CN1296991A - 含羟基和/或羧基的橡胶与疏水化的氧化或硅酸盐类填料的橡胶混合物 - Google Patents
含羟基和/或羧基的橡胶与疏水化的氧化或硅酸盐类填料的橡胶混合物 Download PDFInfo
- Publication number
- CN1296991A CN1296991A CN00128453A CN00128453A CN1296991A CN 1296991 A CN1296991 A CN 1296991A CN 00128453 A CN00128453 A CN 00128453A CN 00128453 A CN00128453 A CN 00128453A CN 1296991 A CN1296991 A CN 1296991A
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- China
- Prior art keywords
- rubber
- weight
- silicon oxide
- hydrophobization
- filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 138
- 239000005060 rubber Substances 0.000 title claims abstract description 137
- 239000000945 filler Substances 0.000 title claims abstract description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 19
- 150000004760 silicates Chemical class 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 title abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title description 42
- 229910052814 silicon oxide Inorganic materials 0.000 title description 33
- 230000002209 hydrophobic effect Effects 0.000 title description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
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- 239000004568 cement Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 4
- 238000013016 damping Methods 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000013040 rubber vulcanization Methods 0.000 abstract 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 239000004594 Masterbatch (MB) Substances 0.000 description 14
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 12
- 239000002480 mineral oil Substances 0.000 description 11
- 235000010446 mineral oil Nutrition 0.000 description 11
- 239000004902 Softening Agent Substances 0.000 description 10
- 239000012190 activator Substances 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- -1 silicon halide Chemical class 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical class CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
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- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 239000005995 Aluminium silicate Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 235000012489 doughnuts Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- 239000008188 pellet Substances 0.000 description 2
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- 239000011164 primary particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- XZKRXPZXQLARHH-XVNBXDOJSA-N [(1e)-buta-1,3-dienyl]benzene Chemical compound C=C\C=C\C1=CC=CC=C1 XZKRXPZXQLARHH-XVNBXDOJSA-N 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
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- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- ZUBNXRHITOZMOO-UHFFFAOYSA-N zinc;octadecanoic acid;oxygen(2-) Chemical compound [O-2].[Zn+2].CCCCCCCCCCCCCCCCCC(O)=O ZUBNXRHITOZMOO-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
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Abstract
本发明的橡胶混合物包括具有羟基和/或羧基的总量为0.1—3%重量的橡胶、和以100重量份橡胶为基础计的5—500重量份疏水化的氧化和/或硅酸盐类填料、以及非必要的橡胶、橡胶助剂和交联剂,该橡胶混合物适宜制备具有改善物理性能、特别是具有改善的动态阻尼性能、降低的开炼机损性和改善的耐湿滑性的橡胶硫化产品。
Description
本发明涉及含羟基和/或羧基的橡胶与疏水化的氧化或硅酸盐类填料的橡胶混合物,和制备该橡胶混合物的方法。以该方法制备的橡胶混合物适宜制备具有改进性能、特别是具有改进的动态阻尼、降低的开炼机损性和改进的耐湿滑性的橡胶硫化产品。这些橡胶混合物特别适合生产具有改进的性能的汽车轮胎。
与具有非疏水填料的橡胶混合物相比,橡胶与疏水化的氧化和硅酸盐类填料的橡胶混合物具有加工工艺方面的优点,如混合物的低粘度。缺点是该填料的增强性能由于疏水作用而通常较低。
WO-A 98/53004介绍了用特定氨基硅烷在水中对氧化硅进行疏水化作用,接着用胶浆处理制得的具有疏水化氧化和硅酸盐类填料的橡胶混合物。非改性标准橡胶用于该橡胶混合物。
EP-A 890,600介绍了一种用疏水填料接合加工橡胶的方法。这里只用标准橡胶。该专利未告知含有羟基和羧基的橡胶用于这种橡胶混合物的特别优点。
EP-A 849,320介绍了橡胶和疏水化的氧化和硅酸盐类填料的混合物、制备疏水化的氧化硅的方法以及用橡胶胶乳的接合加工。该专利也未告知含有羟基和羧基的橡胶用于这种橡胶混合物的特别优点。
DE-A 2,653,144和EP-A 806,452介绍了具有填料的羟基和/或羧基改性的橡胶混合物。然而,这里介绍的橡胶混合物仅包括非疏水化的氧化硅,并且在溶聚橡胶中官能团含量太高或太低。这些文献未告知必须使用特别窄限定含量的羟基或羧基,以同时显著提高有关轮胎的性能,如耐湿滑性、滚动阻力和开炼机损性,而不是牺牲其它性能来提高一个性能。
己意外地发现:羟基和/或羧基的总量为0.1-3%重量并具有疏水化的氧化或硅酸盐类填料的橡胶、尤其是溶聚橡胶的橡胶混合物和橡胶硫化产品具有特别好的性能,这些良好性能使有关轮胎的三个技术性能如耐湿滑性、滚动阻力和开炼机损性同时得到显著改善,而不仅是以牺牲其它性能来改善一个性能。
因此,本发明提供了橡胶混合物,其包括具有羟基和/或羧基的总量为0.1-3%重量、优选为0.1-2%重量的一种橡胶,和以100重量份橡胶为基础计为5-500重量份、优选10-200重量份的疏水化的氧化和/或硅酸盐类填料、及非必要的另外的橡胶、橡胶助剂和交联剂。
本发明还提供了一种制备本发明橡胶混合物的方法,其特征在于将羟基和/或羧基的总量为0.1-3%重量、优选为0.1-2%重量的胶浆与以100重量份橡胶为基础计为5-500重量份、优选10-200重量份疏水化的氧化和/或硅酸盐类填料混合,在混合操作中或之后用热水和/或蒸汽在50-100℃、优选60-150℃除去溶剂。
在这种方法中,胶浆还可包括非改性橡胶和橡胶助剂,如增塑剂和用于加工、活化和稳定的助剂。
通过将溶液中各组分混合以制备橡胶混合物的可类比方法公开在如EP-A 890 600和WO-A 98/53 004中。
因此,疏水化的氧化和硅酸盐类填料是指那些在室温在干燥状态下不被水润湿的氧化和/或硅酸盐类填料(根椐DIN ISO 787/2在105℃进行干燥时损失≤5%重量)。特别优选的疏水化的氧化和硅酸盐类填料是:
A:根椐EP-A 849 320或WO-A 98/53 004在水悬浮液中用有机硅化合物或特定的氨基硅烷疏水化的氧化和/或硅酸盐类填料,
或
B:根椐EP-A 890 600和WO-A 98/47955通过干燥途径疏水化的甲醇可湿性为1至60%重量的氧化和硅酸盐类填料。
根椐方法A和B的特别适宜的疏水化的填料为对下列物质进行疏水化作用而制备的填料:
-高度分散氧化硅如通过沉淀硅酸盐溶液或火焰水解卤化硅而制备,其比表面积为5至1000,优选20至400m2/g(BET表面积),初级粒径为10至400nm。氧化硅也可任选地呈与其它金属氧化物如Al、Mg、Ca、Ba、Zn、Zr或Ti的氧化物混合的氧化物形式,
-合成硅酸盐,如硅酸铝或碱土金属硅酸盐如硅酸镁或硅酸钙,其BET法测的表面积为20至400m2/g,初级粒径为10至400nm,
-天然存在的硅酸盐,如高岭土和其它天然存在的氧化硅,
-玻璃纤维和玻璃纤维产品(垫、绳)或玻璃微珠;
-金属氧化物,如氧化锌、氧化钙、氧化镁或氧化铝;
-金属碳酸盐,如碳酸镁、碳酸钙或碳酸锌;
-金属氢氧化物,如氢氧化铝或氢氧化镁;
所有具有所说羟基和/或羧基总量的非交联橡胶原则上适宜于制备该橡胶混合物。这些橡胶为例如用所需量的羟基和/或羧基改性的选自天然橡胶、聚丁二烯、丁二烯/丙烯酸C1-4烷基酯共聚物、聚异戊二烯、苯乙烯量1至60且优选15至50%重量的苯乙烯/丁二烯共聚物、丙烯腈含量5至60且优选10-40%重量的异丁烯/异戊二烯共聚物、部分氢化或完全氢化的NBR橡胶和乙烯/丙烯/二烯共聚物的橡胶。相应的不含羟基的橡胶描述于例如I.Franta,橡胶和配合剂(Elastomers andCompounding Materials),Elsevier,Amsterdam 1989中。
本发明特别优选的橡胶描述于例如德国专利申请198 32 549.6、19852 648.2、199 14 848.1、199 20 788.7和199 20 814.8及DE-A 2.653.144和EP-A 464.478中并且是在溶液中制备的具有总量为0.1-3%重量的键合羟基和/或羧基的二烯橡胶,以及由二烯和非必要的其它乙烯基芳族单体制备的、其聚合的乙烯基芳族单体的量为0-40%重量和1,2-乙烯基的量为0至60%重量的二烯橡胶。二烯橡胶的改性通过将羟基硫醇和/或羧基硫醇加至其以为基础的溶聚橡胶上而进行。
适宜的二烯具体是1,3-丁二烯、异戊二烯、1,3-戊二烯、2,3-二甲基丁二烯、1-苯基-1,3-丁二烯和1,3-己二烯。特别优选1,3-丁二烯和异戊二烯。
适宜的乙烯基芳族单体是苯乙烯,邻-、间-、和对-甲基苯乙烯,对-叔丁基苯乙烯,α-甲基苯乙烯,乙烯基萘,二乙烯基苯,三乙烯基苯和二乙烯基萘。特别优选苯乙烯。
含有羟基和羧基的橡胶的平均分子量(数均分子量)为20,000-2,000,000、玻璃化转变温度为-110至+20℃。
本发明的橡胶混合物也可含有其它非改性橡胶,如天然橡胶和合成橡胶。优选的合成橡胶描述于例如W.Hofmann,Kautschuktechnologie[橡胶工艺],Gentner Verlag,Stuttgart 1980中。这些合成橡胶尤其包括:
BR-聚丁二烯
ABR-丁二烯/丙烯酸C1-4烷基酯共聚物
CR-聚氯丁二烯
IR-聚异戊二烯
SBR-苯乙烯/丁二烯共聚物,其苯乙烯含量为1-60,优选20-50%重量
IIR-异丁烯/异戊二烯共聚物
NBR-丁二烯/丙烯腈共聚物,其丙烯腈含量为5-60,优选10-40%重量
HNBR-部分氢化或完全氢化的NBR橡胶
EPDM-乙烯/丙烯/二烯共聚物
和这些橡胶的混合物。为了制备借助于表面改性过的填料的汽车轮胎,特别感兴趣的是玻璃化转变温度高于-50℃的可非必要地用甲硅烷基醚或其它官能团改性的天然橡胶、乳聚SBR和溶聚SBR橡胶(如EP-A447.066中描述的),具有高1,4-顺式含量(大于90%)的用基于Ni、Co、Ti或Nd的催化剂制备的聚丁二烯橡胶,和乙烯含量为0~75%的聚丁二烯橡胶以及其混合物。
用于本发明方法的适宜溶剂例如是烃,如丁烷、戊烷、己烷、环己烷、苯、甲苯、二甲苯或其混合物。
本发明橡胶混合物当然可含有其它橡胶助剂,这些助剂例如可改进由本发明的橡胶混合物制备的硫化产品的物理性能以使其适合特定用途,以及含有所谓的交联剂。
用硫或硫供体化合物或过氧化物作为优先考虑的交联剂。硫或硫供体化合物特别优选的量为约0.01-3重量份,以橡胶重量计。另外,如上所述,本发明的橡胶混合物可另外含有助剂,如公知的反应促进剂、防老剂、热稳定剂、光稳定剂、臭氧稳定剂、加工助剂、补强树脂如酚醛树脂、钢丝帘布粘合剂如氧化硅/间苯二酚/六亚甲基四胺或环烷酸钴、增塑剂、增粘剂、发泡剂、染料、颜料、石蜡、增量剂、有机酸、抑制剂、金属氧化物和活化剂。
本发明的橡胶助剂以常规公知的量加以使用,所用的量取决于该橡胶混合物的后继预计用途。例如,常规的橡胶助剂的量为约2-70重量份,以100重量份的橡胶计。
如上所述,除了含羟基和羧基的溶聚橡胶外,其它的橡胶也可混入本发明的橡胶混合物。其量通常为0.5-70%、优选10-50%重量,以橡胶混合物中橡胶的总量计。另外加入的橡胶的量同样取决于本发明的橡胶混合物的特定预计用途。
对于本发明的具有高活性填料的橡胶混合物,特别优选使用另外的填料活化剂。优选的填料活化剂是含硫甲硅烷基醚,特别是双-(三烷氧基甲硅烷基-烷基)多硫化物,如在DE-A 2141159和DE-A 2255577中描述的。对应于DE-A4435311和EP-A670347描述的低聚的和/或聚合的含硫甲硅烷基醚也是可使用的。另外也可使用巯基烷基三烷氧基硅烷,特别是巯基丙基三乙氧基硅烷和氰硫基烷基甲硅烷基醚(参见DE-A19,544,469)和含有氨基的甲硅烷基醚,如3-氨基丙基三乙氧基硅烷和N-油酰基-N-丙基三甲氧基硅烷。该填料活化剂以常规量使用,即0.1-15重量份,以100重量份橡胶计。
除了优选的制备方法,本发明的橡胶混合物也可以例如通过在适宜的混炼机如捏合机、开炼机或挤出机中混合含有羟基和羧基的溶聚橡胶和相应的疏水化填料而制备。
本发明还提供使用本发明的橡胶混合物制备硫化产品的用途,该硫化产品接着用来制备高补强成形橡胶制品,特别是用于制备轮胎。
实施例
实施例1:
用7.5%重量蓖麻油对氧化硅进行疏水化作用(类似于EP-A890,600)
在三颈烧瓶中在220℃下将350g HiSil 233(具有BET表面积的沉淀氧化硅,购自于PPG,USA)和26.3g蓖麻油加热3小时,同时搅拌,在这期间蒸掉水。得到352g甲醇可湿性为19%重量的疏水化氧化硅。(用EP 890,600的方法测定甲醇可湿性)。
实施例2
由干燥的疏水化氧化硅、矿物油增塑剂、硅烷填料活化剂和含羧基的溶聚SBR制备活化母胶
将6.25g 3-巯基丙酸和0.5g二月桂酰过氧化物在80℃下加入500g溶聚SBR橡胶Buna VSL 5025-0(其键合苯乙烯含量为25%重量,1,2-键合丁二烯含量为50%重量,由Bayer AG制造)在4L环己烷中的溶液中。将混合物在80℃下搅拌2.5小时。然后加入2.5g稳定剂Vulkanox_4020(Bayer AG)。用该方法改性的橡胶具有羧基含量为0.5%重量、门尼粘度ML 1+4(100℃)为84。
在70℃下向该胶浆中搅拌加入159.5g芳族矿物油Enerthene 1849(BP)、420g根据实施例1的疏水化的氧化硅和32.4g双-三乙氧基甲硅烷基丙基四硫化物(Silan Si 69,Degussa),接着将该混合物搅拌30分钟。用蒸汽蒸馏除去溶剂。在70℃下真空干燥后,得到1,066g具有83phr疏水化氧化硅、31.5phr矿物油增塑剂、6.5phr硅烷填料活化剂和含羧基溶聚SBR的已活化的氧化硅/橡胶混合物,其门尼粘度ML 1+4(100℃)为162。
实施例3
由干的疏水化氧化硅、矿物油增塑剂、硅烷填料活化剂和含羟基的溶聚SBR制备活化母胶
将12.5g 1-巯基-2-乙醇和1.33g二月桂酰过氧化物在80℃下加入500g溶聚SBR橡胶Buna VSL 5025-0(其键合苯乙烯含量为25%重量,1,2-键合丁二烯含量为50%重量,由Bayer AG制造)在4L环己烷中的溶液中。随后将混合物在80℃下搅拌3小时。然后加入2.5g稳定剂Vulkanox_4020(由Bayer AG制造)。用该方法改性的橡胶具有羟基含量为0.5%重量。
在70℃下向该胶浆中搅拌加入161.4g芳族矿物油Enerthene1849-1(BP)、420g根据实施例1的疏水化的氧化硅和32.8g双-三乙氧基甲硅烷基丙基四硫化物(Silan Si 69,Degussa),接着将该混合物搅拌30分钟。用蒸汽蒸馏除去溶剂。70℃真空干燥后,得到1,099g具有82phr疏水化氧化硅、31.5phr矿物油增塑剂、6.5phr硅烷填料和含羟基的溶聚SBR的已活化的氧化硅/橡胶混合物,其门尼粘度ML 1+4(100℃)为112。
比较例1
由干的疏水化氧化硅、矿物油增塑剂、硅烷填料活化剂和非改性的溶聚SBR制备活化母胶
在70℃下向在4L环己烷中的80g溶聚SBR橡胶Buna VSL 5025-0(其键合苯乙烯含量为25%重量,1,2-键合丁二烯含量为50%重量,由Bayer AG制造)和577.5g溶聚SBR橡胶Buna VSL 5025-1(为一种另外包括37.5phr芳族无机油的相应组合物的橡胶)的溶液中搅拌加入420g实施例1的疏水化的氧化硅和32g双-三乙氧基甲硅烷基丙基四硫化物(Silan Si 69,Degussa),接着将该混合物搅拌30分钟。然后用蒸汽蒸馏除去溶剂。70℃真空干燥后,得到1,099g具有84phr疏水化氧化硅、31.5phr矿物油增塑剂、6.5phr硅烷填料和非改性的溶聚SBR的已活化的氧化硅/橡胶混合物,其门尼粘度ML 1+4(100℃)为100。
实施例4
橡胶混合物和硫化产品
在1.5L捏合机(转速60rpm、填充量65%,开始温度70℃,持续时间:5分钟)中混合下列物质。然后取出该混合物并在开炼机温度40℃下在开炼机上混合硫和促进剂。所述的量为重量份:
混合物组分 | 比较例4.A | 实施例4.1 | 实施例4.2 |
在1.5L捏合机中混合下列组分:根据比较例1的溶聚SBR和疏水化氧化硅的母胶根据实施例2的含羧基的溶聚SBR和疏水化氧化硅的母胶根据实施例3的含羟基的溶聚SBR和疏水化氧化硅的母胶硬脂酸氧化锌RS(Bayer AG)防老剂Vulkanox 4020(Bayer)防老剂Vulkanox HS(Bayer) | 221.9001311 | 0222.401311 | 00222.41311 |
比较例4.A | 实施例4.1 | 实施例4.2 | |
在开炼机上混合下列组分: | 1.821.568 | 1.821.571 | 1.821.563 |
亚磺酰胺促进剂Vulkacit CZ(Bayer)胍类促进剂Vulkacit D(Bayer)硫混合物粘度ML 1+4(100℃) | |||
然后在170℃下硫化该混合物 | |||
硫化时间: | 15 | 15 | 15min |
硫化产品性能;在100%伸长时的模量(MPa)在300%伸长时的模量(MPa)拉伸强度(MPa)断裂伸长(%)23℃时的硬度(邵氏A)在70℃下的回弹性(%)tanδ 0℃(DIN 53 513)tanδ 60℃(DIN 53 513)开炼机损(DIN 53 516) | 2.710.918.547074430.4970.18143 | 3.815.620.940069500.7060.10766 | 2.813.815.833065510.5770.12274 |
测试结果表明:疏水化氧化硅和用0.5%重量羧基改性的(实施例4.1)和用0.5%重量羟基改性的实施例4.2溶聚橡胶的根椐本发明的橡胶硫化产品的所有三个有关轮胎的技术性能显著好于由相同的疏水化氧化硅和非改性的溶聚橡胶制得的硫化产品的性能。在这些结果中,在0℃时高的阻尼值(由在0℃下tanδ测定)对应于高的耐湿滑性,在60℃时的低的阻尼值(由在60℃下tanδ测定)对应于轮胎低的滚动阻力。
实施例5
由80phr用4phr N-油酰基-N-(三甲氧基甲硅烷基)丙基氯化铵疏水化的氧化硅、37.5phr矿物油增塑剂、6.4phr硅烷填料活化剂和含羧基的溶聚SBR制备活化母胶
5.1制备含羧基溶聚SBR橡胶
将7.4g 3-巯基丙酸和0.6g二月桂酰过氧化物在80℃下加入到592g溶聚SBR橡胶Buna VSL 5020-0_(其键合苯乙烯含量为20%重量,1,2-键合丁二烯含量为50%重量,由Bayer AG制造)在4L环己烷中的溶液中。将混合物在80℃下搅拌2.5小时。然后加入2.7gVulkanox_4020稳定剂(Bayer AG)。由此改性的橡胶的羧基含量为0.5%重量、门尼粘度ML 1+4(100℃)为90。最后向该胶浆中加入225g芳族矿物油Mobilsol K(Mobile Oil)。
5.2制备疏水化的活化氧化硅分散液
为了制备疏水化的活化氧化硅分散液,将480g氧化硅HiSil 233_(PPG)在搅拌下分散在1920g去离子水中,并将分散液加热至80℃。在5分钟内,向加热至80℃的氧化硅分散液中加入2.40g N-油酰基-N-(三甲氧基甲硅烷基)丙基氯化铵(为在甲醇中的50%溶液)、接着加入17.79g 2%的氢氧化钠溶液。然后在30分钟内加入38.4g Si69_并继续搅拌30分钟。在最后一步,在15分钟内加入21.60g N-油酰基-N-(三甲氧基甲硅烷基)丙基氯化铵(为在甲醇中的50%溶液)、接着加入16.80g 10%的氢氧化钠溶液。将该混合物接着搅拌5分钟。
5.3将胶浆和疏水化的活化氧化硅分散液混合
将实施例5.2的疏水化活化氧化硅分散液加入到实施例5.1的环己烷溶液(含600g羧基化的SBR橡胶)中,在搅拌下将该混合物混合2小时。
5.4将橡胶和疏水化/活化氧化硅的混合物凝固和脱模
向该混合物中加入4.5L去离子水,搅拌除去溶剂并同时引入蒸汽。生成的母胶粒料接近均匀。通过0.5mm筛分离母胶粒料。胶清仅稍带浑浊,将其用5893优良无灰圆滤纸过滤。将滤纸干燥。干燥的滤纸在过滤前后的重量之差对应于氧化硅损失的量,这个量为所用的氧化硅的0.16%,即橡胶/氧化硅母胶合有99.84%所用的氧化硅。在70℃下在真空干燥柜中干燥湿母胶。
比较例2
由80phr疏水化的氧化硅、37.5phr矿物油增塑剂、6.4phr硅烷填料活化剂和非改性的溶聚SBR橡胶制备的母胶
使用实施例5相同的方法,不同的是用600g非改性的溶聚SBR橡胶Buna VSL 5020-0_(省掉与3-巯基丙酸的反应)。
实施例6:橡胶混合物和硫化产品
使用实施例4相同的方法,只是使用下列混合组分:
将这些混合物在170℃下硫化25分钟。得到下列硫化产品性能:
混合组分 | 比较例6.A | 实施例6.1 |
在1.5L捏合机中混合下列组分: | ||
比较例2的氧化硅/溶聚SBR的母胶 | 227.9 | 0 |
比较例5的氧化硅/溶聚SBR的母胶 | 0 | 227.9 |
氧化锌RS(Bayer) | 3 | 3 |
硬脂酸 | 1 | 1 |
Vulkanox HS(Bayer) | 1 | 1 |
Vulkanox 4020(Bayer) | 1 | 1 |
在开炼机上混合下列组分: | ||
Vulkacit CZ(Bayer) | 1.8 | 1.8 |
Vulkacit D(Bayer) | 2 | 2 |
硫 | 1.5 | 1.5 |
混合组分 | 比较例6.A | 实施例6.1 |
拉伸强度(MPa) | 18 | 20.5 |
在300%伸长时的模量(MPa) | 10.7 | 17.9 |
断裂伸长(%) | 450 | 340 |
硬度(邵氏A) | 68 | 61 |
0℃下tanδ | 0.686 | 0.77 |
60℃下tanδ | 0.119 | 0.085 |
开炼机损(DIN 53 516)(ccm) | 111 | 100 |
Claims (3)
1.橡胶混合物,其包括具有羟基和/或羧基的总量为0.1-3%重量的橡胶、和以100重量份橡胶为基础计的5-500重量份疏水化的氧化和/或硅酸盐类填料、以及非必要的另外的橡胶、橡胶助剂和交联剂。
2.一种制备权利要求1的橡胶混合物的方法,其特征在于将具有羟基和/或羧基的总量为0.1-3%重量的胶浆与以100重量份橡胶为基础计的5-500重量份疏水化的氧化和/或硅酸盐类填料混合,和在混合操作中或之后用热水和/或蒸汽在50-200℃下除去溶剂。
3.权利要求1的橡胶混合物在制备橡胶硫化产品、特别是在制备轮胎和轮胎胎面中的用途。
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DE19956097.8 | 1999-11-22 | ||
DE19956097A DE19956097A1 (de) | 1999-11-22 | 1999-11-22 | Kautschukmischungen aus hydroxyl- und/oder carboxylgruppenhaltigen Kautschuken und hydrophobierten oxidischen oder silikatischen Füllstoffen |
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EP (1) | EP1101794A1 (zh) |
JP (1) | JP2001187828A (zh) |
KR (1) | KR20010051843A (zh) |
CN (1) | CN1296991A (zh) |
CA (1) | CA2326264A1 (zh) |
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CN115160575A (zh) * | 2022-08-16 | 2022-10-11 | 台州耘智科技有限公司 | 一种阻燃三元乙丙橡胶及其制备方法 |
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KR100806662B1 (ko) * | 2000-05-22 | 2008-02-28 | 소시에떼 드 테크놀로지 미쉐린 | 타이어 주행 트레드용 조성물 및 이의 제조방법 |
WO2001092402A1 (fr) * | 2000-05-26 | 2001-12-06 | Societe De Technologie Michelin | Composition de caoutchouc utilisable comme bande de roulement de pneumatique |
DE10060519A1 (de) * | 2000-08-07 | 2002-02-28 | Continental Ag | Vulkanisierbare Kautschukmischung zur Herstellung eines Fahrzeugluftreifens |
KR100429071B1 (ko) * | 2001-06-25 | 2004-04-29 | 한국타이어 주식회사 | 타이어 트래드용 고무 조성물 |
DE60305648T2 (de) | 2002-02-07 | 2007-05-16 | Société de Technologie Michelin | Lauffläche für reifen |
JP6091063B2 (ja) * | 2012-01-13 | 2017-03-08 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP6170247B2 (ja) * | 2014-03-07 | 2017-07-26 | インダストリアス ネグロメックス ソシエダ アノニマ ド キャピタル バリアブルIndustrias Negromex,S.A. De C.V. | エマルジョンゴム及び溶液ゴムと共に製造したシリカマスターバッチ |
CN105924691A (zh) * | 2016-06-06 | 2016-09-07 | 四川远星橡胶有限责任公司 | 应用于泥地路况的车胎面胶料及其制备方法 |
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EP0465669B1 (en) * | 1990-01-30 | 1996-04-03 | Nippon Petrochemicals Co., Ltd. | Photocurable resin composition |
WO1996023027A1 (fr) * | 1995-01-23 | 1996-08-01 | Nippon Zeon Co., Ltd. | Composition de caoutchouc et son procede de preparation |
DE19922639A1 (de) * | 1999-05-18 | 2000-11-23 | Bayer Ag | Verfahren zur Herstellung von Mischungen aus silylgruppenhaltigen Kautschuken und Füllstoffen |
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MXPA00011417A (es) | 2002-05-23 |
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KR20010051843A (ko) | 2001-06-25 |
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