,2 - BR
s - 1,2 - BR
cis - 1,4 - BR
trans - 1,4 - BR
Tm [C]
80
40
Goodyear
+0
- 40
60
70
90
80
100
M
8
15
Bd
C
C
29
22
M
36
Bd
M
43
54
Bd
M
60
90
80
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
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
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.
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
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
4)
AlR 3
(R-CH2 - O)2 Nd
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
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
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)
DIBAH
1. Hexane
2. Butadiene
3. DIBAH
4. Neodymversatate
5. EASC
Polymerization temperature: 60C
Conversion/time-plots
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
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
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
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
2,5*105
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
Nd/Al-ratio
Monomer/Nd-ratio
Monomer Conversion
Polymerization temperature
10
20
30
40
50
60
70
80
90
Influence of Butadiene/Nd-ratio
900
60
ML 1+4 (100C)
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
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]
yes
none
none
high
10-50
high
50-100
very high
200-250
low
100-200
Butadiene
Vinylcyclohexene (VCH)
Overview
EPM and EPDM, Termonomers, Market, Range of Grades and
Property Profiles
EPDM-Production
Chemistry of Polymerization , Producers, Capacities, Brand
Names and Production Technologies
Metallocenes
Ovewrview on Metallocene Patents
Metallocene Activation
Comparison of Catalyst Costs
EPDM
EPM
Sulfur
Peroxides
Phenol resins
etc.
(15%)
EPDM
(85%)
Ethene/Propene-Copolymers
Ethene/Propene/Diene-Terpolymers
Oil additives
Impact modification of thermoplastic
polymers (PP)
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
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
200
45
1995
1994
1993
1992
1991
100
40
300
1990
Automotive
Thermoplast Modification
Building
Technikcal Rubber Goods
Electro/Electronics
Oil Additives
50
400
1989
41%
500
1988
6%
1987
16%
9%
55
1986
13%
15%
EPDM-Consumption / kt
3,5 %/a
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
-45
EPDM/2% ENB
EPDM/1% ENB
EPM /0% ENB
-47,5
-50
Tg [C]
-52,5
-55
-57,5
-60
-62,5
-65
40
45
50
55
60
65
70
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
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)
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
+II
VX2 + R3 Al
{R2VX}
Aktivator
+III
{R2V }
heat
heat
[R2V]
R2AlX
+ 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
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
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
Solvent
and
monomer
Condenser
Evaporator
Flashdrum
High boiling
residue
Evaporator
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
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
1,3
1,7
<1
<1
8,0
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
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
80
Ti
70
60
CMe3
50
40
EPDM/V-Cat.
EPDM/CGC (Dow)
30
20
10
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.
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
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
250
Activation of Metallocenes
Cl
Zr
Alkylation
(BuLi, AlR3 or MAO)
Cl
Alkylation
(BuLi, AlR3 or MAO)
R
Zr
Cl
Activation by MAO
R
Zr
R
R
Zr
+ A
CH2 CH2
Zr
+
R
Zr
+
CH2
CH2
CH2
CH2
R
+
Zr
CH2
CH2
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
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
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
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
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)
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
n :
6 - 20
MW : 2.000-2.500
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
Activation of Metallocenes
R
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
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)
1990
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
Catalyst
[EUR/100 kg]
VOCl3
0,50
V(acac)3
1,25
Et(Ind)2ZrCl2
13,00
Et(Ind)2ZrMe2
Cocat.
Reactivator Total Cat-Costs
[EUR/100 kg] [EUR/100 kg] [EUR/100 kg]
EASC
3,75
DEAC
1,30
MAO
151,00
Borate
3,45
DCPEE
2,00
TEA
0,65
-
6,25
3,20
164,00
5,70
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
IIR
BIIR
CIIR
BIMS
XLIIR
Contents
Overview
Products, Property Profiles and Areas of Application
Market, Market Shares, Producers and Range of Grades
CH3
CH2 C
CH3
CH CH2 CH2 C
CH2 C
CH3
CH3
CH3
20
CH3
CH3
CH2 C
CH3
CH3
CH2
CH2 C
CH CH2 CH2 C
CH2 C
CH3
CH3
CH3
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
Basic Features:
Isoprene content:
0,5 - 2,5 Mol%
Incorporation of Isoprene: random 1,4-trans
Tg:
ca. -72C
Mw/Mn:
3-5
CH3
19
CH3
CH3
CH3
38
39
CH3
5%
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)
CH3
CH2 C
CH3
CH3
CH3
CH2 C
CH3
CH CH2 CH2 C
CH3
CH3
CH2 C
CH3
CH3
CH3
CH2
CH2 C
n
CH CH2 CH2 C
X
CH3
Rebound
Temperature [C]
60
50
100
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)
- 2,3 %/ p.a.
+ 2,3 % p.a.
+ 1,2 % p.a.
(90%:
XIIR:
IIR:
IIR:
Pricing (1996):
700
Company
400
300
200
100
0
20
00
19
97
19
94
19
91
19
88
19
85
Exxon
414
Lanxess
252
Nizhnekamsk
180
Togliatti
Sinopec
(X)
45
80
Total Capacity
19
82
500
19
79
Consumption [kt]
600
IIR:
XIIR:
BIMS:
IIR
XIIR
Sum
50
1.041
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
Mooney Viscosity
ML (1+8) 125C
Mooney Viscosity
ML (1+8) 125C
0
0
10
10
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
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)
Sources:
mixed feed
catalyst
HCl
AlCl3
H2O
+
H + AlCl4
+ AlCl3OH
CH3
Initiation of Polymerization:
CH3
CH3
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
CH3
CH3
CH3
CH3
Transfer Reaction:
CH3
CH3
H
AlCl4
CH3 C
CH3
+
H + AlCl4 + CH2 C
+
CH3 C AlCl4 +
CH3
CH3
+ 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
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
-25
-50
-75
-90
-106
-120
107
EtAlCl2/H2O
AlCl3/H2O
-Strahlung
Mn [g/mol]
-143
106
105
Molar Masses:
BF3/H2O
104
3,5
4,0
4,5
5,0
5,5
3
1/T *10 [K-1]
6,0
6,5
7,0
Halogenation reactor
Neutralization reactor
Addition of AO
Hexane
water
X-IIRSlurry
in water
Antiagglo- steam
merants
Caustic
soda
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
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
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)
IIR -Terpolymer*
100
100
N 762
Carbon black
50
50
Hard Clay
Silicate
20
130
80
Pb3O4
10
Stearic acid
Bis(t-butylperoxy-isopropyl)benzene
1,5
Trimethylolpropanetrimethacrylate
Sartomer 350/Sartomer
1,5
Actor DQ/Kawaguchi
Dibenzo thiazyldisulfide
Vulkacit DM / Lanxess
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
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
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
[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
[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]
Tensile Strength [MPa]
Elongation at break [%]
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
BIIR
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
Vulkacit DM / Lanxess
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
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
Vulkacit DM / Lanxess
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
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
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
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
60
40
20
0
Mechanical Properties
Silicon Rubber
Hydrogenated Nitrile Rubber
Fluoro Rubber
Ethylene-Vinylacetate-Copolymers
Ozone Resistance
Oil Swelling
Bond
energy
[J/mol]
Radius
of atoms
[A]
C-H
413
0,37
C-F
485
0,72
232C
260C
288C
316C
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:
30-40 %
30-40 %
10-15 %
~5%
4.5 %
10 %
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)
Market:
Prices:
Top price:
20 - 50 EUR/kg
(correlated with F-content)
~ 500 /kg (Kalrez)
Growth:
8 - 10% p. a.
Asia
22%
USA
45%
WEurope
33%
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
2,0
2,1
2,0
1,0
2,0
1,0
1,0
[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
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)
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)
180
Benzene/21C
160
reduction of elongation at
break [%]
Tg [C]
Gear Oil/121C
140
120
100
80
60
40
20
0
60
65
70
75
10
0
-10
-20
-30
HNBR
FKM (68% F)
-40
-50
-60
-70
-80
0
200
400
600
time [h]
800
1000
TFE/VDF/PMVE
TFE/VDF/HFP
-5
-10
CF3
HFP Hexafluoropropene
(76% fluorine)
-15
-20
-25
-30
CH3
-35
0
0,5
1,5
TFE Tetrafluoroethylene
(76% fluorine)
CF3
Propen
Source: J. Scheirs Modern Fluoropolymers High Performance Polymers for Diverse Applications John Wiley & Sons
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
CF3
- HF
CF2
CF3
- HF
CH CF CH CF2
CF2
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
CF3
- HF
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
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:
J. Scheirs Modern Fluoropolymers High Performance Polymers for Diverse Applications John Wiley & Sons
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
Bond energies
Si-O
C-O
C-C
C-S
S-S
FMQ
CH3
CH3
- 45
- 45
- 70
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
Haushalt
20%
Medical
Applications
25%
Automotive
industry
40%
Machine building
15%
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
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
Rhodorsil
850.000
*Evonik and Crompton are active in this market without proprietary siloxane production
Japan
25%
Nordamerika
44% Year
1995
Consumption
/t:
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
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
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.
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
Silanol containing
Silicon rubbers
High temperature-Vulcanization
with peroxides (HTV: 120-180C)
Si
OH
HO
OR
RO
Si
- 4 ROH
O
Si
OR
OH
Si
Si
Si
OR
Si
HO
Si
Si
Si
R
RO
OR
OR
Si OR
RO
Si OR
RO
O ( Si
Si
OR
OR
OR
OR
O
)
n
R = Me, Et
OR
Carboxylates:
Tin-(II)-octoate
und
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.
R
Si
OH
Si
Si
- H2
R
Si
HO
Si
Si
Si
For the condensation reaction the catalysts quoted under 1a) are being used.
2)
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
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
Cost Factor
HTV
LTV
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
Overview:
Microstructure, Property Profile and Appliecation Areas
Catalytic Hydrogenation of NBR
Sequence of Process Steps in NBR- and HNBR-Production
Producers and Production Capacities
Chemical and Physical Properties
Comparison of NBR- and HNBR Properties
Speed of Ageing
Tg
Crystallization
Stress/strain-Performance
Vulcanizate Properties of Sulfur- und Peroxide crosslinked Vulcanizates
Performance of HNBR in Power Transmission Belts
HNBR: Microstructure
C
N
CH2
CH
H3C
CH2
Butylidene-Moiety
H
CH CH
C
C
H2
H2
Ethylidene-Moiety
CH
2
CH
2
1
Nitrilo-EhylideneMoiety
Negativ:
Max. service temperature < 155C
High Tg >-30C
Bad incorporation of softeners
High price (~ 20/kg)
Expansion
Joints
15%
45%
25%
7%
Ship Couplings
4%
4%
Riemen
Schluche
Dichtungen
Kabel
lfrderung
Sonstige
Rotor/Stator- Pumps
Roll Covers
C
N
H2/Catalyst
HN
C N
- NH3
R
C
C
N
Catalyst
R
CH 2 H C
C
N
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
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)
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
Br
Emulsionspolymerization
Latexcoagulation
+ crumb wash
Mechanical
dewatering
Thermal
drying
Bale
pressing
Bale wrapping
Packaging
and storage
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
Capacity [t]
Zeon
Takaoka
Houston
Japan
USA
2.800
2.000
Lanxess
Leverkusen
Orange
Germany
USA
3.000
3.600
11.400
Total
Volume [t]
10000
Consumption
capacity
8000
6000
4000
2000
0
1992
1994
1996
1998
2000
2002
2004
Solvent removal
by evaporation
+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
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
100
100
NBR
80
80
60
60
40
20
Tg [C]
40
20
-20
-40
-60
-20
-80
-40
-100
20
40
60
80
100
20
40
60
80
Data for Ethene/Acrylonitrile-Copolymers from: R. E. Uschold, I. B. Finlay, Appl. Polym. Symp. 25 (1974) 205
100
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
20
Crystallinity [%]
1. DSC-Aufheizung
12
2. DSC-Aufheizung
10
8
6
4
2
0
0
10
20
30
40
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
50
Tg [C]
-50
-100
-150
0
10
20
30
40
50
60
70
80
90
100
Tg [C]
-26
-28
-30
-32
-34
0
20
40
60
80
100
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
1000
E'
E''
100
10
0,1
-200
-150
-100
-50
50
100
Temperature [C]
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
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
160
48,3 %
= bleibend
140
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
100,0 phr
0,5 phr
1,0 phr
2,0 phr
2,0 phr
1,0 phr
0,4 phr
45,0 phr
2,0 phr
0,5 phr
1706 S
HNBR-Grade (Therban)
33,7
ACN-content
[wt.%]
4,3
RDB-content
[Mol.%]
60
ML 1+4(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
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
Leather
SBR
200
10.000
180
160
140
120
100 [C]
1.000
CR
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)
1000
CR
HNBR
100
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
CH3
CH3
CH3
O
Positive:
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
Source: H. Bartl, J. Peter, ber thylen/Vinylacetat-Copolymerisate und ihre Vernetzung; Kautschuk und Gummi, Jahrgang 14, 2 (1961) WT 23-32
10000
Products
pressure [bar]
1000
Du Pont
USI
Lanxess
Mitsui
Solution
Solution
Solution process
100-500 bar
50-120C
100
Levapren
Emulsion process
10-100 bar
30-70C
10
Solution process:
EVM-Rubbers
1
0
20
40
60
80
100
Emulsion Process:
Preferred process for latices with
high gel content (paints)
Monomer conversion: ~ 100%
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
CH3
- HAc
O
O
CH3
O
CH3
O
-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
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
80
60
Delta F/F0 x 100 [%]
60
40
20
-20
50
Al2O3:
0 phr
40
30
20
10
-40
20
40
60
80
100
20
40
60
80
100
100,0 phr
MgO
2,0 phr
Stearic acid
1,0 phr
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
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]
Elongation at break [%]
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
-3
-2
10
-12
-2
9
-10
2
11
-11
-2
12
10
-7
15
-8
-15
14
-26
-19
69
-12
-4
47
-8
-4
31
8
2
13
6
8
3
10
-12
-4
[%]
[%]
[%]
EVM/HNBR-Blends
EVM/HNBR
100,0 phr
1)
Rhenogran P 50 var.
Carbon black/N 550 50,0 phr
Carnuba Wax
2,0 phr
MgO
10,0 phr
ZnO
2,0 phr
TAIC
1,75 phr
7,0 phr
Peroxide (40%ig) 2)
Vulcanization time: 15 min
Temperature:
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]
Elongation at break [%]
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
-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.)
[%]
[%]
[%]
Stress [MPa]
15
10
th
wi
e
ur
tc
s
o
t
ou
th
i
w
r
cu
st
o
p
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
time [sec ]
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
Compound properties
Mooney ML 1+4(100C)
[MU]
Vulcanized properties
(ISO-Stab Nr. 2, 2mm)
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
[%]
[%]
-
23
Positve:
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)
mechanical and
reactor-blends
(unvulcanized)
EPM / PP
EPDM / PP
Olefin TPE-V
EPDM / PP
NBR/ PP
NBR / PVC
EVM / PVC
ACM / PVC
Thermoplastic
Polyolefins
(dynamically vulcanized)
Polyblends1
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
Styrenic Block-Copolymers
Multi-BlockCopolymers2
TPE-A
PEBA based on
PA 6 and PA 12
Crosslinking
Principle
Producer
Brand Name
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
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
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%
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
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
104
103
102
Target
101
Reality
100
10-1
-100
- 50
0
50
100
Temperature [C]
150
200
104
103
102
100
150
6
101
100
10-1
- 100
8
- 50
50
Temperature
200
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
stress [MPa]
1. Thermoplastic Polymer
103
Residual elongation
strain [%]
residual elongation (
Residual ) [%]
residual = original
300
200
ASTM D 1566 - 98
Definition of Rubber
100
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
[%]
S BS
S IS
S hore A
10 to 80
71
52
S hore D
P rope rtie s
10 to 35
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
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
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
180
TPE-V
(EPDM / PP-blend,
highly crosslinked)
160
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)
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
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%]
n
ctio
e
r
i
w
D Flo
of
n
ctio
e
r
i
w
D Flo
of
no. of recycles
1
M100 [psi]
650
630
620
600
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
Elongation at break [%]
100
Filter
Filter
ventilator
PE*
PP**
UCC
BASF
BP
Hoechst
Exxon
Amoco
Montell
Montell
Fina
Phillips
Solvay
UCC
BASF
Amoco/Chisso
Sumitomo
Cooler
Product
outlet
Supported
catalyst
Cooler
Ethylene
500
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
packaging
900
E-Modulus [MPa]
800
Catalyst System A
700
600
Catalyst System B
500
400
300
20
30
40
50
60
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)
PP
HOCH 2
CH2 OH
OH
PP
CH2
CH 2 OH
PP
CH2
CH 2 OH
EPDM
OH
PP
CH 2
CH2
EPDM
PP
CH2
EPDM
CH2
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
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
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]
[%]
[%]
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
R
ataktisches
Polymer
R2
Zr
622
595
R1
R
Isotaktisches
Polymer
R2
Zr
R1
R
Cl
Cl
Cl
B
Zr
Et
Et
Cl
Cl
Cl
Temperature
B
Zr
Cl
Cl
P
Et
Et
atactic polymers
PP-Based TPE
4
Schubmodul (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]
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]
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
7. Test Questions
Rubber
Abbreviation
Polybutadiene
Polychloroprene
Chlorinated Polyethylene
Chlorosulfonated Polyethylene
Ethene/Propene/Diene-Terpolymers
Ethene/Propene-Copolymers
Fluororubber
Acrylic Rubber
10
Synthetic Polyisoprene
11
Isobutene/Isoprene-Copolymers
12
Styrene/Butadiene-Copolymers
13
Natural Rubber
14
15
Butadiene/Acrylonitrile-Copolymers
16
Brominated Isobuylen/Isoprene-Copolymers
17
18
19
20
Family Name
Given Name
Chemical
Features
Emulsion
Solution
Dispersion
(slurry)
Mass or
Bulk
GasPhase
Radical
Polymerization
Ziegler/NattaPolymerization
anionic
Polymerization
Cationic
Polymerization
Polyaddition und
Polycondensation
Polymermodification
Family Name
3
Given Name
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
Family Name
Given Name
5
Natural Rubber
Please Mark RIGHT or WRONG
Nr.: Frage
1
2
3
4
5
6
7
8
9
10
Right Wrong
Family Name
Given Name
6
Synthetic Polyisoprene
Please Mark RIGHT or WRONG
Nr.: Question
1
2
3
4
5
6
7
8
9
10
RIGHT WRONG
Family Name
Given Name
7
Emulsion Rubbers
Please Mark RIGHT or WRONG
Nr.: Question
Right Wrong
10
Family Name
Given Name
Question
Right Wrong
COD = 0
BOD = 0
BOD = COD
10
Family Name
Given Name
Crystallization of Rubbers
Please Mark RIGHT or WRONG
Nr.:
1
2
3
4
5
6
7
8
9
Frage
Additives can increas the rate of crystallization
Additives can reduce the rate of crystallization
SBR is a crystallizing rubber
NBR is a crystallizing rubber
NR is a crystallizing rubber
Rubber compounds crystallize slower than raw rubbers
Vulcanizate crystallize faster then the respective rubber compounds
Strain induced crystallization is a wanted property
Low temperature performance of vulcanizates is improved by spontaneous
crystallization
10 The compression set performance of vulcanizates at low temperatures is
is improved by spontaneous crystallization
Right Wrong
Family Name
Given Name
10
Crystallization of Rubbers
Please Mark RIGHT or WRONG
Nr.: Question
1
2
3
4
5
6
7
8
9
10
Right Wrong
Family Name
Given Name
11
NBR
Please Mark RIGHT or WRONG
Nr.: Frage
1
2
3
4
5
6
7
8
9
10
Right Wrong
Family Name
Given Name
12
NBR
Please Mark RIGHT or WRONG
Nr.: Frage
1
2
3
4
5
6
7
8
9
10
Right Wrong
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:
Right Wrong
1
2
Family Name
Given Name
15
CR
Please Mark RIGHT or WRONG
Nr. Question
Right Wrong
1
2
3
4
Family Name
Given Name
16
HNBR:
Please Mark RIGHT or WRONG
Nr.: Question
1
2
3
4
5
6
7
8
9
10
Right Wrong
Family Name
Given Name
17
HNBR:
Please Mark RIGHT or WRONG
Nr.: Question
1
2
3
4
5
6
7
8
9
10
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
Right Wrong
1
2
3
4
5
6
7
8
9
Family Name
Given Name
19
Thermoplastic Elastomers:
Please Mark RIGHT or WRONG
Nr. Question
Right Wrong
1
2
3
4
5
6
7
8
9
Family Name
Given Name
20
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)
21
[phr
[phr]
[phr]
100
-
100
-
100
30
30
30
Rubber A
59
8,8
27,8
560
15
52
17
Rubber B
Shore A Hardness/23C
Modulus300
[MPa]
Tensile Strength
[MPa]
Elongation at break [%]
Rebound/23C
[%]
Goodrich HBU
[C]
CS (24h/70C)
[%]
Volume swell (70h/70C)
ASTM-oil Nr. 1
[%]
ASTM-oil Nr. 2
[%]
ASTM oil Nr. 3
[%]
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
8,0
1,98
Given Name
22
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
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
Vulcanizate Properties
Shore A Hrte (23C)
Modulus 100
[MPa]
Elongation at break [%]
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
[%]
[%]
[%]
Rubber A
Rubber B
Family Name
-10
-4
+24
-17
-11
+34
-36
-29
+49
-50
-34
+67
-56
-45
+83
Given Name
24
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
Hard phase
Soft phase
1
2
3
4
5
Family Name
Given Name
26
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
(ISO-Stab Nr. 2, 2mm)
Shore A Hrte (23C)
S 100
MPa]
Elongation at break [%]
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
-3
-2
10
-12
-2
9
-10
2
11
-11
-2
12
10
-7
15
-8
-15
14
-26
-19
69
-12
-4
47
-8
-4
31
8
2
13
6
8
3
10
-12
-4
[%]
[%]
[%]
Rubber
Family Name
Given Name
100 80
20
-
60
40
40
60
Rubber A
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
0,0
Given Name
28
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
Tensile Strength [MPa]
Elongation at break [%]
CS (70h/150C)
[%]
29