JP6046131B2 - 1,3−ブタジエン−スチレンコポリマーの製造方法及びその加硫性エラストマー組成物における使用 - Google Patents
1,3−ブタジエン−スチレンコポリマーの製造方法及びその加硫性エラストマー組成物における使用 Download PDFInfo
- Publication number
- JP6046131B2 JP6046131B2 JP2014517606A JP2014517606A JP6046131B2 JP 6046131 B2 JP6046131 B2 JP 6046131B2 JP 2014517606 A JP2014517606 A JP 2014517606A JP 2014517606 A JP2014517606 A JP 2014517606A JP 6046131 B2 JP6046131 B2 JP 6046131B2
- Authority
- JP
- Japan
- Prior art keywords
- butadiene
- styrene
- weight
- chloride
- reacting
- 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.)
- Active
Links
- 229920001577 copolymer Polymers 0.000 title claims description 43
- 239000000203 mixture Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 21
- 229920001971 elastomer Polymers 0.000 title description 10
- 239000000806 elastomer Substances 0.000 title description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 58
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 9
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 claims description 8
- 150000003606 tin compounds Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- RIECPYZYOLVSJK-UHFFFAOYSA-N tert-butyl 2-dimethylsilyl-5-methylindole-1-carboxylate Chemical compound C[SiH](C)c1cc2cc(C)ccc2n1C(=O)OC(C)(C)C RIECPYZYOLVSJK-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical group [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- LKGICXFRDGZQHA-UHFFFAOYSA-M tripentylstannanylium;chloride Chemical compound CCCCC[Sn](Cl)(CCCCC)CCCCC LKGICXFRDGZQHA-UHFFFAOYSA-M 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000945 filler Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- -1 alicyclic hydrocarbons Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 3
- 238000004807 desolvation Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920013645 Europrene Polymers 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229920006978 SSBR Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003340 retarding agent Substances 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- LGBYJXBCVZKJBL-UHFFFAOYSA-N 1-[(2-oxoazepan-1-yl)disulfanyl]azepan-2-one Chemical compound O=C1CCCCCN1SSN1C(=O)CCCCC1 LGBYJXBCVZKJBL-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910004786 P-Li Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004796 P—Li Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- UBCPEZPOCJYHPM-UHFFFAOYSA-N dimethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OC)OC UBCPEZPOCJYHPM-UHFFFAOYSA-N 0.000 description 1
- ORHSGYTWJUDWKU-UHFFFAOYSA-N dimethoxymethyl(ethenyl)silane Chemical compound COC(OC)[SiH2]C=C ORHSGYTWJUDWKU-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 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
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SQGBZKZDUMBTIJ-UHFFFAOYSA-N n-prop-2-enylcyclohexanamine Chemical group C=CCNC1CCCCC1 SQGBZKZDUMBTIJ-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UWSYCPWEBZRZNJ-UHFFFAOYSA-N trimethoxy(2,4,4-trimethylpentyl)silane Chemical compound CO[Si](OC)(OC)CC(C)CC(C)(C)C UWSYCPWEBZRZNJ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Description
a)全重量に対して5重量%から40重量%のスチレン及び60重量%から95重量%の1,3−ブタジエンからなる配合物を、少なくとも1種の炭化水素溶媒、一般式LiR1(式中、R1は直鎖又は分岐状のC3〜C10アルキル基を表す)で表される少なくとも1種のリチウム系触媒と、テトラヒドロフラン(THF)、テトラヒドロフルフリルエチルエーテル(THFAエチル)のエーテル類及びN,N,N’,N’−テトラメチルエチレンジアミン(TMEDA)のジアミン類から成る群より選択される少なくとも1種の極性改良剤の存在下でアニオン重合する工程と、
b)任意で、工程(a)で得られたコポリマーを、1,3−ブタジエン、スチレン及びα−メチルスチレンから選択される少なくとも1種の末端モノマーと反応させる工程と、
c)工程(a)又は工程(b)で得られたコポリマー中に存在するリチウム末端ポリマー鎖のうち、10重量%から70重量%、好ましくは20重量%から50重量%を、炭素−リチウム鎖の末端と反応可能な反応サイトを少なくとも3つ有する液体ポリエポキシドから選択される少なくとも1種のカップリング剤と反応させる工程と、
d)任意で、工程(c)で得られたコポリマーを、1,3−ブタジエン、スチレン及びα−メチルスチレンから選択される少なくとも1種の末端モノマーと反応させる工程と、
e)工程(c)又は工程(d)で得られたコポリマー中に残存するポリマー直鎖を、一般式XSn(R2)3(式中、Xは例えば塩素などのハロゲン原子を表し、R2は直鎖又は分岐C1〜C10アルキル基を表す)で表される少なくとも1種のスズ化合物と反応させる工程と、を有する上記製造方法に関する。
ここで注目すべきは、ポリマー−スズ結合が存在することによって、コポリマー/カーボンブラック間の相互作用が特に改善されている点である。
本発明及び下記の請求の範囲において、用語「phr」は、加硫性エラストマー組成物中の(コ)ポリマー100重量部に対する、ある成分の重量部を示す。
前記加硫剤は、例えば溶解性もしくは不溶性の元素硫黄、又は硫黄供与体、又はそれらの混合物から選択することができる。
本発明の対象である加硫性エラストマー組成物には、その他の化合物が添加されていてもよい。
本発明のさらなる目的は、前記加硫性エラストマー組成物の加硫により得られる加硫化最終製品にも関する。
本発明の加硫化最終製品は、好ましくは道路車両用タイヤ、より好ましくは道路車両用タイヤのトレッドである。
16リットル容の反応器に、重量比9/1のシクロヘキサン/ヘキサン無水混合物8000g(充填率80%相当)及び極性改良剤(テトラヒドロフルフリルエチルエーテル、THFAエチル)3.12g(255ppm相当、開始剤の論理量とのモル比約3:1)を仕込み、次いでスチレン300g及び1,3−ブタジエン840gを撹拌下で仕込む。得られた反応混合物を、加熱ジャケットで温度40℃まで加熱する。次いで、n−ブチルリチウム0.51gのn−ヘキサン溶液(15重量%溶液3.41g)を加える。次いで、ジャケットによる加熱を終了するが、反応混合物は、発熱反応により約76℃の最終温度(ピーク温度)まで上昇する。ピーク温度に達してから10分経過後、活性末端がすべてブタジエニル型となるように、1,3−ブタジエン60gを加える(キャッピング)。遊離モノマーが無くなるまでさらに10分待った後、四塩化ケイ素0.170g(論理上、50%のカップリング効率に相当)を加える。さらに5分待ってカップリング反応を完了させた後、クロロトリメチルシラン0.434gを加えて残った活性末端を不活化する。10分後、得られた溶液をタンクに排出し、0.7phrの2,6−ジ−t−ブチルフェノール(BHT)で安定化し、水でストリップすることにより全溶液が脱溶媒部へと達するようにする。
例1の記載と同様の手順にて反応物を撹拌下にて16リットル容反応器に仕込むが、本例では、カップリング剤として四塩化スズ0.261g相当(理論上50%のカップリング効率)を導入する。その後の反応は、実施例1の記載と同様とする。
例1の記載と同様の手順にて反応物を撹拌下にて16リットル容反応器に加えるが、カップリング反応の完了は、四塩化スズ0.261gにより行う。5分後、トリオクチル塩化スズ1.30gを加えて、残った活性末端を不活化する。次いで、10分後、ポリマー溶液をタンクに排出し、そこで0.7phrの2,6−ジ−t−ブチルフェノール(BHT)により安定化し、水でストリップすることにより全溶液が脱溶媒部へと達するようにする。
16リットル容の反応器に、重量比9/1のシクロヘキサン/ヘキサンの無水混合物8000g(充填率80%相当)及び極性改良剤(テトラヒドロフルフリルエチルエーテル、THFAエチル)3.12g(255ppm相当、開始剤の論理量とのモル比約3:1)を仕込み、次いでスチレン300g及び1,3−ブタジエン840gを撹拌下にて仕込む。得られた反応混合物を、加熱ジャケットで温度40℃まで加熱する。次いで、n−ブチルリチウム0.51gのヘキサン溶液(15重量%溶液3.41g)を加える。次いで、ジャケットによる加熱を終了するが、反応混合物は、発熱反応により約76℃の最終温度(ピーク温度)まで上昇する。ピーク温度に達してから10分経過後、活性末端がすべてブタジエニル型となるように、1,3−ブタジエン60gを加える(キャッピング)。遊離モノマーが無くなるまでさらに10分待った後、エポキシ化大豆油0.3g(論理上、およそ50%のカップリング効率に相当)を加える。さらに5分後、トリオクチル塩化スズ1.30gを加えて残った活性末端を不活化する。10分後、得られた溶液をタンクに排出し、そこで0.7phrの2,6−ジ−t−ブチルフェノール(BHT)で安定化し、水でストリップすることにより全溶液が脱溶媒部へと達するようにする。
次いで、ISO規格6502に従って、試料を160℃で加硫化した。
NR:天然ゴム
BR:シス−1,4−ポリブタジエン(Europrene(登録商標)NeocisBR40(Polimeri Europa))
N220:カーボンブラック
シリカ:Ultrasil(登録商標)VN3(EgesylKimia)
ナフテン油:ASTMタイプ103HV(日本サン石油)
6−PPD:Santoflex(登録商標)13(Monsanto)
パラフィンワックス:Riowax(登録商標)721(Andrea Gallo Di Luigi s.r.l.)
Polyplastol(登録商標)6:脂肪酸(パルミチン酸、ステアリン酸、オレイン酸が主体)の亜鉛塩混合物(Great Lakes Chemical社)
シラン:Si69(登録商標)(Evonik)
DPG(促進剤):ジフェニルグアニジン(Rhenogran(登録商標)DPG80(Rhein Chemie))
TBBS(促進剤):N−t−ブチル−ベンゾチアゾール−2−スルフェンアミド(Vulkacit(登録商標)NZ/ECG(Lanxess))
PVI(遅延剤):N−シクロヘキシル−チオフタルイミド(Santogard(登録商標)PVI(Flexsys))
次いで、ISO規格6502に従って、試料を160℃で加硫化した。
BR:シス−1,4−ポリブタジエン(Europrene(登録商標)Neocis BR40(PolimeriEuropa))
N220:カーボンブラック
シリカ:Ultrasil(登録商標)VN3(Egesyl Kimia)
ナフテン油:Nitex(登録商標)840(Nynas)
6−PPD:Santoflex(登録商標)13(Monsanto)
パラフィンワックス:Riowax(登録商標)721(Andrea Gallo Di Luigi s.r.l.)
Polyplastol(登録商標)6:脂肪酸(パルミチン酸、ステアリン酸、オレイン酸が主体)の亜鉛塩混合物(Great Lakes Chemical社)
シラン:Si69(登録商標)(Evonik)
DPG(促進剤):ジフェニルグアニジン(Rhenogran(登録商標)DPG80(Rhein Chemie))
TBBS(促進剤):N−t−ブチル−ベンゾチアゾール−2−スルフェンアミド(Vulkacit(登録商標)NZ/ECG(Lanxess))
PVI(遅延剤):N−シクロヘキシル−チオフタルイミド(Santogard(登録商標)PVI(Flexsys))
「動的歪み分散測定」(60℃におけるtanδ、転がり抵抗)の設定
周波数:10Hz
温度:0℃及び60℃
歪み範囲:0.1%÷10%
形状:矩形ねじり
「動的時間分散測定」(0℃におけるtanδ、濡れグリップ)の設定
温度範囲:2℃/分で、−130℃÷100℃
周波数:1Hz
歪み:0.1%
形状:矩形ねじり
冷却:3℃/分
Claims (9)
- 1,3−ブタジエン−スチレンコポリマーの製造方法であって、
a)全重量に対して5重量%から40重量%のスチレン及び60重量%から95重量%の1,3−ブタジエンを含む配合物を、少なくとも1種の炭化水素溶媒、一般式LiR1(式中、R1は直鎖又は分岐状のC3〜C10アルキル基を表す)で表される少なくとも1種のリチウム系触媒と、テトラヒドロフラン(THF)、テトラヒドロフルフリルエチルエーテル(THFAエチル)のエーテル類及びN,N,N’,N’−テトラメチルエチレンジアミン(TMEDA)のジアミン類から成る群より選択される少なくとも1種の極性改良剤の存在下でアニオン重合する工程と、
b)任意で、工程(a)で得られたコポリマーを、1,3−ブタジエン、スチレン及びα−メチルスチレンから選択される少なくとも1種の末端モノマーと反応させる工程と、
c)工程(a)又は工程(b)で得られたコポリマー中に存在するリチウム末端ポリマー鎖のうち、10重量%から70重量%を、炭素−リチウム鎖の末端と反応可能な反応サイトを少なくとも3つ有する液体ポリエポキシドから選択される少なくとも1種のカップリング剤と反応させる工程と、
d)任意で、工程(c)で得られたコポリマーを、1,3−ブタジエン、スチレン及びα−メチルスチレンから選択される少なくとも1種の末端モノマーと反応させる工程と、
e)工程(c)又は工程(d)で得られたコポリマー中に残存するポリマー直鎖を、一般式XSn(R2)3(式中、Xは塩素などのハロゲン原子を表し、R2は直鎖又は分岐C1〜C10アルキル基を表す)で表される少なくとも1種のスズ化合物と反応させる工程と、を有する上記製造方法。 - 前記アニオン重合が0℃から150℃の温度範囲で行われる、請求項1に記載の方法。
- 前記極性改良剤がテトラヒドロフルフリルエチルエーテル(THFAエチル)である、請求項1又は2に記載の方法。
- 前記極性改良剤が、反応混合物中において500ppmから1000ppmとなる量で用いられる、請求項3に記載の方法。
- 工程(b)において、前記反応性モノマーが0重量%から10重量%の量で用いられる、請求項1〜4のいずれか1項に記載の方法。
- 前記カップリング剤がエポキシ化植物油から選択される、請求項1〜5のいずれか1項に記載の方法。
- 前記エポキシ化植物油が、エポキシ化大豆油、エポキシ化アマニ油又はそれらの混合物から選択される、請求項6に記載の方法。
- 前記スズ化合物が、トリメチル塩化スズ、トリブチル塩化スズ、トリペンチル塩化スズ、トリオクチル塩化スズ又はそれらの混合物から選択される、請求項1〜7のいずれか1項に記載の方法。
- 前記スズ化合物がトリオクチル塩化スズである、請求項8に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI2011A001198 | 2011-06-29 | ||
IT001198A ITMI20111198A1 (it) | 2011-06-29 | 2011-06-29 | "procedimento per la preparazione di copolimeri di 1,3-butadiene e stirene e loro impiego in composizioni elastomeriche vulcanizzabili" |
PCT/EP2012/061981 WO2013000817A1 (en) | 2011-06-29 | 2012-06-21 | Process for the preparation of 1,3-butadiene and styrene copolymers and use thereof in vulcanizable elastomeric compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014523941A JP2014523941A (ja) | 2014-09-18 |
JP6046131B2 true JP6046131B2 (ja) | 2016-12-14 |
Family
ID=44504075
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014517606A Active JP6046131B2 (ja) | 2011-06-29 | 2012-06-21 | 1,3−ブタジエン−スチレンコポリマーの製造方法及びその加硫性エラストマー組成物における使用 |
Country Status (18)
Country | Link |
---|---|
US (1) | US9416200B2 (ja) |
EP (1) | EP2726514B1 (ja) |
JP (1) | JP6046131B2 (ja) |
KR (1) | KR101931841B1 (ja) |
CN (1) | CN103608362B (ja) |
BR (1) | BR112013031905B1 (ja) |
CA (1) | CA2838791C (ja) |
HU (1) | HUE038312T2 (ja) |
IT (1) | ITMI20111198A1 (ja) |
MX (1) | MX362796B (ja) |
MY (1) | MY164463A (ja) |
PT (1) | PT2726514T (ja) |
RU (1) | RU2597016C2 (ja) |
SI (1) | SI2726514T1 (ja) |
TR (1) | TR201802338T4 (ja) |
TW (1) | TWI564311B (ja) |
WO (1) | WO2013000817A1 (ja) |
ZA (1) | ZA201308177B (ja) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10179479B2 (en) | 2015-05-19 | 2019-01-15 | Bridgestone Americas Tire Operations, Llc | Plant oil-containing rubber compositions, tread thereof and race tires containing the tread |
DE102015224450A1 (de) * | 2015-12-07 | 2017-06-08 | Evonik Degussa Gmbh | Kautschukmischungen |
MX2019001542A (es) * | 2016-08-11 | 2019-08-29 | Versalis Spa | Proceso para la purificacion del solvente que se deriva de la produccion de combinaciones elastomericas. |
FR3060452A1 (fr) * | 2016-12-20 | 2018-06-22 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour vehicule portant des lourdes charges comprenant une nouvelle bande de roulement |
KR102161967B1 (ko) * | 2018-10-02 | 2020-10-06 | 금호석유화학 주식회사 | 다기능화 고시스 1,4-폴리부타디엔의 제조방법 |
JP2023513541A (ja) * | 2020-10-12 | 2023-03-31 | エルジー・ケム・リミテッド | 油展変性共役ジエン系重合体、その製造方法、及びそれを含むゴム組成物 |
CN112707994B (zh) * | 2020-12-11 | 2022-10-21 | 北京化工大学 | 一种端环氧功能化溶聚丁苯橡胶的制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0755964B2 (ja) * | 1985-12-28 | 1995-06-14 | 旭化成工業株式会社 | 改良されたゴム状重合体の製造方法 |
US5134199A (en) * | 1987-11-27 | 1992-07-28 | Asahi Kasei Kogyo Kabushiki Kaisha | Diene block polymer and polymer composition |
US5231153A (en) * | 1992-04-06 | 1993-07-27 | The Goodyear Tire & Rubber Company | Anionic polymerization of conjugated dienes modified with alkyltetrahydrofurfuryl ethers |
FI118425B (fi) * | 1994-02-24 | 2007-11-15 | Fina Research | Menetelmä konjugoituneiden vinyyliaromaattisten dieeni-lohkokopolymeerien käsittelemiseksi |
ES2116199B1 (es) * | 1995-07-17 | 1999-04-01 | Repsol Quimica Sa | Procedimiento de preparacion de copolimeros de 1,3 butadieno y estireno utiles para la fabricacion de neumaticos con baja resistencia a la rodadura y copolimeros de 1,3-butadieno y estireno asi obtenidos, |
US6518350B1 (en) * | 1999-07-30 | 2003-02-11 | Jsr Corporation | Rubber composition and tire |
JP4332690B2 (ja) | 1999-11-12 | 2009-09-16 | Jsr株式会社 | ゴム組成物 |
JPWO2008044722A1 (ja) * | 2006-10-11 | 2010-02-18 | 日本ゼオン株式会社 | 油展ゴム組成物、その製造方法、タイヤ用部材及びタイヤ |
FR2915202B1 (fr) * | 2007-04-18 | 2009-07-17 | Michelin Soc Tech | Elastomere dienique couple monomodal possedant une fonction silanol en milieu de chaine, son procede d'obtention et composition de caoutchouc le contenant. |
-
2011
- 2011-06-29 IT IT001198A patent/ITMI20111198A1/it unknown
-
2012
- 2012-06-21 SI SI201231200T patent/SI2726514T1/en unknown
- 2012-06-21 BR BR112013031905A patent/BR112013031905B1/pt active IP Right Grant
- 2012-06-21 MY MYPI2013004547A patent/MY164463A/en unknown
- 2012-06-21 PT PT127313724T patent/PT2726514T/pt unknown
- 2012-06-21 RU RU2014101634/04A patent/RU2597016C2/ru active
- 2012-06-21 US US14/127,339 patent/US9416200B2/en active Active
- 2012-06-21 MX MX2013015040A patent/MX362796B/es active IP Right Grant
- 2012-06-21 EP EP12731372.4A patent/EP2726514B1/en active Active
- 2012-06-21 TR TR2018/02338T patent/TR201802338T4/tr unknown
- 2012-06-21 WO PCT/EP2012/061981 patent/WO2013000817A1/en active Application Filing
- 2012-06-21 KR KR1020147001782A patent/KR101931841B1/ko active IP Right Grant
- 2012-06-21 CA CA2838791A patent/CA2838791C/en not_active Expired - Fee Related
- 2012-06-21 CN CN201280029899.9A patent/CN103608362B/zh active Active
- 2012-06-21 JP JP2014517606A patent/JP6046131B2/ja active Active
- 2012-06-21 HU HUE12731372A patent/HUE038312T2/hu unknown
- 2012-06-28 TW TW101123144A patent/TWI564311B/zh active
-
2013
- 2013-10-31 ZA ZA2013/08177A patent/ZA201308177B/en unknown
Also Published As
Publication number | Publication date |
---|---|
BR112013031905A2 (pt) | 2017-07-18 |
US20140155543A1 (en) | 2014-06-05 |
EP2726514A1 (en) | 2014-05-07 |
SI2726514T1 (en) | 2018-03-30 |
ITMI20111198A1 (it) | 2012-12-30 |
JP2014523941A (ja) | 2014-09-18 |
MX2013015040A (es) | 2014-01-24 |
WO2013000817A1 (en) | 2013-01-03 |
RU2014101634A (ru) | 2015-08-10 |
KR101931841B1 (ko) | 2018-12-21 |
MX362796B (es) | 2019-02-13 |
EP2726514B1 (en) | 2017-11-22 |
US9416200B2 (en) | 2016-08-16 |
KR20140044872A (ko) | 2014-04-15 |
CA2838791A1 (en) | 2013-01-03 |
PT2726514T (pt) | 2018-01-09 |
RU2597016C2 (ru) | 2016-09-10 |
ZA201308177B (en) | 2014-07-30 |
HUE038312T2 (hu) | 2018-10-29 |
CN103608362B (zh) | 2015-07-29 |
CA2838791C (en) | 2019-01-08 |
BR112013031905B1 (pt) | 2020-02-04 |
TWI564311B (zh) | 2017-01-01 |
TW201313758A (zh) | 2013-04-01 |
MY164463A (en) | 2017-12-15 |
TR201802338T4 (tr) | 2018-03-21 |
CN103608362A (zh) | 2014-02-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6046131B2 (ja) | 1,3−ブタジエン−スチレンコポリマーの製造方法及びその加硫性エラストマー組成物における使用 | |
JP6218259B2 (ja) | 変性共役ジエン系重合体、その製造方法、およびこれを含むゴム組成物 | |
US10421767B2 (en) | Aminosilane-functionalized dienes for use in functionalization of elastomeric polymers | |
US10858377B2 (en) | Multivinylaminosilanes as branching agents for functionalized elastomeric polymers | |
US8895684B2 (en) | Modified polymer compositions | |
TW201522385A (zh) | 經矽烷改質之彈性聚合物 | |
TW201714896A (zh) | 彈性體聚合物 | |
JP6263526B2 (ja) | 官能化および分枝化されたエラストマー性コポリマーの調製方法 | |
JP6724018B2 (ja) | 機能化弾性ポリマー組成物、その製造方法及びその架橋ゴム組成物 | |
WO2018150043A1 (en) | Metallated benzylsilanes and their use as polymerization initiators | |
US20200055881A1 (en) | Multivinylaminosilanes as branching agents for functionalized elastomeric polymers | |
WO2023129997A1 (en) | Natural rubber compositions for pneumatic tires | |
JP2010209272A (ja) | 共役ジエン系重合体の製造方法、共役ジエン系重合体および共役ジエン系重合体組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150410 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20151216 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160303 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160713 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161003 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20161101 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161116 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6046131 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |