JPH0678376B2 - Method for producing block copolymer - Google Patents
Method for producing block copolymerInfo
- Publication number
- JPH0678376B2 JPH0678376B2 JP2270600A JP27060090A JPH0678376B2 JP H0678376 B2 JPH0678376 B2 JP H0678376B2 JP 2270600 A JP2270600 A JP 2270600A JP 27060090 A JP27060090 A JP 27060090A JP H0678376 B2 JPH0678376 B2 JP H0678376B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- block copolymer
- polymer
- group
- parts
- 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.)
- Expired - Lifetime
Links
- 229920001400 block copolymer Polymers 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims description 69
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003381 stabilizer Substances 0.000 claims description 20
- 150000001993 dienes Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002900 organolithium compounds Chemical class 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 38
- 238000000034 method Methods 0.000 description 27
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 150000007522 mineralic acids Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 238000004807 desolvation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 150000008039 phosphoramides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000006076 specific stabilizer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-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
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HRECPBLGWOTTIT-UHFFFAOYSA-N 3,9-bis(2-dodecylsulfanylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OC(CCSCCCCCCCCCCCC)OCC21COC(CCSCCCCCCCCCCCC)OC2 HRECPBLGWOTTIT-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-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
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-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
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- APMOEFCWQRJOPS-UHFFFAOYSA-N 5-ethenyl-1,5-dimethylcyclohexa-1,3-diene Chemical compound CC1=CC=CC(C)(C=C)C1 APMOEFCWQRJOPS-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- CORTZJMILBLCKC-UHFFFAOYSA-N decanoic acid;dodecanoic acid Chemical compound CCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O CORTZJMILBLCKC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 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
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical group [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- AWIJRPNMLHPLNC-UHFFFAOYSA-N thiocarboxylic acid group Chemical group C(=S)O AWIJRPNMLHPLNC-UHFFFAOYSA-N 0.000 description 1
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、共役ジエンとビニル芳香族炭化水素とのブロ
ック共重合体又はその水添物の溶液から溶媒を直接脱溶
媒するに際し、特定の処理工程と特定の安定剤を組み合
せることにより熱安定性、透明性、色調及び外観特性に
優れた重合体又はその水添物を回収する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a specific solvent for directly removing a solvent from a solution of a block copolymer of a conjugated diene and a vinyl aromatic hydrocarbon or a hydrogenated product thereof. The present invention relates to a method for recovering a polymer excellent in heat stability, transparency, color tone and appearance characteristics or a hydrogenated product thereof by combining a treatment step and a specific stabilizer.
共役ジエンとビニル芳香族炭化水素からなるブロック共
重合体は、比較的ビニル芳香族炭化水素含有量が少ない
場合、透明で加硫をしなくても加硫された天然ゴム或い
は合成ゴムと同様の弾性を常温にて有し、しかも高温で
熱可塑性樹脂と同様の加工性を有することから、履き
物、プラスチック改質、アスファルト、粘接着分野等で
広く利用されている。又、比較的ビニル芳香族炭化水素
含有量が多い場合は、透明で耐衝撃性に優れた熱可塑性
樹脂が得られることから、食品包装容器分野を中心に近
年その使用量が増加すると同時に用途も多様化しつつあ
る。A block copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon is transparent and has a similar content to vulcanized natural rubber or synthetic rubber without vulcanization when the vinyl aromatic hydrocarbon content is relatively low. Since it has elasticity at room temperature and has the same processability as a thermoplastic resin at high temperature, it is widely used in the fields of footwear, plastic modification, asphalt, adhesive bonding and the like. Further, when the content of vinyl aromatic hydrocarbons is relatively high, a transparent thermoplastic resin having excellent impact resistance can be obtained, so that the amount of its use has increased in recent years mainly in the field of food packaging containers, and at the same time, it has applications. It is diversifying.
これらの共重合体を製造するに際しては、触媒に対して
不活性な炭化水素溶媒中で通常重合が行われ、生成した
共重合体は溶媒に均一に溶融しているか、あるいは懸濁
した状態で得られるため、共重合体と溶媒とを分離し、
共重合体を回収する工程が必要となる。共重合体と溶媒
とを分離する方法としては種々の方法があるが、その一
つとして重合体溶液を直接加熱濃縮し脱溶媒して重合体
を回収する方法が知られている。When producing these copolymers, the polymerization is usually carried out in a hydrocarbon solvent which is inert to the catalyst, and the produced copolymer is uniformly melted or suspended in the solvent. Since it is obtained, the copolymer and the solvent are separated,
A step of recovering the copolymer is required. There are various methods for separating the copolymer and the solvent, and as one of them, a method is known in which the polymer solution is directly heated and concentrated and the solvent is removed to recover the polymer.
例えば、特開昭50−76172号公報、特公昭51−6105号公
報、特公昭57−47685号公報、特公昭57−51407号公報等
にはゴムやプラスチック、或いはブロック共重合体の溶
液から溶媒を２軸ベント押出機を用いて直接脱溶媒する
方法が記載されている。For example, in JP-A-50-76172, JP-B-51-6105, JP-B-57-47685, JP-B-57-51407, etc., rubber or plastic, or a solution of a block copolymer from a solvent is used. Is described as a method for directly desolventizing a solvent using a twin-screw vent extruder.
前述の様に重合体溶液を加熱、濃縮することによって直
接脱溶媒する方法は高温で高粘度液を取り扱う一般的な
困難さに加えて回収された重合体の品質面、得に熱安定
性、透明性、色調に劣り、重合体又は水添物を厳しい条
件下で加工処理したり、押出機で再生処理する様な場
合、ゲル化又はシャッ解を起し、ポリマーが変色すると
いう問題点を有する。As described above, the method of directly removing the solvent by heating and concentrating the polymer solution is not only the general difficulty of handling a high-viscosity liquid at high temperature, but also the quality of the recovered polymer, especially the thermal stability, When the polymer or hydrogenated product is inferior in transparency and color tone, is processed under severe conditions, or is regenerated by an extruder, gelation or shuffling occurs, and the problem of discoloration of the polymer occurs. Have.
本発明者らは重合体溶液から溶媒を直接脱溶媒する方法
において、従来技術の上記欠点を解決すべく鋭意検討し
た結果、熱安定性、透明性、色調及び外観特性に優れる
重合体又はその水添物を回収するに際し、特定の処理工
程と特定の安定剤を組み合せることによりその目的が達
成されることを見い出し、本発明を完成した。In the method of directly desolvating a solvent from a polymer solution, the present inventors have conducted extensive studies to solve the above-mentioned drawbacks of the prior art, and have excellent thermal stability, transparency, color tone and appearance characteristics, or a polymer thereof. It was found that the object can be achieved by combining a specific processing step and a specific stabilizer in recovering the additive, and thus the present invention has been completed.
即ち、本発明は、 炭化水素溶媒中、有機リチウム化合物を開始剤として共
役ジエン及びビニル芳香族炭化水素を重合せしめて得ら
れた、ビニル芳香族炭化水素含有量が５〜95重量％であ
るブロック共重合体又はその水添物の溶液から溶媒を直
接脱溶媒することによりブロック共重合体又はその水添
物を取得するにあたり、 （イ）ブロック共重合体又はその水添物の溶液に、 (a) 水 (b) アルコール (c) 無機酸 (d) 有 機 酸 から選ばれる少なくとも１種の反応停止剤を添加した
後、 （ロ）前記ブロック共重合体又はその水添物の溶液に (A) 下記一般式〔Ｉ〕で示されるフェノール系化合物
を重合体100重量部に対して0.05〜５重量部 （上式において、R1は炭素数５以上のアルキル基、R2は
炭素数２〜４のアルケニル基、R3は炭素数４〜22のアル
キル基又はシクロヘキシル基、R4は水素又は炭素数１〜
18のアルキル基を示す。） (B) 上記一般式〔Ｉ〕で示したフェノール系化合物以
外のフェノール系安定剤を重合体100重量部に対して0.0
1〜３重量部添加すること からなるブロック共重合体の製造方法に関する。That is, the present invention is a block having a vinyl aromatic hydrocarbon content of 5 to 95% by weight, which is obtained by polymerizing a conjugated diene and a vinyl aromatic hydrocarbon with an organic lithium compound as an initiator in a hydrocarbon solvent. In obtaining the block copolymer or its hydrogenated product by directly removing the solvent from the solution of the copolymer or its hydrogenated product, (a) in the solution of the block copolymer or its hydrogenated product, a) Water (b) Alcohol (c) Inorganic acid (d) Organic acid After adding at least one kind of reaction terminator, (b) to the solution of the block copolymer or its hydrogenated product ( A) 0.05 to 5 parts by weight of the phenolic compound represented by the following general formula [I] per 100 parts by weight of the polymer. (In the above formula, R 1 is an alkyl group having 5 or more carbon atoms, R 2 is an alkenyl group having 2 to 4 carbon atoms, R 3 is an alkyl group having 4 to 22 carbon atoms or a cyclohexyl group, and R 4 is hydrogen or a carbon number. 1 to
18 alkyl groups are shown. (B) A phenolic stabilizer other than the phenolic compound represented by the above general formula [I] is added in an amount of 0.0 to 100 parts by weight of the polymer.
It relates to a method for producing a block copolymer, which comprises adding 1 to 3 parts by weight.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明で使用される共役ジエンとビニル芳香族炭化水素
とのブロック共重合体又はその水添物のビニル芳香族炭
化水素含有量は、一般に５〜95重量％、好ましくは10〜
90重量％である。The vinyl aromatic hydrocarbon content of the block copolymer of the conjugated diene and vinyl aromatic hydrocarbon used in the present invention or the hydrogenated product thereof is generally 5 to 95% by weight, preferably 10 to
90% by weight.
ブロック共重合体の製造方法としては、例えば特公昭36
−19286号公報、特公昭43−17979号公報、特公昭46−32
415号公報、特公昭49−36957号公報、特公昭48−2423号
公報、特公昭48−4106号公報、特公昭5628925号公報、
特公昭51−49567号公報、特開昭59−166518公報、特開
昭60−186577号公報などに記載された方法があげられ
る。これらの方法により、ブロック共重合体は一般式、 （Ａ−Ｂ）n,AＢ−Ａ）n,AＡ−Ｂ）ｎ （上式において、Ａはビニル芳香族炭化水素を主とする
重合体ブロックであり、Ｂは共役ジエンを主とする重合
体ブロックである。ＡブロックとＢブロックとの境界は
必ずしも明瞭に区別される必要はない。又、ｎは１以上
の整数である。） あるいは一般式 〔（Ｂ−Ａｎm+1X,〔（Ａ−Ｂｎn+1X, 〔（Ｂ−ＡnBm+1X,〔（Ａ−ＢnAm+1X （上式において、A,Bは前記と同じてあり、Ｘは例えば
四塩化ケイ素、四塩化スズ、エポキシ化大豆油、ポリハ
ロゲン化炭化水素、カルボン酸エステル、ポリビニル化
合物などのカップリング剤の残基又は多官能有機リチウ
ム化合物等の開始剤の残基を示す。ｍ及びｎは１以上の
整数である。） で表わされるブロック共重合体として得られる。尚、上
式において、ビニル芳香族炭化水素を主とする重合体ブ
ロックとはビニル芳香族炭化水素を50重量％以上含有す
るビニル芳香族炭化水素と共役ジエンとの共重合体ブロ
ック及び／又はビニル芳香族炭化水素単独重合体ブロッ
クを示し、共役ジエンを主とする重合体ブロックとは共
役ジエンを50重量％を超える量で含有する共役ジエンと
ビニル芳香族炭化水素との共重合体ブロック及び／又は
共役ジエン単独重合体ブロックを示す。共重合体ブロッ
ク中のビニル芳香族炭化水素は均一に分布していても、
又テーパー状に分布していてもよい。又、諸共重合体部
分はビニル芳香族炭化水素が均一に分布している部分及
び／又はテーパー状に分布している部分がそれぞれ複数
個共存してもよい。本発明で使用するブロック共重合体
は上記一般式で表わされるブロック共重合体の任意の混
合物でよい。Examples of the method for producing the block copolymer include, for example, Japanese Patent Publication Sho 36
-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32
415, JP-B-49-36957, JP-B-48-2423, JP-B-48-4106, JP-B-5628925,
The methods described in JP-B-51-49567, JP-A-59-166518, JP-A-60-186577 and the like can be mentioned. According to these methods, the block copolymer is represented by the general formula: (AB) n, AB-A) n, AA-B) n (wherein A is a polymer block mainly containing vinyl aromatic hydrocarbons). And B is a polymer block mainly composed of a conjugated diene. The boundary between the A block and the B block does not necessarily need to be clearly distinguished, and n is an integer of 1 or more.) Or general Formula [(B-Anm +1 X, [(A-Bnn +1 X, [(B-AnBm +1 X, [(A-BnAm +1 X (wherein A and B are the same as the above. , X is, for example, a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, an epoxidized soybean oil, a polyhalogenated hydrocarbon, a carboxylic acid ester or a polyvinyl compound, or a residue of an initiator such as a polyfunctional organolithium compound. Where m and n are integers of 1 or more.) In the above formula, the polymer block mainly containing vinyl aromatic hydrocarbon means a copolymer block of vinyl aromatic hydrocarbon and conjugated diene containing 50% by weight or more of vinyl aromatic hydrocarbon. And / or a vinyl aromatic hydrocarbon homopolymer block, and a polymer block containing a conjugated diene as a main component means a copolymerization weight of a conjugated diene containing a conjugated diene in an amount of more than 50% by weight and a vinyl aromatic hydrocarbon. Shows a polymer block and / or a conjugated diene homopolymer block, even if the vinyl aromatic hydrocarbon in the copolymer block is evenly distributed,
Further, it may be distributed in a taper shape. In addition, a plurality of portions where the vinyl aromatic hydrocarbons are uniformly distributed and / or portions where the vinyl aromatic hydrocarbons are distributed in a taper shape may coexist in each of the copolymer portions. The block copolymer used in the present invention may be any mixture of the block copolymers represented by the above general formula.
この様にして得られたブロック共重合体はビニル芳香族
炭化水素の含有量が60重量％以下、好ましくは55重量％
以下の場合は熱可塑性弾性体としての特性を示し、ビニ
ル芳香族炭化水素の含有量が60重量％を超える場合、好
ましくは65重量％以上の場合は熱可塑性樹脂としての特
性を示す。The block copolymer thus obtained has a vinyl aromatic hydrocarbon content of 60% by weight or less, preferably 55% by weight.
The following cases show characteristics as a thermoplastic elastic body, and a vinyl aromatic hydrocarbon content of more than 60% by weight, preferably 65% by weight or more, shows characteristics as a thermoplastic resin.
本発明の方法で用いるビニル芳香族炭化水素としてはス
チレン、ｏ−メチルスチレン、ｐ−メチルスチレン、ｐ
−tert−ブチルスチレン、1,3−ジメチルスチレン、α
−メチルスチレン、ビニルナフタレン、ビニルアントラ
センなどがあるが、特に一般的なものとしてはスチレン
が挙げられる。これらは１種のみならず２種以上混合し
て使用してもよい。Examples of the vinyl aromatic hydrocarbon used in the method of the present invention are styrene, o-methylstyrene, p-methylstyrene, p
-Tert-butylstyrene, 1,3-dimethylstyrene, α
-Methyl styrene, vinyl naphthalene, vinyl anthracene, etc., but styrene is particularly common. These may be used alone or in combination of two or more.
本発明で用いる共役ジエンとは、１対の共役二重結合を
有するジオレフインであり、たとえば、1,3−ブタジエ
ン、２−メチル−1,3−ブタジエン（イソプレン）、2,3
−ジメチル−1,3−ブタジエン、1,3−ペンタジエン、1,
3−ヘキサジエンなどがあるが、特に一般的なものとし
ては1,3−ブタジエン、イソプレンが挙げられる。これ
らは１種のみならず２種以上混合して使用してもよい。
ブロック共重合体の製造に用いられる炭化水素溶媒とし
てはブタン、ペンタン、ヘキサン、イソペンタン、ヘプ
タン、オクタン、イソオクタン等の脂肪族炭化水素、シ
クロペンタン、メチルシクロペンタン、シクロヘキサ
ン、メチルシクロヘキサン、エチルシクロヘキサン等の
脂環式炭化水素、或いはベンゼン、トルエン、エチルベ
ンゼン、キシレン等の芳香族炭化水素などが使用でき
る。これらは１種のみならず２種以上混合して使用して
もよい。又、ブロック共重合体の製造に用いられる有機
リチウム化合物は、分子中に１個以上のリチウム原子を
結合した有機モノリチウム化合物であり、例えばエチル
リチウム、ｎ−プロピルリチウム、イソプロピルリチウ
ム、ｎ−ブチルリチウム、sec−ブチルリチウム、tert
−ブチルリチウム、ヘキサメチレンジリチウム、ブタジ
エニルジリチウム、イソブレニルジリチウムなどがあげ
られる。これらは１種のみならず２種以上混合して使用
してもよい。The conjugated diene used in the present invention is a diolefin having a pair of conjugated double bonds, and examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3.
-Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,
There are 3-hexadiene and the like, and particularly common ones are 1,3-butadiene and isoprene. These may be used alone or in combination of two or more.
As the hydrocarbon solvent used in the production of the block copolymer, butane, pentane, hexane, isopentane, heptane, octane, aliphatic hydrocarbons such as isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like. Alicyclic hydrocarbons or aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or in combination of two or more. The organolithium compound used in the production of the block copolymer is an organomonolithium compound having one or more lithium atoms bonded in the molecule, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyl. Lithium, sec-butyllithium, tert
-Butyl lithium, hexamethylene dilithium, butadienyl dilithium, isobrenyl dilithium and the like. These may be used alone or in combination of two or more.
本発明で使用するブロック共重合体の製造においては重
合速度の調整、重合した共役ジエン部のミクロ構造（シ
ス、トランス、ビニルの比率）の変更、共役ジエンとビ
ルニ芳香族炭化水素の反応性比の調整などの目的で極性
化合物やランダム化剤を使用することができる。極性化
合物やランダム化剤としては、エーテル類、アミン類、
チオエーテル類、ホスホルアミド、アルキルベンゼンス
ルホン酸塩、カリウムまたはナトリウムのアルコキシド
などがあげられる。適当なエーテル類の例はジメチルエ
ーテル、ジエチルエーテル、ジフエニルエーテル及びテ
トラヒドロフラン、ジエチレングリコールジメチルエー
テル、ジエチレングリコールジブチルエーテルである。
アミン類としては第三級アミン、例えばトリメチルアミ
ン、トリエチルアミン、テトラメチルエチレンジアミン
の外、環状第三級なども使用できる。ホスフイン及びホ
スホルアミドとしてはトリフエニルホスフイン及びヘキ
サメチルホスホルアミドがある。ランダム化剤としては
アルキルベンゼンスルホン酸カリウムまたはナトリウ
ム、カリウムまたはナトリウムブトキシドなどがあげら
れる。In the production of the block copolymer used in the present invention, the polymerization rate is adjusted, the microstructure of the polymerized conjugated diene part (ratio of cis, trans, vinyl) is changed, and the reactivity ratio of the conjugated diene and the Birni aromatic hydrocarbon is adjusted. A polar compound or a randomizing agent can be used for the purpose of adjusting the above. As polar compounds and randomizing agents, ethers, amines,
Examples thereof include thioethers, phosphoramides, alkylbenzene sulfonates, potassium or sodium alkoxides, and the like. Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether and tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether.
As amines, tertiary amines such as trimethylamine, triethylamine, tetramethylethylenediamine, and cyclic tertiary amines can be used. Phosphines and phosphoramides include triphenylphosphine and hexamethylphosphoramide. Examples of the randomizing agent include potassium or sodium alkylbenzene sulfonate, potassium or sodium butoxide, and the like.
本発明においてブロック共重合体を製造する際の重合温
度は一般に−10℃ないし150℃、好ましくは40℃ないし1
20℃である。重合に要する時間は条件によって異なる
が、通常は48時間以内であり、特に好適には0.5ないし1
0時間である。また、重合系の雰囲気は窒素ガスなどの
不活性ガスをもって置換することが望ましい。重合圧力
は、上記重合温度範囲でモノマー及び溶媒を液相に維持
するに充分な圧力の範囲で行えばよく、特に限定される
ものではない。さらに重合系内には触媒及びリビングポ
リマーを不活性化させるような不純物、たとえば、酸
素、炭酸ガスなどが混入しないように留意する必要があ
る。The polymerization temperature in producing the block copolymer in the present invention is generally -10 ° C to 150 ° C, preferably 40 ° C to 1
20 ° C. The time required for polymerization varies depending on the conditions, but is usually within 48 hours, particularly preferably 0.5 to 1
It's 0 hours. Further, it is desirable to replace the atmosphere of the polymerization system with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is necessary to take care so that impurities that inactivate the catalyst and the living polymer, such as oxygen and carbon dioxide, do not enter the polymerization system.
この様にして得られたブロック共重合体の数平均分子量
は、一般に10,000〜1,000,000、好ましくは20,000〜80
0,000、更に好ましくは30,000〜500,000である。又ブロ
ック共重合体溶液中の炭化水素の量は、一般に重合体10
0重量部に対して150重量部〜2000重量部である。尚、ブ
ロック共重合体の性質によってはブロック共重合体が炭
化水素溶媒に不溶で懸濁の状態で得られる場合もある
が、本発明においてはこれらもブロック共重合体溶液と
よぶことにする。The number average molecular weight of the block copolymer thus obtained is generally 10,000 to 1,000,000, preferably 20,000 to 80.
It is 0,000, more preferably 30,000 to 500,000. The amount of hydrocarbons in the block copolymer solution is generally 10
150 to 2000 parts by weight with respect to 0 parts by weight. Incidentally, depending on the properties of the block copolymer, the block copolymer may be obtained in a state of being insoluble in a hydrocarbon solvent, but in the present invention, these are also referred to as a block copolymer solution.
本発明で使用するブロック共重合体は、重合体の少なく
とも１つの重合体鎖末端に極性基含有原子団が結合した
末端変性ブロック共重合体を使用することができる。こ
こで極性基含有原子団とは、窒素、酸素、ケイ素、リ
ン、硫黄、スズから選ばれる原子を少なくとも１種含有
する原子団を云う。具体的には、カルボキシル基、カル
ボニル基、チオカルボニル基、酸ハロゲン化物基、酸無
水物基、カルボン酸基、チオカルボン酸基、アルデヒド
基、チオアルデヒド基、カルボン酸エステル基、アミド
基、スルホン酸基、スルホン酸エステル基、リン酸基、
リン酸エステル基、アミノ基、イミノ基、ニトリル基、
ピリジル基、キノリン基、エポキシ基、チオエポキシ
基、スルフイド基、イソシアネート基、イソチオシアネ
ート基、ハロゲン化ケイ素基、アルコキシケイ素基、ハ
ロゲン化スズ基、アルキルスズ基、フエニルスズ基等か
ら選ばれる極性基を少なくとも１種含有する原子団があ
げられる。より具体的には、特願昭60−224806号公報に
記載された末端変性ブロック共重合体を使用できる。As the block copolymer used in the present invention, a terminal-modified block copolymer in which a polar group-containing atomic group is bonded to at least one polymer chain end of the polymer can be used. Here, the polar group-containing atomic group means an atomic group containing at least one atom selected from nitrogen, oxygen, silicon, phosphorus, sulfur and tin. Specifically, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid Group, sulfonate group, phosphate group,
Phosphate group, amino group, imino group, nitrile group,
At least one polar group selected from a pyridyl group, a quinoline group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, an alkoxy silicon group, a tin halide group, an alkyltin group, a phenyltin group, and the like. An atomic group containing a seed can be given. More specifically, the terminal modified block copolymer described in Japanese Patent Application No. 60-224806 can be used.
又、本発明においては、上記で得られたブロック共重合
体又は変性ブロック共重合体を水添反応（水素添加反
応）により部分的に、或いは選択的に水添するとができ
る。水添率は任意に選定することができ、未水添重合体
の特性を維持しながら耐熱劣化性等を向上させる場合に
は共役ジエンに基づく脂肪族二重結合を３％以上、80％
未満、好ましくは５％以上、75％未満水添することが、
又耐熱劣化性及び耐候性を向上させる場合には80％以
上、好ましくは90％以上水添することが推奨される。こ
の場合、ビニル芳香族化合物を主体とする重合体ブロッ
クＡ及び必要に応じて共役ジエン化合物を主体とする重
合体ブロックＢに共重合されているビニル芳香族化合物
に基づく芳香族二重結合の水添加率については特に限定
はないが、水素添加率を20％以下にするのが好ましい。
該水添ブロック共重合体中に含まれる末水添の脂肪族二
重結合の量は、赤外分光度計、外磁気共鳴装置等により
容易に知ることができる。水添反応に使用される触媒と
しては、(1)Ni,Pt,Pd,Ru等の金属をカーボン、シリカ、
アルミナ、ケイソウ土等の担持させた担持型不均一系触
媒と、(2)Ni,Co,Fe,Cr等の有機酸塩又はアセチルアセト
ン塩と有機Al等の還元剤とを用いるいわゆるチーグラー
型触媒、あるいはRu,Rh等の有機金属化合物等のいわゆ
る有機錯触媒等の均一触媒が知られている。具体的な方
法としては特公昭42−8704号公報、特公昭43−6636号公
報、あるいは特開昭59−133203号公報、特開昭60−2201
47号公報に記載された方法により、不活性溶媒中で水素
添加触媒の存在下に水素添加して、水添物を得、本発明
に供する水添ブロック共重合体を合成することができ
る。その際、ブロック共重合体中の共役ジエン化合物に
基づく脂肪族二重結合の水添率は、反応温度、反応時
間、水素供給量、触媒量等を調整することにより任意の
値にコントロールできる。In the present invention, the block copolymer or modified block copolymer obtained above can be partially or selectively hydrogenated by hydrogenation reaction (hydrogenation reaction). The hydrogenation rate can be arbitrarily selected. When improving the heat deterioration resistance while maintaining the properties of the unhydrogenated polymer, the aliphatic double bond based on the conjugated diene is 3% or more and 80% or more.
Less than, preferably 5% or more, less than 75% hydrogenation,
Further, in the case of improving heat deterioration resistance and weather resistance, it is recommended to hydrogenate 80% or more, preferably 90% or more. In this case, water of an aromatic double bond based on the vinyl aromatic compound copolymerized with the polymer block A mainly containing the vinyl aromatic compound and, if necessary, the polymer block B mainly containing the conjugated diene compound. The addition rate is not particularly limited, but the hydrogen addition rate is preferably 20% or less.
The amount of the end-hydrogenated aliphatic double bond contained in the hydrogenated block copolymer can be easily known by an infrared spectrometer, an external magnetic resonance apparatus or the like. The catalyst used in the hydrogenation reaction, (1) Ni, Pt, Pd, Ru metal such as carbon, silica,
Alumina, a supported heterogeneous catalyst supported diatomaceous earth, and (2) Ni, Co, Fe, so-called Ziegler type catalyst using an organic acid salt or acetylacetone salt such as Cr and a reducing agent such as organic Al, Alternatively, homogeneous catalysts such as so-called organic complex catalysts such as organic metal compounds such as Ru and Rh are known. Specific methods include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Publication No. 59-133203, Japanese Patent Publication No. 60-2201.
By the method described in Japanese Patent Publication No. 47, hydrogenation can be carried out in the presence of a hydrogenation catalyst in an inert solvent to obtain a hydrogenated product, and the hydrogenated block copolymer used in the present invention can be synthesized. At that time, the hydrogenation rate of the aliphatic double bond based on the conjugated diene compound in the block copolymer can be controlled to an arbitrary value by adjusting the reaction temperature, the reaction time, the hydrogen supply amount, the catalyst amount and the like.
次に上記で得られた重合体又はその水添物の溶液に、
(a)水、(b)アルコール、(c)無機酸、(d)有機酸から選ば
れる少なくとせも１種の反応停止剤を添加する（以後こ
の工程を第一工程と呼ぶ）。反応停止剤をこの工程で添
加しない場合、安定剤とカップリング反応を起したり、
色調に劣る等の問題を生じるため好ましくない。アルコ
ールとしてはメタノール、エタノール、プロパノールな
どの低級アルコールの他、炭素数６〜18の高級アルコー
ル、多価アルコール（エチレングリコール、プロピレン
グリコール、グリセリン等）が使用できる。Next, to the solution of the polymer or its hydrogenated product obtained above,
At least one reaction terminator selected from (a) water, (b) alcohol, (c) inorganic acid, and (d) organic acid is added (hereinafter this step is referred to as the first step). If the reaction terminator is not added in this step, it causes a coupling reaction with the stabilizer,
It is not preferable because it causes problems such as poor color tone. As the alcohol, lower alcohols such as methanol, ethanol and propanol, as well as higher alcohols having 6 to 18 carbon atoms and polyhydric alcohols (ethylene glycol, propylene glycol, glycerin, etc.) can be used.
本発明で使用する無機酸は、塩素、硫黄、窒素、リンな
どの非金属を含む酸基が水素と結合してできた酸、例え
ば塩素、硫黄、硝酸、硼酸、リン酸などがあげられる。
又、本発明で使用する有機酸は広い意味で酸性を有する
有機化合物で、カルボン酸、スルホン酸、スルフイン
酸、フエノールなどの化合物があげられるが、好ましく
はカルボキシル基を含有する有機化合物であって以下の
ものが好ましい。Examples of the inorganic acid used in the present invention include acids formed by bonding an acid group containing a nonmetal such as chlorine, sulfur, nitrogen and phosphorus with hydrogen, such as chlorine, sulfur, nitric acid, boric acid and phosphoric acid.
Further, the organic acid used in the present invention is an organic compound having acidity in a broad sense, and examples thereof include compounds such as carboxylic acid, sulfonic acid, sulfinic acid, and phenol, but an organic compound containing a carboxyl group is preferable. The following are preferred.
(1) 炭素数８以上の脂肪酸 (2) ロジン酸 (3) オキシカルボン酸 (4) 芳香族カルボン酸 特に好ましい有機酸は(1)の脂肪酸で、その具体例とし
てはオクチル酸、カプリン酸ラウリン酸、ミリスチン
酸、パルミチン酸、ステアリン酸、オレイン酸、リノー
ル酸、リノレン酸、リシノール酸、ベヘン酸、ヒマシ硬
化脂肪酸、牛脂脂肪酸或いはこれらの混合物があげられ
る。(1) Fatty acids having 8 or more carbon atoms (2) Rosinic acid (3) Oxycarboxylic acid (4) Aromatic carboxylic acid Particularly preferred organic acid is the fatty acid of (1), and specific examples thereof include octyl acid and lauric acid caprate. Examples thereof include acids, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, behenic acid, castor-cured fatty acid, tallow fatty acid, and mixtures thereof.
本発明の第一工程で使用する反応停止剤の添加量は、反
応停止剤の総量として重合に使用した有機リチウム化合
物に対して当モル以上、好ましくは1.5モル以上であ
る。反応停止剤が水及びアルコールの場合の添加量は、
好ましくは1.5モル〜1000モル、更に好ましくは2.0モル
〜500モルである。又反応停止剤が無機酸及び有機酸の
場合の添加量は好ましくは0.05〜10モル、更に好ましく
は0.2〜５モルである。無機酸及び有機酸の添加量が当
モル未満の場合には他の反応停止剤、好ましくは水と併
用して反応停止剤の総量が当モル以上になる様にしなけ
ればならない。反応停止剤の添加量の総量が当モル未満
の場合は色調に劣るため好ましくない。本発明において
特に好適な反応停止剤は、水、無機酸、脂肪酸から選ば
れる少なくとも１種である。The addition amount of the reaction terminator used in the first step of the present invention is not less than equimolar, preferably not less than 1.5 mole based on the total amount of the reaction terminator with respect to the organolithium compound used in the polymerization. When the reaction terminator is water and alcohol, the addition amount is
It is preferably 1.5 mol to 1000 mol, more preferably 2.0 mol to 500 mol. When the reaction terminator is an inorganic acid or an organic acid, the addition amount is preferably 0.05 to 10 mol, more preferably 0.2 to 5 mol. When the addition amount of the inorganic acid and the organic acid is less than the equimolar amount, the total amount of the reaction terminator must be equal to or more than the equimolar amount by using together with another reaction terminator, preferably water. If the total amount of the reaction terminators added is less than the equimolar amount, the color tone is poor, which is not preferable. The reaction terminator particularly suitable in the present invention is at least one selected from water, inorganic acids and fatty acids.
次に、上記第一工程で得られた重合体又はその水添物の
溶液に、（Ａ）前記一般式〔Ｉ〕で示されるフェノール
系化合物及び（Ｂ）フェノール系安定剤を添加する（以
後この工程を第二工程と呼ぶ）。これらをこの段階で添
加するのは、次の工程で溶媒を除去する際に重合体が酸
化的劣化や熱的劣化を起こすのを防止する上で有効であ
る。これらはそのまま重合体溶液に添加しても、また炭
化水素溶媒に溶解して添加してもよい。Next, (A) the phenolic compound represented by the general formula [I] and (B) the phenolic stabilizer are added to the solution of the polymer or the hydrogenated product thereof obtained in the first step (hereinafter This step is called the second step). Addition of these at this stage is effective in preventing the polymer from causing oxidative deterioration or thermal deterioration when the solvent is removed in the next step. These may be added to the polymer solution as they are, or may be added after being dissolved in a hydrocarbon solvent.
本発明で使用するフェノール系化合物は前記一般式
〔Ｉ〕で示される。特に本発明のR1は炭素数５以上のア
ルキル基であり、R3は炭素数４〜22のアルキル基又はシ
クロヘキシル基、好ましくは炭素数４〜12のアルキル
基、更に好ましくは炭素数５〜８のアルキル基である。
本発明のアルキル基とは直鎖又は分枝アルキル基であ
る。R1の炭素数が４以下の場合には色調、外観特性に劣
り、R3の炭素数が３以下の場合には熱安定性が劣る。該
フェノール系化合物の好適なものはR1がtert−アミル
基、tert−ヘキシル基、tert−ヘプチル基、tert−オク
チル基であり、R2はエテニル基、イソプロペニル基、プ
ロペニル基、イソブテニル基、ブテニル基等があげられ
る。特に好ましいのはエテニル基である。R3の好ましい
ものはtert−ブチル基、tert−アミル基、tert−ヘキシ
ル基、tert−ヘプチル基である。The phenolic compound used in the present invention is represented by the above general formula [I]. Particularly, R 1 of the present invention is an alkyl group having 5 or more carbon atoms, R 3 is an alkyl group having 4 to 22 carbon atoms or a cyclohexyl group, preferably an alkyl group having 4 to 12 carbon atoms, and more preferably 5 to 5 carbon atoms. 8 is an alkyl group.
The alkyl group of the present invention is a linear or branched alkyl group. When the carbon number of R 1 is 4 or less, the color tone and appearance properties are poor, and when the carbon number of R 3 is 3 or less, the thermal stability is poor. Suitable examples of the phenolic compound R 1 is tert-amyl group, tert-hexyl group, tert-heptyl group, tert-octyl group, R 2 is an ethenyl group, isopropenyl group, propenyl group, isobutenyl group, Examples thereof include butenyl group. Particularly preferred is the ethenyl group. Preferred as R 3 are tert-butyl group, tert-amyl group, tert-hexyl group and tert-heptyl group.
置換基R4の具体例としては水素、メチル基、エチル基、
プロピル基、ブチル基があげられるが、特に水素、メチ
ル基、プロピル基が好ましい。Specific examples of the substituent R 4 include hydrogen, a methyl group, an ethyl group,
Examples thereof include propyl group and butyl group, with hydrogen, methyl group and propyl group being particularly preferable.
上記フェノール系化合物は、重合体100重量部に対して
0.05〜５重量部、好ましくは0.1〜４重量部、更に好ま
しくは0.15〜３重量部の範囲で使用される。前記一般式
〔Ｉ〕で示されるフェノール系化合物の使用量が0.05重
量部未満の場合には熱安定性の改良効果が認められず、
逆に５重量部を超えても本発明の範囲以外の効果が発揮
されない。The phenolic compound is based on 100 parts by weight of the polymer.
It is used in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 0.15 to 3 parts by weight. When the amount of the phenolic compound represented by the general formula [I] used is less than 0.05 part by weight, the effect of improving thermal stability is not recognized,
On the contrary, if the amount exceeds 5 parts by weight, the effect outside the range of the present invention is not exhibited.
フェノール系安定剤としては従来公知のものが使用でき
る。好適なフェノール系安定剤としてはテトラキス〔メ
チレン−３−（３′,5−ジ−tert−ブチル−４′−ヒド
ロキシフエニル）プロピオネート〕メタン、1,3,5−ト
リメチル−2,4,6−トリス（3,5−ジ−tert−ブチル−４
−ヒドロキシベンジル）ベンゼン、2,6−ジ−tert−ブ
チル−４−メチルフェノール、４−ヒドロキシメチル−
2,6−ジ−tert−ブチルフェノール、2,4−ビス−（ｎ−
オクチルチオ）−６−（４−ヒドロキシ−3,5−ジ−ter
t−ブチルアニリノ）−1,3,5−トリアジン、オクタデシ
ル−３−（3,5−ジ−tert−ブチル−４−ヒドロキシフ
エニル）プロピオネート、トリエチレングリコールビス
〔３−（３−tert−ブチル−５−メチル−４−ヒドロキ
シフエニル）プロピオネート〕、1,3,5−トリス−（４
−tert−ブチル−３−ヒドロキシ−2,6−ジメチルベン
ジル）イソシアヌル酸、2,2′−メチレン−ビス−（４
−メチル−６−tert−ブチルフェノール）、3,9−ビス
〔２−｛３−（３−tert−ブチル−４−ヒドロキシ−５
−メチルフエニル）プロピオニルオキシ｝−1,1−ジメ
チルエチル〕−2,4,8,10−テトラオキサスピロ〔5,5〕
ウンデカン、４−ヒドロキシメチル−2,6−ジ−tert−
ブチルフェノール、2,6−ジ−tert−ブチル−４−エチ
ルフェノール、ブチル化ヒドロキシアニソール、2,2′
−ジヒドロキシ−3,3′−ジシクロヘキシル−5,5′−ジ
メチル−ジフェニルメタン、1,1,3−トリス（２−メチ
ル−４−ヒドロキシ−５−tert−ブチルフエニル）ブタ
ン、4,4′−ブチリデンビス（６−tert−ブチル−ｍ−
クレゾール、4,4′−チオビス（３−メチル−６−tert
−ブチルフェノール）、ビス（３−シクロヘキシル−２
−ヒドロキシ−５−メチルフエニル）メタン、2,2′−
メチレンビス（４−エチル−６−tert−ブチル−フェノ
ール）、1,1−ビス（２′−メチル−４′−ヒドロキシ
−５′−tert−ブチル−フエニル）ブタンなどがあげら
れる。これらのフェノール系安定剤は、重合体100重量
部に対して0.01〜３重量部、好ましくは0.05〜３重量
部、更に好ましくは0.1〜２重量部の範囲で使用され
る。上記フェノール系安定剤は２種以上組合せて使用す
ることもできる。As the phenol-based stabilizer, conventionally known ones can be used. Suitable phenolic stabilizers include tetrakis [methylene-3- (3 ', 5-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6. -Tris (3,5-di-tert-butyl-4
-Hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-
2,6-di-tert-butylphenol, 2,4-bis- (n-
Octylthio) -6- (4-hydroxy-3,5-di-ter
t-Butylanilino) -1,3,5-triazine, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-tert-butyl- 5-Methyl-4-hydroxyphenyl) propionate], 1,3,5-tris- (4
-Tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 2,2'-methylene-bis- (4
-Methyl-6-tert-butylphenol), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5)
-Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5]
Undecane, 4-hydroxymethyl-2,6-di-tert-
Butylphenol, 2,6-di-tert-butyl-4-ethylphenol, butylated hydroxyanisole, 2,2 '
-Dihydroxy-3,3'-dicyclohexyl-5,5'-dimethyl-diphenylmethane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4'-butylidene bis ( 6-tert-butyl-m-
Cresol, 4,4'-thiobis (3-methyl-6-tert
-Butylphenol), bis (3-cyclohexyl-2)
-Hydroxy-5-methylphenyl) methane, 2,2'-
Examples thereof include methylene bis (4-ethyl-6-tert-butyl-phenol), 1,1-bis (2'-methyl-4'-hydroxy-5'-tert-butyl-phenyl) butane. These phenolic stabilizers are used in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polymer. The above phenolic stabilizers can be used in combination of two or more kinds.
フェノール系安定剤の使用量が0.01重量部未満の場合に
は熱安定性及び色調の改良効果が認められず逆に３重量
部を超えても本発明の範囲以上の効果が発揮されない。When the amount of the phenolic stabilizer used is less than 0.01 part by weight, the effect of improving the thermal stability and color tone is not recognized, and conversely, when it exceeds 3 parts by weight, the effect beyond the range of the present invention is not exhibited.
又、本発明の重合体には従来から使用されてきたイオウ
系安定剤、リン系安定剤等の安定剤を添加してもよい。
イオウ系を安定剤の具体例としては、ジラウリル−3,
3′−チオジプロピオン酸エステル、ジミリスチル−3,
3′−チオジプロピオン酸エステル、ジステアリル−3,
3′−チオジプロピオン酸エステル、ラウリルステアリ
ル−3,3′−チオジプロピオン酸エステル、ペンタエリ
スリト−ル−テトラキス−（β−ラウリル−チオ−プロ
ピオネート）、3,9−ビス−（２−ドデシルチオエチ
ル）−2,4,8,10−テトラオキサスピロ〔5,5〕ウンデカ
ンなどがあげられる。リン系安定剤の具体例としては、
トリス（ノニルフエニル）フォスファイト、サイクリッ
クネオペンタンテトライルビス（オクタデシルフォスフ
ァイト）、トリス（2,4−ジ−tert−ブチルフエニル）
フォスファイト、4,4−ブチリデン−ビス（３−メチル
−６−tert−ブチルフエニル−ジ−トリデシル）フォス
ファイト、4,4′−ビフエニレンジホスフイン酸テトラ
キス（2,4−ジ−tert−ブチルフエニル）、サイクリッ
クネオペンタンテトライルビス（2,4−ジ−tert−ブチ
ルフエニル）フォスファイトなどがあげられる。Further, stabilizers such as sulfur stabilizers and phosphorus stabilizers which have been conventionally used may be added to the polymer of the present invention.
Specific examples of the sulfur-based stabilizer include dilauryl-3,
3'-thiodipropionate, dimyristyl-3,
3'-thiodipropionate, distearyl-3,
3'-thiodipropionic acid ester, lauryl stearyl-3,3'-thiodipropionic acid ester, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis- (2- Dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. Specific examples of the phosphorus-based stabilizer include:
Tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), tris (2,4-di-tert-butylphenyl)
Phosphite, 4,4-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, tetrakis (4,4'-biphenylenediphosphinate) (2,4-di-tert-butylphenyl) ), Cyclic neopentanetetraylbis (2,4-di-tert-butylphenyl) phosphite and the like.
本発明で共重合体と溶媒を分離し、回収する方法として
重合体溶液を直接加熱し脱溶媒する公知のいずれの方法
でもよく、例えば加熱ロールにより溶媒を蒸発させて回
収する方法（ドラムドライヤー法）又、フラッシュ搭な
どで溶液の一部を蒸発させた後、更にベント式押出機で
溶媒を除去する方法などがある。特に好ましい方法はブ
ロック共重合体又はその水添物の溶液を濃縮器により濃
縮した後、２軸ベント押出機に供給し脱溶媒する方法で
ある。更に詳しく述べると該溶液は２軸ベント押出機に
供給する前に濃縮器により重合体濃度が30〜95重量％、
好ましくは40〜93重量％、更に好ましくは50〜90重量％
の濃度にまで濃縮されるのが一般的である。濃縮器で濃
縮された重合体濃度が30重量％未満の場合には２軸ベン
ト押出機での脱溶媒が不充分で残存溶媒の少ない重合体
が得難く、又濃度が95重量％を超える場合は濃縮器から
２軸ベント押出機へ重合体溶液を移送するのが困難にな
る。濃縮器としては１段又は２段以上の多段濃縮が可能
なフラック槽型式濃縮器、攪拌槽式濃縮器、薄膜蒸発式
濃縮器、濡壁搭式濃縮器などが使用できる。濃縮器に供
給される重合体溶液は一般に120〜250℃、好ましくは15
0〜220℃に予め加熱される。予熱温度が120℃未満の場
合には濃縮器での濃縮が不充分となり、又、予熱温度が
250℃を超えると重合体がゲル化する等の問題を生じる
ため好ましくない。As the method of separating and recovering the copolymer and the solvent in the present invention, any known method of directly heating and desolvating the polymer solution may be used, for example, a method of evaporating and recovering the solvent with a heating roll (drum dryer method ) Also, there is a method of further evaporating a part of the solution in a flash tower or the like and then removing the solvent with a vent type extruder. A particularly preferred method is a method in which the solution of the block copolymer or its hydrogenated product is concentrated by a concentrator and then supplied to a twin-screw vent extruder to remove the solvent. More specifically, the solution had a polymer concentration of 30 to 95% by weight in a concentrator before being fed to a twin-screw vent extruder.
Preferably 40-93% by weight, more preferably 50-90% by weight
It is generally concentrated to a concentration of. When the concentration of the polymer concentrated in the concentrator is less than 30% by weight, the solvent removal in the twin-screw vent extruder is insufficient and it is difficult to obtain a polymer with less residual solvent, and when the concentration exceeds 95% by weight. Makes it difficult to transfer the polymer solution from the concentrator to the twin-screw vent extruder. As the concentrator, it is possible to use a flack tank type concentrator capable of multi-stage concentrating in one or more stages, a stirring tank concentrator, a thin film evaporation type concentrator, a wet wall type concentrator, etc. The polymer solution fed to the concentrator is generally 120-250 ° C, preferably 15-250 ° C.
Preheated to 0-220 ° C. If the preheating temperature is less than 120 ° C, the concentration in the concentrator will be insufficient and the preheating temperature will
If the temperature exceeds 250 ° C, problems such as gelation of the polymer occur, which is not preferable.
次に、上記の様に濃縮されたブロック共重合体又はその
溶液は、脱気用のベント部を少なくとも１個、好ましく
は２〜10個、更に好ましくは３〜５個有する２軸ベント
押出機に供給され、ベント部より溶媒が減圧脱気され
る。かかる構造のベント押出機としてはL/D＝10〜60、
好ましくは15〜50（Ｌはスクリューの長さ、Ｄはスクリ
ューの外径）程度のものが好ましく、スクリューのかみ
合い構造は、かみ合い、非かみ合い、いずれでも可能で
あり、また回転方向については同方向、異方向いずれで
もよい。Next, the block copolymer or the solution thereof concentrated as described above has at least one degassing vent part, preferably 2 to 10, more preferably 3 to 5 biaxial vent extruder. And the solvent is degassed under reduced pressure from the vent part. As a vent extruder having such a structure, L / D = 10 to 60,
It is preferably about 15 to 50 (L is the length of the screw, D is the outer diameter of the screw), and the screw meshing structure can be either meshing or non-meshing. , In different directions.
２軸ベント押出機のスクリュー回転数、シリンダー加熱
温度、ベント部の圧力は、押出能力、重合体の特性（粘
度や熱安定性）、製品の品質等を勘案して選定され、一
般にスクリュー回転数20〜500回転／分、好ましくは30
〜400回転／分、シリダー温度100〜300℃、好ましくは1
30〜260℃、ベント部圧力は１〜500mmHg絶対圧、好まし
くは３〜400mmHg絶対圧の範囲である。The screw rotation speed, cylinder heating temperature, and vent pressure of the twin-screw extruder are selected in consideration of extrusion capacity, polymer characteristics (viscosity and thermal stability), product quality, etc. 20-500 revolutions / minute, preferably 30
~ 400 revolutions / minute, cylinder temperature 100 ~ 300 ℃, preferably 1
The pressure of the vent portion is in the range of 1 to 500 mmHg absolute pressure, preferably 3 to 400 mmHg absolute pressure, at 30 to 260 ° C.
本発明の方法により直接脱溶媒され、回収された乾燥重
合体中の残存溶媒量は１重量％未満、好ましくは0.5重
量％以下、更に好ましくは0.2重量％以下である。乾燥
重合体中の残存溶媒量が１重量％以上の場合には、重合
体を成形する際に発泡したり、シルバー等の外観不良を
発生したりするため好ましくない。脱溶媒された重合体
は、発泡したクラム状、粒状或いは粉末状の形態で重合
体を得ることもでき、又ストランド状やペレット状で得
ることもできる。The amount of residual solvent in the dried polymer directly recovered by the method of the present invention and recovered is less than 1% by weight, preferably 0.5% by weight or less, and more preferably 0.2% by weight or less. When the amount of residual solvent in the dried polymer is 1% by weight or more, it is not preferable because foaming occurs when the polymer is molded and appearance defects such as silver occur. The desolvated polymer can be obtained as a foamed crumb-like, granular or powdery form, or as a strand-like or pellet-like form.
本発明の方法において、目的に応じて種々の添加剤を重
合体に添加することができる。例えば、オイル等の軟化
剤、可塑剤、帯電防止剤、滑剤、紫外線吸収剤、難燃
剤、顔料、無機充填剤、有機繊維・無機繊維、カーボン
ブラックなどの補強剤、他の熱可塑性樹脂などが添加剤
として使用できる。In the method of the present invention, various additives can be added to the polymer depending on the purpose. For example, softeners such as oil, plasticizers, antistatic agents, lubricants, ultraviolet absorbers, flame retardants, pigments, inorganic fillers, organic fibers / inorganic fibers, reinforcing agents such as carbon black, and other thermoplastic resins may be used. It can be used as an additive.
本発明の方法で得られた重合体は、熱安定性が良好で透
明で色調と外観特性に優れるためその特徴を生かして、
シート、フィルム、各種形状の射出成形品、中空成形
品、圧空成形品、真空成形品等多種多用の成形品として
活用できる他、各種熱可塑性樹脂の改質材、履物の素
材、粘着剤・接着剤の素材、アスファルトの改質材、電
線ケーブルの素材、加硫ゴム用素材、加硫ゴムの改質
材、家電製品、自動車部品、工業部品、家庭用品、玩具
等の素材などに利用できる。The polymer obtained by the method of the present invention has good thermal stability, is transparent, and is excellent in color tone and appearance characteristics.
It can be used as a variety of molded products such as sheets, films, injection molded products of various shapes, hollow molded products, compressed air molded products, vacuum molded products, as well as modifiers of various thermoplastic resins, footwear materials, adhesives and adhesives. It can be used as an agent material, asphalt modifier, electric wire cable material, vulcanized rubber material, vulcanized rubber modifier, home appliances, automobile parts, industrial parts, household products, toys, etc.
以下に実施例を示し、本発明をより具体的に説明する。
尚、実施例で使用したブロック共重合体は次のようにし
て製造した。得られたブロック共重合体（Ａ）〜（Ｃ）
の重合体溶液の、重合体と溶媒との重量比はいずれも1:
3であった。Hereinafter, the present invention will be described more specifically with reference to examples.
The block copolymer used in the examples was manufactured as follows. Obtained block copolymers (A) to (C)
In the polymer solution of, the weight ratio of the polymer and the solvent is 1:
Was 3.
窒素ガス雰囲気下において、スチレン30重量部とテトラ
ヒドロフラン0.3重量部を含むシクロヘキサン溶液にｎ
−ブチルリチウムを0.08重量部添加し、70℃で１時間重
合した後、更に1,3−ブタジエン20重量部とスチレン50
重量部を含むシクロヘキサン溶液を加えて70℃で２時間
重合した。得られた重合体はスチレン含有量80重量％の
Ａ−Ｂ−Ａ構造のブロック共重合体であった。In a nitrogen gas atmosphere, a cyclohexane solution containing 30 parts by weight of styrene and 0.3 parts by weight of tetrahydrofuran was added to the solution.
-Add 0.08 parts by weight of butyl lithium and polymerize at 70 ° C for 1 hour, then add 20 parts by weight of 1,3-butadiene and 50 parts of styrene.
A cyclohexane solution containing 1 part by weight was added and polymerization was carried out at 70 ° C. for 2 hours. The obtained polymer was a block copolymer having an ABA structure with a styrene content of 80% by weight.
窒素ガス雰囲気下において、スチレン75重量部を含むシ
クロヘキサン溶液にｎ−ブチルリチウムを0.15重量部添
加し、70℃で１時間重合した後、1,3−ブタジエン25重
量部を含むシクロヘキサン溶液を加えて70℃で２時間重
合した。その後エポキシ化大豆油５重量部添加してスチ
レン含有量75重量％のラジカル構造のブロック共重合体
を得た。In a nitrogen gas atmosphere, 0.15 parts by weight of n-butyllithium was added to a cyclohexane solution containing 75 parts by weight of styrene, polymerized at 70 ° C. for 1 hour, and then a cyclohexane solution containing 25 parts by weight of 1,3-butadiene was added. Polymerization was carried out at 70 ° C for 2 hours. Thereafter, 5 parts by weight of epoxidized soybean oil was added to obtain a block copolymer having a styrene content of 75% by weight and having a radical structure.
窒素ガス雰囲気下において、1,3−ブタジエン15重量部
とスチレン20重量部を含むｎ−ヘキサン溶液にｎ−ブチ
ルリチウムを0.11重量部添加し、70℃で２時間重合した
後、さらに1,3−ブタジエン45重量部とスチレン20重量
部を含むｎ−ヘキサン溶液を加えて70℃で２時間重合し
た。得られた重合体は、スチレン含有量40重量％のＢ−
Ａ−Ｂ−Ａ構造のブロック共重合体であった。In a nitrogen gas atmosphere, 0.11 parts by weight of n-butyllithium was added to an n-hexane solution containing 15 parts by weight of 1,3-butadiene and 20 parts by weight of styrene, and the mixture was polymerized at 70 ° C. for 2 hours. -An n-hexane solution containing 45 parts by weight of butadiene and 20 parts by weight of styrene was added and polymerization was carried out at 70 ° C for 2 hours. The obtained polymer is B-containing 40% by weight of styrene.
It was a block copolymer having an ABA structure.
窒素ガス雰囲気下において、スチレン10重量部を含むシ
クロヘキサン溶液にｎ−ブチルリチウムを0.1重量部を
添加し70℃で１時間重合した後、イソプレン80重量部を
含むシクロヘキサン溶液を添加して70℃で２時間重合し
た。その後、更にスチレン10重量部を含むシクロヘキサ
ン溶液を加えて70℃で１時間重合した。得られた重合体
は、スチレン含有量20重量％のＡ−Ｂ−Ａ構造のブロッ
ク共重合体（重合体の濃度20重量％）であった。In a nitrogen gas atmosphere, 0.1 part by weight of n-butyllithium was added to a cyclohexane solution containing 10 parts by weight of styrene and polymerized at 70 ° C. for 1 hour, and then a cyclohexane solution containing 80 parts by weight of isoprene was added and the mixture was heated at 70 ° C. Polymerized for 2 hours. Then, a cyclohexane solution containing 10 parts by weight of styrene was further added, and polymerization was carried out at 70 ° C. for 1 hour. The obtained polymer was a block copolymer having an ABA structure with a styrene content of 20% by weight (polymer concentration 20% by weight).
窒素ガス雰囲気下において、スチレン15重量部とテトラ
メチルエチレンジアミン0.06重量部を含むシクロヘキサ
ン溶液にｎ−ブチルリチウムを0.06重量部添加し、70℃
で１時間重合した後、1,3−ブタジエン70重量部を含む
シクロヘキサン溶液を添加して70℃で２時間重合した。
その後、更にスチレン15重量部を含むシクロヘキサン溶
液を加えて70℃で１時間重合した。得られた重合体は、
スチレン含有量30重量％のＡ−Ｂ−Ａ構造のブロック共
重合体であった。In a nitrogen gas atmosphere, 0.06 parts by weight of n-butyllithium was added to a cyclohexane solution containing 15 parts by weight of styrene and 0.06 parts by weight of tetramethylethylenediamine and heated to 70 ° C.
After polymerizing for 1 hour at 70 ° C., a cyclohexane solution containing 70 parts by weight of 1,3-butadiene was added and the mixture was polymerized at 70 ° C. for 2 hours.
Then, a cyclohexane solution containing 15 parts by weight of styrene was further added, and polymerization was carried out at 70 ° C. for 1 hour. The obtained polymer is
It was a block copolymer with an ABA structure having a styrene content of 30% by weight.
次に、上記で得られたブロック共重合体を特開昭59−13
3203号公報記載のTi系水添触媒で水添し、ブタジエン部
の水添率が95％の水添ブロック共重合体（重合体の濃度
15重量％）を得た。Next, the block copolymer obtained as described above was treated with JP-A-59-13.
Hydrogenated block copolymer hydrogenated with a Ti-based hydrogenation catalyst described in 3203 and having a butadiene portion hydrogenation rate of 95% (concentration of polymer
15% by weight).
窒素ガス雰囲気下において、1,3−ブタジエン15重量部
とスチレン20重量部を含むｎ−ヘキサン溶液にｎ−ブチ
ルリチウムを0.07重量部添加し、70℃で２時間重合した
後に1,3−ブタジエン15重量部とスチレン50重量部を含
むｎ−ヘキサン溶液及びｎ−ブチルリチウム0.02重量部
を加えて70℃で２時間重合した。得られた重合体はスチ
レン含有量70重量％のＢ−Ａ−Ｂ−Ａ構造のブロック共
重合体とＢ−Ａ構造のブロック共重合体からなる混合物
であり、しかも得られた重合体溶液（重合体の濃度30重
量％）は懸濁状であった。In a nitrogen gas atmosphere, 0.07 parts by weight of n-butyllithium was added to an n-hexane solution containing 15 parts by weight of 1,3-butadiene and 20 parts by weight of styrene, and the mixture was polymerized at 70 ° C. for 2 hours, followed by 1,3-butadiene. An n-hexane solution containing 15 parts by weight and 50 parts by weight of styrene and 0.02 part by weight of n-butyllithium were added, and polymerization was carried out at 70 ° C. for 2 hours. The polymer obtained was a mixture of a block copolymer having a B-A-B-A structure having a styrene content of 70% by weight and a block copolymer having a B-A structure, and the obtained polymer solution ( The polymer concentration was 30% by weight) in the form of suspension.
実施例１〜６及び比較例１〜３ ブロック共重合体〔Ａ〕のシクロヘキサン溶液に、反応
停止剤として水をブロック共重合体100重量部に対して
1.0重量部添加し、充分混合して反応を停止させた（第
一工程）後、第１表に示した安定剤を添加して充分混合
した（第二工程）。Examples 1 to 6 and Comparative Examples 1 to 3 In a cyclohexane solution of the block copolymer [A], water as a reaction terminator was added to 100 parts by weight of the block copolymer.
After 1.0 part by weight was added and mixed well to stop the reaction (first step), the stabilizers shown in Table 1 were added and thoroughly mixed (second step).
上記の重合体溶液を熱交換器に通して約200℃に加熱し
た後、円筒状のフラッシュ槽型濃縮器へ導き、溶媒の一
部をフラッシュ蒸発させて重合体濃度が約85重量％の濃
縮重合体溶液を得た。その後、該濃縮重合体溶液を２軸
２段ベント押出機に供給し、ベント部より溶媒を減圧脱
気した。使用した２軸ベント押出機は、スクリュー外径
40mm、L/Dが38.5で、スクリュー回転数約300rpmで運転
した。押出機先端からストランド状で得た乾燥重合体は
カッターにてペレット状にした。After heating the above polymer solution through a heat exchanger to about 200 ° C, introduce it into a cylindrical flash tank type concentrator, and flash evaporate part of the solvent to concentrate the polymer concentration to about 85% by weight. A polymer solution was obtained. Then, the concentrated polymer solution was supplied to a twin-screw two-stage vent extruder, and the solvent was degassed under reduced pressure from the vent. The twin-screw vent extruder used has a screw outer diameter
40 mm, L / D was 38.5, and the screw rotation speed was about 300 rpm. The dried polymer obtained in a strand form from the tip of the extruder was pelletized by a cutter.
結果を第１表に示した。The results are shown in Table 1.
実施例７〜12 第２表に示した安定剤を添加した以外は実施例１〜６と
同様な方法でブロック共重合体を得た。 Examples 7 to 12 Block copolymers were obtained in the same manner as in Examples 1 to 6 except that the stabilizers shown in Table 2 were added.
結果を第２表に示した。The results are shown in Table 2.
実施例13〜17 ブロック共重合体〔Ｂ〕のシクロヘキサン溶液に、第３
表に示した反応停止剤を添加し、充分混合して反応を停
止させた後、フェノール系化合物のAO−１を0.5重量
部、AO−５を0.2重量部添加して充分混合した。 Examples 13 to 17 In a cyclohexane solution of the block copolymer [B],
After the reaction terminators shown in the table were added and thoroughly mixed to stop the reaction, 0.5 parts by weight of phenol compound AO-1 and 0.2 parts by weight of AO-5 were added and mixed well.
上記の重合体溶液の脱溶媒は実施例１と同様に行った。
結果を第３表に示した。第３表に示した様に、反応停止
剤として酸を用いた場合にも熱安定性、透明性、色調に
優れたブロック共重合体が得られた。Desolvation of the above polymer solution was performed in the same manner as in Example 1.
The results are shown in Table 3. As shown in Table 3, even when an acid was used as a reaction terminator, a block copolymer excellent in thermal stability, transparency and color tone was obtained.
実施例18〜22 第４表に示した反応停止剤とフェノール系化合物のAO−
９を0.5重量部、AO−５を0.2重量部添加した以外は実施
例13〜17と同様な方法でブロック共重合体を得た。結果
を第４表に示した。 Examples 18 to 22 AO-of the reaction terminators and phenolic compounds shown in Table 4
A block copolymer was obtained in the same manner as in Examples 13 to 17 except that 0.5 part by weight of 9 and 0.2 part by weight of AO-5 were added. The results are shown in Table 4.
実施例23〜25 第５表に示したブロック共重合体溶液と反応停止剤に実
施例13と同一の安定剤を添加して充分に混合した。上記
の重合体溶液を熱交換器に通して140℃に加熱した後、
表面温度180℃に加熱した直径８インチのダブルドラム
ドライヤーにより脱溶媒を行いポリマーを回収した。回
収したポリマーは30mmφ２軸押出機により200℃でスト
ランド状に押出した後カッターにてペレット状にした。
結果を第５表に示した。 Examples 23 to 25 The same stabilizer as in Example 13 was added to the block copolymer solution and the reaction terminator shown in Table 5 and mixed well. After heating the above polymer solution to 140 ° C. through a heat exchanger,
The solvent was removed by a double drum dryer having a diameter of 8 inches and heated to a surface temperature of 180 ° C. to recover the polymer. The recovered polymer was extruded into a strand at 200 ° C. by a 30 mmφ twin-screw extruder, and then pelletized by a cutter.
The results are shown in Table 5.
実施例26〜28 安定剤を実施例18と同一のものを使用した以外は実施例
23〜25と同様の方法によりブロック共重合体を得た。結
果を第６表に示した。 Examples 26-28 Examples except that the same stabilizer as in Example 18 was used.
A block copolymer was obtained by the same method as in 23 to 25. The results are shown in Table 6.
実施例29 ブロック共重合体（Ｅ）を用い、実施例28と同一の反応
停止剤、安定剤により脱溶媒を行った。 Example 29 Using the block copolymer (E), desolvation was performed with the same reaction terminator and stabilizer as in Example 28.
脱溶媒方法も実施例28と同一の方法で行い色調が良好な
ペレットを得た。得られたブロック共重合体の脱溶媒後
の重合体中の残存溶媒量は0.08重量％、Haze2.9％であ
った。又、熱安定性についても実施例１と同一の方法に
より調べたところシャッ解によるメルトフロー値の上昇
もなく極めて熱安定性に優れるものであった。The solvent removal method was also performed in the same manner as in Example 28, and pellets having a good color tone were obtained. The amount of residual solvent in the polymer after desolvation of the obtained block copolymer was 0.08% by weight and Haze 2.9%. The thermal stability was also examined by the same method as in Example 1. As a result, the melt flow value did not increase due to shattering, and the thermal stability was extremely excellent.
本発明は、重合体又はその水添物の溶液から直接溶媒す
ることによりブロック共重合体又はその水添物を回収す
る方法を提供するものであり、得られる重合体は特定の
フェノール系化合物とフェノール系安定剤を併用するこ
とで熱安定性、透明性、色調及び外観特性に優れるた
め、その特徴を生かして、シート、フイルム、各種形状
の射出成形品、中空成形品、圧空成形品、真空成形品等
多種多用の成形品として活用できる他、各種熱可塑性樹
脂の改質材、履物の素材、粘着剤・接着剤の素材、アス
ファルトの改質材、電線ケーブルの素材、加硫ゴム用素
材、加硫ゴム改質材、家電製品・自動車部品・工業部品
・家庭用品・玩具等の素材などに利用できる。とりわ
け、本発明の方法で得られる重合体は熱安定性と色調に
優れるため高温下の加工が容易であり、色調を必要とす
る用途分野、例えば食品容器、食品包装材料、食品容器
の包装材料、医療用品等に有効に利用できる。The present invention provides a method for recovering a block copolymer or a hydrogenated product thereof by directly using a solvent from a solution of the polymer or a hydrogenated product thereof, and the obtained polymer is a specific phenol compound. The combined use of a phenolic stabilizer provides excellent thermal stability, transparency, color tone and appearance characteristics.By taking advantage of these characteristics, sheets, films, injection molded products of various shapes, hollow molded products, compressed air molded products, and vacuum products. Can be used as a variety of molded products such as molded products, as well as various thermoplastic resin modifiers, footwear materials, adhesive / adhesive materials, asphalt modifiers, wire cable materials, vulcanized rubber materials It can be used for vulcanized rubber modifier, materials for home appliances, automobile parts, industrial parts, household products, toys, etc. In particular, the polymer obtained by the method of the present invention is easy to process under high temperature because of its excellent heat stability and color tone, application fields requiring color tone, such as food containers, food packaging materials, food container packaging materials. , Can be effectively used for medical supplies.
Claims (1)
始剤として共役ジエン及びビニル芳香族炭化水素を重合
せしめて得られた、ビニル芳香族炭化水素含有量が５〜
95重量％であるブロック共重合体又はその水添物の溶液
から溶媒を直接脱溶媒することによりブロック共重合体
又はその水添物を取得するにあたり、 （イ）ブロック共重合体又はその水添物の溶液に、 (a) 水 (b) アルコール (c) 無 機 酸 (d) 有 機 酸 から選ばれる少なくとも１種の反応停止剤を添加した
後、 （ロ）前記ブロック共重合体又はその水添物の溶液に （Ａ） 下記一般式〔Ｉ〕で示されるフェノール系化合
物を重合体100重量部に対して0.05〜５重量部 （上式において、R1は炭素数５以上のアルキル基、R2は
炭素数２〜４のアルケニル基、R3は炭素数４〜22のアル
キル基又はシクロヘキシル基、R4は水素又は炭素数１〜
18のアルキル基を示す。） （Ｂ） 上記一般式〔Ｉ〕で示したフェノール系化合物
以外のフェノール系安定剤を重合体100重量部に対して
0.01〜３重量部添加すること からなるブロック共重合体の製造方法。1. A vinyl aromatic hydrocarbon content of 5 obtained by polymerizing a conjugated diene and a vinyl aromatic hydrocarbon in a hydrocarbon solvent using an organolithium compound as an initiator.
When the block copolymer or its hydrogenated product is obtained by directly removing the solvent from the solution of 95% by weight of the block copolymer or its hydrogenated product, (a) the block copolymer or its hydrogenated product After adding at least one reaction terminator selected from (a) water (b) alcohol (c) organic acid (d) organic acid to the solution of the product, (b) the block copolymer or its 0.05 to 5 parts by weight of (A) a phenolic compound represented by the following general formula [I] is added to the hydrogenated solution with respect to 100 parts by weight of the polymer. (In the above formula, R 1 is an alkyl group having 5 or more carbon atoms, R 2 is an alkenyl group having 2 to 4 carbon atoms, R 3 is an alkyl group having 4 to 22 carbon atoms or a cyclohexyl group, and R 4 is hydrogen or a carbon number. 1 to
18 alkyl groups are shown. (B) A phenolic stabilizer other than the phenolic compound represented by the general formula [I] is added to 100 parts by weight of the polymer.
A method for producing a block copolymer, which comprises adding 0.01 to 3 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2270600A JPH0678376B2 (en) | 1990-07-31 | 1990-10-11 | Method for producing block copolymer |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-201390 | 1990-07-31 | ||
| JP20139090 | 1990-07-31 | ||
| JP2270600A JPH0678376B2 (en) | 1990-07-31 | 1990-10-11 | Method for producing block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04175304A JPH04175304A (en) | 1992-06-23 |
| JPH0678376B2 true JPH0678376B2 (en) | 1994-10-05 |
Family
ID=16440293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2270600A Expired - Lifetime JPH0678376B2 (en) | 1990-07-31 | 1990-10-11 | Method for producing block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678376B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009179669A (en) * | 2008-01-29 | 2009-08-13 | Asahi Kasei Chemicals Corp | Weather resistant heat resistant styrene resin composition and method for producing the same |
| EP2428534A1 (en) | 2004-03-03 | 2012-03-14 | Kraton Polymers US LLC | Elastomeric bicomponent fibers comprising block copolymers having high flow |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5427357B2 (en) * | 2008-01-29 | 2014-02-26 | 旭化成ケミカルズ株式会社 | Heat resistant styrenic resin composition and method for producing the same |
| TWI388577B (en) * | 2008-12-30 | 2013-03-11 | Tsrc Corp | Method for manufacturing hydrogenated block copolymer |
| MX351775B (en) | 2013-01-16 | 2017-10-27 | Asahi Kasei Chemicals Corp | Method for producing polymer. |
| CA2971833C (en) | 2014-12-25 | 2023-04-04 | Kuraray Co., Ltd. | Process for producing aromatic vinyl/conjugated diene copolymer and product of hydrogenation thereof |
-
1990
- 1990-10-11 JP JP2270600A patent/JPH0678376B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2428534A1 (en) | 2004-03-03 | 2012-03-14 | Kraton Polymers US LLC | Elastomeric bicomponent fibers comprising block copolymers having high flow |
| JP2009179669A (en) * | 2008-01-29 | 2009-08-13 | Asahi Kasei Chemicals Corp | Weather resistant heat resistant styrene resin composition and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04175304A (en) | 1992-06-23 |
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