Professional Documents
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4. Overview on Solution Rubbers 4.1. Overview on Polybutadiene 4.2. Li-Polybutadiene and Solution-Styrene/Butadiene-Rubber with an Emphasis on Integral Rubber 4.3. Chemistry and Production Technology of High cis-1,4-BR with a Special Emphasis on Nd-BR 4.4. Ethylene/Propene-Co- und Terpolymers 4.5. Butyl- and Halobutyl Rubber 5. 5.1. 5.2. 5.3. 5.4. 6. 7. High Performance Rubbers Fluoro Rubber Silicon Rubber Hydrogenated Nitrile Rubber Ethylene/Vinylacetate-Copolymers Thermoplastic Elastomers Test Questions
Definition of the Terms Rubber, Elastomer and Thermoplastic Elastomer Nomenclature Market Important Rubbers and Property Profiles Rubber Producers Production Technologies Producers of Synthetic Rubber and Production Capacities Available Vulcanization Methods and Network Properties
DISCUSSION
- A rubber in its modified state, free of diluents, retracts within 1 min to less than 1,5 times its original length after being stretched at room temperature (18 to 29 C) to twice its length and held for 1 min before release.
= residual
TPV SBS
In English, the term Rubber is ambiguous as this term refers to unvulcanized as well as to vulcanized rubber: rubber tree natural rubber rubber boot unvulcanized (=uncrosslinked) rubber vulcanized (=crosslinked) rubber
~ -130 C -18 C
Polyvinylacetate
+30 C
O O CH3
O O CH3
O O CH3
O O CH3
+100 C
Si
Si
Si
Si
Si
Si
Si
Silicon Rubber
-120C
Polyisoprene
Cl Cl CN
Cl
Polychloroprene
Cl
Nitrile Rubber
CN
Influence of Tg on Rebound of Vulcanized Rubbers (50 phr carbon black, black, without plasticizer)
80 1,4-cis BR NR EPDM 40 IIR 20 SBR NBR
Rebound [%]
60
Temperature [ C]
With increasing temperature rebound elasticity passes throug a minimum The temperature at the rebound minimum correlates with Tg, except for butyl rubber The temperature at the rebound minimum is significantly higher than the Tg of the respective rubber In this respect, butyl rubber performs different from the other rubbers Source: Butyl And Halobutyl Compounding Guide For Non-Tyre Applications, 12/92 Bayer AG -KA
1000
100
10
Temperature [C]
Examples
CM, CSM, EAM, ACM, EPM, EPDM, NBR, HNBR CO, ECO, GPO MQ, MVQ, PMVQ, FMQ NR, SBR, BR, NBR, CR, IIR OT, EOT AU, EU
FZ
Natural Rubber
12000
10000
8000
6000
4000
2000
0 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010 2020
Sources: IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions Outlook for Elastomers 1996-97 (Wembley 1998) Rubber World, 21916 (1999) 13-14 European Rubber Journal (Quotation of IISRP Statistics), various editions LMC International Ltd, Rubber March 2005: Verbrauch 2001-2005
Volume Shares
CR (0.3 Mio t)
Price
FKM
MVQ
General GeneralPurpose PurposeRubbers Rubbers Special Rubbers Special Rubbers High HighPerformance PerformanceRubbers Rubbers
ACM HNBR
EU AU
CR
SBR
BR
NR
20
40
60
80
100
120
140
no requirement
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) *Ullmanns Encyclopedia of Industrial Chemistry, VCH Weinheim 1993, Vol. A23, Rubber 3. Synthetic; W. Obrecht Introduction
FZ HNBR MVQ FKM ACM EVM AU NBR AEM EPDM ECO CSM CM IIR CR FMVQ
Performance Index
30 25 20 15 10 5 0 0,1 1
NR BR SBR
10
100
1000
[Mio US $]
1 2 3 4 5 6 7 8 9 10 11 Michelin Bridgestone Goodyear * Continental Sumitomo** Pirelli Yokohama Cooper Tire Toyo Kumho Hankook 13.425,0 12.950,0 12.470,0 4.901,0 2.598,2 2.534,5 2.272,2 1.705,3 1.247,6 1.246,5 118,9
Bridgestone
Michelin
Goodyear
55.469,2 68.500,0
81,0 100,0
* Dunlop is not included ** Goodyear und Sumitomo operate in NA und WE in 75/25 joint ventures (Dunlop)
Source: European Rubber Journal, vol. 184, no. 10, Oktober 2002, S. 28-30
Continental
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
Hutchinson SA Bridgestone Corp. Freudenberg Group Tomkins plc. Parker Hannifin Cooper Tire & Rubber Trelleborg AB Continental AG Federal Mogul Corp. Goodyear Tire & Rubber NOK Inc. Tokai Rubber Industries Ltd. Metzeler Automotive Profile Syst. Toyoda Gosei Co. Ltd. Mark IV Automotive GenCorp. Inc. Ansell Ltd. Sumitomo Rubber Ind. Yokohama Rubber Co Ltd. Dana Corp. Toyo Tire Rubber Co. Ltd. Phoenix AG
JSR Corporation 5.2% Sinopec 5.2% Sibur 5.1% Korea Kumho 4.8%
Source: R. J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008Globalization of Synthetic Rubber Industry
Petro-China 3.6%
Technological Features
Emulsion
E-SBR, CR, NBR, E-BR, ACM, FKM, EVM
Solution
EVM
Dispersion
EVM
Bulk
AEM EVM BR* Q
Gas-Phase
EPM, EPDM
IIR
AU
* Technology not established (only patents for the hydrogenation of NBR-latex) ** Technology not established (only patents for the gas phase polymerization of butadiene)
Temperature: 35-65C Temperature: 35-65C Pressure: 5-10 Pressure: 5-10bar bar Residence Time: 30 Residence Time: 30min min Solids 10 SolidsContent: Content: 10-12 -12wt.% wt.% Moisture Content: < 3 ppm Moisture Content: < 3 ppm
Stripper Dewatering screw Waste Air
Flash Vessel
Ethene Hexane
Purification
Propene
Reactor
External cooler steam PHControl Antioxydant Stripping aid Oil
Waste water
Purification
Abwasser
Dryer
Dryer
Baler
Modifier Reactivator
Purification/ Drying Purification/ Drying Wrapper
EASC VOCl3
Hexane
ENB
8 10 5 0 0 5
28
27
41
39
45
(Gas-Phase) > Dispersion > Bulk >> Emulsion > Solution comparable running times
M-Rubbers
Other Rubbers
Influence of Vulcanization Method and Crosslinking Density on Tensile Strength (unfilled NR-Vulcanisates)
30
20
10
Sx S1 C C C C
accelerated sulfur cure TMTD-cure peroxide cure high energy radiation cure
Type of Bond
covalent
physical
Rubber
Oil Resistance Low temperature flexibility Resistance to heat- and ageing Adhesion to cord, fibres and fabrics Covulcanisation of layers Tensile Strength Elongation at break Static and dynamic moduli Shore A Hardness Abrasion Resistance Compression Set Cut growth Resistance during dynamic stress Heat-buid-up Electical conductivity . .. .. .
Vulcanization Method
NR-Production
NR-Latex and Latex Finishing General Features of NR and Hevea brasiliensis NR Grades and Specifications
Vulcanization of NR
Positive:
Low price and good ratio of price versus performance Standardized NR-grades High level of mechanical properties (Tensile Strength, Modulus Abrasion) Good Dispersability of Fillers (due to high viscosities at the start of the mixing cycle) Low rolling resistance (truck tyres) High abrasion resistance (truck tyres) Slow spontaneous crystallization Significant strain induced crystallization
H3C
C 1 CH2
CH 4 CH2
Negative:
Poor resistance to swelling with hydrocarbons (fuels, oils and grease) Need for mastication prior to compounding bad wet skid performance Poor resistance to heat ageing Physical Properties:
Tg: 1,4-cis-content Tm (equilibrium): max. rate of crystallization: max. degree of crystallinity: Strain induced crystallization -72 C ~ 97% + 30 C -25 C ~ 30 %
Special Grades:
OENR Oil Extended NR L-Grades Light Grades (with colour specification) produced by the selection of latices and removal of carotinoids by latex creaming, addition of Na-HSO3, and intenisve wash etc. SP-Grades Superior Processing (Sol/Gel-Blends) CV-Grades Constant Viscosity NR obtained by the addition of hydroxyl amin prior to latex finishing ENR Epoxidized NR
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
NR: Production
3500
0 1985 1990 1995 2000 2005 Sources: 1980 K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591 LMC International Ltd; Rubber April 2005
1997 Thailand Indonesia Malysia
1.934 31,90% 1.530 25,20% 1.070 17,60%
2004
2.988 34,50% 1.942 22,40% 1.175 13,58%
2004
741 8,60% 585 6,70% 92 1,10% 423 4,90%
1997 Ivory coast Philippines Camerun Cambodsha Brasil Liberia Burma Nigeria
87 1,40% 60 1,00% 56 0,90% 49 35 25 21 13 0,80% 0,60% 0,40% 0,40% 0,20%
Total
4.534
75% 6.105
70%
1.193
20% 1.841
21%
346 5,7%
Source:
Rmpp Lexikon Chemie; Version 1.5; Stuttgart/New York Thieme-Verlag 1998 LMC International Ltd; Rubber April 2005
Automotive (other than tyre) 2% Shoes 4% None automotive 5% Others 7% Latex-Products 11%
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
Tread [wt.%]
NR 45 60 77 86 86 100 SBR 21 12 7 5 5 BR 34 28 16 9 9
Carcass [wt.%]
NR 71 84 100 100 100 100 SBR 20 11 BR 9 4
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 Indonesia India Malaysia Brasil Sri Lanka Ivory Coast 95% 83% 83% 81% 70% 33% 29%
Source: http://www.therubbereconomist.com
Area cultivated per smallholder: Number of trees: Annual tappings per tree: Total number of tappings per year: Annual yield: Annual earnings: Earnings/different source*:
Source:
NR-Production by smallholders:
1,25 ha; 625 trees in total; 520 trees under tap 180/a 95.000 tappings for 625 trees/a 850 kg/a ca. 250 /a (0,30 /kg) 1020 /a (1,2 /kg)
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
Euphorbiaceae Equator + 15
< 300 m 25-30 C > 70% 1800-2000 mm/year good drainage (not at the bottom of vallleys)
max. age of tree: Height of tree: tapping age of tree: Tappings: Yield per tree: Yield per tap: density of trees: Rubber yields:
Plantation: Maximum yield: Smallholder:
30-40 Jahre (plantation), 100 Jahre (rain forest) 20 m (plantation), 40 m (rain forest) 5-7 years every 2nd day = 180 days/year 1-2 kg/a 5-11g 500/ha 400-1.200 kg/ha
1.000 kg/ha 3.000 kg/ha 850 kg/ha
Dothidella Ulei (Yellow leaf blythe) so far, endemic and restricted to Brasil
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer, Encyclopedia of Chemical
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)
SMR 5 60% Baled or Crumb Rubber wet and dry blending processes 40% field grades
SMR L
SMR CV 50 SMR CV 60
SMR GP
SMR 10
SMR 20
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
NR Grade
Strainer Residue [wt.%] (mesh width: 45 mm)
SMR 5
0,05
SMR GP
0,10
SMR 10
0,10
SMR 20
0,20
SMR 50
0,50
Besides NR purity, price is also an important factor for the selection of an appropriate NR grade. As a consequence of price and quality, the ranking of NR grades for tyre building is as follows: SMR 20 > SMR 10 > SMR GP > SMR 5 > RSS
Monsanto-Rheometer (160 C)
Delta F [J/cm2] TS 2 [min] 29,4 2,2 33,9 1,8 37,2 1,5 40 1,3 41,1 1,2 t90 [min] 11,6 9,7 7,8 6,8 6,8
ACS 1- Compound
NR Stearic Acid ZnO Sulfur: MBT 100 phr 0,5 phr 6,0 phr 3,5 phr 0,5 phr
With increasing impurity level, the following features are observed: reduction of scorch time reduction of vulcanization time Increase of crosslinking density
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591 (ISO 1658: Natural Rubber - Test Recipes and Vulcanization Characteristics, International Organization for Standardization, Geneva, Switzerland, 1973
Fraction Nr.:
bale 1 2 3 4 5 6 Soluble portion
share [wt.%]
100 24,4 19,7 15,5 8,0 12,9 12,8 6,7
1,2content [%]
0,6 0,6 0,5 0,5 0,7 0,6 0,5 -
Source: Rubber Chem. Technol. 57, 104 (1984) Source: Rubber Chem. Technol. 82, 283-314
NR has a broad distribution of molar masses (polydispersity or physical inhomogenity) The polydispersity increases with the age of the tree NR fractions with a low molar mass have a higher content of 1,4-trans moieties than the fractions with a higher molar mass (chemical inhomogenity)
[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr]
NNNN
NNNN
NNNN
HHHH CCCC
3333
First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272
HHHH NNNN
SSSS SSSS
HHHH NNNN
HHHH
3333
3333
HHHH CCCC
OOOO
3333
3333
NR contains polymer bound functional groups (-NH2, -COOH, -OH, -CONH2) which react with isocyanates
Mastication of NR
184 kJ/mol *C C*
Pentachlorothiophenol
343 kJ/mol
C*
*C
Degree of Mastication
2,2'-Dibenzamidodiphenyl-Disulfide (DBD)
S S
SH Cl Cl
NH Cl Cl Cl O O
HN
100 Temperature [ C]
200
At low temperatures (<120 C) mechanical chain scission prevails At temperatures >120 C thermo-oxidative chain scission prevails In the temperature range 100-130 C the mastication effect shows a minimum
By the use of mastication additives the mastication of NR is accelerated (oxidation catalysts and radical scavengers) Pentachlorothiophenol is an effective mastication aid; it is banned in WE Today, disulfides as well as Fe-complexes are used for the acceleration of NR mastication Source: C. Clarke, M. Hensel, Rubber World, November 2009, 28-31 Improved natural rubber processing and physical properties by use of selected compounding additives
Crystallinity [%]
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)
NR: Dependence of Crystallization Rate and Crystallite Melting Temperature on Storage Temperature
1000
40
melting temperature [ C]
-50 -30 -10 10
100
10
storage temperature [ C]
storage temperature [ C]
Source:
U. Eisele Intorduction to Polymer Physics, Springer-Verlag 1990
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 21, 4th ed., 562-591
30 25
stress [MPa]
20 15 10 5 0 0 200
NR SBR
Strain induced crystallization
400
600
800
1000
strain [%]
20
NR SBR
Tack-Index
15
10
0 0 20 40 60 80 100 120
temperature [C]
Modification
Hydroxyl amine (CV-Grades)
Application
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
H H O
H2 N
- H2 O
H H N H
10 9 8 7 6 5 4 3 2 1 0 0
20
During storage at ambient and elevated temperatures, the viscosity of NR increases to a greater extent than for synthetic IR (storge hardening) It is assumed that the viscosity increase of NR is caused by the chemical reaction of polymer bound NH2 and polymer bound CH=O groups By the addition of hydroxylamine to the NR latex prior to latex coagulation CH=O groups are chemically eliminated CV-Grades (Constant Viscosity) exhibit an improved storage stability
NR: CV-Grades
Mooney-Viscosity ML1+4 (100 C)
140 130 120 110 100 90 80 70 60 50 0 0,02 0,04 0,06 0,08 before hot air ageing after hot air ageing
Hexanediamine [mol/kg]
H H O
H2 N
NH2
Specification of CV-Grades
H
Grade
- 2 H2 O H H N N H H
CV 50 CV 60 CV 70 LV 50
NR: CV-Grades
Increase of Mooney Viscosity [%] 70 60 50 40 30 20 10 0 0 0,05 0,1 0,15 0,2 hydroxyl amine [wt. %]
H H C O - H2O + H2N OH
H H C N OH
NR CV-Grades (Constant Viscosity) are obtained by the addition of hydroxylammonium chloride to the latex prior to latex finishing
Tg [C]
20
40
60
80
100
NR: SP-Grades
SP-Grades (Superior Processing) are obained by blending crosslinked NR with uncrosslinked NR in the latex stage. The crosslinked NR-latex (NR-gel) is obtained by sulfur cure in the latex The SP-series of grades comprises different blend ratios of ucrosslinked and unrosslinked NR as well as oil extended grades
Grade Precrosslinked Uncrosslinked Oil NR NR [wt.%] [wt.%] [phr] SP 20 20 80 0 SP 21 40 60 0 SP 22 50 50 0 SP 23 80 20 40 SP 24 80 20 0
NR (SMR 5) N 330 Oil ZnO Stearic Acid Sulfur TBBS CBS TMTD Santoflex 13 TMQ DCP Novor 924 Caloxol ZDMC ZMBT
[phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr]
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical
Technology, vol 21, 4th ed., 562-591
N O O
NH
HN O
O N
Thermal Cleavage
O N N O N O H O C N O N C O H O N O
Tautomerization
Tautomerization
O N H
O H O
H O
O H
- H2 O
N N N O O NH O HN O O
- H2 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
Sulfur (konv.)
Shore A Hardness/23 C M100 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23 C [%] Fatigue to Failure [kZ] Goodrich HBU [ C] CS/24h/70 C [%] TS (7d/100 C) [%] 65 2,08 28,8 515 70 223 29 27 73
Capped Di-Isocyanate
70 2,60 24,0 460 66 90 30
Li
IR Ti
Nd
93 97 99 no mastication needed -
Poly-3,4-Isoprene
C C4
Poly-cis-1,4-Isoprene
Poly-trans-1,4-Isoprene
Solvent
unpolar (benzene) unpolar hydrocarbon Hexane/Additive unpolar hydrocarbon
Li Ti Li Nd
1) E. Schoenberg, H. A. Marsh, S. J. Walters, W. M. Saltman, Polyisoprene, Rubber Chemistry and Technology, Vol 52, S. 526-604 2) Data sheet of Hls AG: Vestogrip (Production by Karbochem / South Africa: ca. 3.000t) 3) WO 02/38635 A1 (Michelin), Erf.: P. Laubry, Prior.: 13.11.2000 3) WO 02/48218 A1 (Michelin), Erf.: P. Laubry, Prior.: 28.11.2001
Sources:
2,5 2 1,5 1 0,5 0 1980 1985 1990 1995 2000 2005 2010
IR NR (RSS)
Company
Goodyear Kraton Polymers Kauchuk Sterlitamak Nishnekamskneftekhim Togliattikauchuk JSR Corporation Zeon Corporation Karbochem Total Capacity [kt]
Plant Location
Beaumont/Texas/USA Rotterdam-Pernis/Nederland Sterlitamak/Russia Nishnekamsk /Russia Togliatti Kashima / Ibaraki Pref. Mitzushima / Okayama Pref. Newcastle / Natal /South Africa
Capacity [kt]
90 25 100 200 130 36 40 3 624
Source: R.J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008 Globalization of Synthetic Rubber Industry
9 8 7
Stress [MPa]
6 5 4 3 2 1 0 0
100
200
300
400
500
Strain [%]
NR
Mastication Mixing cycle Die swell Tack Green strength
Li + + + -
IR Ti + + + -
Nd + + + + +
+ +
Vulcanizate Properties
NR
Modulus Tensile Strength Cut growth resistance Rebound Elastivity Abrasion resistance
Li -
IR Ti -
Nd + + + + +
+ + + + +
Source: P. Roch (Goodyear) KGK 48,6 (1995) 430-434Compounding for Wet Grip
Emulsionrubber
E-SBR NBR CR ACM FKM
Latex Coagulation
electrolyte electrolyte freezing electrolyte electrolyte
Disadvantages:
Waste water Product impurities (residuals from emulsifier and coagulants) no water resistant catalysts available (Stereospecifity)
Polymerization
Wasser
Monomer emulsion
M M M M
Monomer droplet Diameter: concentration:
M
0,1-10*10 -6 m 1013 lw-1
M M M
Literature: Polymerization occurs only in P. E. Lovell, M. S. El-Aasser, Emulsion Polymerization, Wiley 1998 monomer loaded micelles and Blackley, Emulsion Polymerization, 1975 H. Gerrens, Advances in Polymer Science, volume 1 not in monomer droplets
Phase II
Phase III
Arbitrary Units
60 50 40 30 20 10 0
20
40
60
80
100
Phase III:
Number of latex particles formed: x y NL = k * (E-CMC) * I Polymerization rate in Phase II: VBr = NL * kw* [n]* [M] Prediction by the Smith Ewart Theory:
NL: E-CMC: I: kw: [n]: [M]:
number of latex particles [lw-1] effective emulsifier concentration [lw-1] Initiator concentration [lw-1] propagation rate constant [l * mol-1 * sec-1] average concentration of radicals per particle [without dimension] monomer concentration in latex particle [Mol * l-1]
Vapour condensation
Recovered butadiene
Butadiene Styrene Aqueous emulsifier solution Hydroperoxide Aqueous catalyst solution
Mixer/Settler
Brdenkondensation
Stripping column
Flash evaporation
Abstoppkessel
Polymerisa -tionskessel
Polymerisa -tionskessel
Polymerisa -tionskessel
Polymerisa -tionskessel
Polymerisa -tionskessel
Short stop
Vapour
Latexstorage
Latex
AO
Mass Balance:
Latex volume : Rubber (25%): Water serum (75%): Wash water: Waste water: 400.000 t 100.000 t 300.000 t 100.000 t 400.000 t
Puffertank
Washtank
Coagulation tank
Dewatering screw
dryer
stripped Latex
Finishing of CR-Latex
dryer dewatering rolls
Latex-surge tank
Acidic acid
Freezing roll
Powdering
Chopper
packaging
Abwasserabgabegesetz (AbwAG)
Legislation on Charges for the emission of polluted water of November 6th, 1990, BGB1. I, S. 2432
Abwasserherkunftsverordnung (AbwHerkV)
Legislation on the provinence of waste water" Of July 3rd, 1987, BGB1.I, S. 1578
Trinkwasserverordnung (TrinkwV)
Legislation on the quality of drinking water and on water which is used in food production of December, 5th, 1990, BGB1. I, S. 2612 Source:
W. Guhl und U. Werner; Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
Everybody who uses water is obliged under the necessary circumstances to act in a careful and responsible manner in order to avoid water pollution and negative impacts on the properties of water.
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
Polymerisation
Polymerization Recipe (Cold Rubber) Ingredients of a Polymerization Recipe Sequence of Reaction Steps Copolymerisation of Styrene und Butadiene Influence of Chain Modification Agents
Product Properties
Tg Influence of None Polymeric Residues on Compound and Vulcanizate Properties
Microstructure of E-SBR
4
2
HC HC
3
CH 1 2
4
CH2 CH
2
CH2
CH CH2
1
C H2
CH CH
4
CH CH2
1 2
CH2
1,4-cis
1,4-trans
Vinyl
Styrene
Negative:
poor ageing resistance poor resistance to swelling in oils no variation of microstructure low / no profits / no R&D-activities
Others 2%
mechanical parts 8%
Site
Baton Rouge Houston Port Arthur/Odessa Sarnia Pto. Gral, San Martin Duque de Caxias/Triunfo Altamira La Wantzenau Schkopau Ravenna Pernis Oswiecim Kralupy Zrenjanin Onesti Burgas Kawasaki Yokkaichi Tokuyama/Kawasaki Chiba Ulsan Daesan Kaohsiung Mab Ta Phut, Rayong Altona Bombay/Bareilly Omsk/Sterlitamak/Togliatti/Voronezh Lanzhou/JiLin
Country Capacity
USA USA USA Can. Argentinia Brasil Mexico France Germany Italy Netherlands Poland Czech Rep. Crotia Rumania Bulgaria Japan Japan Japan Japan Korea Korea Taiwan Thailand Indonesia Australia India USSR China 150.000 267.000 336.000 20.000 53.500 255.000 74.500 90.000 120.000 295.000 120.000 104.000 76.000 40.000 100.000 20.000 195.000 65.000 200.000 50.000 190.000 60.000 105.000 60.000 60.000 35.000 75.000 486.000 200.000
Sum
Market: Capacity: Capacity utilization: 2,0 Mio t 3,9 Mio t 51%
3.902.000
Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.
Company
Lanxess France Dow Enichem. Dow (prior owner: Shell)
Site
La Wantzenau Schkopau Ravenna Pernis
Country
France Germany Italy Netherlands
Capacity
45.000 120.000 295.000 120.000
Production [t]
Sum
Dwory Chemopetrol HIP Petrohemija Combinatul Petrochimic Neftochim Oswiecim Kralupy Zrenjanin Onesti Burgas Poland Czech Republic Croatia Rumania Bulgaria
580.000 415.000
104.000 76.000 40.000 100.000 20.000
Sum
340.000
2000 2002
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 without Carbon Blackadditives Masterbatch X X X Oil-extension (<14 phr) X Oil extension (>14 phr) X X -
Hot Rubber X -
Source: The Synthetic Rubber Manual, 14th edition IISRP (International Institute of Synthetic Rubber Producers, Houston (1999)
1507
23,5
30-35
NS
1509
23,5
30-35
NS
NS S S S S
N 110 N 330
4 76
NAPH: HAR:
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
1,5 0,03
wt.% wt.%
CH3
H CH3 COOH
Abietic Acid
CH2
SO3 Na 2 Na + SO3 Na
Pd
CH3
CH3
CH3
+
H CH3 COOH H CH3 COOH
+
H CH3 COOH
Dehydroabietic Acid
Dihydroabietic Acid
Tetrahydroabietic Acid
CH3 CH
CH
CH2 CH2
Na-Formaldehydesulfoxylate Na-Hydroxymethanesulfinate H O S H Ethylenedinitrilotetraacetic Acid (EDTA) O O CH2 N HO O CH2 CH2 CH2 N CH2 O OH CH2 OH O Na
+
Reducing agent
HO
Growth Reaction:
R-O-Mon* + n Monomer P*
Transfer Reaction:
P* + R-H R - H + P*
Termination Reaction:
P* + P* P- P
80 60 40 20 0
140 105 70 35 0
0,2
0,4
Tert-dodecylmercaptane [phm]
Tert-dodecylmercaptane [phm]
Copolymerization Parameters (Styrene = M1; Butadiene = M2) r1 = 0,7 r2 = 1,4 As a Consequence of these copolymerization parameters there is no azeotropic composition
80
Monomer Feed Styrene/Butadiene: 30/70 Polymerization Temperature: + 50C Hot Polymerisation - 20C (Cold Polymerisation)
20
0 0 20 40 60 80 100
Probability [%]
r1 = r2 =
9 10 11 12
E-SBR: Microstructure
BR-Microstructure 1,4-cis 1,4-trans Vinyl [%] [%] [%] 0,8 7,7 14,8 27,6 79,6 71,5 62,0 51,4 19,6 20,8 23,2 21,0
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
Tg [C]
Fox-Flory-Equation
1 w w2 = 1 + Tg2 Tg Tg1
Tg of copolymers in K Tg of homopolymer 1 in K Tg of homopolymer 2 in K weight fraction of copolymers 1 und 2
20
40
60
80
100
Influence of None Polymeric Residues on Compound and Vulcanizate Properties: Analytical Data
Product Mw [g/mol] Mw/Mn ML 1+4 (100C) [ME] 45 51 52 54 Al [ppm] 655 1 Tg [C] -51 -53 -50 -50 chloride [ppm] 0,110 0,079 0,230 0,045
Krylene 1500 mod. Krylene 1500* Krylene 1712 mod. Krynol 1712* Product
424.280 429.210 740.170 716.760 Ash cont. (850C) [wt.%] 0,33 0,23 0,41 0,20
==>
27,27 wt.% oil
Krylene 1500 mod.* Krylene 1500 Krynol 1712 mod.* Krynol 1712
* Modification of latex finishing (coagulation and crumb wash) in order to obtain a rubber with a reduced content of residues with low molar mass
Influence of None Polymeric Residues on Compound and Vulcanizate Properties: Compound Composition
Krylene 1712 Krylene 1500 mod. Krylene 1712* mod. Krylene 1500* Carbon black N 339 Carbon black N 234 Mineral oil TMQ IPPD DTBD Stearic acid Zinc oxide Sulfur CBS DPG [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] [phr] 103,13 25,0 80,0 10,0 0,5 0,75 0,75 2,5 2,5 1,9 1,1 0,55 103,13 25,0 80,0 10,0 0,5 0,75 0,75 2,5 2,5 1,9 1,1 0,55 68,75 50 80 20,0 0,5 0,75 0,75 2,0 2,5 1,9 1,2 0,3 68,75 50 80 20,0 0,5 0,75 0,75 2,0 2,5 1,9 1,2 0,3
* Modification of latex finishing (coagulation and crumb wash) in order to obtain a rubber with a reduced content of residues with low molar mass
Compound-Mooney ML1+4 (100C) [MU] Rheometer (160 C) L F ts1 t50 t90 Vulcanizate Properties: Tensile Strength Elongation at break M100 M300 Shore A Hardness/23C Shore A Hardness/70C Rebound/23 C Rebound/70 C [dNm] [dNm] [min] [min] [min] [MPa] [%] [MPa] [MPa] [%] [%]
Manufacturing
CR-Microstructure Monomer Manufacturing Processes Basic Features of Polymerization Recipes
Rubber Grades
Standard Grades Sulfur Grades Precrosslinked Grades
CR-Vulcanization
Mechanism
Substitution of CR
Sources:
- W. Obrecht, Houben Weyl-Mller Makromolekulare Stoffe (1987), volume E20/Teil 2, S. 842-859 - P. R. Johnson, Rubber Chem. Technol. 49 (1976) 650-702
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
Capacity Site
100 75 45 32 28 25 25 20 10 Omi/Japan Dormagen/Germany Pontchartrin/USA Nanyo/Japan Chongquing/China Datong/China India Kawasaki/Japan Yerewan/Armenia
Butadiene Acetylene
X X X X X X X X X
Total
360
Plant Closures
Stagnant CR-Consumption in WE and USA Growing Consumption in South-East Asia
Producer
DuPont Bayer
Capacity Site
30 50 25 25 Maydown/N.-Ireland Louisville/USA Houston/USA Grenoble/France
Polimeri (BP)
CH2 CH CH CH2+ CH2 CH CH CH2 (ca. 40 %) HC CH CH2 Side products: chlorinated C8-Compounds Tetrachlorobutane CuCl Cl Cl H2C CH CH CH2 - HCl
HCl/CuCl (30-60 C)
+ NaOH/85 C
- HCl
Cl H2C C
Cl C CH2
Cl HC CH CH CH2
2-Chloroprene
DE 1149001; Knapsack AG, Prior.:10.07.1961 Erf.: W. Vogt, K. Kaiser, H. Weiden
1-Chloroprene (impurity)
GB 804254; Distillers Co. Ltd. , Prior.:21.03.1956; Erf.: F. J. Bellringer
50 45 40 35 30 25 20 15 10 0
0 1 2 3 4 5 6 7
Latex Grades
Rubber Grades
(Standard Grades, precrosslinked grades and sulfur grades)
Application Areas of Rubber Grades Profiles 11% Belts 12% Cables 21% Hoses 44%
Adhesive Grades
1,2
Cl CH2 C
2 3
3,4
H CH2 C
3
C CH2
C CH2
Cl
1,4-trans-Content [Mol %]
95
90
Adhesive grades
85 0
10
50 60 70 20 40 30 Polymerization Temperature [ C]
80
For commercially available CR-grades small differences in the polymerization temperature and in the 1,4-trans content are an important factor
Adhesive grade
100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 5 - 20 60 - 85
Latex grade
100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 20-50 60 - 85
Standard grades
90-100 0 - 10 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 30-50 60 - 85
Sulfur grades
90-100 0 - 10 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 0,3-0,7 30-50 60 - 85
Precrosslinked grades
100 100-200 2,5-5,0 0,5-1,0 0,3-0,7 0,05-0,5 0,2-1,0 0,0125 0,1-0,3 30-50 70 - 85
CH3
+
CH3
+
CH3
CH2
H CH3 COOH
Dehydroabietic Acid
H CH3 COOH
Dihydroabietic Acid
H CH3 COOH
Tetrahydroabietic Acid
Mercury dilatometry for the determination of crystallization rate (Tc =-5C pretreatment: 30 min at 80C)
0 10
Volume [mm3]
20 30 40 50 60 70 80
0,1 1 10 100 1000
0,1
10
Polymerization temperature [ C]
Dependence of Tg and Crystallization Rate at -10C on Monomer Feed and Polymerization Temperature
Sym- T bol [C] 45 35 25 15 5
- 31 - 33 - 34
103 45
Polymerizationtemperature [C]
102
35
25
15
t 1/2 [h]
0 6 9
Tg [C]
- 35 - 36
101
100
- 37 - 38 3 12 15
10-1 0 3 6 9 12 15
B. 110 VSC
s
400
CR-bases vu
t1/2 [h]
300
U nv ul ca ni ze d
200
Un
d ize n a lc vu
CR
nd ou p m -c o
B. 110 100 B. 210 0 100 200 300 400 500 KA 8418 B. 112
CR Carbon black (N 762) Polyetherthioether Vulkanox DDA Vulkanox 4010 NA Stearic acid Magnesium oxide Zinc oxide
600
700
800
Dependence of Crystallization Rate on Blending Ratio of Two CR-Grades and on Type of Plasticizer
25 20 15
Influence of Plasticizers
(CR-grade: Neoprene W (~ Baypre 210) 300 250 200
Neoprene W + mineral oil
t1/2 [h]
t1/2 [h]
150
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
Temperature [C]
Bayer-Brouchure: Chloropren-Kautschuk von Bayer: Der vielseitig einsetzbare Werkstoff
Standard CR-Grade
S S
S S S
Sulfur Grade
Sulfur S S S
CH3 O
O O CH2 O
n
CH3 CH2
Precrosslinked CR-Grade
Dimethacrylate
CH2
Molar mass control by Xanthogendisulfides results in the formation of polymer molecules with two identical (xanthate) end groups. Xanthate end groups participate in vulcanization. As a consequence, vulcanizates based on xanthate modified CR exhibit better mechanical properties than mercaptane modified CR
16 Vulcanization: 40 min/150C
22
15 14
21
M300 [MPa]
13 12 11 10
20
19
18 10 11 12 13 14 15
ML 1+4 (100C)
250
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
u
Cl
v w
Cl
Production:
CR-Sulfur Grades are obtained by two consecutive production steps (1. Polymerization and 2. Chemical break down of high molar masses) In the 1st production step chloroprene and sulfur are copolymerized. The copolymers obtained have a high molar mass and long sulfur bridges. In the 2nd production step, the molar mass of the copolymers is reduced by a break down of sulfur bridges (peptization). As a consequence of the chemical breakt down of the sulfur bridges dithiocarbamate end groups are incorporated. These end group participate in vulcanization.. As a consequence, the number of dangling chain ends is reduced and vulcanizate properties are improved.
Critical Aspects:
During storage, the Mooney viscosity of sulfur modified CR can increase or decrease. Heat resistance of vulcanizates based on sulfur modified CR is inerior to that of standard CR.
S8
2)
Chemical break down of high molar masses by the use of disulfides, particularly Thiuramdisulfides
Cl Sa ( CH2 CH CH2 )n S Sw ( CH2 v S NR2 S S S NR2 Cl CH CH2)x
Cl Sa ( CH2 CH CH2)n S v S
S NR2 NR2
S S Sw ( CH2 CH CH2) x
48 46 44 42 40 38 36 34 32 30 0 2 4 6
Baypren 510
80
Baypren 610
Incorporated Sulfur
10
Sulfur [phm]
Compound Ingredients:
CR Ru (N 762) Polyetherthioether Vulkanox DDA Vulkanox 4010 NA Stearic acid Magnesium oxide Zinc oxide 100 75 10 2,0 0,5 0,5 4,0 5,0 phr phr phr phr phr phr phr phr
CR-Sulfur grades (which are fully commercially available) contain dithiocarbamate end groups which are attached via sulfur bridges. These end groups are active in vulcaniaztion. CR-Sulfur grades can be considered as "rubber bound intermediates which are known from theoretical considerations on the mechanism of sulfur cure. As a consequence, CR sulfur grades are vulcanized by the use of ZnO and MgO (+ Stearinsure) without using accelerators. CR sulfur grades exhibit a critical stability of Mooney viscosities during storage particularly at elevated temperatures.
H C N S S S Sx S N SH S N
Precrosslinked CR-Grades
Production:
Precrosslinked CR-rades are blends of gelled CR and ungelled (soluble) CR. The two blend components are produced separately by emulsion polymerization. Prior to finishing, the two latices are blended. By the latex blending process a good dispersion of the gelled CR paricles in the soluble CR phase is achieved. CR-Gel
Application:
Unvulcanized CR compounds which contain CR gel exhibit good processing features, particularly a low die swell. Major application areas are extruded articles (wiper blades as well as window and door seals In these applications CR is being substituted by EPDM and TPEs.
Die swell Rubber Compound = de do x 100
Ungelled (soluble) CR
d0
de
CH2
CH
CH2 S
+
Vulcanization of CR
Cl
+ NH
NH NH NH
CH2 CH2
CH2
NH
NH
+ ZnO - ZnCl +
O NH
CH2 S
CH2CH2 S S N CH3
NH
CH2 CH2 CH2 CH CH2 S NH NH CH2 CH CH2 S CH2 CH2 CH CH2 CH2 CH2
CH2CH2
NR2
+ ZnCl +
- ZnCl2
CH2 CH
Substitution of CR
250
FKM
MVQ
225 200 FZ 175 150 125 100 EU 75 50 0 20 40 60 80 100 120 140 no requirements AU FMVQ
Resistance to high temperatures 80 % VAc
ACM
HNBR
NBR
EVM
(H)IIR
EPDM
CR
SBR
BR
NR
Polymerisation
NBR: Microstructure
C C N N
HC HC
3
CH 1 2
4
CH2
+
CH2 CH CH CH2
CH CH
2
C H2
CH2
1
CH 2 CH 2 1
1,4-cis
1,4-trans
Vinyl
Acrylonitrile
Microstructure of Butadiene Sequences 1,4-cis 1,4-trans Vinyl [%] [%] [%] 0,8 7,7 14,8 27,6 79,6 71,5 62,0 51,4 19,6 20,8 23,2 21,0
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
Standard grades
Special grades
X-NBR Precrosslinked NBR NBR/PVC-Blends NBR-powder grades liquid NBR -HO-terminated -COO-terminated -NH2-terminated NBR mit bound antioxydant
Positive:
Low degree of swelling in oil, fuels, greases and fats High kevel of mechanical properties High abrasion resistance especiall for carboxalated grades Broad range of grades Low gas permeability Low price level / high competition
Negative:
Maximal service temperature: < 110 C (Criterium: 1000 h / b=0,5*b0) Standard grades are not applicable for outdoor use (contrary to NBR/PVC-Blends)
building 5%
300
NR
SBR CR NBR
0 14 21 7 time in ASTM-L3 [days]
Consumption [j/y]
19 85
19 90
19 95
20 00
20 05
20 10
Lanxess
JSR Polimeri Paratec Korean Kumho Lucky Gold President Eliokem Nitriflex PASA S&C Sibur
Negromex/Uniroyal
Hyundai Kaoshing / Taiwan Sandouville / FR Goodyear Valia /Gujarat - Indien Goodyear Duque de Caxais / BRA Santa Fe Bareilly Omsk
45 20 35 28 15 15 100 35 25 30 35 30 25 20 16 15 11 25 10 5 2 424
Nipol Nipol Hycar Chemigum Breon (Nysin) Perbunan / Krynac Perbunan Perbunan / Krynac Perbunan JSR NBR Europrene Paratec Kumho NBR Chemigum (Powder) Chemigum (bales) Nitriflex/Nitriclean
Total:
NBR-Standard Grades
50
45 40 35 30 25 20 15 20 30 40 50 60 70 80 90 100 125
Tg [C]
s de a gr l a ci
40
50
60
70
80 90
100
vvvvvWeight Change[%]
70 60 50 40 30 20 10 0 -10 0 5
Fuel C (Isooctan/Toluene: 50/50) Fuel B (Isooctan/Toluene: 70/30) ASTM l Nr. 3 (aromatic/naphthenic) ASTM l Nr. 1 (paraffinic)
10 15 20 25 30 35 40 45 50
50 40 75C
Rebound [%]
20C
40 30 20 10 0 0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile-content [wt.%]
Source: Rubber, 3 Synthetic Ullmann s Encyclopedia of Technical Chemistry, Vol A 23 (1993)
Growth reaction:
R-O-Mon* + n Monomer P*
Transfer Reaction:
P* + R-H R - H + P*
Deactivation:
P* + P* P- P
CH3
CH3
CH3
CH3
Pd
H CH3 COOH H CH3 COOH
+
H CH3 COOH
+
H CH3 COOH
Abietic Acid
CH2
CH2 CH2
CH2 OH
H Ethylenedinitrilotetraacetic acid (EDTA) O O HO HO O Ion-(II) sulfate Fe SO4 CH2 N CH2 CH2 CH2 N CH2 O OH CH2 OH
CH2 CH2 OH
Triethanolamine
r1 = r2 =
40 50 60 70 80 90 100
100 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100
Incremental composition
Integral composition
Monomer Feed: Acrylonitrile: 73,7 wt.% Butadiene: 26,3 Gew.% Copolymerizatin parameters: r1 = 0,023; r2 = 0,30
For the production of a NBR-grade with a high chemical homogenity one or both of the two monomers (ACN respectively butadiene) have to be incrementally added during the course of the polymerization in order to compensate for changes in the composition of the monomer feed, unless polymerization is performed in the azeotropic monomer composition
[C]
5 5 5 50 50 50 50 50 50 50
[C]
[C]
-19 -22 -33 -13 -26 -32 -33 -40 -53 -31
Batchwise NBR-Polymerization may result in chemically inhomogenous blends which exhibit two separate Tg-peaks
Source:
V. R. Landi (Uniroyal) Presented at a meeting of the Divison of Rubber Chemistry of the American Chemical Society, Cleveland, Ohio, October 12-15 (1971) Rubber Chemistry and Technology
120 100 TDM / Lanxess 80 60 40 20 0 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 TDM / Phillips Chevron
- H+ + "Triisobutene (TIB)"
Patent No.
Jp 07 316 126 Jp 07 316 127 Jp 07 316 128 DE 102007024009
Company
Zeon Zeon Zeon Lanxess
Priority
27.12.1994 27.12.1994 27.12.1994 22.05.2007
Patent Title
Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol TDM-Mischung: Herstellung und Anwendung
Company
Zeon Zeon Zeon
Priority
30.03.1993 (Jp) 29.08.1994 (Jp) 29.08.1994 (Jp)
Patent Title
Unsatuarated Nitrile/Conjugated Diene copolymer, process for Producing the same, and Rubber Composition
Influence of Ions on Speed of Cure: accelerating: Na-, K- Ions retarding: Mg-, Ca- Ions
Patent No.
DE 102007024011 DE 102007014010 DE 102007024010
Company
Lanxess Lanxess Lanxess
Priority
22.05.2007 22.05.2007 22.05.2007
Patent Title
Nitrile Rubber with Specific Ion Number Nitrile Rubber with Specific Ion Number Nitrile Rubber with Specific Ion Number
70
Ion-Number (IN)
10 9 8
M300 [MPa]
Ion-Number (IN)
O (R*)
NBR
O
C C
+ 2 R-H
X-linking efficiency =
H O
H O
H O S
H O
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
CH2
+ ZnO - H2O
Vulcanization with metal oxides is used for X-NBR and CSM. The following metal oxides are used: CaO, MgO, ZnO and ZnO2 For scorch safety ZnO2 is superior over ZnO Usually, vulcanization with metal oxides is combined with sulfur cure Dual vulcanization results in a hybride-network-structure In a hybride network chemical as well as physical networks are present.
Sources: Eisenberg, A. Macromolecules, Vol 3, 2 (1974) 147 Clustering of Ions in Organic Polymers - A Theoretical Approach
Ibarra, L., Alzorriz, M. Polym. Int. 48: 580-586 (1999) Naskar, N., Debnath, S. C., Basu, D. K.; J. Appl. Pol. Sc., Vol 80, 1725-1736 (2001) Brown, H. P. Rubber Chemistry and Technol, 30 (1957) 1347 Crosslinking Reactions of Carboxylated Elastomers
elongation [%]
CS [%]
Precrosslinked NBR
Properties: Properties:
Reduction Reductionof ofdie dieswell swell Increased dimension Increased dimensionstability stabilityafter afterextrusion extrusion Improvement of surface quality of extruded/calendered Improvement of surface quality of extruded/calenderedarticles articles Increase of Moduli Increase of Moduli Improvement Improvementof ofCS CS Reduction Reductionof ofTS TS Reduction Reductionof ofelongation elongationat atbreak break
Precrosslinked NBR
Precrosslinked NBR-grades provide for high dimensional stability after extrusion which is only matched by standard NBR-grades with considerably increased Mooney viscosities
Krynac VP KA 8769 Krynac 34.50 Lanxess Henkel KGaA Lanxess Degussa Lanxess Kali Chemie Lanxess Lanxess
phr phr phr phr phr phr phr phr phr phr phr
Zincmethylmercaptobenzimidazol Lanxess
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)
Reaction Medium
solvent solvent solvent solvent solvent solvent solvent solvent solvent solvent
Catalyst/Process
Z/N* Z/N* Z/N* Z/N* anionic anionic Z/N* polymer modif. polymer modif. cationic * Z/N = Ziegler-Natta Catalysis Solution-BR
High-cis1,4-BR
Solution Rubbers
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
oil Antioxydant Expander screw US 2,592,814 (Du Pont) Prior.: 20.12.1947 Inventor: J. L. Ludlow
Waste water
US 5266211 Bunawerke Huels GmbH Prior.: 13.06.19990 Inventor: W. Breuker, H. Wagner, E. Moeller, B. Schleimer
Source:
US 2003007709 (Bayer AG) Prior.: 05.07.2001 Inv.: N. Schweigler H. Goebel, T.-O. Neuner
In order to obtain rubber crumbs a cutting device is often attached at the end of a dewatering screw
Source:
US 3672641 (French Oil Mill Machinery) Prior.: 14.09.1970 Inv.: R. K. Slaby
BR: Overview
Property Profile and Areas of Application Microstructure, Glass Transition Temperature and Crystallization Producers and Production Capacities Market- und Market Development
Performance Requirements for Tyres and Impact Modification Comparison of Production Technologies for High-cis-BR Summary
Negative:
Poor resistance to heat and ageing High degreee of swelling in fuels, oils and greases high gas permeability Spontaneous crystallization
Application Areas
Technical Rubber Products 5% Rubber Toughening 23% Tyres 71%
CH2
4
CH2 CH
1 3 3
CH2
2
CH2
CH CH
4
CH
4
CH CH
3
CH2
1,4-cis
1,4-trans
Catalyst Tg
Li* -93
Co -106
Ni -107
Ti -103
Nd -109
E-BR** -80
* aliphatic, cycloaliphatic aromatic solvents without polar additives ** Polymer Handbook/Polymerisation temperature: 25C
*** E. Thorn-Csanyi, H.-D. Luginsland, Rubber Chem. Technol. (1977) 222-230
0,1 -100
-80
-60
-40
-20
Temperature [C]
200
Nd Ni Co Ti
-5
Nd Ni Co Ti
150
-10
100
-15
50
-20
1,4-cis-content [%]
1,4-cis-content [%]
Capacity [kt]
Li Ni Ti Co Nd Li/Co/Nd Ni/Nd
Capacity [kt]
Golf balls 1%
Li-BR 48%
Ti-BR 18%
Co-BR 22%
Co-BR 52%
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
Stress [MPa]
Li-BR
Ti-BR
Co-BR
Nd-BR
Strain [%]
Source: Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Improvement
1000
10000
Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Nd [MPa] [%] [MPa] [%] [mm3] 15,3 400 9,4 65 49 23 85 33 [ C] [mm/kc] [cycles] 27 1,9 460
Co
Ti
Butadiene Rubber for the rubber industry Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Improvement
Ti
Ni
Co
Nd
Source: D. J. Wilson Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes Makromol. Chem., Macromol. Symp. 66, 273-288 (1993)
Improvement
Abrasion [mm3]
40 35 30 25 20 0
Source:
15
D. J. Wilson Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes Makromol. Chem., Macromol. Symp. 66, 273-288 (1993)
Soft Phase
BR BR EPDM EPM NBR
Hard Phase
SAN PS SAN PP PP
Examples
ABS HIPS AES EPM/PP NBR/PP
The impact resistance of hard and brittle thermoplastic and duroplastic polymers is improved by rubber particles Prerequisites for an efficient impact modification are: 1) good dispersion of the rubber phase in the matrix 2) good mechanical bonding across the phase boundaries 3) x-linking of the rubber phase
Source:
C. Schade, H.-J Renner, W. Heckmann (BASF) Predictive property Adjustment Kunststoffe international 7/2010, 36-39
80
52
47
37
33 25
ho he
-40
-20
20
Temperature [ C]
Source:
H. Schwager (BASF); Kunststoffe 82, 499 (1992) T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 New Polymers from New Catalysts
Viscosity [mPa*s]
60 40 20 0 0 10
Star shaped BR
20
30
40
50
60
70
80
The performance profiles for HIPS/ABS und for tyres differ significantly
Co
Ni
Ti
Benzene Toluene 120 <95 low
Nd
Hexane Aliphatics 100-120 <100 Very low fully adiabatic 18-22 no low 100-200
Benzene, Benzene Toluene Toluene (Aliphatics) Hexane 150 120 [min] [%] 55-80 high partially adiabatic 14-22 yes high [ppm] 10-50 <85 high
partially partially adiabatic adiabatic 15-16 11-12 yes high 50-100 no Very high 200-250
Positive feature
Summary
From the different BR grades, Nd-BR is advantageous from two points of view: Tyre applications (particularly tyre treads) Production technology For the impact modification of thermoplatics (HIPS and ABS) Li-BR and Co-BR are superior for Nd-BR a highly branched grade with a low solution viscosity is required
Green Tyre Technology Recent Developments in S-SBR Technology Towards Improving Tyre Performance
Functionalisation of S-SBR
Plant Location
Western Europe
EniChem Bayer Michelin Repsol Qimica Fina Polymers Dow Ravenna Grangemouth Lillebonne Bassens Santander Antwerp Schkopau Louisville, Ky Lake Charles Orange Orange Beaumont, Tx Cabo Salamanca Altamira Oita Tokuyama Yokkaichi Yeochon Kaohsiung Newcastle
Americas
ASR Bridgestone/Firestone Bayer Goodyear Petroflex Negromex incl. TPEs incl. TPEs
Japan
Asahi Japan Elastomer Nippon Zeon JSR incl. TPEs incl. E-SBR incl. Hydrogenated polymers incl. TPEs
Others
Korean Kumho Taiwan Synthetic Dow (Carbochem)
Total Capacity
* Source: IISRP Worldwide Rubber Statistics 2001
2.274.500
Until today, the technologies have merged and there are only small differencies in the technologies of the leading companies
Basic Patents:
Firestone: Phillips: Bridgestone:
US 3317918, CA 966949, US 3205211, FR 1546396, FR 1539429, FR 1539427, BE 718549, US 3681304, OS 2134656, US 3558575, US 3726844, US 3726844, US 3787377 US 3458490, US 3438952, US 3502746 JP 75-015271
CH2 R
Li
CH2
+
Li
Under ideal polymerization conditions, there is neither chain transfer nor termination reactions and the active species are truly living. All polymer chains are initiated at the start of the polymerization and all chains grow up to total monomer consumption. The resulting polymer molecules have a narrow molar mass distribution and a high chemical homogeinity
nInitiator * f
DP: degree of po0lymerization number average of molar mass Mn: X: monomer conversion nMonomer : amount of monomer [moles] MWMonomer: molar mass of monomer amount of initiator [moles] nInitiator : f: functionality of initiator u, v, w: amounts of initiator
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)
Basis of calculation: 65 DM/kg BuLi (4 DM/mol BuLi; MwBuLi: 61 g/mol) Ideally Living Polymerization
1,4-insertion:
P
Li + Li + P
Li Na K Cs
1,2-insertion:
P
Li X X X X
+
Li X X
Solvent
R. Casper in Ullmanns Encyclopedia of Technical Chemistry G. Sylvester u. P. Mller in Houben Weyl, Methoden der organischen Chemie, Band E 20/Teil2, Makromolekulare Stoffe, S. 801
Dependence of the Vinyl-Content on Polymerization Temperature and Modifier (Type and Concentration)
90 80 DME 30C DME 50C DME 70C THF 30C THF 50C THF 70C Modifier: DME: Dimethoxyethane THF: Tetrahydrofuran
Vinyl-Content [mol%]
70 60 50 40 30 20 10 0 0,1
1,0
10
100
Tg [ C]
-50 -60 -70 -80 -90 -100 0 10 20 30 40 50 60 70 80 90 100 Standard-Li-BR (without modifiers)
Vinyl-Content [%]
S. L. Aggarwal, T. G. Hargis, R. A. Livigni, H. J. Fabris, L. F. Marker, Advances in Elastomers & Rubber Elasticity, J. Lal a. J. E. Mark, Eds., Plenum Press, New York, 1986, p. 17
Wet Skid Performance (Laboratory) Portable Test Device* 84 Retreaded Tyre Concrete Asphalt Abrasion Resistance
109
104
120
100
70 70 140
95 90 100
92 92 80
93 93
CH2 Li
CH
Li
R
n
CH2 Li
R
n
CH
Li
4 (SnCl4 as alternative)
Si
+ 4 Li Cl
exclusive se is for tyres; during compound preparation the Sn-C bonds seems to break and the bound rubber content is increased. As a consequence hysteresis of vulcanizates is reduced. Many patents in this area, for example: US 6271317 (Goodyear) Prior.: 19.01.1998, Inv.: A. F. Halasa, S. Futamura, W. L. Hsu, B. A. Matrana Asymmetrical Tin-Coupled Rubbery Polymers and Method of Making (Star shaped rubbers with at least 3 brances; 1 branch with MW <40.000 g/mol and 1 branch with MW>80.000 g/mol)
Improvement
Mooneymeasurement
Viscosity
Improvement
Narrow molar mass distribution Highly branched (Star shaped) 100 101 102 103 Broad molar mass distribution 104 105 106
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, Ru (IRB Nr. 2): 50 phr, Zink oxide: 3 phr, Mineral oil : 10 phr, Stearic acid: 2 phr, Sulfur: 1,75 phr, Accelerator: 0,8 phr; Vulcanization: 135 C/35 min
S-SBR: Solution-SBR
Consumption [t]
90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100
Parameters of copolymerization (styrene = M1; butadiene = M2) Radical copolymerization (emulsion) r1 = 0,7 r2 = 1,4 Anionic colymerisation in hexane (Bu-Li/no randomizers/50C) r1 = 0,04 r2 = 11,8
For tyre applications block styrene blocks have to be avoided as they cause high hysteresis losses.
Styrene/Butadiene-Copolymerisation
Differential styrene content in the polymer [wt. %]
100 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100
E-SBR
ond rs Ra ize m
S-SBR in Hexane
T [C]
Benzene Cyclohexane Hexane THF Diethylether Triethylamine Anisol Diphenylether THF THF THF 25 25 25 25 25 25 25 25 -78 0 25
r1
0,04 0,04 0,03 4,0 0,4 0,5 0,3 0,1 11,0 5,3 4,0
r2
10,8 15,5 12,5 0,3 1,7 3,5 3,4 2,8 0,04 0,2 0,3
70
60
50
40
30
20
10
0 0 20 40 60 80 100
Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization, Principles and Practical Applications, Marcel Dekker, Inc. Y. Melenevskaya, V. Zgonnik, V. Denisov, E. Dolinskaya, K. Kalnish; Polym. Sci. (USSR), 21, 2215 (1979)
+10 C + 0 C - 10 C
30 20 10 0
- 20 C - 30 C - 40 C
- 70 C
- 60 C
- 50 C
10
20
30
40
50
60
Vinyl [%]
In the variation of the microstructure (vinyl-content) the S-SBR technology has a greater versatility than the E-SBR-technology.
Source: H. Mouri, J. E. Hall, (Firestone) 146th ACS meetin in Pittsburgh, PA., USA
Tg [C]
In order to comply with many conflicting tyre tread properties the preparation of rubber blends is essential in rubber technology. An alternative to macroscopic blending would be microscopic blending as with integral rubber.
SBR 1700
tan
10-2 10-3
Integralrubber
20
40
60
80
100
Temperature [ C]
Integral Rubber is a multi block copolymer the building blocks of which have well defined Tgs
Source: K. H. Nordsiek, K. M. Kiepert, Kautschuk Gummi Kunststoffe 38 (1985), p. 178-185
Segment: Tg [C]
Vinyl-BR -90C
S-SBR -20C
3,4-IR ~ 0C
Segment: Tg [C]
Medium-cis BR -90C
Vinyl-BR -50C
S-SBR -20C
3,4-IR ~ 0C
Vulcanization
t10 t90 t90 - t10
Mechanical Properties
Moduli Tensile Strength Tear resistance Abrasion resistance Heat build up Rolling resistance Wet grip
Price
* fully depreciated plants
150
Carbon black loaded tread Green tyre
100 50 0
E-SBR Ru ++ ++
Abrasion Resistance
Wet Skid
Functionalisation of SS-SBR Partial or total substitution of activator Improvement of silica dispersion Iprovement of silica reinforcement Reduction of hysteresis loss Improvement of wet skid Reduction of abrasion loss
N C
91
Li
Si OR CH2 OR
R2
Li
OR Si OR N C CH2 OR R1 R2
80
EP 1113024 A1; Prior.: 02.12.1999, Bridgestone, Inv.: K. Morita, H. Kondo "Polymer process for making the polymer and rubber composition using the polymer
CH2
Li
Cl
+
Cl
- 2 Li
Cl
O R
n n nR
DE 10057508; Bayer AG, Prior.: 21.11.2000; Erf.: T. Scholl, W. Obrecht, Braubach, E. Giebeler, Grn, A. Mller, M. Graf Polyether/Diolefin-Kautschuke enthaltende Kautschukmischung
Incorporation of Aminoisoprene
CH3 N CH2 CH2 C CH CH2 CH3
Dimethyl-Aminoisoprene
is incorporated initially at the chain end it acts as a randomizer during the whole course of the polymerization the aminoisoprene containing rubber exhibits increased interaction with silica
EP 01165641; Bayer AG, Prior.: 03.02.1999; Erf.: T. Scholl, W. Obrecht, R. Stadler, R. Morschhuser, G. Mannebach "Kautschukmischungen basierend auf Aminoisopren"
+ H3C H3C
Si
Source: EP 0778 311; Michelin, Prior.: 07.11.1995; Erf.: J.-L. Cabioch Composition de caoutchouc base de silice et de polymre dinique fonctionnalis ayant une fonction silanol terminale
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
nBu-Li Co(II)Octanoate / DEAC / H20 1 / 7 0-80 / 20-30 Ni(II)Naphthenate /Bu2O.HF/TIBA 1 / 100 / 40 TiJ3(OEt) / TiCl4 / TEA 1 / 0,7 / 5 Nd(III)Versatate / DIBAH / EASC 1 / 10-15 / 3
Abbreviations:
nBu-Li DEAC TIBA TEA DIBAH EASC n-Butyl-Lithium Diethyl Aluminum Chloride Triisobutyl Aluminum Triethyl Aluminum Diisobutyl Aluminum Chloride Ethylaluminum Sesquichloride
cis-1,4-Content [%]
98 97 96 95 94 93 92 0 1 2 3 4
For the achievement of high 1,4-cis contents the presence of a halide source is essential
Source: Shiro Kobayashi; Transition in Precision Polymerization (1997) Part 1. H. Watanabe, T. Masuda, Diene Polymerization, pages 55-66
Nd(CH2Ph)Cl2 + TIBA
Co(Oct)2 + AlR2Cl + H2O Co(Oct)2 + AlR2Cl + H2O + PPh3 Co(Oct)2 + AlR3 + CS2 Ni(Oct)2 + BF3 - OEt2 + AlR3 Ni(Oct)2 + BF3 - OEt2 + AlR3 + PPh3
The coordination of electron donors to vacant catalyst sites results in a significant reduction of 1,4-cis contents. As a consequence, syndiotactic BR or trans-1,4 BR are obtained.
Tm [ C]
40 +0 - 40 60 70 80 90
Goodyear
100
M
8
M
15
C C
`
29
C
22
Bd
M
36
M
43
M
54
Bd
60
M
C
For the achievement of high 1,4-cis contents, a vacant coordination site on the transition metal is a prerequisite. To this site butadiene has to be coordinated in a cisoid mode. The formation of trans-1,4-BR is thermodynamically favourable whereas the formation of 1,4-cis-BR ist kinetically controlled.
Source: Porri, Giarrusso, J. Polymer Science, Vol. 4, 93
U m satz [% ]
60 50 40 30 20 10 0 La Ce Pr Nd Pm Sm Eu Gd Tb Dy
Ho
Er
Tm
Yb
Source: Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian J. Pol. Sci., Chem. Ed. 18 (1980)3345-3357
Contrary to other ZieglerCatalysts, aromatic solvents have a negative impact on Nd-based catalyst systems
Source: F. Cabassi,G. Ricci, L. Porri; Transition Metal Catal. Polym. (Proc. Int. Symp. 1988, 2nd vol. 655-670) Neodymium Catalysts For 1,3-Diene Polymerization. Some Observations On their Activity And Steoreospecificity
Lu
Al
Cl Cl Al Al Et Et Cl Et
NdV 1
DIBAH 10 - 15
EASC 3
Literature: http://dx.doi.org/10.1007/12_094 Neodymium-Based Ziegler/Natta Catalysts and their Application in Diene Polymerization
1) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner; Adv. Polym. Sci. (2006) 204, 1-154 (Review); 2) Friebe, Lars; Mueller, Julia; Nuyken, Oskar; Obrecht, Werner; Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (2006), 43(6), 841-854. Comparison of the solvents n-hexane, tert-butyl benzene and toluene in the polymerization of 1,3-butadiene with the Ziegler catalyst system neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride. 3) Friebe, Lars; Mueller, Julia M.; Nuyken, Oskar; Obrecht, Werner. Pure and Applied Chemistry (2006), 43(1), 11-22. Molar mass control by diethyl zinc in the polymerization of butadiene initiated by the ternary catalyst system neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride. Journal of Macromolecular Science, Part A: 4) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner. Macromolecular Science, Part A: Pure and Applied Chemistry (2005), A42(7), 839-851. A Comparison of Neodymium Versatate, Neodymium Neopentanolate and Neodymium Bis(2-ethylhexyl)phosphate in Ternary Ziegler Type Catalyst Systems With Regard to their Impact on the Polymerization of 1,3-Butadiene. 5) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2004), 45(1), 758-759. Novel investigations and applications for neodymium based catalysts. 6) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Abstracts of Papers, 227th ACS National Meeting, Anaheim, CA, United States, March 28-April 1, 2004 (2004) Novel investigations and applications for neodymium based catalysts. 7) Friebe, Lars; Windisch, Heike; Nuyken, Oskar; Obrecht, Werner. Journal of Macromolecular Science, Pure and Applied Chemistry (2004), A41(3), 245-256. Polymerization of 1,3-Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/Ethylaluminum Sesquichloride: Impact of the Alkylaluminum Cocatalyst Component. 8) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Materials and Engineering (2003), 288(6), 484-494. In situ preparation of a compatibilized poly(cis-1,4-butadiene)/poly(e -caprolactone) blend. 9) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Chemistry and Physics (2002), 203(8), 1055-1064. Polymerization of 1,3-butadiene initiated by neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride: kinetics and conclusions about the reaction mechanism.
Al O Al
Nd ( OOC - R )3 + 3 H Al
Nd (O-CHR- R )3 + 1
Al O
Nd (O-CH2- R )3 + H Al
CH3 (R-CH2-O)2 Nd CH2 C H CH3
(R-CH2-O)2 Nd
+ R-CH2-O
Al
(R-CH2-O)2 Nd - H
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
4)
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
ClAlR3 Cl R
AlR3
ClAlR3
+ Nd
+ Nd
ClAlR3 Cl
+ Nd
ClAlR3 Cl R
Cl R AlR3 R
AlR3
AlR3
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
Nd L L R Nd L L R
H Al
H Nd L L
+ R
Al
Al
Nd L L
+ R
Al
Addition Sequence:
1. Hexane 2. Butadiene 3. DIBAH 4. Neodymversatate 5. EASC Polymerization temperature: 60C
ln(1-x)
60
time [min]
Time [min]
Sources: Lars Friebe: Diplomarbeit and der TU Mnchen, Dezember 2.000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
6 6 .4
5 5 .1
5 0 .0
4 3 .5
3 5 .6
3 0 .7
2 2 .7
1 2 .2
7 .8
20
30 40 50
60 70 80 90 100
4 .8
30
30
35
35
40
40
45
45
50
50
55
55
60
60
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
e lu t io n t im e / m in
Mn [g . mol-1]
nDIBAH/nNd
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
Polymerization Temperature [ C]
Influence of Butadiene/Nd-ratio
D. J. Wilson, Polymer 1993, 34,16, 3504-3508 900 800
ML 1+4 (100C)
0 0,05 0,1 0,15 0,2 0,25 0,3
50 40 30 20 10 0 0 20 40 60 80 100
Ni
Benzene Hexane Toluene 120 min < 85% high
Ti
Benzene Toluene 120 min < 95% low Partially adiabatic 11-12% none very high 200-250
Nd
N-Hexane Cylcohexane 100-120 min < 100% Very low fully adiabatic 18-22% none low 100-200
Residence time Monomer conversion Gel formation process Max. solids concentation Molar mass regulator Formation of VCH Residual transition metal Content [ppm]
Partially adiabatic Partially /isothermal adiabatic 14-22% 15-16% yes high 10-50 yes high 50-100
Overview
EPM and EPDM, Termonomers, Market, Range of Grades and Property Profiles
EPDM-Production
Chemistry of Polymerization , Producers, Capacities, Brand Names and Production Technologies
Metallocenes
Ovewrview on Metallocene Patents Metallocene Activation Comparison of Catalyst Costs
EPDM
EPM
(15%)
EPDM
(85%)
Ethene/Propene/Diene-Terpolymers
(30% of grades are oil extended)
EPDM-Termonomers
Relative polymerization rates of termonomer double bonds in Vanadium catalysed polymerizations
~ 40 : 1
~ 15 : 1
~5:1
Large reactivity difference of double bonds during polymerization Low impact on the reduction of the polymerization rate Low impact on the reduction of the molar mass during polymerization Sufficiently long scorch time and high crosslinking efficiency during vulcanization Low termonomer costs
70 60 Torque [Nm] 50 40 30 20 10 0 0 1,0 2,0 3,0 4,0 5,0 6,0 time [min]
15%
EPDM-Consumption / kt
13%
9%
500 400 300 200 100 1987 1988 1991 1986 1989 1990 1992 1993 1994 1995 0 Automotive production (world)
50
16%
41%
45
Automotive Thermoplast Modification Building Technikcal Rubber Goods Electro/Electronics Oil Additives
40
55
Range of EP(D)M-Grades
Ethene Content
[wt.%]
50 - 75
1,7 - 3 4-7 ENB-Content: [wt.%] 0 8 - 12 Mooney Viscosity: [MU] 16 - 20 20 - 60 60 - 90 [ML 1+4 (125C)] Oil Content: [phr] 0, 25, 30, 50, 100
Tg [C]
Dependence of the Cristallinity on the Ethene Content and on the Polymerization Temperature of V-Catalysed EPM
30 35-39C 25 20 15 10 5 0 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64
Process Features
Emulsion
E-SBR, CR, NBR, E-BR, ACM,FKM, EVM
Solution
EVM
Dispersion
EVM
Bulk
AEM, EVM, (ENM)
Gas-Phase
BR
(G-BR)
EPM/EPDM
BR, LSBR. IR ECO, CO IIR
EPM/EPDM
Q Q
(G-EPM/EPDM)
AU, Q
Process
Solution
Slurry
Solvent: Catalyst System Catalysts: Cocatalysats: Reactivators: Modifier: Short stos: Antioxidans: Stripping aids: Oil:
Propene/ethene Hydrocarbon mix. Ziegler/Natta CGC/Borane CGC-Catalyst VOCl3, VCl4, V(acac)3,VO(OR)3, TiCl4 EASC, DEAC Borane (MMAO) PDCAE, TCAE, BPCC H2, ZnEt2, (NH3) Stearic acid, water, antioxidants sterically hindered phenols, phosphites water soluble polymers etc. mineral oil fraction with high b. p. -
Hexane
Reactivators:
PDCAE
Cl O
BPCC Cl
O
Cl C2H5
O O C4H9
9
Cl Cl Cl
TCAE O O C 2H 5
Cl Cl Cl Cl
{R2V }
heat
+ R2AlX2
+II
VX2 + R3 Al
[R2V] R2AlX
[RVX] R3Al
[heterogeneous species]
Source: K.J. Cann, J.W. Nicoletti, X. Bai, F.D. Hussein, K.H. Lee, D.P. Zilker, Presentation at FLEXPO `97
total capacity
1076
ENB
Boiling point: Max. exposure limit/MAK: Smell limit: 146C 1 ppm 3-5 ppm
Waste water
Azeotropic destillation Condenser Flash drum Stripper Waste air dewtering screwg
Propene
Hexane Ethene
destillation
Polymerization reactor
destillation
Stripping aid
Waste water
drier
Precoller -32/-35C
Process Features
Propene precooling: Temperature: Pressure: Residence time: Soldis conc.: H2 O: -32C/-35C 20-65C 5-10 bar 6-15 Min. 3 -7 Gew.% < 3 ppm
baling
Drier
drier
Packaging
Hexane
VNB/ENB
Condenser
In the Dow-HT-Process low amounts of CGC- catalyst are required. The catalyst is not washed out and no steam stripping is applied (leave-in-catalyst)
Flashdrum
Evaporator
Evaporator
Ta Antioxidant (AO)
Polymerization reactor
baler
Ageing drum
Scavenger
"Insite-Kat."
packaging
Purification
Purification
Purification
Ethene
Propene
ENB
R Zr R
Product V Ti Fe
Dow-CGC <1 1,0 EPDM # 2 8,0 <1 EPDM #3 EPDM #4 EPDM #5 1,9 <1 2,4 <1 5,1 <1 4,8 1,9 1,3 4,3 4,3 2,0 2,8 63
Al Ca Na Sum
1,7 31 31 6,7 9,6 440 <1 1,7 1,7 64 160 64 <1 1,8 1,8 5,7 4,6 9,4 8,0 22,3 48,8 82,8 184,1 584,1
Activation by MAO
(molar excess of MAO: 10.000 - 10.000 fold)
Activation by Borane/Borates:
(with molar B/Zr-ratios)
R
Zr +
EPDM#6
Source: J. G. Pillow (Dow) Ethylene Elastomers made using Constrained Geometry Catalyst Technology Kautschuk Gummi Kunststoffe 51, 12/98, 855-859
EBTHI-Cat.
DOW-Insite-Cat.
Me2Si N
Ti X
X
V-Catalysis
CMe3
Low-Temperature-Compression-Set [%]
100 90 80 70 60 50 40 30 20 10 0
8, 5 10 ,0 0 37 ,5 0 32 ,5 37 ,5 47 ,5 18 8, 5 21 12 35 0 3 5 7 7
Me2Si N CMe3 Ti X X
Patents:
Product EP 1099715 EP 1099473 EP 1086995 EP 1083192 US 6180738 WO 0000333 WO 9965953
ENB
Boiling point: Maximum exposure level: Smell limit 146C 1 ppm 3-5 ppm
Baling of Product etc.
Source: Carbide starts up Seadrift plant with new technology European Chemical News, 1-8 February 1999 ($ 12m charge for replacing the purge unit)
Solution
V-Catalysis
Slurry
V-Catalysis
HT-Solution Gas-Phase
CGC/Dow V-Catalysis
4
10 10 10 5 7
5
10 10 8 10 10
7
10 10 10 3 3
10
10 0 0 10 0
42 46
48 53
36 43
20 30
The Thewell wellestablished establishedvanadium vanadiumbased basedsolution solutionand andslurry slurryprocesses processes are inferior in investment and operation costs, but provide are inferior in investment and operation costs, but providea ahigher higher flexibility. flexibility. The TheHT-solution HT-solutionand andthe thegas-phase gas-phasetechnology technologyare arelow lowcostcosttechnologies, which are superior in the production of specific technologies, which are superior in the production of specificgrades grades
2.923 Documents
USUS-Patents and EPEP- and WOWO-Patent Applications
200
150
100
50
0
hs t Do w BA S Ph F il l i ps T ar Mi go ts ui r Pe tr o l Sh el l UC C M on Mi ts t el ui Ch l em Id em . i ts u DS M al i s Fi na EN Mo I b il Du P Ci b a on t Ge i Al b e gy m Nr . 2 ar l e 2B ay er xo ec Ex re Bo BP n Ho
Activation of Metallocenes
Cl Zr Cl
Alkylation (BuLi, AlR3 or MAO)
R Zr Cl
R Zr R
Activation by MAO
R
Zr + A
R
Zr +
CH2 CH2
R
Zr +
CH2 CH2
R
+ Zr
CH2 CH2
X Zr X
B Zr
X X
Me2C
ZrCl2
Me2Si
ZrCl2
B = Bridge
EP 35242 EP 129368 EP 468537 (29.12.1980) (06.06.1983) (30.01.1987) BASF Exxon Exxon (Turner) (Kaminsky) (Ewen) EP 69951 (09.07.1981) Hoechst (Kaminsky) MAOMAOBorateActivation Activation* Activation HDPE, LLDPE, a-PP HDPE, LLDPE, i-PP, EP(D)M
* H. C. Welborn, Jr.; J. A. Ewen US 5324800 (Exxon) Prior.: 30.08.1991 MAO-Activation of Bridged Metallocenes
N B R B R Zr
R X X
Y B X Zr X B Y
Cl Cl B Zr P Ph Ph Cl SiMe3 Cl
Me P Me2Si Ph
Me Me ZrCl2
WO 96/34021 WO 98/01455 (25.04.1995) (05.07.1996) Lyondell Bayer AG (Ostoja-Starzewski) WO 97/2351 (22.12.1995) Hoechst AG (Herberich)
MAO-/Borate- MAO-/BorateActivation Activation Polyolefins HDPE, PP PE, PP HDPE, LLDPE, PP, EPM, EPDM, COC HDPE, LLDPE, PP, EPM, EPDM
Me2Si N
Ti CMe3
(IV)
X X
Ti RxE X X E= N, O
Ti NR2
III
X X
EP 416 815 (31.08.1998) Dow EP 420436 (13.09.1989) Exxon MAO-/BorateActivation HDPE LLDPE EP(D)M ES
Borate-Activation PO
CH3 CH3
O Ti N P X
Ar
S
X
X
Ti O O
N O O N X Zr X
Polyacetylens
R R N M R R N X R R X
N Cl N N Fe Cl
N O Cl Ti O Cl N
M = Ni, Pd
WO 96/23010 (24. 01. 1996) DuPont (Brookhart) polar/unpolar Copolymers, LDPE DuPont (Brookhart) BP EP 0874005 (24.01.1998) Mitsui HDPE, EPM EP 1881014 (10.05.2006) Mitsui EPM, EPDM
HDPE, (PP)
HDPE(PP)
n :
6 - 20
MW : 2.000-2.500
R
Zr
F F F F F F H Ph F F F
Borane
F F F F _
R
-R -
B
F F
F F
N+
Me Me
B
F F F F
Anilinium Borate
4 _
R
Zr +
Ph
+
Ph
Ph
B
F F
F 4
Triphenylcarbenium Borate
For the Activation of metallocenes molar quantities of borane/borates are required Polymerizations activated by boranes/borates are very susceptible to impurities
Activation of Metallocenes
R
Zr
R. F. Jordan Turner M. Bochmann Turner (1990) (1986)
1987 1987
R
-R -
Ag
BPh4
H Ph Me N+ Me A
+ Ph A
Ph +R
B F5 F5 +R
+R
CH3CN
+R - RH
F5
R
Zr +
Ag+1/2 R2 + BPh4 N Ph Me
F F F F F F F F B F F F F F F F
R Me
Ph Ph
Ph
- F5
A :
F F
- F
EP (Exxon) EP468 468537 537 (Exxon) Prioritt: Prioritt:1987 1987 EP 561 479 (Exxon) Prioritt: EP 561 479 (Exxon) Prioritt:1987 1987 Nicht Nicht oder oderschwach schwachkoordinierende koordinierendeAnionen Anionen "NCA"oder "NCA"oder"WCA" "WCA" (insbesondere: (insbesondere:Tetrakis(Pentafluorophenylborat) Tetrakis(Pentafluorophenylborat) US Prioritt: US5599761 5599761(Exxon) (Exxon) Prioritt:04.02.1987 04.02.1987 Erfinder: H. W. Turner Erfinder: H. W. Turner Ionic IonicMetallocene MetalloceneCatalyst CatalystCompositions Compositions
F5
FF
Activation by boranes (Fina/Ewen) EP 427 697; Prior.: 10. 10. 1989 CGC-Activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993
CGC/Diene-activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993 Activation of metalloenes by Al- Alkyls R >C8 - Al-Oxanes (Montell) 1995
F F F F F F F F F F B F F
F
F F F F F F F F F F F F F F F F F F
B B
F
F - F F F F
F F F
Si
F
F F
FF
B B
F FF F F F F F F
F F F
F F
F F
FF
F F F F
EP 468537 (Exxon) WO 01/08691 (Bayer AG) Prior.: 30.01.1987 Prior.: 18.08.2000 Inv.: Turner, Hlatky Inv.: Becke, Kahlert, Denninger, Windisch, Obrecht EP 561479 (Exxon) WO 01/10124 (Bayer AG) Prior.: 30.01.1987 Prior.: 11.09.2000 Inv.: Turner, Hlatky Inv.: Becke, Denninger, Kahlert, Obrecht, Schmid, Windisch,
EP 1066296 (Bayer AG) Prior.: 24.03.1998 Inv.: Becke, Denninger, Mager, Windisch EP 111927 (Bayer AG) Prior.: 23.06.1999 Inv.: Becke, Mager, Zahalka
Cocat. Reactivator Total Cat-Costs [EUR/100 kg] [EUR/100 kg] [EUR/100 kg]
EASC 3,75 DEAC 1,30 MAO 151,00 Borate 3,45 DCPEE 2,00 TEA 0,65 6,25 3,20 164,00 5,70
MAO-activation MAO-activationof ofmetallocenes metallocenesis isnot noteconomical economicalin inaasolution solutionprocess process Borate-activation results in catalyst costs which are comparable Borate-activation results in catalyst costs which are comparablewith with Vanadium-systems Vanadium-systems For Foran animprovement improvementin inoverall-economy overall-economymetallocene-technology metallocene-technologyhas hasto tobe be combined with process improvements combined with process improvements Increased Increasedcatalyst catalystcosts costsmight mightbe becompensated compensatedby bythe theimproved improvedproperty property profile of new products profile of new products
Contents
Overview
Products, Property Profiles and Areas of Application Market, Market Shares, Producers and Range of Grades
CH3 C
19
39
CH3 C
29
30
H3C CH C 2 23 H3C
45
CH3 C 27 CH 28
CH2
123
15
38
CH3
CH 2 21
16
CH3
CH 2 26
X = Cl: Chloro Butyl Rubber (CIIR) X = Br: Bromo Butyl Rubber (BIIR)
CH3 CH2 C
CH3 n
Basic Features: Isoprene content: 0,5 - 2,5 Mol% Incorporation of Isoprene: random 1,4-trans Tg: ca. -72C Mw/Mn: 3-5
CH2Br
CH3
Butyl- and Halo Butyl Rubber (X)IIR: Property Profile and Areas of Application
Property Profile
Positive:
Tyres Others Chewing gum 4% Pharmaceutical Adhesives Automotive 3% 1% 1%
5%
Low gas permeability high resistance to heat and vapour high resistance to chemicals good insulation properties good covulcanization (XIIR)) product purity (grades without antioxydants)
Negative:
low elasticity /highly damping
Areas of Applications:
86%
Source:
CHEManager 20/2006, Seite 8 (GIT Verlag Darmstadt)
XIIR based Innerliners (passenger tyres) IIR b ased tubes (truck tyres) bladders (IIR) ABC-protection clothes Cable and wiring Pharmaceutical stoppers Adhesives and sealants absorbers for noise and fenders chewing gum
Rebound
60
50
1,4-cis BR 60
1,4-cis-BR NR EPDM
10
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)
Tyres and Tyre Production) Inner liners Truck tyre tubes heating bladders ca. 1,80 /kg ca. 2 /kg ca. 3,5 /kg
Pricing (1996):
Consumption [kt]
500 400
Total Capacity
1.041
AlCl3solution drum
catalyst cocatalyst drum H2O slop isoprene Storage tank for mixed feed Storage units for IIR-slurry in water Reactor Steam- Flashunit Strippingunit
Ethylene (liquid)
Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993 US 2,356,128; US 2,491,752; US 2,491,710; US3,968,076; US 4,474,924; US 4,068,051; US 5,532,312
+ AlCl3OH CH3
CH3 C CH3
AlCl4
CH3
+ CH2 C AlCl4
CH2 C CH3
CH3 H
CH3
+ C + CH3 C AlCl4
CH3
CH3
CH2 C CH3
n
CH3
+ MX n+1 CH3
CH2 C
MX n+1
Propagation: CH3 R
CH3 CH2 C
+
CH2 C
MX n+1
CH3
CH2 C
MX n+1
CH2 C CH3
Cl
MX n
CH3
CH3
MXn (Metal halides) and R-Cl used for the preparation of Isobutylene based blockcopolymers: BCl3 and TiCl4 Cl Cl
Cl
Cl
Cl
-Strahlung
Mn [g/mol] 106
105
Molar Masses:
BF3/H2O 104 3,5 4,0 4,5 5,0 5,5 3 1/T *10 [K-1] 6,0 6,5 7,0
Addition of AO Hexane
Reaction Conditions:
Solvent: IIR-solids Ratio of Halogen/Isoprene: Reaction temperature : Residence time: Stripping-Vapour : Antioxydants / stabilizers: Hexane 20 - 25 wt.%: 1:1 Mol/Mol 40 60 C lh 2 - 2 kg/ kg XIIR Ca-Stearate, Epoxydized Soy bean oil (ESB)
CH3 H X CH2 C
n
+ X
CH3 H CH2 C
n
CH3
+ X
- HX CH3 CH2 C CH3 CH3 CH2 C CH3 CH3 CH2 C CH3 CH3 CH2 C CH3 CH3 X CH2 C
n
Source:
CH3
Patents:
US 2631984; US 3099644; US 4288575; US 4554326; US 4632963; US 4681921; US 4650831; US 4384072; US 4513116; US 5681901
CH2 X CH2 C
n
X-linking efficiency ~ 100 1) 12,5 10,5 1,5 0,4 - 0,7 1,0 1,0 0,5 <<1 1,0 <<1
+ 2 R-H
C C
X-linking efficiency =
CH2 CH2 C
n
CH3 CH2 C
CH2 CH2 C
n
CH3
+ DCP - 2 X*
CH3 CH2 C CH3 CH3 CH2 C CH3 CH2 C
n
X
CH2
CH3
CH2 C
n
CH2
CH2 C CH3
CH2 O
X + ZnO - ZnOHX
CH3
CH2 CH2 C
n
CH3
O
CH CH CH2 C CH3
O CH3
CH CH CH2 C CH3
Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92 J. Rogers, W. H. Waddell (Exxon) Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturbersicht, GAK 9/1999-Jahrgang 52, 670-682
Vulcanization Compound Properties ML 1+4 (100 C) [MU] MS5 (125 C) [min] MS5 (135 C) [min] Physical Properties Shore A Hardnes [MPa] M100 M300 [MPa] Tensile Strength [MPa] Elongation at break [%] CS (70h/150 C) [%]
Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92 J. Rogers, W. H. Waddell (Exxon) Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturbersicht, GAK 9/1999-Jahrgang 52, 670-682
BIIR Carbon black Paraffin Oil Resin Stearic Acid MBTS Zinc oxide Sulfur
Polysar Brombutyl 2030 N 660 Sunpar/Sunoco Inc. Pentalyn A / Hercules Vulkacit DM / Lanxess
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
5,7 5,1 7,1 5,7 8,9 4,3 10,0 10,7 12,8 10,3 14,7 9,7 620 620 560 560 490 580 7,6 9,8 420 5,4 7,9 11,0 465 5,7 8,4 9,3 320 9,2 7,7 9,2 365 7,5 6,7 8,8 370 13,8 3,6 5,8 475 13,2
Mechanical Properties
Ozone Resistance
Oil Swelling
Rubber goods:
Negative:
High price Poor low temperature flexibility (except Kalrez) Poor resistance to amines and bases Poor compounding Necessity to oven ageing after vulcanization
Sources:
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)
World Market
Asia 22%
USA 45%
Top price:
Growth:
WEurope 33%
Producer
Du Pont DuPont-Showa
Trade names
Viton/Kalrez
Site
Deepwater, NJ Dordrecht, NL Utsonomiya, Jp Kawasaki, Jp Decatur, AL
Capacity* [kt]
3,0 1,0 1,0
22 15 10 5 5
80
VDF
[w .t% ] 40 60
TFE
HF P
60
HFP
80
20
TFE
80
60 40 TFE [wt.%]
VDF [%] 33 55 22 TFE [%] 33 23 12
20
VDF
X Y Z Soures:
HFP [%] 33 22 65
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)
Copolymers
Tg [C]
10 0 -10 -20 -30 -40 -50 -60 -70 -80 0 200 400 HNBR FKM (68% F)
70
75
600
800
1000
time [h]
TFE/VDF/PMVE TFE/VDF/HFP
H F F F F F F H
1,5
Source: J. Scheirs Modern Fluoropolymers High Performance Polymers for Diverse Applications John Wiley & Sons
peroxidisch
Aflas
Viton A PVDF
Viton B, GF
55
2. Crosslinking by Diamines, which are used in "capped form" (such as carbamates) in order to increase scorch resistance CF CF
3 3
CF2
CF2
CH N R N
CH2 CF2
CF2 CF3
CH CF CH2 CF2
CF2 CF3
CH
CH2 CF2
Diamine cure yields crosslinks which are liable to hydrolysis (not steam resistant)
CF3 CF2 CH N R N CF2 CF3 CH CH2 CF2 CF2 CF3 CH CH2 CF2 H2O O CF3 CF2 CH O CH2 CF2 NH2 R NH2 CH2 CF2
Sources:
W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978) W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979)
2. Crosslinking with Bisphenols ( such as Bisphenol AF) in the presence of BTPPC (Benzyl triphenyl phosphonium chloride) BTPPC acts as phase transfer catalyst and is often referred to as "accelerator"
+ CF3 HO CF3 n CF3 CF3 HO CH CF CH CF2 CF3 O CF2 CH CF CH2 CF2 O OH + CH2 P
+
Cl
- HCl HO
CF3 CF2
CF2 CF3
CH CF CH CF2
CF3
CF3
Sources:
T. L. Smith, W. H. Chu, J. Polym. Sci A-2, 10, 133 (1972) O A. W. Fogiel, J. Polym. Sci., Symp., 53, 333 (1975) W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978) CF2 CH CF CH2 CF2 W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979) CF3 A. Neppel, M. v. Kuzenko, J. Guttenberger, Rubber Chem. Technol., 56, 866 (1983) D. J. Plazek, I. C. Choy, F. N. Kelley, E. von Meerwall, L.-J. Su, Rubber Chem. Technol., 56, 866 (1983) A. N. Theodore, M. Zinbo, R. O. Carter, III, J. Appl. Polym. Sci., 61, 2065 (1996)
CF2
CF2 CF2
CF2 CF2
n
CF CF2
CF2
Br
J
C H2J2 C F2J2
CF2
J-( C F 2 ) - J 4 -6
CF2 CF2 Br
C-F bonds have a high bond energy. As a consequence, F-radicals cannot be abstracted by peroxides and FKM with high fluorine contents (> 70 wt.%) cannot be vulcanized by the use of peroxides. For the vulcanization of FKM with F-contents > 70 wt% special cure sites are required. For this purpose bromine and iodine are incorporated into FKM. C-Br and C-I bonds have a lower bond energy thqn C-F bonds. Therefore Br- and I-radicals can be abstracted by the use of peroxides. Br- and I- based cure sites are incorporated by chain modifiers and by special comonomers which contain Br- and/or iodine. In the presence of Br- and I- containing compounds (modifiers and monomers) the polymerization proceeds as a living radical polymerization (this probably was the first example of a living radical polymerization). During the course of the polymerization Br- and I are incorporated as end groups. During peroxide cure of Br- and I- containing FKM and during subsequent annealing toxic compounds are released which contain bromine and iodine.
Source:
D. F. Lyons GAK 3/2005, Jahrgang 58 Einfluss der Molmasse auf die Eigenschaften von Bisphenol-AF-vernetzten Fluorkautschuken
FKM: Vulcanization
The method of FKM-cure depends on the fluorine content. Copolymers based on vinylidene fluoride and propene (Aflas) are crosslinked by the use of peroxides. Fluoro rubbers with a fluorine content<70 wt.% (such as copolymers based on VDF and HFP) are liable to HF-elimination which is a prerequisite for the vulcanization with diamines and bisphenols. MgO and Ca(OH)2 are added to the rubber compound in order to react with HF which is eliminated during vulcanization. FKM vulcanizates which are cured by diamines and bisphenols contain double bonds. As a result, their resistance to heat and ageing is inferior to FKM without double bonds. Also, diamine cured FKM is liable to hydrolysis. Fluor rubbers with a fluorine content > 70 wt. % (FKM which contains no or only a small amount of VDF) cannot elimiminate HF. Therefore vulcanization cannot be achieved by diamines or bisphenols. FKM with F-contents > 70 wt.% requires special cure site monomers which enable peroxide cure.
Source:
J. Scheirs Modern Fluoropolymers High Performance Polymers for Diverse Applications John Wiley & Sons
Grade
MQ VMQ PVMQ FMQ
Tg [ C]
- 120 - 120 - 120 - 69
Tm [ C]
- 45 - 45 - 70
CH3 ( Si CH3
Vulcanizate Properties:
Positive:
Low temperature performance High temperature resistance Low dependence of properties on temperature changes Ozone-, UV- and Weather resistance Hydrophopic character Physiological inertness Low reistance against acids, bases, vapour and hydrocarbons (significant improvement with FMVQ) Mechanical properties RTV: poor HTV: better / DVR ! High gas permeability
Negative:
CH3 ( Si CH3 O
CF3 ) n FMQ
Bond energies
Si-O C-O C-C C-S S-S
[kJ / mol]
444 339 348 272 266
Application Areas:
Automotive industry 40%
Pharmaceutical- and medical rubber goods Rubber goods with food contact
Temperature [C]
90 121 150 200 250 315
Sources:
duration
40 years 10-20 years 5-10 years 2-5 years 3 months 2 months
K. Polmanteer, Rubber Chemistry Technology, Vol 61: 471-502Silicon Rubber, its Development and Technological Progress T. Maxson GAK 12/1995, Jahrgang 48, 873-884 Fluor-Silikonkautschuk D. Klages, U. Raupbach, GAK 4/1995, Jahrgang 48, 49-51 Fluorsilicon-Kautschuk: Ein sehr moderner Werkstoff E. L. Warrick, O. R. Pierce, K. E. Polmanteer, J. C. Saam, Rubber Chemistry Technology, Vol 52: 437-526 Silicone Elastomer Developments 1967-1977 Winnacker/Kchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Dow Corning
Shin-Etsu Wacker
Rhodia
Rousillon, FR
850.000
*Evonik and Crompton are active in this market without proprietary siloxane production
Japan 25%
Consumption
Europe 31%
Source: Winnacker/Kchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
2 CO
Rochow-Process: 2 CH3-Cl +
Cl
- HCl
CH3 O
n
Dn
CH3 Si CH3 OH
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 H3C Si O Si H3 C O O CH3 Si O Si CH3 CF3 H3C H2C O H3C Si O Si CH2 O CF3 CH2 CH3
Si O Si
CH3 C H2
CF3
Modified silicon rubbers are obtained by the copolymerization with the respective cyclic monomers. As a consequence multibloc copolymers are obtained initially. At extended reaction times randomization occurs.
Liquid Rubber
1.000 Highly viscous Transfer moulding
RTV-Rubber
200 liquid / pourable
Vulcanization Method
Condensation at room temperature (RTV) Platinum catalyzed hydrosilylation at low or elevated temperature C) (RT to 80 C, LSR: 110-200 High temperature-Vulcanization with peroxides (HTV: 120-180 C)
Products
Silanol containing Silicon rubbers Silicon rubbers with silanol and vinyl groups MQ, PVMQ, MVQ, FVMQ
R Si O Si O Si R R R
Si
- 4 ROH
R R Si
O O R
R = Me, Et
Metal carboxylates are often used for catalysis : Metals: Carboxylates: Pb, Zn, Zr, Sb, Fe Sn Ba, Ca Naphthenate, Octoate, Hexoate, Laurate, Acetate
Tin-(II)-octoate
und
R Si R O
O C O
R Si R + H 2O - CH3COOH R R Si
R O Si O Si R
R Si O O Si R R R
R Si R O
O C
O C O
R Si R
For the condensation reaction the catalysts quoted under 1a) are being used.
R Si R R OH H
O Si O Si O H HO R R Si R - H2
R Si R R O
O Si O Si O O R R Si R
For the condensation reaction the catalysts quoted under 1a) are being used.
2)
Inhibitors:
Cost Factor
Raw materials [$/pound] Vulcanization time [sec] Overhead-Costs [$/h] salaries [$/h] Hours per shift Shifts per week Number of nests per mould Weight per article + 10% loss Number of articles per week Material consumption per week Raw material costs per week [$] Total cost per week [$] Cost per article [$] Savings per article [%] Financial result per year [$] Increase of financial result [%]
HTV
3,50 120 60,00 12,00 10 8 3 59,5 7200 885 3.097,31 8.857,31 1,23 0 44.286,55 0
LTV
5,00 60 60,00 12,00 10 8 3 59,5 14.400 1.770 8.849,45 14.609,45 1,01 21,25 230.563,76 420,62
Overview:
Microstructure, Property Profile and Appliecation Areas Catalytic Hydrogenation of NBR Sequence of Process Steps in NBR- and HNBR-Production Producers and Production Capacities Chemical and Physical Properties Comparison of NBR- and HNBR Properties Speed of Ageing Tg Crystallization Stress/strain-Performance Vulcanizate Properties of Sulfur- und Peroxide crosslinked Vulcanizates Performance of HNBR in Power Transmission Belts
HNBR: Microstructure
N
C C N
H CH CH C C H2 H2
C CH 2 CH 2 1
Butylidene-Moiety
Ethylidene-Moiety
Nitrilo-EhylideneMoiety
Negativ:
Max. service temperature < 155C High Tg >-30C Bad incorporation of softeners High price (~ 20/kg)
25%
Ship Couplings
Riemen Kabel
7%
4%
4%
Dichtungen Sonstige
Schluche lfrderung
C C N H2/Catalyst C C N
Requirements for Hydrogention Catalyst: Selective and quantitative hydrogenation of C=C- double bonds in the presence of nitrile groups without gel formation Low catalyst loadings and/or catalyst recovery Homogenous Catalyst Systems:
(PPh3)3 RhI Cl and (PPh3)4RhI H
(US 3700637, DE 2539132, EP 134023, DE 3541689, DE 3540918, EP 298386, DE 3529252, DE 3433 392, US 4,464,515, US 4,503,196, DE 3921264, US 6084033)
Relative prices of noble metals [/g]: Rh (150) > Ru (75) > Pd (12,50)
R C C N
Catalyst
R CH 2 H C C N
Ru
Ph
Ru
PPh 3
BH 3 P Ru P
2Ph
Cl
2 K
Ph
Grubbs-I-Catalyst
Cl
Ru P
+
BF 4
R1
PCy3 Cl Ru PCy3
Ph
BH 3
Cl
PCy3 Piers-Catalyst
SnCl3 Cl
Cl
Ph
R2 R3
Frstner-(I)-Nolan-Catalyst (Umicore)
2Ph P N Ph Ph P Ph Ph
+
Cl
SnCl 3
2-
Ru
SnCl3
Cl
Ph
Ru
SnCl 3
Cl
2
Catalyst from Prof. Berke' s group (University of Zurich)
2
Catalyst from Prof. Berke' s group (University of Zurich)
CF 3 COO
Ru
Cl
Cl
Ru Cl R1 P
+
Cl
Ru PCy 3
CF 3COO O
R2 R3
Mes
Mes
N
Cl
Mes
Cl
Ru
Cl
Cl Cl O
Ru
N Cl
Ru N
O NO 2
Br
Br
*Sources: Julia-Maria Mller, Dissertation TU Mnchen; M. Schneider, Dissertation TU Mnchen, M. Kellner, MSc-Thesis TU Mnchen; K. Langfeld, MSc-Thesis TU Mnchen; C. Gantner, MSc-Thesis TU Mnchen
Sequence of Process Steps in NBR and HNBRProduction NBR-Production: Sequence of Process Steps:
Emulsionspolymerization Removal of residual monomers Latexcoagulation + crumb wash Mechanical dewatering Thermal drying Bale pressing Bale wrapping Packaging and storage
Bale cutting
Cemement preparation-
dilution
Catalyst recovery
Thermal crumbdrying
Bale pressing
Capacity [t]
2.800 2.000 3.000 3.600 11.400
Volume [t]
1994
1996
1998
2000
2002
2004
100 80 60 40 20 0
NBR
Tg [C]
20 0 -20
-40 0 20 40 60 80 100
-100 0 20 40 60 80 100
Data for Ethene/Acrylonitrile-Copolymers from: R. E. Uschold, I. B. Finlay, Appl. Polym. Symp. 25 (1974) 205
Ethene/Vinylacetate-Copolymers
Levapren Nielsen et al.*
Ethene/Vinylchloride-Copolymers
Tg [ C]
20 0 -20 -40 0 20 40 60 80
100
20
40
60
80
100
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
Crystallinity [%]
12 10 8 6 4 2 0 0 10 20 30
2. DSC-Aufheizung
40
50
60
Tgs of Ethylene-Copolymers
100 50
Tg [C]
-50
-100
-150
-200
0 10 20 30 40 50 60 70 80 90 100
50
Tg [C]
-50
-100
?
0 10 20 30 40 50 60
-150 70 80 90 100
Tg [C]
Influence of Residual Double Bond Content on Stress/StrainProperties of HNBR-based Vulcanizates (34 wt.% ACN; unfilled; sulfur vulcanized)
12 10 stress [MPa] 8 6 4 2 0 0
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 100 phr HNBR 0,07 phr Schwefel 2,63 phr TMTD 2,07 phr DTDC* * Dithiodicaprolactam
100
200
300
400
500
600
700
strain [%]
1000
100
E' E''
10
Temperature [ C]
NBR
0,7 0,6
HNBR
45 40 35 18,9 wt.% 28 wt.% 33,9 wt.% 38,5 wt.% 48,3 wt.%
Stress [MPa]
stress [MPa]
4000
0,5 0,4 0,3 0,2 0,1 0 0 1000 2000 3000 19,2 wt.% 28 wt.% 34,2 wt.% 39,1 wt.% 49 wt.%
30 25 20 15 10 5 0 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
250
200
150
100
50
Yield-Strength [MPa]
Influence of Extention on Permanent Elongation of Fully Hydrogeanted, Unvulcanized HNBR (Variation of ACN-Content)
extension
160 140 120 100 80 60
120
280%
= bleibend
48,3 %
100 80
200%
18,8 %
60 40 20 0
39,0 %
40 20 0 0 100 200 300 400
120% 80%
28,2 % 34,9 %
20
40
60
elongation [%]
ACN-content [wt.%]
Vulcanization time: 20 min temperature: 160 C H-NBR 100,0 phr ZnO 2,0 phr MgO 2,0 phr DDA 1,0 phr ZMB-2 0,4 phr N 550 45,0 phr TAIC 1,5 phr Perkadox 1440* 7,0 phr Vulcanization time: 15 min Temperature: 180 C Annealing: 6h/150 C
Perkadox 1440 Bis(t-butylperoxyisopropylbenzol 40%ig
Vulcanizate Properties of Sulfur- and Peroxide Cured HNBR (Partially and Fully Hydrogenated)
HNBR-Grade (Therban) 1706 S ACN-content [wt.%] 33,7 Residual double bond cont. [Mol.%]4,3 ML 1+4(100 C) [ME] 60 Compound Properties Compound Mooney [ML 1+4(100 C)] 64 Mooney-Scorch (120 C) [min.] 12,5 Fmax [N] 56,4 Vulcanizate Properties Sulfur Core (Press 160 C/20`) Peroxide Cure (Press 180 C/15`) Shore A Hrte (23 C) 72 Shore A Hrte (70 C) 69 M 100 [MPa] 3,4 M 200 [MPa] 8,8 M 300 [MPa] 14,7 Tensile Strength [MPa] 27 Elongation [%] 510 Rebound [%] 38 Compression Set 70h/-10 C [%] 73 70h/23 C [%] 70h/100 C [%] 73 70h/150 C [%] Hot Air Ageing D/D0 (150 C/ 5 d) [%] 55 C/24 d) [%] D/D0 (150 Degree of Vol. Swelling in Fuel 100*(V/V0 -1) (48h/50 C) [%] 75 1706 S 33,7 4,3 60 66 14 51,2 1706 34,5 0,4 63 74 16 52
10.000
200
180
160
140
120
100 [ C]
1.000
10 2,1
-1
2,2
2,3
2,4
2,5
2,6 10 -3 (
1 -1 K ) T
1000
CR
100 10
HNBR
Tear-Analyzer-Test / Exp. Conditions
Frequency: Strain Ampli tude: Attenuation mode: Rate of crack growth: 4 Hz 20% sinuoidal 1/co (dc/dn)
Source: M. Mezger; D. Achten Therban: The high performance elastomer in power transmission systems 9. Tagung Zahnriemengetriebe am Institut fr Feinwerktechnik und Elektronik-Design der TU Dresden
Temperature [ C]
Positive:
Ozone-, UV-, and weather resistance Maximum service temperature 175C High filler loadability FRNC-applicability (Flame resistant non corrosive) Resistance to water/glycole Braod range of grades No necessity for post cure in oven
Application Araeas:
Automotive- and engineering: seals and membrandes Hoses in high temperature environment FRNC-products: cables and floorings Sound protection FRNC Conveyor belts Hot Melt and pressure sensitive adhesives Protecting foils Blending component for HNBR, EPDM, CM, NBR) Rubber modification of thermoplasts (PVC, TPU, SAN, PC etc.) Oil additive Shoe soles
Negative:
fair mechanical properties Low temperature flexibility (depending on VAccontent) Fair oil resistance Range of products limited to ML 1+4 = 20 - 35 Vulcanization only peroxides
Source: H. Bartl, J. Peter, ber thylen/Vinylacetat-Copolymerisate und ihre Vernetzung; Kautschuk und Gummi, Jahrgang 14, 2 (1961) WT 23-32
Producer Process
High pressure bulk process 750-3000 bar 120-300C
Products
Exxon, BP, High pressure Escorene Mitsui ctc. Du Pont USI Lanxess Mitsui High pressure Elvax High pressure Vynathene Solution Solution Levapren
1000
pressure [bar]
100
Solution process 100-500 bar 50-120C Emulsion process 10-100 bar 30-70C
10
Preferred process for EVM-r rubbers (VAc-cont. 40-90%) Monomer conversion: 60- 70% Solvents: t-Butanol; Methanol
Emulsion Process:
Preferred process for latices with high gel content (paints) Monomer conversion: ~ 100%
High Pressure Bulk Process: US 5089579 (Bayer AG), Prio.: 11. 12.1989; Erf.: H. Sutter, A. Kolwert, W. Obrecht Solution Process: US 4937303 (Bayer AG), Prio.: 01.05.1989; Erf.: B. A. Wolf, B. Will, W. Obrecht, R. Casper, W. Baaade, G. Sylvester, K-P. Meurer, H. Zimmermann EP 0632067 (Bayer AG), Prio.: 30.06.1993; Erf.: R. Steiger, E. Asch, W. Baade, W. Obrecht
Rubber
Enthalpy of fusion (DH)[J/g]
O O O O
O O
CH3
350 C
OCN
N C N
106
Temperature [C]
NCO
n n = ca. 4
100000
O N C N
135
N O H
n n = ca. 4
O nCH3
10000
20000 h
1000
1000 h
The addition of acid scavengers such as carbodiimides and isocyanates does not improve hot air performance
temperature in C
EVM: Dependence of Oil Swell and LOI (Limiting Oxygen Index) on Vinyl Acetate Content
Storage time in SAE-oil SAE 90 (3 d/125C)
80
Delta F/F0 x 100 [%]
50
Al2O3:
0 phr
40
40
20
30
20
-20
10
0 0 20 40 60 80 100
Vinyl acetate content [wt.%] Compound properties Mooney ML 1+4(100 C) C [min] t10/180 t90/180 C [min] C [N] FH-FL/180 Vulcanised properties (ISO-Stab Nr. 2, 2mm) Shore A Hrte (23 C) S 100 MPa] Elongation at break [%] Tenjsile Strength [MPa] Compression Set 70h/100 C 70h/125 C 70h/150 C [%] [%] [%]
40 20 1,2 7,2 17
45 24 1,2 6,6 20
50 23 1,2 6,6 19
60 25 1,2 6,2 21
70 20 1,3 6,9 19
80 20 1,3 6,1 17
Styrenated Diphenyl amine (SDPA) Dioctylsebacate (DOS) 3) 1,3-Bis(tert.-butylperoxyisopropyl)benzene (Perkadox 14/40) Source: E. Rohde DKG-Bezirksgruppentagung NRW in Bad Honnef 07.-08. Mai 1992
Hot air ageing (14d/150 C) [%] F/F0 x100 [%] D/D0 x100 H/H0 x100 [%] Storage in SAE Oil90 (3d/150 C) F/F0 x100 [%] D/D0 x100 [%] V/V0 x100 [%]
-26 -19 69
-12 -4 47
-8 -4 31
8 2 13
6 8 3
10 -12 -4
EVM/HNBR-Blends
EVM/HNBR 100,0 phr 1) Rhenogran P 50 var. Carbon black/N 550 50,0 phr Carnuba Wax 2,0 phr MgO 10,0 phr ZnO 2,0 phr TAIC 1,75 phr 7,0 phr Peroxide (40%ig) 2) Vulcanization time: 15 min Temperature: 177 C Anealing: 16 h
1) 2
Therban 1707 Levapren 500 Rhenogran P 50 Compounc properties Relative compound price ML 1+4(100 C) [ME] C [min] t2/177 t90/177 C [min] Vulcanized properties Shore A Hrte (23 C) S 100 [MPa] Elongation at break [%] Tensile Strength [MPa] Compression Set 70h/23 C 70h/150 C 70h/175 C [%] [%] [%]
Carbodiimide Vulcup 40 KE
Hot air ageing(14d/150 C) [%] F/F0 x100 [%] D/D0 x100 [%] H/H0 x100
Source: Test Report WR 26/83 (Mobay, Chem. Corp.)
Storage in ASTM oil Nr. 3 (7d/150 C) F/F0 x100 [%] D/D0 x100 [%] [%] V/V0 x100
-10 -4 +24
Stress [MPa]
th wi
5
e ur tc s o
t ou th i w
r cu st o p
O-Ring: Mechanical properties without post with post cure cure Tensile Strength [MPa] 10,4 11,8 [%] 285 230 b M100 [MPa] 1,8 3,1 CS 72 h / 150C [%] 63 31 CS 168 h / 150C [%] 71 50
strain [%]
10 9 8
torque [dNm]
7 6 5 4 3 2 1 0
= 75 % of total cure
Sources:
cycle time for IM
H. Meisenheimer, Kautschuk Gummi Kunststoffe, 52 (1999) 724 P. J- Pazur, L. Ferrari, H. Meisenheimer, ACS Rubber Div. 165th Spring Meeting, Grand Rapids, Michigan H. Magg, A. Welle, Nordic Rubber Conf. 2005, Kge, Denmark
20
40
60
time [sec ]
CH
O
2
Zn
2+
Levapren grade Levapren TMQ N 762 ZnO ZMB-2 Ficon 153 1) Saret SR 633 2) Vul-CUP 40 KE Compound properties Mooney ML 1+4(100 C) Vulcanized properties (ISO-Stab Nr. 2, 2mm) Shore A Hrte (23 C) Shore A Hrte (150 C) Tensile strength Elongation at break M 50 M100 Rebound/23 C Rebound/100 C [MU]
500 100
3)
(liequid rubber) 2) Zn diacrylate 3) For further ompound ingredients see Stuey on variation of vinyl acetate content Source: T. A. Brown, Polysar Rubber Corporation, Technical Report TR 552.92,17 vom 22.05.92
23
68 [MPa] 12,6 [%] 285 [MPa] [MPa] 4,4 [%] [%] -10 2 11
77 72 13,5 80 6,6 43 62 1 -8 6
Hot air ageing (14d/150 C) [%] F/F0 x100 [%] D/D0 x100 H/H0 x100 [%] Storage in SAE-oil 90 (3d/150 C) F/F0 x100 [%] [%] D/D0 x100 [%] V/V0 x100
-8 -4 31
-13 -6 13,7
Positve:
Good vulcanizate properties at low / moderate temperatures No compounding and vulcanization know-how necessary Short cycle times no time consuming vulcanization Recycling of waste (due to thermo labile/reversible crosslinks)
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)
TPE-O
EPM / PP EPDM / PP EPDM / PP NBR/ PP NBR / PVC EVM / PVC ACM / PVC HNBR / PA HNBR / PBT NBR / PA EVM / PA EVM / PBT SBC (SBS, SIS, SEBS, SIBS) Polyester-Urethanes, Polyether-Urethanes COPE based on aromatic Polyesters (Terephthalates) PBT/ PTHF; PET / PTHF PEBA based on PA 6 and PA 12
Thermoplastic Polyolefins
(dynamically vulcanized)
Olefin TPE-V
Polyblends1
Styrenic Block-Copolymers
TPE-S
Multi-BlockCopolymers2
TPE-U
TPE-E
Polyamide Block Copolymers 1 Consists of an elastomer finely dispersed in a thermoplastic matrix 2 Rubber and thermoplastic segments are chemically bonded by block- or graft copolymerization
TPE-A
Crosslinking Principle
Crystallization Crystallization Dipol/Dipol
Producer
UCC Bassell Exxon AES (Advanced Elastomer Systems) AES (Advanced Elastomer Systems) Denki KK Zeon Shell BASF Firestone, Polimeri Dow Kaneka Boston Scientific Innovia Bayer BASF Goodrich DuPont Toyobo Atochem Dow Du Pont
Brand Name
Flexomer Spherilene Exxtral Santoprene Geolast Denka LS ? Kraton Styrolux Sibstar Taxus SIBS Desmopan/Texin Elastollan Estane Hytrel Pelprene Pebax Estamid Surlyne
Areas of Application
Hoses 5% Cables 3% Medical Appl. 3% Adhesives 12% Automotive 32% IRP 18% Shoe 15%
TPO-V
TPOBlends
Price [/kg]
0,90-1,20 2,00-2,50 1,00-3,30 1,30-1,50 1,50-1,70 2,60-3,30 3,00-4,00 3,50-4,40 3,60-7,00
Tempeature of Use
Temperature of Processability
Schematic Presentation of the Dependence of the Shear Modulus on Temperature for Different Engineering Polymers
104 103 102 101 100 10-1 - 100 7 5 6 4 3 2 1
104 1. Thermoplastic Polymer Shear Modulus [MPa] 103 102 101 100 10-1 - 100 7 5 6 4 3 2 1 2. Thermoplastic (Polystyrene, PMMA) 3. Rubber Modified Thermoplastic 4. Elastomer (crosslinked) 5. TPE 6. TPE 7. Elastomer (crosslinked) 8 - 50 0 50 100 150 200 8. Unvulcanized Rubber
(Polycarbonate, PP.PA)
Temperature
stress [MPa]
Residual elongation
strain [%]
Residual ) [%]
300
residual = original
200
residual elongation (
100
300 [%]
SBS with 27 wt.% styrene NR/BR-tyre tread (with filler) vulcanized gum stock (unfilled NR)
original )
Compression - Set
ho
h1
h2
CS = ho- h1 h2 h1 ho- h2
ho- h2 ho- h1
x 100
[%]
ho
In compression set (CS) measurements ho , h1, compression, exposition time, and exposition temperature are well defined (DIN, ASTM). Most commonly, the deformation is 25%. In order to achieve the same deformation ho-h1 the pressure has to be adjusted to the degree of x-linking
Comparison of Technological Properties of Chemically and Physically Crosslinked Rubbers (Data from Product Data Sheets)
S BC P rope rtie s Cla ssica l E la stome rs S BS S IS T P E -U S E BS E ste r E the r T P E -A T P E -E T PO me ch. T PV T PV E P D M/ P P E P D M/ P P E P D M/ P P ble nd (pa rtia lly (highly x-linke d) x-linke d) 78 25 79 40 36 63 51 32 15,4 880 54 47 660 12 650 75 60 60 62 21 5 90 53 88 44 5,5 350 60 8,5 490 38 72 75
10 to 80 10 to 35
71
52
75
92 44
93 42 40 380
32 880
20 1200
34 500
45 450
E longa tion a t bre a k [% ] 300 to 800 CS (22h/ 70 C) CS (24h/ 70 C) CS (22h/ 100 C) CS (70h/ 150 C) 5 to 30 5 to 40 5 to 40 30 (H N BR , FKM)
200 Gebrauchstemperatur [ C]
TPE-V
(EPDM / PP-blend, highly crosslinked)
160
140
120
TPE/SEBSBlends
100
TPE-V
3
80
60
TPE-O
(mechanical blends)
40
20
Low Price High Softening Temperaure High Softening Temperaure Good Ageing Resistance Good Ageing Resistance
(Residual Catalyst Content) (Residual Catalyst Content)
TPE-O
(ReactorBlends)
0 20 40 60 80 100
0 0 0,5 1 1,5 2
Isotacticity [%]
Source: T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 New Polymers from New Catalysts
Price [$/kg]
Source: Robert Eller Associates, Inc. 1996
TPE-V
(PP/EPDM-Blend with partially crosslinked EPDM-phase) 72 5,5 350 60
TPE-V
(PP/EPDM-Blend with highly crosslinked EPDM-Phase) 75 20 490 38
Shore A-Hardness Tensile Strength [MPa] Elongation at break [%] Compression Set (22 h /70 C) [%] Volume Swell in ASTMOil Nr. 3 [Vol%]
soluble
90
50
n ctio e r i w D Flo of
n ctio e r i w D Flo of
no. of recycles
2 3 5
35 30 25 20 15 10 5 0
0
1,0-1,5
Stress [MPa]
Shore A Hardness: 64
100
200
300
400
500
Elongation [%]
TPE-O: PP/EPM-Reactor-Blends
PP**
Montell Fina Phillips Solvay UCC BASF Amoco/Chisso Sumitomo
ventilator
Filter
Filter
ventilator
Cooler
* Ind Eng. Res. 33 (1994) 449-479 ** Chem. Systems (April 1992) "Polypropylene"
Sources:
Supported catalyst
Propylene Ethylene
purification purification
packaging
Catalyst System A
Catalyst System B
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
PP
HOCH 2
CH2 OH
1) Melting PP at 185 - 190 C 2) Addition of dimethylol resin at 185 -190 C (5 Min.) 3) Addition of the catatalyst SnCl2 x 2H20 (2 Min.)
OH
PP
CH2
CH 2 OH
Preparation of a TPE-V by the Dynamic Vulcaniztion of a EPDM/PP blend with Phenol Resin
1b) Preparation of block copolymer by the reaction of activated PP with EPDM
OH
PP
CH2
CH 2 OH
EPDM
1) Addition of EPDM and additional Phenol Resin at 185 - 190 C (5 Min.) 2) Addition of more SnCl2 x 2H20 at 185 - 190 C (5 Min.)
OH
PP
CH 2
CH2
EPDM
Preparation of a TPE-V by the Dynamic Vulcaniztion of a EPDM/PP blend with Phenol Resin
2) Addition of PP und EPDM with subsequent vulcanization of the EPDM-Phase
OH
PP
CH2
CH2
EPDM
1) Addition of EPDM and PP at 185 - 190 C (5 Min.) 2) Addition of of more SnCl2 x 2H20 at 185 - 190 C (5 Min.)
PP PP Phase
CH2
OH CH2
EPDMEPDM 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
185-190 C Polypropylene 5 min. NBR + Aminino terminated NBR Dimethylolphenol resin + 5 min. SnCl2 . 2 H2O Tensile Strength M100 E-Modulus Elongation at break Permanent elongation [MPa] [MPa] [MPa] [%] [%]
1000
100
10
40 30 20 10 0
0 10 20 30 40 50 60 70 80 90 100
EPDM-content [wt.%]
Sources:
M. Vierle: MSc Thesis TU Munic December 2001 DE 10127402, Bayer AG, Prior.: 06.06.2001, Inv.: M. Vierle, N. Steinhauser, O. Nuyken, W. Obrecht M. Vierle, N. Steinhauser, O. Nuyken, W. Obrecht, Macromol. Mater. Eng. 2003, 288, 209-218Blend Preparation by Reactive Processing
R R2
Zr
R1
ataktisches Polymer
622
Preparation of PP-Blockcopolymers by the use of the Waymouth-Catalyst The length of building blocks is determined by the ratio of propagation rates versus Rotation rate
Source:
R. Waymouth, J. Coates, A-L. Mogstad, K. Stein, D. Fischer, S. Borkowsky Stepol `94; Milano June 6-10, 1994 "Stereospecific Polymerization and Copolymerization of Functionalized Olefins"
595
R R2
Zr
R1 R
Isotaktisches Polymer
BP/Amoco started to manufacture PPPP-based multimulti-block copolymers in the pilotpilot-plant scale in California (Menlo Park) Baxter Healthcare Corp., Round Lake, IL cooperates in the performance of tests towards the replacement of soft PVC in medical devices A. Khare; Khare; S. Y. Ding; M. T. K. Ling; L. Wood; Modern Plastics, Plastics, September 1999; 9494-99 HeatHeat-resistant, resistant, flexible olefins meet tough medical demands demands-SingleSingle-Site metallocene catalysts yield autoclavable, autoclavable, highhigh-clarity elastomers with cost/performance benefits of flexible PVC.
Cl Cl
Temperature
atactic polymers
PP-Based TPE
10
4
G'
10
3
Elastomeric PP
Schubmodul (MPa)
10
G''
10
1
10
-120 10
0
-80
-40
40
tan
10
-1
10
-2
-160
-120
-80
-40
40
PP-Based TPE
6 Elast.PP
PP-Based TPE
Komplex modulus (G*) [MPa] komplexer Schubmodul [MPa]
10
4
G' G'
10
10
10
10
10
-1
10
-120
-80
-40
40
80
10
-1
tan()
10
-2
10
-3
-160
-120
-80
-40
40
80
120
Temperature [ C]
Temperatur [C]
PP-Based TPE
6
HAIFA-1 HAIFA-2
7. Test Questions
Please do not forget to write your name on each page of the questionnaire Family Name Given Name
1
Rubber
Polybutadiene Polychloroprene Chlorinated Polyethylene Chlorosulfonated Polyethylene Ethene/Propene/Diene-Terpolymers Ethene/Propene-Copolymers Epoxydized Natural rubber Fluororubber Acrylic Rubber Synthetic Polyisoprene Isobutene/Isoprene-Copolymers Styrene/Butadiene-Copolymers Natural Rubber Silicon Rubber with Viny Groups Butadiene/Acrylonitrile-Copolymers Brominated Isobuylen/Isoprene-Copolymers Vinylmethylsilicon Rubber, which also contains fluorine Polyphosphazene modified with perfluorinated alcohols Standardized NR from Vietnam Smoked Sheets based on NR
Abbreviation
Please Assign the following Rubbers to the Correct Position in the Matrix:
ACM, BIIR, BR, CM, CSM, EVM, FKM, HNBR, IIR, SBR
Chemical Features
Radical Polymerization Ziegler/NattaPolymerization anionic Polymerization Cationic Polymerization Polyaddition und Polycondensation Polymermodification Family Name Given Name
3
Process Features
Emulsion Solution Dispersion (slurry) Mass or Bulk GasPhase
Which of the Curves Matches the Performance of the Materials Mentioned Below ?
300
200
2 3 4 5 6
0 100 200 300
100
elongation [%]
Nr.: Questions
1 2 3 4 5 6 7 8 9 10 Thermoplastic Polymer ? Unvulcanized HNBR at 20C ? Unvulcanized HNBR at 120C? Unvulcanized BR with Mn = 10 kg/mol at 50C ? Unvulcanized BR with Mn = 500 kg/mol at 20C? SBS at 20C? SBS at 120C TPU at 20C NR (unfilled and vulcanized) at 60C NR (filled and vulcanized) at 60C
Answers
Family Name
4
Given Name
Nr.: Frage
1 2 3 4 5 6 7 8 9 10 Unvulcanized NR does not crystallize Today, Malaysia is NR-Producer No. 1 For NR plantations China is ideal. For NR plantations Brasil is ideal. A smallholder earns ~ 10000 /a SMR 20 is a NR-grade with high purity SMR CV vulcanizes faster than SMR 10 NR has to be masticated before use IR has to be masticated before use For the mastication of NR, mastication aids have to be used
Right Wrong
Right Wrong
RIGHT WRONG
Right Wrong
Question
COD = 0 BOD = 0 BOD = COD COD < BOD BOD < COD There are no biodegradable emulsifiers Emulsion rubbers yield considerable amounts of water water Dry finishing of solution rubbers does not cause water pollution Rubber recovery from a solution by steam stripping causes waste water Emulsion rubbers cause air pollution
Right Wrong
Right Wrong
11
NBR
Please Mark RIGHT or WRONG
Nr.: Frage
1 2 3 4 5 6 7 8 9 10 NBR which is polymerized under azeotropic conditions has 2 Tgs NBR which is polymerized under azeotropic conditions has 1 Tg A batch polymerization with incremental monomer addition can result in 2 Tgs Low monomer conversions result in NBR with chemical heterogenity High amounts of emulsifier improve chemical homogenity High amounts of modifier improve chemical homogenity Rebound of NBR increases with the content of acrylonitrile The degree of oil swelling increases with acrylonitrile content Shore A hardness of NBR vulcanizates dempend on acrylonitrile content The compression set of NBR vulcaniaztes depend on acrylonitrile content
Right Wrong
Right Wrong
The properties of NBR depend on the emulsifier used for polymerization The properties of NBR depend on the electrolytes used for latex coagulation The tendency to gelling increases with increasing polymerization temperature The tendency to gelling decreases with increasing polymerization temperature Molar masses increase with increasing monomer conversion Molar masses do not depend on monomer conversion Molar masses do not depend on modifier level Molar masses decrease with increasing amounts of modifier Molar masses increase with increasing amounts of modifier The properties of NBR depend on the modifier used
NBR
In the literature you find the following Tgs for polybutadiene (BR) and polyacrylonitrile (PAN:
BR (Li-catalysis) BR (Ti-catalysis) BR (Nd-catalysis) BR (emulsion polymerization) PAN -90 C -100C -110C -80 C +100 C
Please select the relevant Tgs and calculate the Tg of an NBR grade which contains 50 wt.% acrylonitrile. acrylonitrile. The calculated Tg is: is: .. C ..
NBR:
Right Wrong
Right Wrong
16
Nr.: Question
1 2 3 4 5 6 7 8 9 10 Tg of HNBR does depend on the degree of hydrogenation The rebound of HNBR vulcanizates depends on ACN content HNBR and EVM are fully compatible at all copolymer compositions The compatibility of PVC and HNBR depends on the acrylonitrile content of HNBR Compatibility of HNBR and EVM depends on the vinyl acetate content of EVM The crystallinity of HNBR depends on acrylonitrile content Ethene sequences are prone to crystallization Tg of amorphous PE is at -200C Tg of amorphous PE ist at + 0C Unvulcanized HNBR with a low acrylonitrile content performs like a TPE
Right Wrong
Nr.: Question
1 2 3 4 5 6 7 8 9 10 Pd-Catalysats can be used for the selective hydrognation of C=C bonds in NBR Raney-Nickel can be used for the selective hydrogenation of C=C bonds in NBR Li[AlH4] can be used for the selctive hydrogenation of C=C bonds in NBR NN=NH can be used for the selective hydrogenation of C=C bonds in NBR Supported catalaysts can be recovered by centrifugation Supported catalaysts are not quantitatively recovered after hydrogenation Homogeneous catalysts can be recovered by filtration Ethene and acrylonitrile can be radically copolymerized Metallocenene-based catalysts readily copolymerize ethene and propene In the hydrogenation on NBR, gel formation is a major problem
Right Wrong
18
Right Wrong
19
Right Wrong
20
Schubmodul [MPa]
103
4 3 2
1 5 6 7 8 9
-100
Nr.: Frage
1 2 3 4 5 6 7 8 9 10
-50
0 50 100 Temperatur
150
200
Number of curve(s)
Which curve(s) matches the performance of unvulcanized NR ? Which curve(s) matches the performance of unvulcanized SBR ? Which curve(s) matches the performance of vulcanized SBR ? Which curve(s) matches the performance of unvulcanized NBR ? Which curve(s) matches the performance of vulcanized NBR ? Which curve(s) matches the performance of isotactic Polypropylene? Which curve(s) matches the performance of Polycarbonate? Which curve(s) matches the performance of atactic Polytyrene? Which curve(s) matches the performance of ABS with 30 wt.% BR ? Which of the curve(s) matches the performance of SBS ?
21
Which series of modified rubbers and which modification results in the following properties
Rubber A Rubber B Rubber C [phr [phr] [phr] 100 30 100 30 100 30 59 8,8 27,8 560 15 52 17 -5 6 21 1,98
22
Carbon black (N 220) [phr] Shore A Hardness/23C Modulus300 [MPa] Tensile Strength [MPa] Elongation at break [%] Rebound/23C [%] Goodrich HBU [C] CS (24h/70C) [%] Volume swell (70h/70C) ASTM-oil Nr. 1 [%] ASTM-oil Nr. 2 [%] ASTM oil Nr. 3 [%]
59 56 7,8 6,9 27,1 25,9 550 590 78 25 44 60 17 46 66 114 191 73 28 108 8,0
Which Metal is used for the production of BR in order to obtain the Properties below ?
1
CH2
4
CH2 CH
1 3 3
CH2
2
CH2
CH CH
4
CH
4
CH CH
3
CH2
CH2
Metal
Microstructure [%] 1,4-cis 36-38 1,4-trans 52 Vinyl 10-11 1 Vinyl/ H-NMR*** 10,4 Vinyl/FT-IR*** 11,4 Vinyl/Metathese*** 10,7 Tg -93 97 1 2 1,9 1,0 1,7 -106 97 2 1 93 3 3-4 4,0 5,4 4,6 -103 98 1 <1 <1 0,6 0,7 -109 12,9 68,3 18,8 18,1 17,7 17,8 -80
-107
23
Rubber A Rubber B
Heat ageing (14d/150 C) [%] F/F0 x100 [%] D/D0 x100 [%] H/H0 x100 Oil swelling (7d/150 C) ASTM-l Nr. 3 F/F0 x100 [%] [%] D/D0 x100 V/V0 x100 [%]
Family Name
-10 -4 +24 -17 -11 +34 -36 -29 +49 -50 -34 +67 -56 -45 +83
Given Name
24
Rubber A Rubber B
Dehnung
CS (70 h/121C)
Please assign 5 polymer blends for which the scheme below applies
Hard phase (coherent phase or matrix) Soft phase (dispersed phase)
Nr.:
1 2 3 4 5
Hard phase
Soft phase
Which Series of Rubbers Yields the Properties Given in the Table Below?
Rubber Compound properties Mooney ML 1+4(100 C) C [min] t10/180 C [min] t90/180 FH-FL/180 C [N] Vulcanised properties (ISO-Stab Nr. 2, 2mm) Shore A Hrte (23 C) S 100 MPa] Elongation at break [%] Tenjsile Strength [MPa] Compression Set 70h/100 C 70h/125 C 70h/150 C [%] [%] [%] A 20 1,2 7,2 17 B 24 1,2 6,6 20 C 23 1,2 6,6 19 D 25 1,2 6,2 21 E 20 1,3 6,9 19 F 20 1,3 6,1 17
Rubber Variation
C) Hot air ageing (14d/150 [%] F/F0 x100 [%] D/D0 x100 H/H0 x100 [%] Storage in SAE Oil90 (3d/150 C) [%] F/F0 x100 D/D0 x100 [%] [%] V/V0 x100
-26 -19 69
-12 -4 47
-8 -4 31
8 2 13
6 8 3
10 -12 -4
28
Rubber A [phr] Carb. black (N 774) [phr] Vulcanization Compound Properties ML 1+4 (100 C) [MU] MS5 (125 C) [min] MS5 (135 C) [min]
Physical Properties Shore A Hardnes M100 [MPa] [MPa] M300 Tensile Strength [MPa] Elongation at break [%] CS (70h/150 C) [%]