Académique Documents
Professionnel Documents
Culture Documents
6. Thermoplastic Elastomers
7. Test Questions
1. Overview on Rubbers, Definitions, Market, Properties,
Production, and Applications
300 ε = ε residual
Residual Elongation [%]
200
TPO
Definition of „Rubber“
according to Thermoplastic
ASTM D 1566 - 98 TPV Elastomers
100
SBS
NR/BR based tyre tread
0 NR gum stock
0 100 200 300
Elongation (εε) [%]
Thermoset resins (or duroplasts) are highly crosslinked polymers which do not soften with
increasing temperature, but will deteriorate at high temperatures
Polyethylene ~ -130°C
Polypropylene -18°C
(atactic / amorphous)
Polystyrene +100°C
(ataktisch / amorph)
O O O O O O O
Si Si Si Si Si Si Si Silicon Rubber -120°C
-115°C
Polybutadiene (100% 1,4-cis)
-75°C
Polyisoprene (100% 1,4-cis)
Cl Cl -45°C
Polychloroprene (100% 1,4-trans)
Cl
Cl
CN
NR
60
40
IIR
20
0
-75 -50 -25 0 25 50 75 100
Temperature [°C]
100
10
0,1
-150 -100 -50 0 50 100 150 200
Temperature [°C]
Designation of Rubbers (DIN/ISO 1629)
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
Automotive
15%
Modification
Tyres of Plastics
45% 14%
Others
Cable and 15%
Wire
Construction Machine
3%
3% building
5%
Price and Volume of Rubbers (without Latex)
FZ Volume Shares
FQ High General Purpose Rubbers: 82%
FKM Performance
HNBR Q
AU/EU EVM
Rubbers
CR (0.3 Mio t)
Price
Volume High
Performance Special
Rubbers 10% Rubbers 30%
Source: Rubber World, 21916 (1999) 13-14
General
GeneralPurpose
PurposeRubbers
Rubbers
250 Special Rubbers
Special Rubbers
max. service temperature [°C]
100 CR
EU SBR BR
NR
75 AU
50
0 20 40 60 80 100 120 140 no
requirement
Degree of Swelling in ASTM-Oil Nr. 3 [Vol %]
Evaluation of Vulcanizate Properties
1 2 3 4 5 6 7 8 9 10
Improvement
Criteria of Evaluation:
• Maximal Service Temperature
• Low Temperature Flexibility
• Oil Swell
• Mechanical Properties
• Ozone Resistance
E-SBR and S-SBR may not be evaluated according to these criteria as SBR is designed for high Tgs (improvement of wet skid)
*Ullmann‘s Encyclopedia of Industrial Chemistry, VCH Weinheim 1993, Vol. A23, Rubber 3. Synthetic; W. Obrecht „Introduction“
Correlation of Rubber Price and Vulcanizate
Performance
45
40 FZ
FMVQ
35 HNBR
MVQ FKM
Performance Index
EVM ACM
30 NBR AEM AU
EPDM ECO
25 CSM
NR IIR CM
20 BR CR
SBR
15
10
0
0,1 1 10 100 1000
Michelin
Goodyear
Source: European Rubber Journal, vol. 184, no. 10, Oktober 2002, S. 28-30
Ranking of Top 22 Producers of Technical Rubber Products
(without Tyres)
Rank Company Company Sales 2001 Return on Sales
Site [Mio US$] [%]
*) not available
Source: European Rubber Journal 184,9 September 2002
12,097 KMT
Sinopec 5.2%
Petro-China
3.6%
Source:
R. J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008„Globalization of Synthetic Rubber Industry“
Chemical and Technological Features of
Rubber Manufacturing Processes
Chemical Technological Features
Aspects
Emulsion Solution Dispersion Bulk Gas-Phase
Waste Air
Modifier
Reactivator Wrapper
Purification/ Purification/ EASC
Drying Drying
VOCl3
Hexane ENB
Evaluation of Rubber Manufacturing Processes
Polymerization Process
Emulsion Solution Dispersion Bulk Gas-Phase
Aspect
Slurry
Viscosity 8 2 8 1 10
Heat Removal 10 3 8 3 5
max. Solids Cont. 5 2 5 9 5
Stereoregularität 0 10 10 8 10
Waste Water 0 5 5 10 10
Waste Air 5 5 5 8 5
Sum 28 27 41 39 45
Ranking: (Gas-Phase) > Dispersion > Bulk >> Emulsion > Solution
Prerequistes: comparable running times
20
0
0,2 0,4 0,6 0,8 1,0 1,2 1,4
Reciprocal chain length 1/Mc x 10-4
• For high moduli and high tensile strength the vulcanization method and the length of rubber
chains between two crosslinking sites are decisive factors
• There is an optimum in tensile strength for Mc ~10.000 g/mol
• The tensile strength of rubber vulcanizates is only 1/100 - 1/1000 of the theoretical values
Sources: R. Houwink, H. K. de Dekker „Elasticity, Plasticity and Structure of Matter“ University Press, Oxford 3. Auflage (1971)
K. Dinges, Kautschuk und Gummi. Kapitel 2 in H. Batzer „Polymere Werkstoffe“
Georg Thieme Verlag Stuttgart, New York (1984)
Positive:
• Low price and good ratio of price versus performance
• Standardized NR-grades
• High level of mechanical properties
(Tensile Strength, Modulus Abrasion) 5
• Good Dispersability of Fillers H3C 2 3
(due to high viscosities at the start of the mixing cycle) C CH
1 4
• Low rolling resistance (truck tyres)
• High abrasion resistance (truck tyres)
CH2 CH2
• Slow spontaneous crystallization
• Significant strain induced crystallization
Negative:
• Poor resistance to swelling with hydrocarbons Physical Properties:
(fuels, oils and grease) Tg: -72°C
• Need for mastication prior to compounding 1,4-cis-content ~ 97%
• bad wet skid performance Tm (equilibrium): + 30 °C
• Poor resistance to heat ageing max. rate of crystallization: -25°C
max. degree of crystallinity: ~ 30 %
Strain induced crystallization
NR: Designation of Grades and Glossary
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
Synthesekautschuk (Fest + Latex)
10
Mio tons
0
1880 1900 1920 1940 1960 1980 2000 2020
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“
Source: European Rubber Journal, January/February 2011, 16
NR: Production
3500 Malaysia
Indonesia
3000 Thailand
x 1000 metric tons
2500 others
2000
1500
1000
500
0
Sources: 1980 1985 1990 1995 2000 2005
• 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
Source: Römpp Lexikon Chemie; Version 1.5; Stuttgart/New York Thieme-Verlag 1998
LMC International Ltd; Rubber April 2005
NR: Application Areas
Tyres
71%
Automotive
(other than tyre)
2%
Shoes Latex-Products
None automotive Others
4% 11%
5% 7%
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
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: Production
Share of smallholders
in rubber production:
Thailand 95%
Indonesia 83%
India 83%
Malaysia 81%
Brasil 70%
Sri Lanka 33%
Ivory Coast 29%
Source: International Rubber Study Group
Source: http://www.therubbereconomist.com
NR-Production by smallholders:
Area cultivated per smallholder: 1,25 ha;
Number of trees: 625 trees in total; 520 trees under tap
Annual tappings per tree: 180/a
Total number of tappings per year: 95.000 tappings for 625 trees/a
Annual yield: 850 kg/a
Annual earnings: ca. 250 €/a (0,30 €/kg)
Earnings/different source*: 1020 €/a (1,2 €/kg)
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
*Broadcast in German TV (ZDF) “Mission“ about Charles Goodyear on 17.10.2004
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 60°C/1 week for RSS-production (“RSS” = Ribbed Smoked Sheet)
• Drying in air at 40°C/2 months (“ADS“ = Air Dried Sheet)
centrifugation,
creaming, Sheet-Material „Cup lump“
evaporation of (RSS, ADS)
water „Smallholder‘s
lump“
SMR 5
60% 40%
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical
Technology, vol 21, 4th ed., 562-591 (ISO 1658: Natural Rubber - Test Recipes and Vulcanization Characteristics,
International Organization for Standardization, Geneva, Switzerland, 1973
Chemical and Physical Composition of NR
NR (TSR 5, Defo 700) [phr] 100 100 100 100 100 100
Carbon black/Corax N 2200 [phr] - - - - 50 50
Stearic Acid [phr] 3 3 3 3 3 3
Zinc oxide [phr] 3 3 3 3 3 3
Antilux 654 [phr] 1,5 1,5 1,5 1,5 1,5 1,5
IPPD (Vulkanox® 4010 NA) [phr] 1 1 1 1 1 1
TMQ (Vulkanox® HS/LG) [phr] 1 1 1 1 1 1
Mineral oil/Enerthene 1849 [phr] 3 3 3 3 3 3
Sulfur [phr] 1,6 1,6 1,6 1,6 1,6 1,6
TBBS (Vulkacit® NZ) [phr] 1 1 1 1 1 1
Desmodur® TT [phr] 0 0 15 25 0 10
OOOO
OOOO
CCCC
NNNN
CCCC
HHHH
CCCC HHHH CCCC
HHHH
NNNN
3333CCCC
HHHH
CCCC
NNNN
NNNN
CCCC
HHHH
3333
NNNN
HHHH
NNNN
HHHH
CCCC
SSSS
NNNN
HHHH
HHHH
3333
3333
3333
SSSS
HHHH
CCCC
HHHH
OOOO
NNNN
CCCC
OOOO
3333
3333
IPPD (Vulkanox® 4010 NA) TBBS (Vulkanox® NZ) Desmodur® TT (TDI Uretdione)
First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272
NR: Vulcanization with Multifunctional Isocyantes
NR (masticated TSR 5) 100 100 100 100 100 100
Carbon black (Corax N 220) 0 0 0 0 50 50
Desmodur TT 0 0 15 25 0 10
Shore A Härte/23°C 43 40 66 68 66 75
Shore A Härte/70°C 45 38 - 65 - -
Rebound/23°C [%] 74 69 59 55 - -
Rebound/70°C [%] 81 78 - 60 - -
Mastication of NR
*C
C* C* *C
Pentachlorothiophenol 2,2'-Dibenzamidodiphenyl-Disulfide
(DBD)
Degree of Mastication
SH S S
Cl Cl
NH HN
Cl Cl O O
Cl
30
Crystallinity [%]
25
20
15
Pale Crepe
10 pale crepe after acetone extraction
0
0 5 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 (40°C-50°C)
• The decrystallization in the interior of bales needs 2 weeks at 30°C
• 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 40
30
melting temperature [°C]
20
100
half time [h]
10
10 -10
-20
-30
1 -40
-50 -30 -10 10 -50 -30 -10 10 30
Source: Source:
U. Eisele Intorduction to Polymer Physics, Springer-Verlag 1990 K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural
in Kirk-Othmer Encyclopedia of Chemical Technology,
Vol. 21, 4th ed., 562-591
Stress/Strain-Performance of Unfilled NR- and SBR-
Vulcanizates (gum stocks)
30
25
NR
stress [MPa]
20 SBR
Strain induced crystallization
15
10
0
0 200 400 600 800 1000
strain [%]
25
20
NR
SBR
Tack-Index
15
10
0
0 20 40 60 80 100 120
temperature [°C]
Chemically Modified NR-Grades
Modification Application
Hydroxyl amine (“CV”-Grades) improved compounding, no mastication
required
Blend with NR-gel (“SP”-Grades) Improved processability of NR-compounds
Epoxydation (ENR) Improved oil resistance
Improved wet skid
Improved silica interaction
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
NR: CV-Grades
10 SMR 20
9 IR/Natsyn 2200 (IR / Ti)
Mooney- Increase [MU]
H
H + H2 N H 8
O
7
6
- H2 O 5
4
3
H 2
H 1
N H
0
0 5 10 15 20
storage time [days]
Mooney-Viscosity ML1+4
130
120
(100°C) 110
100
90
80
70 before hot air ageing
60 after hot air ageing
50
0 0,02 0,04 0,06 0,08
Hexanediamine [mol/kg]
H
Specification of CV-Grades
H NH2
H + H2 N + H
O O Grade Ml 1+4 (100°C)
- 2 H2 O Minimum Maximum
CV 50 45 55
CV 60 55 65
H
H
CV 70 65 75
N
N H LV 50 54 55
H
NR: CV-Grades
70
Increase of Mooney Viscosity [%]
60
H
H C + H2N OH 50
O
40
- H2O
30
H 20
H C 10
N OH
0
0 0,05 0,1 0,15 0,2
hydroxyl amine [wt. %]
40
20
Tg [°C]
Epoxidation with -20
peracids in the
latex stage
-40
O O
-60
-80
O 0 20 40 60 80 100
NR [phr] 100 - -
ENR 25 (Degree of Epoxidation: 25%) [phr] - 100 -
ENR 50 (Degree of Epoxidation: 50%) [phr] - - 100
Carbon black (N 220) [phr] 30 30 30
Shore A Härte/23°C 59 56 59
M300 [MPa] 7,8 6,9 8,8
Tensile Strength [MPa] 27,1 25,9 27,8
Elongation at break [%] 550 590 560
Elasticity/23°C [%] 78 25 15
Goodrich HBU [°C] 44 60 52
CS/24h/70°C [%] 17 46 17
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: Vulcanization with A Capped Diisocyanate (Novor 924)
O
N N
O N O NH O HN O N O
Novor 924: TDI based diisocyanate O O
Novor 950: MDI based diisocyanate
Thermal Cleavage
Due to health and safety reasons Novor
924 has been replaced by Novor 950 O
N N
O N O H H O N O
O C N O N C O
Tautomerization Tautomerization
H O N O
O N O H
H H
O
- H2 O - H2 O
N N
N O NH O HN O N
O O
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
Contents:
• Differences between IR and NR
• IR-Grades, Catalysts and Microstructures
• Price, Producers, and Production Capacities
• Comparison of Unvulcanized NR- and IR- Properties
• Vulcanizate properties of NR and IR
• Compound and Vulcanizate Properties of Poly-3,4-Isoprene
IR
NR
Li Ti Nd
cis-1,4-content [mol % ] 98 93 97 99
Need for Mooney adjustment before use yes no mastication needed
Gel yes - - -
functional groups yes - - -
Poly-cis-1,4-Isoprene Poly-trans-1,4-Isoprene
Type of IR Catalyst Solvent Microstructure
Trade Name cis-1,4 trans-1,4 1,2- 3,4-
1)
Cariflex IR-309 Li unpolar (benzene) 93 0 0 7
1)
Natsyn 200 Ti unpolar hydrocarbon 97 0 0 3
2)
Vestogrip Li Hexane/Additive 60
3)
IR Nd unpolar hydrocarbon 99 - - -
Sources:
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 Hüls AG: “Vestogrip“ (Production by Karbochem / South Africa: ca. 3.000t)
3) WO 02/38635 A1 (Michelin), Erf.: P. Laubry, Prior.: 13.11.2000
3) WO 02/48218 A1 (Michelin), Erf.: P. Laubry, Prior.: 28.11.2001
IR: Development of Prices, Producers and Production
Capacities
3
2,5
1,5
0,5 IR
NR (RSS)
0
1980 1985 1990 1995 2000 2005 2010
Source: R.J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008 „Globalization of Synthetic Rubber Industry“
7 NR (SMR 5)
High cis-IR/Ti (97%)
Stress [MPa]
0
0 100 200 300 400 500
Strain [%]
Evaluation of Compound- and Vulcanizate Properties of
NR and IR
Compound Properties
IR
NR
Li Ti Nd
Mastication - + + +
Mixing cycle - + + +
Die swell - + + +
Tack + - - +
Green strength + - - +
Vulcanizate Properties
IR
NR
Li Ti Nd
Modulus + - - +
Tensile Strength + - - +
Cut growth resistance + - - +
Rebound Elastivity + - - +
Abrasion resistance + - - +
Source: P. Roch (Goodyear) KGK 48,6 (1995) 430-434“Compounding for Wet Grip“
3.0. Overview on Emulsions Rubbers
Emulsifier
Initiator
Monomer
Polymerization
Wasser
M M
M M M M
Monomer droplet
Diameter: 0,1-10*10 -6 m
concentration: 1013 lw-1 M M
M M M
Literature: Polymerization occurs only in
• P. E. Lovell, M. S. El-Aasser, Emulsion Polymerization, Wiley 1998
• Blackley, Emulsion Polymerization, 1975 monomer loaded micelles and
• H. Gerrens, Advances in Polymer Science, volume 1 not in monomer droplets
Phases in Emulsion Polymerization
70
Surface tenison
60
pressure
Arbitrary Units
polymerization rate
50
40
30
20
10
0 20 40 60 80 100
Monomer Conversion [%]
Vapour
Mixer/Settler condensation
Wate water
Flash
Hydroperoxide
treatment
evaporation
Butadiene
-tionskessel
Polymerisa
Abstopp-
Styrene
kessel
-tionskessel
Polymerisa
-tionskessel
Polymerisa
-tionskessel
Polymerisa
-tionskessel
Polymerisa
Short stop
Vapour
Latex-
storage
AO
Wash water
Mass Balance:
Additives (oil, etc)
Dewatering dryer
Coagulation screw
tank
Baler and
packaging
Waste water treatment
stripped
Latex
Finishing of CR-Latex
dryer
Acidic acid
Freezing
roll
Powdering Chopper
packaging
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
1. COD = 0
2. BOD = 0
3. COD = BOD
4. COD < BOD
5. BOD < COD
Explanation:
Microstructure of E-SBR
4
CH2
2 CH
1 2 1
HC CH2 3 CH
3 3
HC 4
CH CH CH
C 2 2
CH
H2 CH2 CH2 CH2
2
4 1
1
• no variation of microstructure
• low / no profits / no R&D-activities
Others
mechanical
2%
Buildings parts
Shoes Automotive
5% 8%
5% 8%
Sum 3.902.000
Market: 2,0 Mio t
Capacity: 3,9 Mio t
Capacity utilization: 51%
Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.
E-SBR: Producers and Capacities in Europe
(without Latex Capacities):
700
Company Site Country Capacity
Lanxess France La Wantzenau France 45.000
600 Dow Schkopau Germany 120.000
Enichem. Ravenna Italy 295.000
Dow (prior owner: Shell) Pernis Netherlands 120.000
500
Sum 580.000
Production [t]
415.000
400 Dwory Oswiecim Poland 104.000
Chemopetrol Kralupy Czech Republic 76.000
HIP Petrohemija Zrenjanin Croatia 40.000
300
Combinatul Petrochimic Onesti Rumania 100.000
Neftochim Burgas Bulgaria 20.000
200 Sum 340.000
100
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.
Cold Rubber
Hot Rubber
Source: The Synthetic Rubber Manual, 14th edition IISRP (International Institute of Synthetic Rubber Producers, Houston (1999)
E-SBR: Selected Grades
E-SBR Styrene- ML 1+4 Antioxydant Mineral Oil Carbon Black Remarks & Application
grade content (100°C) System grade loading grade loading Areas
[wt.%] [MU] - [phr] - [phr]
General purpose rubber for
1500 23,5 50-52 S - - - - tyre treads and for technical
rubber goods
1502 23,5 50-52 NS - - - - uncoloured technical goods
Compounds with good
processability
1507 23,5 30-35 NS - - - - (calandered and injection
moulded products)
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
Reaction medium:
Water 65,4 wt.%
Emulsifier System:
K-salt of disproportionated rosin 1,5 wt.%
Na-salt of methylen-bis-naphthalinsulfonic acid 0,03 wt.%
Initiator-System:
p-Menthylhydroperoxide 0,04 wt.%
FeSO4 * 7 H20 0,01 wt.%
Di-sodium salt of ethylenediaminotetraacetic acid 0,02 wt.%
Na-salt of Formaldehydesulfoxylate 0,03 wt.%
Na3PO4*12 H2O 0,16 wt.%
E-SBR: Ingredients of Polymerization Recipe I
(Emulsifiers)
Disproportionation of Abietic Acid
H
CH3 COOH -
SO3
Abietic Acid Na
CH2 2 Na +
Pd -
SO3
Na
+ +
H H H
CH3 COOH CH3 COOH CH3 COOH
p-Menthanehydroperoxide (p-MHP)
Na-Formaldehydesulfoxylate
Na-Hydroxymethanesulfinate
H O
Reducing agent +
H O S O Na
HO CH2 CH2 OH
Sequestering agent N CH2 CH2 N
for Fe-Ions HO CH2 CH2 OH
O O
E-SBR: Sequence of Reaction Steps
Redox Initiation:
R-OOH + Fe2+ R-O* + OH- + Fe3+
Fe3+ + Reducing agent Fe2+ + oxydized reducing agent
R-O* + Monomer R-O-Mon*
Growth Reaction:
R-O-Mon* + n Monomer P*
Transfer Reaction:
P* + R-H R - H + P*
Termination Reaction:
P* + P* P- P
100 175
(ML 1+4 (100°C) [ME]
80
Gel content [wt.%]
140
60 105
40 70
20 35
0 0
0 0,2 0,4 0 0,2 0,4
Tert-dodecylmercaptane [phm] Tert-dodecylmercaptane [phm]
E-SBR: Styrene/Butadiene-Copolymerization (Differential
Styrene Incorporation)
Styrene Content of Polymer [wt. %]
100
Copolymerization Parameters
90 (Styrene = M1; Butadiene = M2)
80 r1 = 0,7
r2 = 1,4
70
60 As a Consequence of these
copolymerization parameters
50 there is no azeotropic composition
40
30
k11
20 r1 =
k12
10
k22
0 r2 =
k21
0 10 20 30 40 50 60 70 80 90 100
r1 (Styrene) = 0,78
80 r2 (Butadiene) = 1,39
60
Ideal (random) Copolymerization for Monomer Feed
Monomer Feed Styrene/Butadiene: 30/70 Styrene/Butadiene:
40
30/70
20 Polymerization Temperature:
+ 50°C Hot Polymerisation
- 20°C (Cold Polymerisation)
0
0 20 40 60 80 100
Monomer Conversion [%]
E-SBR: Distribution of Styrene Sequences
in E-SBR 1502
Copolymerization-
parameter
Styrol = M1
80 Butadien= M2
r1 = 0,7
70 r2 = 1,4
Probability [%]
60
k11
50 r1 =
k12
40 k22
r2 =
30 k21
20
10
0
1 2 3 4 5 6 7 8 9 10 11 12
Number of Styrene Units
E-SBR: Microstructure
Polymerization- BR-Microstructure
temperature 1,4-cis 1,4-trans Vinyl
[°C] [%] [%] [%]
Source:
The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
E-SBR: Dependence of Tg on Styrene Content
60
40
Tg [°C]
20
0
-20 Fox-Flory-Equation
1 w w2
-40 = 1 +
Tg Tg1 Tg2
-60 Tg: Tg of copolymers in K
Tg1: Tg of homopolymer 1 in K
-80 Tg2: Tg of homopolymer 2 in K
Tg of wn: weight fraction of copolymers 1 und 2
-100 E-BR
0 20 40 60 80 100
Styrene Content [Gew.%]
Source: T. G. Fox, P. J. J. Flory; Appl. Sci., 21,581 (1950)
Rheometer (160°C)
ΜL [dNm] 8,3 8,8 9,1 10,1
∆F [dNm] 35,3 38,2 37,3 39,2
ts1 [min] 4,8 4,3 4,7 4,5
t50 [min] 7,5 6,8 8,2 7,9
t90 [min] 11,2 9,3 12,6 11,1
Vulcanizate Properties:
Tensile Strength [MPa] 17,3 18,5 17,9 18,9
Elongation at break [%] 425 410 480 470
M100 [MPa] 2,5 2,7 2,3 2,3
M300 [MPa] 12,6 14,3 10,9 11,8
Shore A Hardness/23°C 69 71 72 71
Shore A Hardness/70°C 63 64 64 64
Rebound/23°C [%] 25 27 22 25
Rebound/70°C [%] 38 42 33 36
3.2. Polychloroprene (CR)
• Overview
– Property Profile and Application Areas
– Producers and Poroduction Capacities
– Grades and Application Areas
• Manufacturing
– CR-Microstructure
– Monomer Manufacturing Processes
– Basic Features of Polymerization Recipes
• Influence of CR-Microstructure on Chemical and Physical Properties
– Crystallization, Glass Transition Temperature, CR-Vulkanization
• Rubber Grades
– Standard Grades
– Sulfur Grades
– Precrosslinked Grades
• CR-Vulcanization
– Mechanism
• Substitution of CR
Sources:
- W. Obrecht, Houben Weyl-Müller Makromolekulare Stoffe (1987), volume E20/Teil 2, S. 842-859
- P. R. Johnson, Rubber Chem. Technol. 49 (1976) 650-702
Negative Aspects:
• High density (2,5 g/cm3)
• High compound price
• Modest resistance against chemicals and oils
• Crystallization at low temperatures
• poor ageing resistance at elevated temperatures
CR: Producers and Production Capacities (2010)
Producer Capacity Site Butadiene Acetylene
Denki Kagaku Kogyo KK 100 Omi/Japan - X
Lanxess 75 Dormagen/Germany X -
DuPont 45 Pontchartrin/USA X -
Tosoh 32 Nanyo/Japan X -
Chonquin Changshou Chemicals 28 Chongquing/China - X
Shanxi Syntheic Rubber Co 25 Datong/China - X
Pidilite 25 India X -
Showa Denko KK 20 Kawasaki/Japan X -
Nairit Scientific Industrial 10 Yerewan/Armenia - X
Total 360
Plant Closures
Stagnant CR-Consumption in WE and USA Producer Capacity Site
Growing Consumption in South-East Asia DuPont 30 Maydown/N.-Ireland
50 Louisville/USA
Bayer 25 Houston/USA
Source: Various Press Releases Polimeri (BP) 25 Grenoble/France
CuCl
+ NaOH/85°C - HCl
HCl/CuCl Cl Cl
(30-60°C)
H2C CH CH CH2
+ NaOH - HCl Cl Cl
(85°C) H2C C C CH2
Cl Cl
Only DuPont, Lanxess und Denki
H2C CH CH2 + HC CH CH CH2
produce DCB
2-Chloroprene 1-Chloroprene (impurity)
Latex Rubber
applications Applications
5% 60%
Latex based 50
adhesives
1,2 Cl 3,4 H
CH2 C 2 CH2 C 3
3
C H 2
C Cl 90
CH2 CH2
Adhesive Rubber- and Latex Grades
Microstructure trans-1,4 cis-1,4 grades
> 89% > 95%
Tg [°C] -45 -20 85 0 10 20 30 40 50 60 70 80
Tm [ °C] 105 70
Polymerization Temperature [°C]
-
SO3
CH3 CH3 CH3
Na
+ CH2 2 Na +
+
H H -
H SO3
CH3 COOH CH3 COOH CH3 COOH
Na
He 0
10
Shore A Hardness
He-Hi
20
Volume [mm3]
30
1/2(He- Hi) 40
Hi 50
60
t1/2
70
80
0,1 1 10 100 1000 10000 0,1 1 10 100 1000
Storage time [h]
Storage time [h]
Source: U. Eisele: Internal Bayer-Reporting System
CR: Crystallization Rate and Crystallite Melting Temperature
Dependence of t1/2 on Storage Dependence of Crystallite Melting
Temperature Temperatures on Polymerization
(Baypren 210; Pretreatment: 1 h / 60°C) Temperature
30 80
60
20
50
15
t1/2 [h]
40
10 30
5 20 lowest figures
highest figures
10
0
-20 -15 -10 -5 0 5 10 15 20 0
-60 -10 40
Storage Temperature [°C]
Polymerization temperature [°C]
Polymerization-
Sym- T temperature [°C]
- 31 bol [°C] 103
45
- 33 35
25 45 35 25 15 5
15 102
- 34 5
t 1/2 [h]
Tg [°C]
- 35 101
- 36
100
- 37
- 38 10-1
0 3 6 9 12 15 0 3 6 9 12 15
DCB-Content of Monomer Feed [%] DCB-Content of Monomer Feed [%]
Crystalliaztion Rates of Unvulcanized CR, Unvulcanized CR-
Compounds and CR-Vulcanizates at - 10°C
500
B. 110 VSC
400 lcanizates
s
nd
R
ou
C
p
vu
d
300 -c o
ze
t1/2 [h]
CR
CR-bases
ni
ca
d
ize
ul
nv an
lc CR 100,0 phr
vu
U
200 Un Carbon black (N 762) 75,0 phr
Polyetherthioether 10,0 phr
B. 110 Vulkanox DDA 2,0 phr
Vulkanox 4010 NA 0,5 phr
KA 8418 Stearic acid 0,5 phr
100 Magnesium oxide 4,0 phr
B. 112 Zinc oxide 5,0 phr
B. 210
0
0 100 200 300 400 500 600 700 800
t1/2 [h] (unvulcanized CR)
t1/2 [h]
10 150
100
5
Neoprene® W + Butyloleate
50
0
0
100 80 60 40 20 0
Baypren 110 VSC (slowly crystallizing) -20 -15 -10 -5 0 5 10 15 20
Temperature [°C]
0 20 40 60 80 100 Source:
Baypren 210 (normally crystallizing) R. M. Murray, J. D. Detenber Rubber Chem . Technol. 34 (1961)
668-685 “First and Second Order Transitions in Neoprene“
Dependence of Compression Set (CS) of Different CR-
Grades on Storage Temperature
100
CS (168 h / variable temperatures)
90
80 DCB-containing rubber grade (Baypren® 110)
DCB-free rubber grade (Baypren® 210)
70
CR Adhesive grade (Baypren® 320)
60
50
40
30
20
10
0
-60 -40 -20 0 20 40 60 80 100 120 140 160 180
Temperature [°C]
Bayer-Brouchure: „Chloropren-Kautschuk von Bayer: Der vielseitig einsetzbare Werkstoff“
• Standard CR-Grade
Cl Cl
S S
S S
• Sulfur Grade Sulfur
S S
S S
CH3 O O CH3
• Precrosslinked CR-Grade Dimethacrylate CH2 O CH2 O CH2
n
Molar Mass Control by Mercaptanes and by
Xanthogendisulfides
Molar mass control by mercaptanes
P* + HS - R P- H + R - S*
R - S* + nM R - S - M n*
R - S - Mn* + HS - R R - S - Mn - H + R - S*
RO - CS - S* + Mn RO - CS - S - Mn*
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
15
Tensile Strength [MPa]
21
14
M300 [MPa]
13 20
12
19
11
10 18
30 40 50 60 70 80 90 100 110 10 11 12 13 14 15
ML 1+4 (100°C) Modulus M300 [MPa]
Dynamic Resistance of CR-Standard Grades (Monsanto Test)
Xanthate modified CR-Grade (Baypren 121) unaged
7 days / 100°C
Mercaptane modfied CR-grade (Baypren 110 VSC) unaged
250
7 days / 100°C
ISO-Compound 2475
Cycles until failure [kcycles]
50
0
52 54 56 58 60 62 64 66 68
Strain Amplitude[%]
Source: R. Musch presented at the 140th ACS Rubber Division Meeting, Detroit October 8-11, 1991
CR-Sulfur Grades
S Cl Cl S
NR2 C S ( CH2 C CH CH2 ) S (CH2 C CH CH2 ) x Sy C NR2
u v w
Application:
Vulcanizates which are based on CR sulfur grades perform particularly well in dynamic
applications. As a consequence, belts which meet the requirements of different applications are
a major application area (conveyor belts, V-belts, poly-v-belts, timing belts)
Production:
CR-Sulfur Grades are obtained by two consecutive production steps (1. Polymerization and 2.
Chemical break down of high molar masses)
In the 1st production step chloroprene and sulfur are copolymerized. The copolymers obtained
have a high molar mass and long sulfur bridges. In the 2nd production step, the molar mass of
the copolymers is reduced by a break down of sulfur bridges (peptization). As a consequence of
the chemical breakt down of the sulfur bridges dithiocarbamate end groups are incorporated.
These end group participate in vulcanization.. As a consequence, the number of dangling chain
ends is reduced and vulcanizate properties are improved.
Compounding and Vulcanization:
During compounding residual sulfur bridges are broken down "Mastication". Sulfur grades
can be vulcanized by the addition of ZnO and/or MgO (without the addition of accelerators).
Critical Aspects:
During storage, the Mooney viscosity of sulfur modified CR can increase or decrease. Heat
resistance of vulcanizates based on sulfur modified CR is inerior to that of standard CR.
Production of CR-Sulfur Grades
1) Copolymerization of Chloroprene and Sulfur
Cl
CH2 C CH CH2 + S8
S S
NR2 S S NR2
Cl S S
Sa ( CH2 CH CH2)n S v S NR2 NR2 S Sw ( CH2 CH CH2) x
Baypren 610
Change of M100 (7d/100°C) [%]
46
Incorporated Sulfur
60
44
42 50
40 40
38 30
36
20
34
10
32
30 0
0 2 4 6 8 10 0 0,2 0,4 0,6
Sulfur [phm]
Mastication time [min]
Compound Ingredients:
Mastication: CR 100 phr
Ruß (N 762) 75 phr
Mill size: 200 x 400 mm Polyetherthioether 10 phr
Friction: 1:1,2 Vulkanox DDA 2,0 phr
Revolutions: 20 min-1 Vulkanox 4010 NA 0,5 phr
Width: 1,2 mm Stearic acid 0,5 phr
Amount: 600 mg Magnesium oxide 4,0 phr
Zinc oxide 5,0 phr
Vulcanization of CR-Sulfur Grades
H H
CR-Sulfur grades (which are fully
commercially available) contain
dithiocarbamate end groups which are
H C attached via sulfur bridges. These end
S
groups are active in vulcaniaztion.
N N
CR-Sulfur grades can be considered as
S Sx
"rubber bound intermediates“ which are
S S known from theoretical considerations
H
H
on the mechanism of sulfur cure.
As a consequence, CR sulfur grades are
H
C
vulcanized by the use of ZnO and MgO
N
(+ Stearinsäure) without using
S N accelerators.
S
S
Sx CR sulfur grades exhibit a critical
S stability of Mooney viscosities during
storage particularly at elevated
N temperatures.
SH
S
Precrosslinked CR-Grades
Production:
Precrosslinked CR-rades are blends of CR-Gel
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 Ungelled
in the soluble CR phase is achieved. (soluble)
CR
Application:
Unvulcanized CR compounds which
contain CR gel exhibit good processing
features, particularly a low die swell. de
Die swell = x 100
do
Major application areas are extruded
articles (wiper blades as well as window
and door seals In these applications CR Rubber d0 de
is being substituted by EPDM and TPEs. Compound
Properties of Precrosslinked CR-Grades
20
50
42 16
38
14
34
12
30
26 10
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Gel content [wt.% %]
Gel content [wt.% %]
CH2
Mechanism of CR-Vulcanization
according to Pariser/Du Pont CH Vulcanization of CR
CH2
S
Cl
Chemicals for CR-Vulcanization
Cl S
+
CH2 + NH NH S
CH CH2 CH2 NH NH
CH2
CH2 CH2 NH NH Ethylenethiourea
CH2
CH2 (ETU/Vulkacit(R) NPV)
CH
CH2CH2
CH
+ ZnO CH2
S
CH2
- ZnCl + O S "cyclic Dithiocarbamate"
Cl S
S N CH3 (Vulkacit(R) CRV)
NH NH
NH NH
CH2CH2
CH2 CH2
CH2 CH2
CH2
CH2
CH
End groups which participate in
CH CR-Vulcanization
O CH2
CH2
S
S
O S - NH NH Dithiocarbamate end groups are
CH2
present in sulfur modified CR
NH NH
CH2 CH2 S NR2
CH
CH2 CH2 Cl
+ ZnCl + CH2 Sx
CH2 + CH2
- ZnCl2 S
S
CH CH Xanthate end groups are present
CH2 in in xanthate modified CR
CH2 CH2 S O
CH
S
CH2 R
Substitution of CR
250
FKM MVQ
max. service temperature [°C]
225
FMVQ
200
FZ Resistance
80 % VAc to high temperatures
175 EVM
ACM AEM to high temperatures, flame resistance
Resistance
150 HNBR
CM (H)IIR EPDM
Resistance to dynamic stress CSM
125 NBR
Price
100
EU CR SBR BR
NR
75 AU
50
0 20 40 60 80 100 120 140 no
requirements
max. Volume Swell in ASTM-Öl Nr. 3 [Vol %]
Nitrile Rubber (NBR)
• Overview
– 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
• Product groups and Properties
– Standard grades
– Carboxylated grades
– Precrosslinked grades
• Vulcanization and Vulcanizate Properties
NBR: Microstructure
N
C
C
N
4
2 CH
1 2
CH2 δ−
HC CH2 δ+ N
3 CH
3
CH CH C
HC 4
CH
C CH2 2 CH2
H2 CH2 CH
1 2
1
Source:
The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
slow cure
peroxide cure
Precrosslinked NBR
Positive:
• Low degree of swelling in oil, fuels, greases and fats
NBR/PVC-Blends
•High kevel of mechanical properties
•High abrasion resistance especiall for carboxalated
NBR-powder grades
grades
• Broad range of grades
• Low gas permeability liquid NBR
-HO-terminated
• Low price level / high competition -COO-terminated
-NH2-terminated
Negative: NBR
mit bound antioxydant
• Maximal service temperature: < 110 °C
(Criterium: 1000 h / εb=0,5*εεb0)
• Standard grades are not applicable for outdoor use
(contrary to NBR/PVC-Blends)
NBR-Application Areas in Western Europe
Automotive Rubber Goods
35% (without
automotive)
34%
Rubber
Adhesives modification of
1% Thermoplastic
and
Others duroplastic
Cable and shoes
4% 5% building polymers
wiring
5% 11%
5%
300
NR
Volume swell [%]
250
200
150
100 SBR
50 CR
NBR
0
0 7 14 21
time in ASTM-ÖL3 [days]
400
350
Consumption [j/y]
300
250
200
150
100
50
0
85
90
95
00
05
10
19
19
19
20
20
20
NBR: Production Capacities
(European Rubber Journal 181, no
no 4, April, S. 10 1999; updated in July 2010)
NBR-Standard Grades
50
Acrylonitrile content [wt. %]
45
40
35
30
25
20
15
20 30 40 50 60 70 80 90 100 125
Mooney Viscosity ML 1+ 4 (100°C)
without pretreatment (DIN 53523)
NBR: Dependence of Tg on Acrylonitrile Content
100 PAN
80
60
40
s
Tg [°C]
a de
20
l gr Gordon-Taylor-Equation*
ci a
+0 er TgCopolymer = w1*Tg1 + w2*Tg2
m
-20 Com
o f
e TgE-BR = - 80°C
-40 ang TgPAN = + 100°C
R
-60 *Gordon M., Taylor J. S., J. Appl. Sci., 21, 581 (1950)
-80 E-BR
-100
0 10 20 30 40 50 60 70 80 90 100
90
Expt. Conditions:
80 14 days
70 Fuel B and C: 20°C
vvvvvWeight Change[%]
ASTM-Oils: 140°C
60
50
40
30
20 Fuel C (Isooctan/Toluene: 50/50)
Fuel B (Isooctan/Toluene: 70/30)
10
ASTM Öl Nr. 3 (aromatic/naphthenic)
0 ASTM Öl Nr. 1 (paraffinic)
-10
0 5 10 15 20 25 30 35 40 45 50
90 50
75°C
80 40
20°C
Rebound [%]
Shore A Hardness
70 30
60 75°C 20
50 10 20°C
40 0
0 5 10 15 20 25 30 35 40 45 50 0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile content [wt.%] Acrylonitrile [wt.%]
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile-content [wt.%]
Growth reaction:
R-O-Mon* + n Monomer P*
Transfer Reaction:
P* + R-H R - H + P*
Deactivation:
P* + P* P- P
Pd + +
H H H
H CH3 COOH CH3 COOH
CH3 COOH CH3 COOH
Abietic Acid Dehydro abietic acid Dihydro abietic acid Tetrahydro abietic acid
Producer Brand name C14 ges. C14 ges. C18 ges. C18 unges.
BAX AG IS/1 3,1 32,5 33,5 31
Holm THT 1618W 0,4 27,5 34,8 37,3 Methylen-Bis (Naphthalin-
Oleon Radiacid 40 3,5 35,1 24,8 36,6 sulfonsäure), Na-Salz
Unichema Prifac 5910 2,6 37,7 31,5 28,3
(Baykanol PQ(R))
Cognis Edenor C1618 1,2 40,3 26,4 32,1
-
SO3
Na
Sulfates- und Sulfonates (Examples) 2 Na +
CH2
Na-Laurylsulfate (Texapon)
Na-Alkylarylsufonate (Marlon) -
SO3
Na-Alkylsufonate (Mersolat) Na
Activatator Systems for NBR-Polymerization
“Organic“ Activation System
p-Menthylhydroperoxide (p-MHP) “Inorganic“
CH2 CH2 CH3 Activation System
CH3 CH CH O O H (NH4)2 S2O8
O O
Ion-(II) sulfate Fe SO4
100
Acrylonitrile content of polymer [wt. %]
Copolymerization Parameters
90 Ideal
Copolymerisation (ACN = M1; Butadiene = M2)
80 5°C: r1 = 0,02; r2 = 0,28
50°C: r1 = 0,04; r2 = 0,42
70
Azeotropic Azeotropic composition:
60 Composition
(calculated for 5°C)
50 Acrylonitrile: ca. 38+5 Gew.%
40 Butadiene: ca. 62+ 5 Gew.%
30
k11
20 r1 =
k12
10
k22
0 r2 =
k21
0 10 20 30 40 50 60 70 80 90 100
Acrylonitrile content of monomer feed [wt.%]
80 Acrylonitrile content
of monomer feed:
70
60 wt.%
60
50 wt.%
50
40 38 wt.%
33 wt.%
30 28 wt.%
20 20 wt.%
10 10 wt.%
5 wt.%
0
0 10 20 30 40 50 60 70 80 90 100
Monomer Conversion [%]
W. Hofmann, Nitrilkautschuk, Berliner Union Verlag
Source:
V. R. Landi (Uniroyal) Presented at a meeting of the Divison of Rubber Chemistry of the American Chemical Society, Cleveland, Ohio, October 12-15 (1971)
Rubber Chemistry and Technology
140
Mooney Viscosity
120
ML1+4 (100°C)
100
TDM / Lanxess
80
TDM / Phillips Chevron
60
40
20
0
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
- H+
+ +
"Triisobutene (TIB)"
H2S / Cat. SH
+
H3C C CH3
CH2 CH CH CH2 SH
CH2
Vulcanization +
CH2 CH CH CH2 S C CH3
CH3 CH3
CH2
H3C C CH2 C CH C CH3
H3C C CH3
CH3 CH3 CH3
CH3
70
Mooneyscorch MS5 (120°C)
60
50
40
[min]
30
20
10
0
0,00 20,00 40,00 60,00 80,00 100,00 120,00
Ion-Number (IN)
Dependence of NBR-Properties on Metal Ion
Content
cCa cMg cNa cK ppm
_
Ion-Number = 3 + +
40 24 23 39 Atomic Weight
10
9
8
7
M300 [MPa]
6
5
4
3
2
1
0
-20 0 20 40 60 80 100 120
Ion-Number (IN)
Number of x-links
X-linking efficiency = H H
O O
Peroxide-
Peroxide-functions
R - Rubber >1
Degradating rubbers <1
Vulcanization of NBR: Compound Study
Ingredients EV 1 EV 2 EV 3 Peroxide
NBR (18 wt.% ACN)* [phr] 100 100 100 100
Zinc oxide [phr] 5,0 5,0 5,0 -
Stearic acid 0,5 1,0 0,5 -
Vulkanox OCD - - 2,5 -
TMQ 1,0 1,5 - 1,0
Vulkanox MB-2 - 1,5 2,5 -
Carbon black (N 550) 50 30 80 40
Carbon black (N 772) - 50 - -
Dioctylphthalat (Vestinol/Hüls) 5,0 - - 5,0
Etherthioether (Vulkanol OT) - 6,0 20 -
Vulkalent E - 1,0 1,0 -
Sulfur (Rhenocure IS-60-50) 0,4 0,3 0,3 -
Vulkacit CZ 2,0 - 1,5 -
Vulkazit NZ - 1,5 - -
Vulkacit Thiuram 2,0 2,0 2,5 -
Perkadox BC 40 (Akzo) - - - 4,0
Vulcanization t [min]/T [°C] 25/160 16/160 25/160 12/180
Shore A 71 72 71 70
TS [MPa] 16,9 19,5 15,8 18,3
εb [%] 310 365 310 260
M100 [MPa] 4,3 4,4 4,7 4,2
M300 [MPa] 16,3 17,3 15,4 13,0
CS (70h/100°C) [%] 12 20 16 -
CS (70h/120°C) [%] - - - -
CS (70h/125°C) [%] - 31 - 14
Advantages:
• High tensile strength
• High moduli
• Good dynamic performance (cut growth resistance)
• High abrasion resistance
Disadvantages:
• Scorchiness of Compounds
• Cost of ZnO2 in relation to ZnO
• high Compression Set
• high heat-built-up bei dyn. Beanspruchung
• Reduced ageing resistance
Application
ApplicationAreas:
Areas:
••Spinning
SpinningCods
Codsund
undspinning
spinninghoses
hoses
•• high
highperformance
performanceshoe
shoesoles
soles
•• pump
pump stators / Pumpseals
stators / Pump seals
•• belts
belts
•• Hydraulic
Hydraulichoses
hoses
Sources: Eisenberg, A. Macromolecules, Vol 3, 2 (1974) 147 „Clustering of Ions in Organic Polymers - A Theoretical Approach“
Ibarra, L., Alzorriz, M. Polym. Int. 48: 580-586 (1999)
Naskar, N., Debnath, S. C., Basu, D. K.; J. Appl. Pol. Sc., Vol 80, 1725-1736 (2001)
Brown, H. P. Rubber Chemistry and Technol, 30 (1957) 1347 Crosslinking Reactions of Carboxylated Elastomers“
Compound- and Vulcanizate Properties of NBR and X-NBR
X-NBR 100,0 50,0 0
NBR 0 50,0 100,0
Fmin. [Nm] 9,0 10,2 8,0
X - NBR 100 50 0 Fmax. 86,3 78,7 60,0
NBR 0 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 5 5 5 t95 [min] 21,5 11,0 8,3
2 2 2 Shore A 83 80 67
Stearic acid
M100 [MPa] 5,2 4,5 1,7
Wingstay 29 1 1 1
M200 [MPa] 11,0 10,0 4,8
Sulfur 0,5 0,5 0,5
M300 [MPa] 18,6 15,5 11,0
TMTD 2 2 2
TS [MPa] 25,5 21,0 18,2
MBS 1 1 1 εb [%] 430 415 500
Zinc oxide 5 5 5 Abrasion Index 493 159 73
Ageing at 70h/121°C
∆ elongation [%] - 42 - 35 - 30
CS [%] 34,1 27,1 14,7
Precrosslinked NBR
Properties:
Properties:
••Reduction
Reductionofofdie
dieswell
swell
••Increased
Increased dimensionstability
dimension stabilityafter
afterextrusion
extrusion
••Improvement
Improvement of surface quality of extruded/calenderedarticles
of surface quality of extruded/calendered articles
••Increase of Moduli
Increase of Moduli
••Improvement
ImprovementofofCS CS
••Reduction
ReductionofofTS
TS
••Reduction
Reductionofofelongation
elongationatatbreak
break
Precrosslinked NBR-grades provide for high dimensional stability after extrusion which is
only matched by standard NBR-grades with considerably increased Mooney viscosities
Precrosslinked NBR: Compound Study
NBR* (34 Gew.% ACN) Krynac VP KA 8769 phr 10 20 30 40
NBR (34 Gew.% ACN) Krynac 34.50 phr 90 80 70 60
Zincoxide Lanxess phr 3,0 3,0 3,0 3,0
Stearic acid Henkel KGaA phr 1,0 1,0 1,0 1,0
TMQ (Vulkanox HS) Lanxess phr 1,5 1,5 1,5 1,5
Zincmethylmercaptobenzimidazol Lanxess phr 1,5 1,5 1,5 1,5
Carbon black (Corax N 550) Degussa phr 30 30 30 30
Vulkanol 81 Lanxess phr 10 10 10 10
Sulfur Kali Chemie phr 0,3 0,3 0,3 0,3
TBBS (Vulkacit NZ) Lanxess phr 1,5 1,5 1,5 1,5
TMTD (Vulkacit Thiuram) Lanxess phr 1,5 1,5 1,5 1,5
* Precrosslinked NBR
Source: Bayer AG, Marinelli/Welle, KALIS-Nr.: 9588 vom 05. 10. 2000
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)
Examples
Rubber Reaction Catalyst/Process
Medium
Z/N*
Solution-BR
Ti-BR solvent
High-cis-
1,4-BR
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
Solvent Removal by Steam Stripping
Isolation of CSM from Solution
Stripping
unit Dewatering
(expeller)
screw
Steam oil
Expander
Antioxydant screw US 2,592,814
Steam (Du Pont)
Prior.: 20.12.1947
PH- Waste water Inventor: J. L. Ludlow
Control
Stripping
aid
US 5266211
Bunawerke Huels GmbH
Prior.: 13.06.19990
Inventor: W. Breuker,
H. Wagner, E. Moeller,
B. Schleimer
CH
CH2 CH2 CH2
CH CH CH CH CH CH CH2 CH
Negative:
• Poor resistance to heat and ageing
• High degreee of swelling in fuels, oils and greases
• high gas permeability
•Spontaneous crystallization
Application Areas
Technical Tyres
Rubber 71%
Products
5%
Rubber
Toughening
23% Golf ball cores
1%
BR: Microstuctures and Glass Transition
Temperatures 2
1
CH2 CH2 CH
1
1
4 3
CH2 CH2 CH CH
2
3
CH
CH CH
2 3 CH2
4
CH2 4
100
Raw Rubber
Vulcanizate
10
t 1/2 [min]
0,1
-100 -80 -60 -40 -20 0
Temperature [°C]
250 0
Ti
150 -10
[°C]
100 -15
50 -20
0 -25
90 92,5 95 97,5 100 90 92,5 95 97,5 100
450
400
350
300
Capacity [kt]
250
200
150
100
50
0
im
lin
rs
hi
R
c
r
ur
ho
nd
on
oo s
FS
be
C
ow
er
ea
pe
es
JS
sa
R
he
ch
ib
he
im
Ze
um
U
ila
S/
dy
TS
no
nx
ot
fte
ic
ha
ol
K
La
Si
M
ne
T
G
sk
am
ek
hn
iz
N
Lanxess, Dormagen, DE
Capacity [kt]
HIPS/ABS
23% Golf balls
1%
Nd-BR
8% Ti-BR
Co-BR 18% Co-BR
22% 52%
Anatomy of a Passenger Tire and Use of BR
Tread
SBR/BR: 70/30
Sub Tread
NR/BR: 80/20
Sidewall Carcass
NR/BR: 60/40 NR/BR: 90/10
Rim Cushion
NR/BR: 80/20
Apex
NR/BR: 80/20
Source:
Source:
Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
ASTM Designation: D 3189 - 90 „Standard Test Methods for Rubber-Evaluation of Solution BR
Green Strength of BR-Compounds
3
Stress [MPa]
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
300
Ti-BR
250 Co-BR
Improvement
Nd-BR
200
150
100
50
0
100 1000 10000
critical load for separation [g]
Source:
„
Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Vulcanizate Properties of BR Grades
BR Grade Nd Co Ti Li
Vulcanizate properties
Tensile Strength [MPa] 15,3 14,5 13,4 13,0
Elongation at break [%] 400 525 510 480
M300 [MPa] 9,4 8,6 8,1 8,0
Shore A-Hardness 65 63 64 66
Rebound [%] 49 47 45 47
DIN-Abrasion [mm3] 23 27 33 52
Pendulum -Skid
Asphalt, dry 85 85 85 89
Asphalt, wet 33 33 33 35
Dynamic properties
Goodrich-HBU [°C] 27 32 36 18
De-Mattia crack growth [mm/kc] 1,9 6,0 1,5 5,6
Monsonto-FTF/εε =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
40
35
30
Improvement
25
20
15
10
5
0
Ti Ni Co Nd
30
25
20
0 5 10 15
Modulus at 300% elongation [MPa]
Source:
D. J. Wilson „Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes“ Makromol. Chem.,
Macromol. Symp. 66, 273-288 (1993)
80 52 47 37 33
25
60
Rubber content
[wt.%]
40
20 ho
20
he
0 -20 0 20
-40
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“
10000
Viscosity [mPa*s]
1000
100
Star shaped BR
BR sli
40
ed nd
ch a
20
an ear
br in
0
L
0 10 20 30 40 50 60 70 80
Mooney-Viscosity (ML1+4/100°C) [MU]
Source: „Rubbers as Impact Modifiers for Plastics“ Bayer AG, Rubber Business Group, Order No.: KA 34271e
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
Until today, the technologies have merged and there are only
small differencies in the technologies of the leading companies
Basic Patents:
Firestone: US 3317918, CA 966949, US 3205211, FR 1546396, FR 1539429, FR 1539427, BE 718549,
US 3681304, OS 2134656, US 3558575, US 3726844, US 3726844, US 3787377
Phillips: US 3458490, US 3438952, US 3502746
Bridgestone: JP 75-015271
Mechanism of the Anionic Polymerization
Initiation:
+
CH2 +
R Li + R Li
Chain growth:
CH2 +
CH2 +
n R Li
Li +
R n
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)
Impact of Initiator Concentration on Molar
Masses and on Catalyst Costs
rubber]
25 Basis of calculation:
[[Pf/kg] • 65 DM/kg BuLi (4 DM/mol BuLi; MwBuLi: 61 g/mol)
• Ideally “Living Polymerization“
20
[Pf/kg
BuLi
15
Bu-Li
for for
10
Costs
5
Costs
0
0 50000 100000 150000 200000 250000 300000 350000 400000
Molar mass [g/mol]
Molar mass [g/mol]
Consequences from the living nature of the polymerization:
• Catalyst costs increase with decreasing molar masses.
• Star shaped polymers are obtained by the coupling of low molar mass
polymers. Therefore star shaped polymers are bound to be more expensive
than standard rubbers at the same molar mass.
Hexane 35 55 10
X X
Toluene 35 52 13 Ether with two coordination sites
THF 0 9 91
Sources:
R. Casper in Ullmann‘s Encyclopedia of Technical Chemistry
G. Sylvester u. P. Müller in Houben Weyl, Methoden der organischen Chemie,
Band E 20/Teil2, Makromolekulare Stoffe, S. 801
Dependence of the Vinyl-Content on Polymerization
Temperature and Modifier (Type and Concentration)
90
80
DME THF
30°C
Vinyl-Content [mol%]
70 30°C
60 DME THF
50°C 50°C
50
THF
DME 70°C
40
70°C
30 Modifier:
DME: Dimethoxyethane
20
THF: Tetrahydrofuran
10
0
0,1 1,0 10 100
Ether [mol/mol Li]
Source: Ullmann‘s Encyclopedia of Technical Chemistry
-50
-60
-70
-80
-90 Standard-Li-BR (without modifiers)
-100
0 10 20 30 40 50 60 70 80 90 100
Vinyl-Content [%]
Vinyl-BR SBR
1712
Vinyl Content 10 47 64 66 88 18
1,4-cis 40 26 21 18 7 8
1,4-trans 50 27 15 16 5 74
Retreaded Tyre
Concrete 70 95 92 93 - 100
Asphalt 70 90 92 93 - 100
+ +
R CH2 Li R Li
n n CH
+
+
R CH2 Li R CH Li
n n
Branching by Chain End Coupling
Chain end coupling with SiCl4, SnCl4 etc.:
Coupling with SiCl4:
• Reduction of Cold-Flow
4 C +
• low viscosity of BR-solutions
Li
• Application for HIPS and Bulk-ABS
SiCl 4 • Highly filler loaded rubber compounds
(SnCl4 as alternative) with good processability and high Shore-
A Hardness (roll covers, tyre beads etc.)
ding
Improvement
Viscosity
Narrow molar
mass distribution
Broad molar mass
Highly branched
distribution
(Star shaped)
10
Cold Flow [mg/min]
8 Star shaped
polymer with
Divinylbenzene
6 3 branches
[phm]
4 0,03
2 0,06
0
0 20 40 60 80 100
Mooney-Viscosity ML 1+4 (100°C) [MU]
Linear BR has an extremely high cold flow which results in the instability of
rubber bales. BR has to be branched in order to improve the stability of bales.
Compound Preparation:
BR: 100 phr, Ruß (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
600
Consumption [t]
500
400
300
200
100
0
1989 1991 1993 1995 1997 1999 2001
90
Parameters of copolymerization
80 (styrene = M1; butadiene = M2)
70
Radical copolymerization
60 (emulsion)
50 E-SBR r1 = 0,7
r2 = 1,4
40
S-SBR Anionic colymerisation in
30 in hexane hexane
20 (Bu-Li/no randomizers/50°C)
10 r1 = 0,04
r2 = 11,8
0
0 10 20 30 40 50 60 70 80 90 100
Styrene-content of monomer feed [wt. %]
50 E-SBR
40
Ra ize
S-SBR
m
30 in Hexane
nd rs
o-
20
10
0
0 10 20 30 40 50 60 70 80 90 100
60
t-BuOK/n-Buli: 0,38/1
Benzene 25 0,04 10,8
Cyclohexane 25 0,04 15,5 50
Hexane 25 0,03 12,5
40
[wt.%]
Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization, Principles and Practical Applications, Marcel Dekker, Inc.
Y. Melenevskaya, V. Zgonnik, V. Denisov, E. Dolinskaya, K. Kalnish; Polym. Sci. (USSR), 21, 2215 (1979)
Tg of S-SBR: The Impact of Styrene and Vinyl
Content
40
+10°C
randomizers
Solution technology with
- 20°C
20 randomizers
- 30°C
10 - 40°C
Source: H. Mouri, J. E. Hall, (Firestone) 146th ACS meetin in Pittsburgh, PA., USA
10-1
tan δ
10-2
Integral-
rubber
10-3
Performance of the green tyre Additional costs for the green tyre
Rolling Resistance Ruß Silica
Compound Compound
150
Rubber E-SBR L-SBR
Carbon black - NR
loaded tread 100 Filler
- BR
Green tyre Ruß Silika
Silane - Si 69
50 Additive - DPG
Raw Materials ++ --
Mixing Costs ++ --
0
Patents:
DE 2447614; Degussa, Prior.: 05.10.1974; Erf.: K. Burmester, S. Wolf,
E. Klötzer, F. Thurn
US 4,709,065; Shin-Etsu; Prior.: 20.09.1985; Erf.: H. Yoshioka et al.
EP 299074; Bridgestone; Prior.: 03.10.1987; Erf.: T. Hamada et al.
Abrasion Wet DE 3813678; Bridgestone; Prior.: 23.04.1987; Erf.: M. Takeshita et al.
Resistance Skid EP 501 227; Michelin, Prior.: 25. 02. 1991; Erf.: R. Rauline
EP 447066; Bridgestone; Prior.: 27.02.1991; Erf.: T. Hamada
Recent Developments in S-SBR Technology
Towards Improving Tyre Performance
Functionalisation of S-
S-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
n
R2
+
Li
OR
N Si OR
R n C 80
CH2 OR
R1 R2
O
+
2 R CH2 Li + Cl Cl
n n
+
- 2 Li Cl
O
R n nR
n
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
R CH2
+
Li + H3C CH3
Si Si
n O
H3C CH3
D3
Si Si Si
+
R O O O Li
n
Source: EP 0778 311; Michelin, Prior.: 07.11.1995; Erf.: J.-L. Cabioch „Composition de caoutchouc
à base de silice et de polymère diénique fonctionnalisé ayant une fonction silanol terminale“
H
X
S
X SH
X: - OH (US 6252008)
X: - COOH (US 6365668)
Sources:
US 6252008; Bayer AG; Prior.: 18.07.1998; Inv.: T. Scholl, U. Eisele, J. Trimbach, S. Kelbch
WO 02/31028 A1; Bayer AG; Prior.: 10. 10. 2000; Inv.: Th. Scholl, J. Trimbach, W. Nentwig, R. Engehausen
US 6365668; Bayer AG; Prior.: 16.11.1998; Inv.: Th. Scholl, J. Trimbach
4.3. Chemistry and Production Technology of High-
cis-1,4 BR with an Emphasis on Nd-BR
Li-BR nBu-Li 36 - 38
Co-BR Co(II)Octanoate / DEAC / H20 1 / 7 0-80 / 20-30 97
Ni-BR Ni(II)Naphthenate /Bu2O.HF/TIBA 1 / 100 / 40 97
Ti-BR TiJ3(OEt) / TiCl4 / TEA 1 / 0,7 / 5 93
Nd-BR Nd(III)Versatate / DIBAH / EASC 1 / 10-15 / 3 98
Abbreviations:
nBu-Li n-Butyl-Lithium
DEAC Diethyl Aluminum Chloride
TIBA Triisobutyl Aluminum
TEA Triethyl Aluminum
DIBAH Diisobutyl Aluminum Chloride
EASC Ethylaluminum Sesquichloride
Influence of Halides on 1,4-cis-Content
98
cis-1,4-Content [%]
Metal Component of
97
Halide Catalyst System
96
Ti Co Ni Nd
95
F 35 93 98 95,7
Cl 75 98 85 96,2 94
Br 87 91 80 96,8 93
J 93 50 10 96,7 92
0 1 2 3 4
Molar Cl/Nd - Ratio
Source: Sources:
Zhinquan Shen, Jun Ouyang, Fasong Wang, •Lars Friebe: Diploma Thesis TU Munich 2000
Zehnya Hu, Fusheng Yu, Baogong Qian; •L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;
J. Pol. Sci., Chem. Ed. 18 (1980) 3345-3357 Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
120
Data from:
US 5134199 Enoxy Chem Ltd.
80
GB 2161169 (Asahi)
Tm [°C]
US 4931376 (Asahi)
US 5596053 (Bridgestone/Firestone)*
40
Goodyear
+0
- 40
60 70 80 90 100
1,4 - trans-content [Mol %]
*US 5596053 (Bridgestone/Firestone) Prior. 31. 05. 1995; Erf.: J. W. Kang; J. T. Poulton
"High Trans-1,4-BR and Catalyst and Process for Preparing Crystalline High Trans-1,4-BR“
US-A-5089574 (trans-1,4-BR-Herstellung/Goodyear)
EP-A-1092565 Prior.: 11.10.99 D. J. Zanzig, P. H. Sandstrom, J. J. Verthe, E. J. Blok, G. M. Holtzapple
„Tire with silica-reinforced tread comprised of trans-1,4-BR, solution-SBR, polyisoprene and defined amount
of carbon black and amorphous silica“
`
Bd
Bd M
M M M
54 60
36
C 43
C C C
60
50
40
30
20
10
0
La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
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“
Mechanism of Neodymium Catalyzed Butadiene
Polymerization
O R1
Et Cl Cl
Nd O R2 H Al Al Al
Et Cl Et
R3
3
NdV DIBAH EASC
1 10 - 15 3
Literature:
http://dx.doi.org/10.1007/12_094
1) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner; Adv. Polym. Sci. (2006) 204, 1-154 (Review);
Nd ( OOC - R )3 + 6 H Al Nd (O-CH2- R )3 + 3 Al O Al
O Al
Nd ( OOC - R )3 + 3 H Al Nd (O-CHR- R )3 + 1 Al O
O Al
H
Nd (O-CH2- R )3 + H Al (R-CH2-O)2 Nd + R-CH2-O Al
CH3
CH2 C CH3 CH3
(R-CH2-O)2 Nd (R-CH2-O)2 Nd - H + H2C
H CH3
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Reaction Scheme of Butadiene Polymerization
by Nd-Catalysis
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
AlR3 -
ClAlR3
Cl Cl +
AlR3 Nd
Nd Nd Cl
Cl Cl AlR3
AlR3 R
R R
- - ClAlR3
-
ClAlR3 ClAlR3
+ +
+ Nd Nd
Nd Cl Cl
Cl AlR3 AlR3
R
AlR3
R
R
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Reaction Scheme of Butadiene Polymerization
by Nd-Catalysis
Nd L + H Al H Nd L + R Al
L L
R
Nd L + Al Nd L + R Al
L L
R
100
Monomer Conversion [%]
0
80
-1
60 -2
ln(1-x)
40 -3
nDIBAH/nNd = 10 nDIBAH/nNd = 10
nDIBAH/nNd = 20 nDIBAH/nNd = 20
20 nDIBAH/nNd = 30 -4 nDIBAH/nNd = 30
nDIBAH/nNd = 50 nDIBAH/nNd = 50
0 -5
0 50 100 150 200 250 0 50 100 150 200 250 300
time [min] Time [min]
Sources:
Lars Friebe: Diplomarbeit and der TU München, Dezember 2.000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Mechanism of Nd-Catalyzed Butadiene Polymerization
Dependence of Molar Mass Dependence of PDI (Mw/Mn)
Distribution on Monomer on Monomer Conversion
Conversion
c o n v e r s io n / %
nDIBAH/nNd = 10
8 2 .5
nDIBAH/nNd = 20
4,0 nDIBAH/nNd = 30
index Indices
6 6 .4
nDIBAH/nNd = 50
5 5 .1 3,5
Refractive
5 0 .0
3,0
Mw/Mn
inof refraction
4 3 .5
2,5
3 5 .6
difference
2,0
Difference
3 0 .7
2 2 .7 1,5
1 2 .2
1,0
7 .8 0 10 20 30 40 50 60 70 80 90 100
4 .8
Monomer Conversion [%]
30 35 40 45 50 55 60 65
30 35 40 45 50 55 60 65
e lu t io n t im e / m in
Elution time[min]
Source:
L. Friebe: Diploma Thesis at TU Munich, December 2.000
L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
16
Formal Number of Polymer
nDIBAH/nNd = 10 nDIBAH/nNd = 10
nDIBAH/nNd = 20 14 nDIBAH/nNd = 20
2,0*105 nDIBAH/nNd = 30
12 nDIBAH/nNd = 30
Mn [g . mol-1]
nDIBAH/nNd = 50 nDIBAH/nNd = 50
1,5*105 10
8
1,0*105
6
4
0,5*105
2
0 0
0 10 20 30 40 50 60 70 80 90 100
0 10 20 30 40 50
Monomer Conversion [%] 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
Technical Options for the Control of Molar Mass in
Nd-BR Production
Influence of Polymerization Temperature
G. Sylvester, B. Stollfuss ACS, Rubber Div. Dallas 1988 „Synthesis of
Contrary to Catalysts based on Co, cis-1,4-Polybutadienes by rare earth catalysts“
Ni and Ti, for Nd-based catalysts 2500
there is no agents for the control of
[kg/mol]
Therefore in Nd-BR technology 1500
molar mass has to be controlled by:
• Nd/Al-ratio 1000
• Monomer/Nd-ratio
500
• Monomer Conversion
• Polymerization temperature 0
0 10 20 30 40 50 60 70 80 90
Polymerization Temperature [°C]
ML 1+4 (100°C)
50
700
[kg/mol]
600 40
500
30
400
300 20
200
10
100
0 0
0 0,05 0,1 0,15 0,2 0,25 0,3 0 20 40 60 80 100
Nd (mmol/100 wt.-parts of butadiene] Monomer Conversion [%]
• Overview
– EPM and EPDM, Termonomers, Market, Range of Grades and
Property Profiles
• EPDM-Production
– Chemistry of Polymerization , Producers, Capacities, Brand
Names and Production Technologies
• Production Technologies (Flow Charts)
– Solution Process
– High Temperature Solution Process
– Gase Phase Process
– Comparison of Manufacturing Technologies
• Metallocenes
– Ovewrview on Metallocene Patents
– Metallocene Activation
– Comparison of Catalyst Costs
EPDM Sulfur
Peroxides
Phenol resins
etc.
Dicyclopentadiene
(DCPD) ~ 15 : 1
1,4-Hexadiene
(HD) ~5:1
70
ENB
60 DCPD
50 1,4-HD
Torque [Nm]
40
30
20
10
0
0 1,0 2,0 3,0 4,0 5,0 6,0
time [min]
Property Profile of EPM/EPDM based
Vulcanizates
Advantages:
– good price/performance-ratio
– high maximum service temperature
– good low temperature performance
– broad spectrum of grades (oil extended grades etc.)
– ability for vulcanization with sulfur, peroxides and others
– high loadability with extender oils and fillers (reduction of compound price)
– good mechanical properties of vulcanizates
– good weathering and ozone resistance (outdoor applications)
– good electrical insulation (low salt content)
– Low density
Disadvantages:
– low resistance to oil and chemicals
– fair ability to covulcanization
– low resistance to fungi and bacteria
15% 6% 600
500
50
16% 400
41%
300
Automotive production (world) 45
200
Automotive
Thermoplast Modification 100
Building 0 40
1987
1988
1995
1991
1993
1986
1989
1990
1992
1994
-50
-52,5
Tg [°C]
-55
-57,5
-60
35-39°C
25
Enthalpy of fusion [J/g]
40-44°C
45-49°C
20 50-54°C
55-59°C
15 60-64°C
65-70°C
10
0
46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64
Reactivators:
PDCAE BPCC TCAE
Cl O Cl O Cl O
O C2H5 Cl O C4H9 9
Cl O C 2H 5
Cl Cl Cl Cl Cl
+V VOCl3
+IV VCl4
heat
heat
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
Baton Rouge, Louisiana 180
Exxon Vistalon
Notre Dame de Gravenchon 85
Geleen, Niederlande 135 Keltan
DSM
Triunfo, Brasilien 35 Nitriflex EP
Plaquemine, Louisiana 100 Nordel-IP
DPDE
Seadrift, Texas 90 Elastoflo (UCC)
Marl, Deutschland 60 Buna EP G
Lanxess
Orange, Texas 55 Buna EP T
Lion Copolymer Geismar, Louisiana 91 Royalene / Trilene
Polimeri Ferrara, Italien 85 Dutral
Mitsui Chiba, Japan 60 Mitsui EPT
JSR Kashima, Japan 25
JSR EP
Yokkaichi, Japan 45
Sumitomo Chiba, Japan 40 Esprene
Kumho Yeochon, Südkorea 40 KEP
Petro China Jilin, China 30
Nizhnekamsk Nizhnekamsk, Russland 30
Herdillia Maharashtra, Indien 10
total capacity 1076
Waste water
Azeotropic Condenser Flash
destillation drum
Stripper
Propene Waste air
dewtering
screwg
destillation
Hexane Ethene Steam
Polymerization
reactor Expeller
Settler
Steam
oil
destillation PH-
drier Control drier
Waste water Antioxydant Waste water
Stripping
aid
Precoller
drier -32/-35°C
Water
Modifier
Process Features baling
Propene precooling: -32°C/-35°C
Reactivator Temperature: 20-65°C
Pressure: 5-10 bar
Drier drier EASC
Residence time: 6-15 Min.
VOCl3 /VCl 4 Packaging
3/1 Soldis conc.: 3 -7 Gew.%
H2 O: < 3 ppm
Hexane VNB/ENB
Dow‘s High-Temperature Solution Process
(Source: Dow-Patents, Publications etc.)
Plant location: Plaquemine/Lousiana In the Dow-HT-Process low
amounts of CGC- catalyst
Destillation are required. The catalyst
is not washed out and no
Solvent Condenser steam stripping is applied
and
monomer („leave-in-catalyst“)
Evaporator Evaporator
Flash-
High boiling drum
residue
(ENB, AO, etc.)
Ta
Antioxidant
(AO)
Polymerization
reactor
baler
Ageing
drum
"Insite-Kat." packaging
Scavenger
Temperature: 40 - 80 °C
Purification Purification Purification Ta: 80°C (>130°C)
Pressure: 9-15 bar
Residence time: < 20 Min.
Ethene Propene ENB MMAO Borane
Activation of Metallocenes
Cl R
Alkylation
Zr
Cl
Zr Product V Ti Fe Al Ca Na Sum
R
Dow-CGC <1 1,0 1,3 1,7 <1 <1 8,0
Activation by MAO Activation by EPDM # 2 8,0 <1 4,3 31 1,7 1,8 22,3
(molar excess of MAO: Borane/Borates:
10.000 - 10.000 fold) (with molar
B/Zr-ratios) 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 82,8
EPDM #5 5,1 <1 2,8 9,6 160 4,6 184,1
R EPDM#6 4,8 1,9 63 440 64 9,4 584,1
Zr + A
Source: J. G. Pillow (Dow) „Ethylene Elastomers made using Constrained Geometry Catalyst Technology“
Kautschuk Gummi Kunststoffe 51, 12/98, 855-859
Crystallinity of Metallocene-Based EPDM
30
EBTHI-Cat.
CH2 CH2 DOW-Insite-Cat.
CH2
25
CH2
Enthalpy of fusion [J/g]
ZrCl2
CH2 Me2Si X
20 Ti
CH2 N
X
CMe3 V-Catalysis
15 CH2 CH
2
10
0
40 42 44 46 48 50 52 54 56 58 60 62
Ethene Content [wt.%]
100
Low-Temperature-Compression-Set [%]
90
80 Me2Si
Ti X
70 N
X
60 CMe3
50
40
EPDM/V-Cat.
30 EPDM/CGC (Dow)
20
10
0
0
0
,5
,5
,5
5
12
18
21
35
0
,0
,5
8,
8,
32
37
47
10
37
Cooler
Purification
Patents:
ENB Product EP 1099715
Fluidizing Aid Desactivation EP 1099473
Suported Catalyst Monomer EP 1086995
degassing EP 1083192
unit
US 6180738
WO 0000333
WO 9965953
Ethene Purification
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
Process Economy 4 5 7 10
EPM 10 10 10 10
EPDM 10 10 10 0
Low Mooney 10 8 10 0
High Mooney 5 10 3 10
Oil Extended Grades 7 10 3 0
Process Flexibility 42 48 36 20
Overall Process
Performance 46 53 43 30
••The
Thewell
wellestablished
establishedvanadium
vanadiumbased
basedsolution
solutionand
andslurry
slurryprocesses
processes
are
are inferior in investment and operation costs, but provideaahigher
inferior in investment and operation costs, but provide higher
flexibility.
flexibility.
••The
TheHT-solution
HT-solutionandandthe
thegas-phase
gas-phasetechnology
technologyarearelow
lowcost-
cost-
technologies,
technologies, which are superior in the production of specificgrades
which are superior in the production of specific grades
Metallocene-Patents 1980-2000 (Oct. 2000)
250
2.923 Documents
Number of Patents (US) + Pat. - Appl.
US-
US-Patents and EP-
EP- and WO-
WO-Patent Applications
200
150
100
50
0
C
Mo I
t
b a on t
u
BP
Ph F
na
w
el l
n
ps
b il
r
er
Ch l
EN
em .
l
hs
b e gy
. 2 ar l e
tr o
em
el
go
S
al i
UC
i ts
xo
Do
DS
ay
Sh
il l i
Fi
t
BA
ec
i
P
on
Ge
ar
Pe
re
Ex
m
2B
Ho
Du
T
Bo
M
Id
ui
ui
Al
ts
ts
Ci
Nr
Mi
Mi
Activation of Metallocenes
Cl Alkylation
R Alkylation
(BuLi, AlR3 or MAO) (BuLi, AlR3 or MAO) R
Zr Zr Zr
Cl
Cl R
R
Zr
+ A
Cossee-Mechanism of Metallocene Catalysed
Olefin Insertion
R
R R
CH2 CH2
Zr Zr
+ Zr
+ CH2 + CH2
CH2
CH2
R
+
Zr CH2
CH2
X Me2C
X
Zr B Zr ZrCl2 Me2Si ZrCl2
X X
B = Bridge
* H. C. Welborn, Jr.; J. A. Ewen US 5324800 (Exxon) Prior.: 30.08.1991 „MAO-Activation of Bridged Metallocenes“
Key Patents in Metallocene- und Single-Site-Catalysts
1.2. Isoelectronic Bicyclopentadienyl Systems
Y Cl
E N R B Me
B Cl
X X Cl Me Me
R´ Zr X B
Zr Zr Zr P
X X Cl Me2Si Ph
X P ZrCl2
E B N Ph
R B
E = N, P R´ Y Ph SiMe3
US 5539124 WO 97/2351
(19.12.1994) (22.12.1995)
Lyondell Hoechst AG
(Herberich)
MAO-/Borate- MAO-/Borate-
Activation Activation
Me2Si III
(IV) Ti
Ti Ti X Ti X
MeO N X
OMe X RxE X
X NR2
MeO CMe3
E= N, O
F
F CH3
Ti
F CH3
N O
CH3
F F Ti N C Ti
N CH3
t-Bu N N
P X
t-Bu P
t-Bu
Ar Ar Ar
S
P N
X X X
Ti N
Pd Ti
X X
X´ X O O
P N Zr
O X
t-Bu
O
Ar Ar Ar
t-Bu N
R
R´ R
N X´ N
M Cl Cl Cl
N X N Fe
R´ R Cl N N
Ti
R N O O
M = Ni, Pd
WO 96/23010 DuPont BP EP 0874005 EP 1881014
(24. 01. 1996) (Brookhart) (24.01.1998) (10.05.2006)
DuPont Mitsui Mitsui
(Brookhart)
polar/unpolar HDPE, (PP) HDPE(PP) HDPE, EPM EPM, EPDM
Copolymers, LDPE
F F F F
- F F
-R H F F
_
N+ B F Anilinium Borate
Ph
Me
Me
R F F 4
_
F F
+ Ph
Zr + Ph
B F Triphenylcarbenium
Ph Borate
F F 4
Activation of Metallocenes
R. F. Jordan Turner M. Bochmann M. D. Rausch, T. J. Marks (1991;
(1986) Turner (1990) J. C. W. Chien JACS 113, 3623)
R 1987
1987 (1991) F5
Zr H
- Ph + Ph
+ N+ -
R Ag BPh4 A
Me A
Ph B
Me Ph
F5 F5
-R
-
+R
- - - -
+R +R +R
CH3CN - RH
R -
R R
- - F5
Zr + Ag+1/2 R2 + BPh4 Ph
N - Ph Ph
A
B F5
Me A
Me Ph
F
F5
- F EP
EP468
468537
537 (Exxon)
(Exxon) Priorität:
Priorität:1987
1987
A : F EP 561 479 (Exxon)
EP 561 479 (Exxon) Priorität:1987
Priorität: 1987
F Nicht
F
F F F Nicht oder
oderschwach
schwachkoordinierende
koordinierendeAnionen
Anionen
"NCA"oder
"NCA"oder"WCA"
"WCA"
F - F
F B
F
(insbesondere:
(insbesondere:Tetrakis(Pentafluorophenylborat)
Tetrakis(Pentafluorophenylborat)
F FF
F US
F
F US5599761
5599761(Exxon)
(Exxon) Priorität:
Priorität:04.02.1987
04.02.1987
F Erfinder: H. W. Turner
Erfinder: H. W. Turner
F „Ionic
„IonicMetallocene
MetalloceneCatalyst
CatalystCompositions“
Compositions“
Key Patents for the Activation of Metallocenes
Year of
Priority
1980 Activation of Cp2ZrCl2 by MAO (BASF/Kaminsky) EP 35242; Prior. 29.12.80
Activierung of Cp2ZrRCl by MAO (Hoechst/Kaminsky) EP 69951; Prior.: 09.07.81
1985
Activation of metallocenes EP 468 537; Prior.: 30.01.87 [Cp2MX]+ [BR4]
by borates (Exxon/Turner) EP 561 479; Prior. 30. 01. 1987
US 559 976; Prior. 04. 02. 1987
Ionic metallocene catalyst comosition
Activation by borates (Dow/Stevens) EP 418044; Prior.: 14.09.89 [Cp1MXn]+ [BR4]-
Activation by boranes (Fina/Ewen) EP 427 697; Prior.: 10. 10. 1989
1990
CGC-Activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993
1995
F F
- F F
B
F F
F FF
F F F F
F
F F F F F B FF
F F F F F F FF
F F F
F
- F F
F
F Si F
F B
F
F
F - F
F F F B F
F
F
F FF F F F
F
F
F F
F F F B F
F F F
F
F F FF
F
F F F FF
F F F
F F F F
F F F F
F
F
•• MAO-activation
MAO-activationof ofmetallocenes
metallocenesisisnot
noteconomical
economicalininaasolution
solutionprocess
process
•• Borate-activation
Borate-activation results in catalyst costs which are comparablewith
results in catalyst costs which are comparable with
Vanadium-systems
Vanadium-systems
•• For
Foran
animprovement
improvementin inoverall-economy
overall-economymetallocene-technology
metallocene-technologyhashastotobe
be
combined with process improvements
combined with process improvements
•• Increased
Increasedcatalyst
catalystcosts
costsmight
mightbe
becompensated
compensatedby bythe
theimproved
improvedproperty
property
profile of new products
profile of new products
4.5. Butyl- and Halobutyl Rubber
Abbreviations:
Butyl Rubber: IIR
Bromo Butyl Rubber: BIIR
Chloro Butyl Rubber: CIIR
Brominated Isobutene Paramethylstyrene Rubber: BIMS
IIR-Terpolymer (mainly with Divinyl benzene): XLIIR
Contents
• Overview
– Products, Property Profiles and Areas of Application
– Market, Market Shares, Producers and Range of Grades
• Polymerization Mechanism and Production Technologies
– Standard-Butyl Rubber (IIR)
– Halo Butyl Rubber (XIIR)
• Vulcanization and Vulcanizate Properties
n
CH3
CH3 CH2
CH3 CH3 45
CH 2
C
Butyl Rubber (IIR) 19 123° 15
C C27 CH 23
C 28
CH
35 2 CH CH H3C
21 2 26 2
38 CH3 16 CH3
CH3 CH3 CH2 CH3
CH2Br CH3
Isobutene-Terpolymers
Butyl- and Halo Butyl Rubber (X)IIR: Property Profile and
Areas of Application
Property Profile
Positive:
• Low gas permeability
Tyres Pharmaceutical • high resistance to heat and vapour
Others Adhesives • high resistance to chemicals
Chewing gum Automotive • good insulation properties
• good covulcanization (XIIR))
• product purity
5% 4% 3% 1%1%
(grades without antioxydants)
Negative:
low elasticity /highly damping
Areas of Applications:
• XIIR based Innerliners (passenger tyres)
• IIR b ased tubes (truck tyres)
86%
• bladders (IIR)
• ABC-protection clothes
• Cable and wiring
• Pharmaceutical stoppers
Source: • Adhesives and sealants
CHEManager 20/2006, Seite 8 (GIT Verlag Darmstadt) • absorbers for noise and fenders
• chewing gum
X2 (Cl2 / Br2)
80
1,4-cis BR 1,4-cis-BR
Luftdurchlässigkeit(Q x 10exp8)
SBR
NR
Rebound Elasticity [%]
NR NBR EPDM
60
10 SBR
EPDM
NBR/28 ACN
40
NBR/33 ACN
IIR NBR/38 ACN
IIR
20 1
0
-75 -50 -25 0 25 50 75 100
Temperature [°C] 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)
82
85
88
91
94
97
00
19
19
19
19
19
19
19
20
Range of Commercial IIR and XIIR Grades
Range of Standard Butyl Grades Range of XIIR Grades
100 100
90 90
80
bu l
80
om uty
tyl
Mooney Viscosity
70
ML (1+8) 125°C
Mooney Viscosity
70
Br lorb
ML (1+8) 125°C
60 60
Ch
50 50
40 40
30 30
20 20
10 10
0 0
0 2 4 6 8 10 0 2 4 6 8 10
Content of double bonds [Mol%] Halogen Content [Mol%]
AlCl3- Al2O3
solution
drum
Cond
enser
“catalyst cocatalyst
drum“
H2O „slop isoprene“ H2O
Storage tank
for
„mixed feed“
Storage
units for
IIR-slurry
NH3- Ethene- in water
Heat exchangers
Isobutene- Isoprene Reactor Steam- Flash- Stripping-
drying unit unit unit
Features of IIR Production Technology
Process: Slurry polymerization
Catalyst: AlCl3
Cocatalysts: HCl (Exxon)
H2O (Lanxess) Ethylene
(gas)
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) Ethylene
(liquid)
0,4 - 1,0 wt.%
Antioxydants: 0,02-0,15 wt.%
-discolouring: alkylated Phenylene Diamines
-None discolouring: phenolic AO Inlet and Drain
for light
(+ alk. Phenyl phsophites) hydrocarbon
-chewing gum: without AO wash
+ -
H CH2 C CH2 C AlCl4 H CH2 C CH2 C Cl + AlCl3
n n
CH3 CH3 CH3 CH3
IIR: Living Cationic Polymerization
Generation of Carbo Cation:
R - Cl + MX n + -
R + MX n+1
Initiation: CH3
CH3
+
+ CH2 C
+
MX n+1
-
R R CH2 C
CH3
Propagation: CH3
CH3 CH3 CH3
CH3
R CH2 C MX n+1
+ - + n CH2 C R CH2 C CH2 C
+ -
MX n+1
CH3 n
CH3 CH3 CH3
Reversible Termination:
CH3 CH3 CH3 CH3
R CH2 C CH2 C
+ -
MX n+1 R CH2 C CH2 C Cl + MX n
n n
CH3 CH3 CH3 CH3
Cl
107 EtAlCl2/H2O
γ-Strahlung AlCl3/H2O
Mn [g/mol]
106
105
Molar Masses:
BF3/H2O
γ-Strahlung > EtAlCl2 > BF3 > AlCl3
104
3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0
1/T *10 [K-1]
3
IIR-solution
in hexane
Addition of AO
Hexane
water
X-IIR-
Slurry
in water
CH3
Solvent: Hexane
CH3 CH3 CH3 H
X IIR-solids 20 - 25 wt.%:
CH2 C CH2 C CH2 C C CH2 CH2 C Ratio of Halogen/Isoprene: 1:1 Mol/Mol
+
CH3 CH3 n
CH3 Reaction temperature : 40 – 60 °C
X
Residence time: lh
Stripping-Vapour : 2 - 2 kg/ kg XIIR
CH3 CH3 CH3 H CH3 Antioxydants / stabilizers: Ca-Stearate,
X
Epoxydized Soy
CH2 C CH2 C CH2 C C CH2 CH2 C
+ bean oil (ESB)
n
CH3 CH3 X CH3
- HX Source:
Kirk-Othmer Encyclopedia of Chemical Technology,
CH3 CH3 CH3 X CH3
Fourth Edition, Volume 8, 1993
CH2 C CH2 C CH2 C CH CH2 CH2 C
Source: C. A. Moakes, Bayer „Polynotes“ No B11 „An Improved Seal for Chemical Condensers
Based on Polysar Butyl Terpolymer“
Properties of Sulfur- and Peroxide Cured IIR and XLIIR
Butyl Rubber Grade IIR XLIIR
Compound Properties
Compound Mooney (ML 1+4/100°C) 105 98
Mooney-Scorch (125°C) [min.] 4,0 6,2
Vulkanizate Properties (160°C/12 min.)
Shore A Härte (23°C) 81 76
S100 [MPa] 6,0 6,5
Elongationat break [%] 155 105
Tensile Strength [MPa] 6,8 7,5
Compression Set (70h/105°C [%]) 75 15
Hot air ageing (100°C/96h)
Shore A Härte (23°C) 83 78
S100 [MPa] 7,8 -
Elongation at break [%] 110 95
Tensile Strength [MPa] 8,0 8,2
Electrolyte permeability (g*mm/day*m2)
Ethylenglycol 0,38 0,21
g-Butyrolactone 1,0 0,8
Dimethyl formamide 7,8 1,8
O
CH3 CH3 n
X CH3 C
+ ZnO C N
- ZnOHX O
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 Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682
IIR und XIIR: Methods of Vulcanization
and Vulcanizate Properties
IIR [phr] 100 100 100 - - - -
XIIR [phr] - - - 100 100 100 100
Carb. black (N 330) [phr] 50 50 50 - - - -
Carb. black (N 774) [phr] - - - 50 50 50 50
Vulcanization
S/MBT Chinon Resin ZnO DCP DCP/BMI ZnO/BMI
Compound Properties
91 94 82 83 88 88 89
ML 1+4 (100°C) [MU]
17 7 >30 - - - -
MS5 (125°C) [min]
- - - 16 12 14 16
MS5 (135°C) [min]
Physical Properties
66 64 64 48 40 54 58
Shore A Hardnes
2,5 2,1 1,9 0,9 0,5 0,12 0,19
M100 [MPa]
M300 [MPa] 5,2 1,8 9,5 10,2
Tensile Strength [MPa] 16,6 12,8 15,8 12,4 8,9 10,5 13,6
Elongation at break [%] 530 400 590 580 680 325 360
CS (70h/150°C) [%] 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 Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682
BIIR 100 - 80 - 60 - 40 -
CIIR 0 100 0 80 0 60 0 40
NR 0 0 20 20 40 40 60 60
Carbon black (N 660) 60 60 60 60 60 60 60 60
Paraffin oil 7 7 7 7 7 7 7 7
Pentalyn A* 4 4 4 4 4 4 4 4
Stearic acid 1 1 1 1 1 1 1 1
Zinc oxide 3 3 3 3 3 3 3 3
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
Source: W. Hopkins, R. H. Jones, J. Walter “Bromobutyl and Chlorobutyl. A Comparison of Their Chemistry,
Properties and Uses“ paper 16A10 presented at IRC ‘85 Kyoto; International Rubber Conference
Influence of (X)IIR/NR-Blend Ratio on Vulcanizate
Properties
BIIR [phr] 100 - 80 - 60 - 40 -
CIIR [phr] - 100 - 80 - 60 - 40
NR [phr] - - 20 20 40 40 60 60
Unaged:
M300 [MPa] 4,2 3,7 5,7 5,1 7,1 5,7 8,9 4,3
Tensile Strength [MPa] 9,3 9,9 10,0 10,7 12,8 10,3 14,7 9,7
Elongation at break [%] 740 770 620 620 560 560 490 580
Aged (168h/100°C)
M300 [MPa] 6,8 5,5 7,6 7,9 8,4 7,7 6,7 3,6
Tensile Strength [MPa] 10,0 10,9 9,8 11,0 9,3 9,2 8,8 5,8
Elongation at break [%] 550 640 420 465 320 365 370 475
Air permeation at 2,9 2,9 5,4 5,7 9,2 7,5 13,8 13,2
50psi/65°C (Q x 10-8]
Adhesion at 100°C
Self adhesion / tack [kN/m] 16,8 4,4 14,7 4,7 15,2 9,1 15,4 5,2
Adhesion to NR [kN/m] 7,5 1,3 10,0 1,6 14,7 1,9 20,8 2,9
Fatigue to failure after
ageing at 168h/120°C [kcycles] 61,8 72,7 23,6 3,9 0,3 0,1 0,0 0,0
5. Rubber Specialities:
Performance Profiles of Vulcanizates
Oil Swelling
Silicon Rubber
Hydrogenated Nitrile Rubber
Fluoro Rubber
Ethylene-Vinylacetate-Copolymers
5.1. Fluoro Rubber (FKM / FPM)
Bond Bond Radius
energy of atoms Maximum Service Temperature:
[J/mol] [A]
3.000 h 232°C
C-H 413 0,37 1.000 h 260°C
240 h 288°C
C-F 485 0,72 48 h 316°C
VD
C C VDF
20
80
F[
H F
wt
Z F F
.%
60
40
]
C C TFE
Am olymbers)
.t%
]
P
F F
orp er
(ru
[w
F CF3
40
ho s
P
60
HF
C C
us
HFP
X F F
80
20
Y
Copolymers fluorine cont.
TFE [wt.%]
80 60 40 20 VDF TFE/P 54
TFE [wt.%] VDF/HFP 65
VDF/HFP/TFE 67
VDF TFE HFP
[%] [%] [%] VDF/HFP/TFE/CSM* 69
X 33 33 33 TFE/PMVE/CSM* 71
Y 55 23 22
Z 22 12 65 *Cure Site Monomer
Soures: 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)
0
140
-10
120
-20
break [%]
HNBR
100 -30
FKM (68% F)
80 -40
60 d -50
40 -60
20 -70
0 -80
60 65 70 75 0 200 400 600 800 1000
Fluorine Content [wt.%] time [h]
FKM: Glass Transition Temperatures
H F
0 VDF Vinylidene fluoride
Glass transition temperature [°C]
-25 F O CF3
PMVE Perfluoromethyl-
-30 F F vinyl ether
(69% fluorine)
H CH3
-35
0 0,5 1 1,5 2 P Propen
H H
Hydrogen content [wt.%]
Source: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons
Vulcanization with
Peroxides
peroxi-
Vulcanization with
disch
Bisphenols
Vulcanization
with Diamines
55 65 75
Fluorine Content [wt. %]
FKM: Vulcanization with Diamines
1. Elimination of HF by MgO, CaO und PbO.
CF3 CF3 CF3
- HF - HF
CF2 CH2 CF2 CH2 CF2 CF2 CH CF2 CH2 CF2 CF2 CH CF CH CF2
F
Diamine cure yields crosslinks which are liable to hydrolysis (not steam resistant)
CF3
CF3
CF2 CH CH2 CF2
CF2 CH CH2 CF2
O
N NH2
H2O
R R
N NH2
O
CF2 CH CH2 CF2
CF2 CH CH2 CF2
CF3
CF3
Sources: W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978)
W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979)
CF3
CF3
+ - HCl
HO OH + CH2 P Cl CH2 P
+
HO O
CF3
CF3
n n
CF3
CF2 CH CF CH CF2
CF3 CF3
CF3
• 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.
•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
5.2. Silicon Rubber (Q)
CH3 CH3
Grade Tg [°C] Tm [°C]
( Si O Si O ) MQ - 120 - 45
n MQ VMQ - 120 - 45
CH3 CH3 PVMQ - 120 - 70
FMQ - 69
CH3 CH3
Vulcanizate Properties:
( Si O Si O ) VMQ Positive:
n
Low temperature performance
CH3 CH High temperature resistance
CH2 Low dependence of properties on temperature
changes
Ozone-, UV- and Weather resistance
Hydrophopic character
Physiological inertness
CH3 Negative:
Low reistance against acids, bases, vapour and
( Si O Si O ) PVMQ hydrocarbons (significant improvement with
n FMVQ)
Mechanical properties
CH3 CH RTV: poor HTV: better / DVR !
CH2 High gas permeability
Adhesives
Temperature [°C] duration
90 40 years Moulded articles
121 10-20 years
150 5-10 years Hoses, sealants (Automotive, Machine
200 2-5 years building and E&E)
250 3 months
315 2 months
Sources:
•K. Polmanteer, Rubber Chemistry Technology, Vol 61: 471-502“Silicon 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/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Producers Capacities and Silicon Rubber Market
Manufacturer* Site Siloxane- Silicone
Capacity Rubber-
[kt] Brand Name
Dow Corning Carollton, USA 260.000 Silastic®
Barry, GB 110.000
Waterford, 110.000
Momentive USA
(formerly: GE + Bayer) Ohta, Japan 40.000
Leverkusen, 65.000 Silopren®
DE
Shin-Etsu Isobe, Japan 95.000 KE, Sylon®
Wacker Burghausen, 90.000 Elastosil®
DE
Nünchritz, DE 30.000
Rhodia Rousillon, FR 60.000 Rhodorsil®
Japan
25% Nord-
amerika
44% Year 1995 2005
Consumption /t: ~ 110.000 ~ 200.000
Growth rate 2005: ca. 3,5 % / a; LSR ca. 10 % / a
Europe
Source: 31%
Winnacker/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Rochow-Process: CH3
2 CH3-Cl + Si Cl Si Cl
CH3
H3C CH3
Si
O O D3
H3C CH3
Si Si
H3C O CH3
H3 C O CH3
CH3
- HCl H3C Si Si CH3
n Cl Si Cl + 4 H2O O O D4
CH3 Si Si
H3C O CH3
H3C CH3
H3C CH3
Si O n Dn
Silicon Rubber: Production
H3C O CH3
H3C Si Si CH3 85 % CH3 CH3
O O O Si O Si OH
n
Si Si 15 % CH3 CH3
H3C O CH3
H3C CH3
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.%)
CF3 CF3
CH2 CH2
H3C CH3
HC CH H2C O CH2
O O
H3C Si Si CH3 Si Si H3C Si Si CH3
O O O O O O
Si Si Si Si Si Si
H3 C O CH3 O H3C O CH3
CH CH H3 C CH3 CH2 C
H2
CF3 CF3
CH2 CH2
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.
OR R OR OR
RO Si OR RO Si OR RO Si O ( Si O ) R = Me, Et
n
OR OR OR OR
R O O R
R R
Si O C CH3 CH3 C O Si Si Si
+ H 2O O O R
R R R
RO OR - CH3COOH
Si
Si O R
R O
R O RO OR O R Si
Si
R R
Si O C CH3 CH3 C O Si
R R
For the condensation reaction the catalysts quoted under 1a) are being used.
RTV-Vulcanization of Silicon Rubber
(2K-System)
R O
R O
Si OH H Si R
- H2 Si O Si R
R O R
R O R
R Si H HO Si
R Si O Si
O R
O R
For the condensation reaction the catalysts quoted under 1a) are being used.
Inhibitors:
HT-Vulcanization of Silicon Rubber
3) Peroxide Cure (120-180°C)
R R R R R R
R R R
Si O Si O Si Si O Si O Si
Si O Si O Si
R R R R R* R
Peroxide R R R
- 2 H* R R R
R R R R R* R
Si O Si O Si
Si O Si O Si Si O Si O Si
R R R
R R R R R R
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
N
C
C
N
δ−
CH2 H H
δ+ N
C
CH CH CH
C C CH 2
H3C CH2 H2 H2 CH
1 2
45%
25%
Ship Couplings 7% 4% 4%
Riemen Schläuche Dichtungen
Kabel Ölförderung Sonstige
Rotor/Stator- Pumps
H
H
C NH2 + HN
C N
- NH3
PCy3 Ph Ph
BH 3
BF 4
-
Cl Cl
Ru Ru
R1 Cl
Cl +
Catalyst from Prof. Berke' s
P R2 PCy3 group (University of Zurich)
PCy3 Ph
R3
Piers-Catalyst Fürstner-(I)-Nolan-Catalyst (Umicore)
2- + 2- +
SnCl3 Ph SnCl 3
Ph
Cl Cl
Ru P Ru
Ph
Cl Cl
N N
SnCl3 SnCl 3
Ph
P
Ph
Ph
2 2
Catalyst from Prof. Berke' s group (University of Zurich) Catalyst from Prof. Berke' s group (University of Zurich)
Cl
CF 3 COO Cl
Ru Ru
Ru Cl
CF 3COO Cl R1
+ PCy 3
O P R2
R3
Mes N N Mes
Mes N N Mes Mes N N Mes
Cl
Cl
Ru Cl N Ru
Ru
Cl
Cl Cl
O N
O
Br
NO 2
Br
Grubbs-Hoveyda-Catalst Grela-Catalyst Grubbs-III-Catalyst
TON=53 / 23°C TON=78 / 23°C TON=120 / 23°C
Removal of
Cemement Solvent removal
Bale cutting oxygen and dilution Catalyst recovery
preparation- by evaporation
hydrogenation
12000
10000 Consumption
Volume [t]
capacity
8000
6000
4000
2000
0
1992 1994 1996 1998 2000 2002 2004
Ageing of Unvulcanized NBR and HNBR
(Increase of Mooney Viscosity ML 1+4/100°
1+4/100°C))
+1 NBR Hydriergrad: 0 %
+0 HNBR Hydriergrad: 96 %
HNBR Hydriergrad: 99,5 %
-1
-2
-3
-4
ln Vbr
-5
-6
-7
-8
1/T *103 [K-1]
2,0 2,4 2,6 2,8 3,0 3,2
T [°C]
180 160 140 120 100 80 60 40
Source: W. Obrecht, H. Buding, U. Eisele, Z. Szentivani, J. Thörmer, Angew. Makromol Chem. 145/146 (1986) 161-179 (2373)
„Hydrierter Nitrilkautschuk: Ein Werkstoff mit neuen Eigenschaften“
20
40
Tg [°C]
0
20
-20
0 -40
-60
-20
-80
-40 -100
0 20 40 60 80 100 0 20 40 60 80 100
Acrylonitrile Cont. [wt.%] Acrylonitrile Cont. [wt.%]
Data for Ethene/Acrylonitrile-Copolymers from: R. E. Uschold, I. B. Finlay, Appl. Polym. Symp. 25 (1974) 205
Tg of Ethene/Vinylacetate- und Ethene/Vinylchloride-Copolymers
100 Ethene/Vinylacetate-Copolymers 100 Ethene/Vinylchloride-Copolymers
80 80
Levapren
Nielsen et al.*
60 60
40 40
Tg [°C]
20 20
0 0
-20 -20
-40 -40
0 20 40 60 80 100 0 20 40 60 80 100
Vinylacetate Cont. [wt.%] Vinylchloride Cont. [wt.%]
Source: Ethene/Vinylacete Copolymers: L. E. Nielsen, J. Pol. Sci. 42 (1960) 357-366
Ethene/Vinylchloride Copolymers: F. P. Reding, J. A. Faucher, R. D. Whitman, J. Pol. Sci. 57 (1962) 483-498
16
14
1. DSC-Aufheizung
12
2. DSC-Aufheizung
Crystallinity [%]
10
0
0 10 20 30 40 50 60
Acrylonitrile Content [wt. %]
Tgs of Ethylene-Copolymers
100
50
0
Tg [°C]
-50
EPM
-100
HNBR
EVC
EVM
-150
-200
0 10 20 30 40 50 60 70 80 90 100
50
0
Tg [°C]
-50
HNBR (fully hydrogenated)
NBR
-100
?
-150
0 10 20 30 40 50 60 70 80 90 100
-26
Tg [°C]
-28
-30
-32
-34
0 20 40 60 80 100
Degree of Hydrogenation [%]
Source:
U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation Between
Network Structure and Properties of Sulfur- and Peroxide-Cured HNBR Vulcanizates“
8 11,0%
7,9%
4,0%
6
1,9%
0,5%
4
0
0 100 200 300 400 500 600 700
strain [%]
Source:
U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation Between
Network Structure and Properties of Sulfur- and Peroxide-Crosslinked HNBR Vulcanizates“
Dependence of E‘ and E‘‘ on Temperature (HNBR with
38,5 wt .% ACN)
10000
1000
E' and tan δ [MPa]
E'
E''
100
10
0,1
-200 -150 -100 -50 0 50 100
Temperature [°C]
40
0,6
35 18,9 wt.%
28 wt.%
0,5
Stress [MPa]
stress [MPa]
30 33,9 wt.%
38,5 wt.%
0,4 25
48,3 wt.%
0 0
0 1000 2000 3000 4000 0 500 1000 1500
elongation [%] elongation [%]
Influence of ACN-Content of Unvulcanized NBR and HNBR on
Maximum Stress (Yield-Stress) on “True“ Tensile Strength
300
200
150
100
50
0
1
Yield-Strength
0,8
[MPa]
0,6
0,4
0,2
0
0 10 20 30 40 50
100
permanent elongation [%]
120
80
100 200%
60 40
39,0 % 120%
28,2 %
40
20 80%
34,9 %
20
0
0
0 20 40 60
0 100 200 300 400
100
SBR CR
10
1 -1
CR 2,1 2,2 2,3 2,4 2,5 2,6 10 -3 ( K )
-1 T
1000
rate of crack growth
HNBR CR HNBR
(Sulfur cured) 100
0,1
-20 0 20 40 60 80 100
Temperature [°C]
Source:
M. Mezger; D. Achten “Therban: The high performance elastomer in power transmission systems”
9. Tagung “Zahnriemengetriebe” am Institut für Feinwerktechnik und Elektronik-Design der TU Dresden
5.4. EVM: Profile of Properties and Applications
O O O
O C O C C O
Source: H. Bartl, J. Peter, Über Äthylen/Vinylacetat-Copolymerisate und ihre Vernetzung; Kautschuk und Gummi, Jahrgang 14, 2 (1961) WT 23-32
Enthalpy of fusion
80
Glass Transition 60
(DH)[J/g]
40
20
0
-20
-40
0 20 40 60 80 100
Vinyl acetate content [wt.%.]
100
Temperature of Fusion
80
60
(Fp)[°C]
40
20
0
-20
-40
0 20 40 60 80 100
Vinyl acetate content [wt.%]
O - HAc O -40
O CH3 -50 350 °C
-60
O
-70
-80
-90
-100
200 300 400 500 600
Temperature [°C]
Elastostab H 02 OCN N C N NCO
time till elongation becomes <50 % in h
106
100000
Stabaxol P 200 n n = ca. 4
O O
20000 h
H3C O nO N N C N
135 N O O nCH3 10000
H H
n
n = ca. 4
1000
1000 h
20 30
0 20
-20
10
-40
0
0 20 40 60 80 100 0 20 40 60 80 100
Vinyl acetate content [wt.%]
Vinyl acetetate content [wt.%]
0
0 50 100 150 200 250 300
strain [%]
10
9
8
7
torque [dNm]
6
5
= 75 % of
4 total cure
3 Sources:
2 cycle time
for IM H. Meisenheimer, Kautschuk Gummi Kunststoffe,
1 52 (1999) 724
0 P. J- Pazur, L. Ferrari, H. Meisenheimer, ACS Rubber
0 20 40 60 80 100 120 140 160 180 200 220 240 Div. 165th Spring Meeting, Grand Rapids, Michigan
Negative:
• High permanent set after (tension set, compression set)
• Poor mechanical properties at elevated temperatures (tensile strength, compression set)
• Deterioratioon of mechanical properties in appropriate solvents
• High heat-build-up in dynamic applications
• Limited range of grades (particularly no soft grades available)
• Anisotropic properties of injection moulded articles (particularly for TPEs with uncrosslinked rubber phase)
Nomenclature and Range of Available TPEs
Examples
TPE-O EPM / PP
mechanical and
reactor-blends EPDM / PP
(unvulcanized)
Thermoplastic
Polyolefins EPDM / PP
Olefin TPE-V NBR/ PP
(dynamically vulcanized)
NBR / PVC
EVM / PVC
Polyblends1 PVC based blends ACM / PVC
(without dynamic vulcanization)
Elastomers SBC
TPE-S (SBS, SIS, SEBS, SIBS)
Styrenic Block-Copolymers
TPE-U Polyester-Urethanes,
Polyurethane Block Copolymers Polyether-Urethanes
Multi-Block-
Copolymers2
COPE based on aromatic
TPE-E Polyesters (Terephthalates)
Copolyester Block Copolymers PBT´/ PTHF; PET / PTHF
104
103
Shear Modulus [MPa]
Tempeature Temperature of
of Use Processability
102
101
100
10-1
Temperature Softening
Tg of Temperature of
Rubber Thermoplast Phase
Phase
Dependence of Modulus on
Temperature: Target and Reality
104
103
Shear Modulus [MPa]
102
101 Target
Reality
100
10-1
-100 - 50 0 50 100 150 200
Temperature [°C]
104
103
Shear Modulus [MPa]
4 3 2 1
102 5
6
101
7
100
10-1 8
- 100 - 50 0 50 100 150 200
Temperature
Dependence of Shear Modulus on Temperature for Different
Engineering Polymers
104
1. Thermoplastic Polymer
103 (Polycarbonate, PP.PA)
2. Thermoplastic
Shear Modulus [MPa]
(Polystyrene, PMMA)
4 3 2 1
102 5 3. Rubber Modified
Thermoplastic
6
4. Elastomer (crosslinked)
101
5. TPE
7 6. TPE
100
7. Elastomer (crosslinked)
Residual elongation
stress [MPa]
strain [%]
Dependence of Residual Elongation on Original
Elongation for Different Engineering Polymers
200
TPE-O (EPDM / PP: 60/40)
residual elongation (
ASTM D 1566 - 98
„Definition of Rubber“ TPE-V (EPDM / PP: 78/22)
100
Compression - Set
ho h1 h2
ho- h2
CS = x 100 [%]
ho- h1
ho- h2
ho- h1
ho In compression set (CS) measurements ho ,
h2
h1, compression, exposition time, and
h1 exposition temperature are well defined
(DIN, ASTM). Most commonly, the
deformation is 25%. In order to achieve the
same deformation „ho-h1“ the pressure has
to be adjusted to the degree of x-linking
Comparison of Technological Properties of
Chemically and Physically Crosslinked Rubbers
(Data from Product Data Sheets)
S BC T P E -U T PO
me ch. T PV T PV
Cla ssica l
P rope rtie s T P E -A T P E -E E P D M/ P P E P D M/ P P E P D M/ P P
E la stome rs S BS S IS S E BS E ste r E the r
ble nd (pa rtia lly (highly
x-linke d) x-linke d)
S hore A 10 to 80 71 52 75 92 93 78 72 75
S hore D - 44 42 25 40 63 32 54
E longa tion a t bre a k [% ] 300 to 800 880 1200 500 450 380 715 485 380 880 660 650 350 490
CS (22h/ 70°C) 5 to 30 75 60 38
CS (24h/ 70°C) 5 to 40 60 60 62 21 5 90 53
CS (22h/ 100°C) 5 to 40 88 44
klassische
200 Elastomere
Gebrauchstemperatur [°C]
PEBA
TPO
100 TPU
COPE
SBC
0
-100
0 50 80 100
Shore A Härte
30 40 50 60 70 80
Shore D Härte
PP-Performance and Price of EPDM/PP-Blends
180 7
TPE-V
(EPDM / PP-blend,
highly crosslinked)
160
6
140
5 TPE/SEBS-
120
Blends
4
100
TPE-V
(EPDM/PP partially
cross-linked)
80 3
60
2 TPE-O
(mechanical
40 PP-Properties:
PP-Properties: blends)
• Low Price
• Low Price
• •High 1 TPE-O
HighSoftening
SofteningTemperaure
Temperaure (Reactor-
20 • •Good
Good AgeingResistance
Ageing Resistance
(Residual Catalyst Content) Blends)
(Residual Catalyst Content)
0 0
20 40 60 80 100 0 0,5 1 1,5 2
Shore A-Hardness 78 72 75
Tensile Strength [MPa] 12 5,5 20
Elongation at break [%] 650 350 490
Compression Set 75 60 38
(22 h /70°C) [%]
Volume Swell in ASTM- soluble 90 50
Oil Nr. 3 [Vol%]
n n
ir ectio ir ectio
D Flo w D Flo w
of of
TPE-O and TPE-V: Mechanical Properties
Stress [MPa]
30 1,0-1,5
Particle diameter [ µm] 10
25
5,4
20
17 5
15 Shore A
72 39 Hardness: 64
10
0
5
0 100 200 300 400 500
0
0 200 400 600 Elongation [%]
Elongation at break [%]
Product
outlet
Supported Removal
of
catalyst residual
monomer
Cooler
Propylene purification
Ethylene
purification
700
600
Catalyst System B
500
400
300
20 30 40 50 60
Rubber Content [wt.%]
Source:
H. Schwager (BASF); Kunststoffe 82, 499 (1992)
T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“
Definitions:
1) “Reactive Processing” stands for a chemical reaction in the course of which
polymers are modified without the use of solvents.
2) “Dynamic Blending” stands for the solvent free blending process during which
a chemical reaction occurs.
3) “Dynamic Vulcanization” is used for vulcanization reactions (without solvent)
with simultaneous shearing.
4) Every vulcanization method can be performed dynamically
5) Resin cure was the first vulcanization method applied for the production of
EPDM/PP based TPE-V
Preparation of a TPE-V by the Dynamic Vulcaniztion
of a EPDM/PP blend with Phenol Resin
1. Preparation of a PP/EPDM-Block Copolymer in order to partially compatibilize
PP and EPDM
OH
HOCH 2 CH2 OH
PP +
OH
PP CH2 CH 2 OH
OH
PP CH2 CH 2 OH + EPDM
OH
PP CH 2 CH2 EPDM
Preparation of a TPE-V by the Dynamic Vulcaniztion of a
EPDM/PP blend with Phenol Resin
2) Addition of PP und EPDM with subsequent vulcanization of the EPDM-Phase
OH
PP CH2 CH2 EPDM
PP - OH
EPDM-
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
Polypropylene 185-190°C 0 50 50 50
Dimethylolphenol resin 5 min. 0 2 2 2
SnCl2 . 2 H2O 2 min. 0 0,4 0,4 0,4
Polypropylene 185-190°C 50 0 0 0
NBR + 5 min. 50 50 50 45
Aminino terminated NBR 0 0 0 5
Dimethylolphenol resin + 5 min. 0 0 1,67 5
SnCl2 . 2 H2O 0 0 0 0,5
1000
100
[%]
10
1
40
Tensile Strength [MPa]
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, 209-218„Blend Preparation by Reactive Processing
Advanced technologies for the production of PP-
based TPEs
608 R
R2 ataktisches Preparation of PP-Blockcopolymers by the
Zr Polymer
R1 use of the „Waymouth-Catalyst“
The length of building blocks is determined
622 R
by the ratio of propagation rates versus
Rotation rate
595 R
Source:
R2 Isotaktisches
R. Waymouth, J. Coates, A-L. Mogstad, K. Stein, D. Fischer,
Zr Polymer
R1 S. Borkowsky
Stepol `94; Milano June 6-10, 1994 "Stereospecific
R Polymerization and Copolymerization of Functionalized Olefins"
Cl
Cl
Cl B
Cl Temperature Cl
B Cl Zr
Zr Cl Cl
P
Et P
Et
Et Et
Schubmodul (MPa)
2
10
G''
1
10
0
10
tan δ
-1
10
-2
10
-160 -120 -80 -40 0 40
Temperatur[°(°C)
Temperature C]
Sample from Prof. Aladyshev
PP-Based TPE
6
Elast.PP
2] ]
2
[N/mm
4
stress σσ[N/mm
Spannung
Probenform: S1-Stab
Anlieferzustand: Platte
Meßdatum: 05.06.02
Dateiname: S14308sd (Graph 1)
0
0 200 400 600 800
strain (εεε) [%]
Dehnung [%]
Abb.
Sample from Prof. Aladyshev
PP-Based TPE 4
10
2
10
1
10
Komplex
0
10
-1
10
-1
10
tan(δ) -2
10
-3
10
-160 -120 -80 -40 0 40 80 120
Temperatur [°C]
Temperature [°C]
Sample from Prof. Eisen/Haifa
PP-Based TPE
6
HAIFA-1
HAIFA-2
2] ]
4
2
[N/mm
stress σσ[N/mm
Spannung
0
0 100 200 300 400 500 600 700 800 900
strain εε [%]
Dehnung [%]
Sample from Prof. Eisen/Haifa
TPEs from the Viewpoint of a Producer of Technical
Rubber Goods
• Reduction of Manufacturing Costs
– Reduction in number of raw materials and associated costs for logistics (ordering,
transportation and storage,)
– Reduction/elimination of compounding costs including energy savings
– Significant reduction of cycle time and increase of output (seconds instead of minutes)
– Cost reduction by recycling of waste (no costs for incineration and land fill)
Family Name
2
Given Name
Please Assign the following Rubbers to the
Correct Position in the Matrix:
ACM, BIIR, BR, CM, CSM, EVM, FKM, HNBR, IIR, SBR
Chemical Process Features
Features Emulsion Solution Dispersion Mass or Gas-
(slurry) Bulk Phase
Radical
Polymerization
Ziegler/Natta-
Polymerization
anionic
Polymerization
Cationic
Polymerization
Polyaddition und
Polycondensation
Polymer-
modification
Family Name
Given Name 3
200 2
100 3
4
5
0 6
0 100 200 300
elongation [%]
Nr.: Questions Answers
1 Thermoplastic Polymer ?
2 Unvulcanized HNBR at 20°C ?
3 Unvulcanized HNBR at 120°C?
4 Unvulcanized BR with Mn = 10 kg/mol at 50°C ?
5 Unvulcanized BR with Mn = 500 kg/mol at 20°C?
6 SBS at 20°C?
7 SBS at 120°C
8 TPU at 20°C
9 NR (unfilled and vulcanized) at 60°C
10 NR (filled and vulcanized) at 60°C
Family Name
4
Given Name
Natural Rubber
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name
5
Natural Rubber
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name
6
Synthetic Polyisoprene
Family Name
Given Name
7
Emulsion Rubbers
Family Name
Given Name 8
Pollution of Water and Air:
Please Mark „RIGHT“ or „WRONG“
Nr. Question Right Wrong
1 COD = 0
2 BOD = 0
3 BOD = COD
4 COD < BOD
5 BOD < COD
6 There are no biodegradable emulsifiers
7 Emulsion rubbers yield considerable amounts of water water
8 Dry finishing of solution rubbers does not cause water pollution
9 Rubber recovery from a solution by steam stripping causes waste water
10 Emulsion rubbers cause air pollution
Family Name
9
Given Name
Crystallization of Rubbers
Nr.:
Frage Right Wrong
1 Additives can increas the rate of crystallization
2 Additives can reduce the rate of crystallization
3 SBR is a crystallizing rubber
4 NBR is a crystallizing rubber
5 NR is a crystallizing rubber
6 Rubber compounds crystallize slower than raw rubbers
7 Vulcanizate crystallize faster then the respective rubber compounds
8 Strain induced crystallization is a wanted property
9 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
Family Name
Given Name 10
Crystallization of Rubbers
Family Name
Given Name 11
NBR
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name 12
NBR
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name 13
NBR
In the literature you find the following Tgs for polybutadiene (BR) and
polyacrylonitrile (PAN:
BR (Li-catalysis) -90°C
BR (Ti-catalysis) -100°C
BR (Nd-catalysis) -110°C
BR (emulsion polymerization) -80°C
PAN +100°C
Please select the relevant Tgs and calculate the Tg of an NBR grade
which contains 50 wt.% acrylonitrile.
acrylonitrile.
Family Name
Given Name 14
NBR:
Family Name
Given Name 15
CR
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name 16
HNBR:
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name 17
HNBR:
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name 18
IIR, CIIR and BIIR:
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name 19
Thermoplastic Elastomers:
Please Mark „RIGHT“ or „WRONG“
Family Name
Given Name 20
Please assign the Curves
104
1
103
Schubmodul [MPa]
4 3 2
5
102
6
7
101 8
9
100
10-1
-100 -50 0 50 100 150 200
Temperatur
Nr.: Frage Number of curve(s)
1 Which curve(s) matches the performance of unvulcanized NR ?
2 Which curve(s) matches the performance of unvulcanized SBR ?
3 Which curve(s) matches the performance of vulcanized SBR ?
4 Which curve(s) matches the performance of unvulcanized NBR ?
5 Which curve(s) matches the performance of vulcanized NBR ?
6 Which curve(s) matches the performance of isotactic Polypropylene?
7 Which curve(s) matches the performance of Polycarbonate?
8 Which curve(s) matches the performance of atactic Polytyrene?
9 Which curve(s) matches the performance of ABS with 30 wt.% BR ?
21
10 Which of the curve(s) matches the performance of SBS ?
CH2
1
CH2 CH
1
1
4
CH2
3
CH2 CH CH
2
3
CH
CH CH
2 3 CH2
4
CH2
4
Metal
Microstructure [%]
1,4-cis 36-38 97 97 93 98 12,9
1,4-trans 52 1 2 3 1 68,3
Vinyl 10-11 2 1 3-4 <1 18,8
1
Vinyl/ H-NMR*** 10,4 1,9 4,0 <1 18,1
Vinyl/FT-IR*** 11,4 1,0 5,4 0,6 17,7
Vinyl/Metathese*** 10,7 1,7 4,6 0,7 17,8
Tg -93 -106 -107 -103 -109 -80
23
Compound Properties
ML 1+4(100°C) [MU] 123 99 58 40 32
t2/177°C [min] 1,5 1,6 1,5 1,6 1,6
t90/177°C [min] 11,7 11,0 10,2 10,2 9,5
Vulcanizate Properties
Shore A Härte (23°C) 78 80 80 81 77 Rubber A
Modulus 100 [MPa] 10,7 13,1 12,6 12,0 8,3
Elongation at break [%] 240 190 170 145 165 Rubber B
Tensile Strength [MPa] 26 24 22,5 18,8 18,5
Compression Set
70h/23°C [%] 12 12 12 14 14
70h/150°C [%] 20 17 17 14 9
70h/175°C [%] 27 27 25,5 20 15
Hard phase
(coherent phase or matrix)
Soft phase
(dispersed phase)
Family Name
Given Name
26
Which Series of Rubbers Yields the Properties Given in
the Table Below?
Rubber A B C D E F
Compound properties
Mooney ML 1+4(100°C) 20 24 23 25 20 20
t10/180°C [min] 1,2 1,2 1,2 1,2 1,3 1,3
t90/180°C [min] 7,2 6,6 6,6 6,2 6,9 6,1
FH-FL/180°C [N] 17 20 19 21 19 17 Rubber
Vulcanised properties Variation
(ISO-Stab Nr. 2, 2mm)
Shore A Härte (23°C) 75 74 68 71 68 72
S 100 MPa] 5,0 5,7 4,4 5,4 4,2 4,7
Elongation at break [%] 295 275 285 280 300 300
Tenjsile Strength [MPa] 11,7 13,6 12,6 12,8 11,5 10,5
Compression Set
70h/100°C [%] 23 20 20 22 21 27
70h/125°C [%] 25 23 25 26 24 31
70h/150°C [%] 41 38 41 40 46 51
Physical Properties
Shore A Hardnes 48 40 54 58
M100 [MPa] 0,9 0,5 0,12 0,19
M300 [MPa] 5,2 1,8 9,5 10,2
Tensile Strength [MPa] 12,4 8,9 10,5 13,6
Elongation at break [%] 580 680 325 360
CS (70h/150°C) [%] 58 53 28 13
29