JP2008231371A - Method for producing mixture containing block copolymers having different compositions or hydrogenated products thereof - Google Patents
Method for producing mixture containing block copolymers having different compositions or hydrogenated products thereof Download PDFInfo
- Publication number
- JP2008231371A JP2008231371A JP2007077076A JP2007077076A JP2008231371A JP 2008231371 A JP2008231371 A JP 2008231371A JP 2007077076 A JP2007077076 A JP 2007077076A JP 2007077076 A JP2007077076 A JP 2007077076A JP 2008231371 A JP2008231371 A JP 2008231371A
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- Prior art keywords
- component
- weight
- vinyl aromatic
- solution
- aromatic hydrocarbon
- Prior art date
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 76
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000003381 stabilizer Substances 0.000 claims abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008188 pellet Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims description 95
- 229920002554 vinyl polymer Polymers 0.000 claims description 91
- 150000001993 dienes Chemical class 0.000 claims description 59
- 229920000642 polymer Polymers 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 32
- 238000003860 storage Methods 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 230000003068 static effect Effects 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical group CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 claims description 3
- UYQYTUYNNYZATF-UHFFFAOYSA-N 6-methyl-4,6-bis(octylsulfanylmethyl)cyclohexa-1,3-dien-1-ol Chemical compound CCCCCCCCSCC1=CC=C(O)C(C)(CSCCCCCCCC)C1 UYQYTUYNNYZATF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 23
- 238000004807 desolvation Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 29
- 238000006116 polymerization reaction Methods 0.000 description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000013557 residual solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001502 inorganic halide Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 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
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil 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
- 239000010936 titanium Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- 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
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-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
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- OHDSHGBRKMRPHC-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-dimethylethanamine Chemical compound CN(C)CCC1=CC=C(C=C)C=C1 OHDSHGBRKMRPHC-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-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
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-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
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-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
- 241000251468 Actinopterygii Species 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 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
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ISSNPJKOQBEGHD-UHFFFAOYSA-N [2-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CCCCC1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1OC(=O)C=C ISSNPJKOQBEGHD-UHFFFAOYSA-N 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
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals 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
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 150000001412 amines Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
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- 229940116226 behenic acid Drugs 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 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
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- 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
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Landscapes
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Abstract
Description
本発明は、ビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体又はその水添物を含む混合物を、均一混合を維持した状態で溶媒を直接脱溶媒するに際して、ペレット中のゲルが少なく、色調及び透明性に優れ、残留溶媒量が少なく、且つ、良好な加工安定性を有する、組成の異なる少なくとも２種類のブロック共重合体又はその水添物を含む混合物の製造方法に関する。 In the present invention, when a solvent containing a block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene or a hydrogenated product thereof is directly desolvated while maintaining uniform mixing, the amount of gel in the pellet is small. The present invention relates to a method for producing a mixture containing at least two types of block copolymers having different compositions or hydrogenated products thereof, which are excellent in color tone and transparency, have a small amount of residual solvent, and have good processing stability.
ビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体は、優れた透明性と耐衝撃性を備えた樹脂であることから、シート、フィルム、射出成形品等に広く使用されている。 A block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene is a resin having excellent transparency and impact resistance, and thus is widely used for sheets, films, injection molded articles and the like.
これらのブロック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、生成したブロック共重合体は溶媒に均一に溶解しているか、或いは懸濁した状態で得られるため、ブロック共重合体と溶媒とを分離する工程が必要となる。 In producing these block copolymers, polymerization is usually performed in a hydrocarbon solvent inert to the catalyst, and the resulting block copolymer is uniformly dissolved or suspended in the solvent. Therefore, a process for separating the block copolymer and the solvent is required.
ブロック共重合体と溶媒を分離する方法としては種々の方法があるが、その一つとしてブロック共重合体溶液を直接脱溶媒するに際し、ベント押出機から１段階で脱溶媒してブロック共重合体を製造する方法が知られている。 There are various methods for separating the block copolymer and the solvent, and as one of them, when directly removing the block copolymer solution, the solvent is removed from the vent extruder in one step. A method of manufacturing is known.
例えば、残存溶剤量が少なく、ゲル化、着色性に優れたブロック共重合体を得るため、２軸多段ベント押出機で脱溶媒する方法が開示されている（例えば、特許文献１、特許文献２参照。）。また、残留揮発成分の含有率が低い弾性ポリマーを得るため、エンドレススクリューを備えた２軸ベント押出機に導入し、溶媒を除去する方法が開示されている（例えば、特許文献３参照。）。さらに、溶媒、水、モノマー等の残存含有量を下げるため、スクリュー先端部とダイ部の間にポンプを設けた２軸ベント押出機を用いて重合体を回収する方法が開示されている（例えば、特許文献４参照。）。またさらに、熱安定性、透明性、色調及び外観特性に優れる重合体を得るため、特定の安定剤を添加した後、２軸多段ベント押出機を用いて直接脱溶媒する方法が開示されている（例えば、特許文献５参照。）。さらにまた、剛性や耐衝撃性、透明性に優れたブリスター容器を得るため、末端のブロック部を規定した２種類のブロック共重合体を特定の比率で組み合わせたブロック共重合体混合物が開示されている（例えば、特許文献６参照。）。 For example, in order to obtain a block copolymer having a small amount of residual solvent and excellent gelation and colorability, a method of desolvating with a biaxial multistage vent extruder is disclosed (for example, Patent Document 1 and Patent Document 2). reference.). Moreover, in order to obtain an elastic polymer with a low content of residual volatile components, a method of introducing it into a twin-screw vent extruder equipped with an endless screw and removing the solvent is disclosed (for example, see Patent Document 3). Furthermore, in order to reduce the residual content of solvent, water, monomer, etc., a method of recovering the polymer using a twin-screw vent extruder provided with a pump between the screw tip and the die is disclosed (for example, , See Patent Document 4). Furthermore, in order to obtain a polymer having excellent thermal stability, transparency, color tone and appearance characteristics, a method of directly removing the solvent using a biaxial multistage vent extruder after adding a specific stabilizer is disclosed. (For example, refer to Patent Document 5). Furthermore, in order to obtain a blister container excellent in rigidity, impact resistance, and transparency, a block copolymer mixture in which two types of block copolymers defining the terminal block portion are combined at a specific ratio is disclosed. (For example, refer to Patent Document 6).
しかしながら、組成の異なる２種類のビニル芳香族炭化水素と共役ジエンからなるブロック共重合体又はその水添物の混合物の重合体溶液を、２軸ベント押出機を用いて直接脱溶媒する方法では均一混合を維持した状態を維持することが十分ではないため、得られるブロック共重合体又はその水添物の組成の均一性及び物性安定性の点でも満足できるものではなく、その解決が望まれている。
本発明は、組成の異なる２種類のビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体又はその水添物の混合物を、均一混合を維持した状態で溶媒を直接脱溶媒するに際して、ペレット中のゲルが少なく、色調及び透明性に優れ、残留溶媒量が少なく、尚且つ、良好な加工安定性を有するブロック共重合体又はその水添物の混合物の製造方法の提供を目的とする。 In the present invention, when a block copolymer containing two types of vinyl aromatic hydrocarbons having different compositions and a conjugated diene or a mixture of hydrogenated products thereof is directly desolvated while maintaining uniform mixing, the pellets An object of the present invention is to provide a method for producing a mixture of a block copolymer or a hydrogenated product thereof having a small amount of gel, excellent color tone and transparency, a small amount of residual solvent, and having good processing stability.
本発明者らは、鋭意検討した結果、組成の異なる少なくとも２種類のビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体又はその水添物の混合物を製造するに際し、反応停止剤の添加、溶液のＰＨ調整後に、各々個別の貯蔵槽から移送中に合流させた後、配管途中に設けた連続混合機を用いて混合することによって、均一混合を維持した状態で溶媒を直接脱溶媒が可能となり、上記の目的が達成されることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have added a reaction terminator when producing a block copolymer containing at least two kinds of vinyl aromatic hydrocarbons and conjugated dienes having different compositions or a hydrogenated mixture thereof. After adjusting the pH of the solution, it is merged during transfer from each individual storage tank, and then mixed using a continuous mixer provided in the middle of the piping, so that the solvent is removed directly in a state where uniform mixing is maintained. It has become possible to find that the above-mentioned object is achieved, and the present invention has been completed.
即ち、本発明は、
[１] ビニル芳香族炭化水素と共役ジエンとを含む第１のブロック共重合体又はその水添物と、ビニル芳香族炭化水素と共役ジエンとを含み、前記第１のブロック共重合体又はその水添物とは組成が異なる第２のブロック共重合体又はその水添物と、を含む混合物の製造方法であって、
下記（ａ）〜（ｆ）の工程；
（ａ）ビニル芳香族炭化水素含有量が８５〜９５重量％及び共役ジエン含有量が５〜１５重量％である前記第１のブロック共重合体又はその水添物（成分（Ｉ））と、ビニル芳香族炭化水素含有量が２５重量％以上８５重量％未満及び共役ジエン含有量が１５重量％を越え７５重量％以下である前記第２のブロック共重合体又はその水添物（成分（ＩＩ））とを、各々個別に重合する工程と、
（ｂ）前記成分（Ｉ）と前記成分（ＩＩ）の活性重合体溶液に反応停止剤を添加する工程と、
（ｃ）前記成分（Ｉ）と前記成分（ＩＩ）の溶液に、炭酸ガス及び／又は有機酸の少なくとも１種を添加し、溶液のＰＨを６．０〜９．５の範囲に調整する工程と、
（ｄ）前記成分（Ｉ）の溶液と前記成分（ＩＩ）の溶液を配管途中に設けた連続混合機を用いて同時に供給して混合後、フェノール系安定剤の１種以上を添加する、或いは前記成分（Ｉ）の溶液と前記成分（ＩＩ）の溶液に、フェノール系安定剤の１種以上を添加後、配管途中に設けた連続混合機を用いて同時に供給して混合する工程と、
（ｅ）前記成分（Ｉ）と前記成分（ＩＩ）の混合溶液をフラッシュ型濃縮器で溶媒の一部をフラッシュ蒸発させる工程と、
（ｆ）前記成分（Ｉ）と前記成分（ＩＩ）の混合溶液を２軸エンドレススクリューと後方排気ゾーンを有する多段ベント押出機で、脱溶媒する工程と、
を含む混合物の製造方法、
[２] 前記工程（ｄ）の連続混合機の混合能力が、ＥＳＰ≧１×１０-6（ＫＷｈ／ｋｇ）であるスタティックミキサー及び／又はＰ／Ｖ値≧１０3（Ｐ：混合機の動力（ＫＷ）、Ｖ：混合部の空間容積（ｍ3））の連続混合式の乳化分散機である、前項[１]に記載の混合物の製造方法、
[３] 前記工程（ｆ）の脱溶媒後に、ペレット状の形態を得る工程を、さらに含む前項[１]又は[２]に記載の混合物の製造方法、
[４] 前記成分（Ｉ）は、２５℃の貯蔵弾性率が１．５×１０9〜２．８×１０9Ｐａの範囲であり、前記成分（ＩＩ）は、２５℃の貯蔵弾性率が０．１×１０9Ｐａ以上、１．５×１０9Ｐａ未満の範囲である、前項[１]ないし[３]のうち何れか一項に記載の混合物の製造方法、
[５] 前記フェノール系安定剤は、２００℃の蒸気圧が５ｍｍＨｇ以下である、前項[１]ないし[４]のうち何れか一項に記載の混合物の製造方法、
[６] 前記成分(Ｉ)のビニル芳香族炭化水素含有量が８８〜９２重量％であり、前記成分（Ｉ）の共役ジエン含有量が８〜１２重量％であり、前記成分(ＩＩ)のビニル芳香族炭化水素含有量が３０〜７０重量％であり、前記成分（ＩＩ）の共役ジエン含有量が３０〜７０重量％である、前項[１]ないし[５]のうち何れか一項に記載の混合物の製造方法、
[７] 前記フェノール系安定剤が、２−〔１−（２−ヒドロキシ−３，５−ジ−ｔ−ペンチルフェニル）エチル〕−４，６−ジ−ｔ−ペンチルフェニルアクリレート、２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート及び２，４−ビス〔（オクチルチオ）メチル〕−ｏ−クレゾールから選ばれる少なくとも１種の安定剤を含む、前項[１]ないし[６]のうち何れか一項に記載の混合物の製造方法、
[８] 前記混合物は、ビニル芳香族炭化水素含有量が７０〜９２重量％であり、共役ジエン含有量が８〜３０重量％である、前項[１]ないし[７]のうち何れか一項に記載の混合物の製造方法、
を提供する。
That is, the present invention
[1] A first block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene or a hydrogenated product thereof, a vinyl aromatic hydrocarbon and a conjugated diene, and the first block copolymer or the same A second block copolymer having a different composition from the hydrogenated product or a hydrogenated product thereof, and a method for producing a mixture comprising:
The following steps (a) to (f);
(A) the first block copolymer having a vinyl aromatic hydrocarbon content of 85 to 95% by weight and a conjugated diene content of 5 to 15% by weight or a hydrogenated product thereof (component (I)); The second block copolymer having a vinyl aromatic hydrocarbon content of 25% by weight or more and less than 85% by weight and a conjugated diene content of more than 15% by weight and 75% by weight or less, or a hydrogenated product thereof (component (II )) And polymerizing each individually,
(B) adding a reaction terminator to the active polymer solution of component (I) and component (II);
(C) adding at least one of carbon dioxide and / or organic acid to the solution of the component (I) and the component (II) to adjust the pH of the solution to a range of 6.0 to 9.5. When,
(D) The solution of the component (I) and the solution of the component (II) are simultaneously supplied and mixed using a continuous mixer provided in the middle of the pipe, and then one or more phenol-based stabilizers are added, or A step of adding and mixing one or more phenolic stabilizers to the solution of component (I) and the solution of component (II), and simultaneously supplying and mixing them using a continuous mixer provided in the middle of the piping;
(E) flash evaporating a part of the solvent of the mixed solution of the component (I) and the component (II) with a flash-type concentrator;
(F) Desolvating the mixed solution of the component (I) and the component (II) with a multistage vent extruder having a twin-screw endless screw and a rear exhaust zone;
A method for producing a mixture comprising
[2] A static mixer in which the mixing capacity of the continuous mixer in the step (d) is ESP ≧ 1 × 10 −6 (KWh / kg) and / or P / V value ≧ 10 3 (P: power of the mixer) (KW), V: The method for producing the mixture according to [1] above, which is a continuous mixing type emulsifying disperser having a space volume (m 3 ) of the mixing unit,
[3] The method for producing the mixture according to [1] or [2], further including a step of obtaining a pellet-like form after the solvent removal in the step (f),
[4] The component (I) has a storage elastic modulus at 25 ° C. in the range of 1.5 × 10 9 to 2.8 × 10 9 Pa, and the component (II) has a storage elastic modulus at 25 ° C. The method for producing a mixture according to any one of [1] to [3], which is in a range of 0.1 × 10 9 Pa or more and less than 1.5 × 10 9 Pa,
[5] The method for producing a mixture according to any one of [1] to [4] above, wherein the phenol-based stabilizer has a vapor pressure at 200 ° C. of 5 mmHg or less.
[6] The vinyl aromatic hydrocarbon content of the component (I) is 88 to 92% by weight, the conjugated diene content of the component (I) is 8 to 12% by weight, and the component (II) Any one of [1] to [5], wherein the vinyl aromatic hydrocarbon content is 30 to 70% by weight and the conjugated diene content of the component (II) is 30 to 70% by weight. A method for producing the described mixture,
[7] The phenol-based stabilizer is 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2-t- At least one stability selected from butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 2,4-bis [(octylthio) methyl] -o-cresol A method for producing the mixture according to any one of [1] to [6] above, comprising an agent;
[8] The mixture according to any one of [1] to [7], wherein the mixture has a vinyl aromatic hydrocarbon content of 70 to 92% by weight and a conjugated diene content of 8 to 30% by weight. A method for producing the mixture according to claim 1,
I will provide a.
本発明によれば、組成の異なる少なくとも２種類のビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体又はその水添物の混合物が、均一で、その物性が安定したものを製造することができる。 According to the present invention, a block copolymer containing at least two kinds of vinyl aromatic hydrocarbons having different compositions and a conjugated diene or a mixture of hydrogenated products thereof is produced with a uniform and stable physical property. Can do.
以下、本発明を詳細に説明する。
本発明は、組成の異なる、少なくとも２種類の成分(Ｉ)と成分(ＩＩ)から構成される、ビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体又はその水添物の混合物において、ビニル芳香族炭化水素の含有量が７０〜９２重量％であり、共役ジエンの含有量が８〜３０重量％であり、好ましくはビニル芳香族炭化水素の含有量が７２〜９０重量％であり、共役ジエンの含有量が１０〜２８重量％であり、さらに好ましくはビニル芳香族炭化水素の含有量が７５〜８７重量％であり、共役ジエンの含有量が１３〜２５重量％である、ブロック共重合体又はその水添物の混合物の製造方法に関するものである。
Hereinafter, the present invention will be described in detail.
The present invention relates to a mixture of a block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, or a hydrogenated product thereof, which is composed of at least two components (I) and (II) having different compositions. The vinyl aromatic hydrocarbon content is 70 to 92 wt%, the conjugated diene content is 8 to 30 wt%, preferably the vinyl aromatic hydrocarbon content is 72 to 90 wt%, The block copolymer having a conjugated diene content of 10 to 28% by weight, more preferably a vinyl aromatic hydrocarbon content of 75 to 87% by weight, and a conjugated diene content of 13 to 25% by weight. The present invention relates to a method for producing a polymer or a mixture of hydrogenated products thereof.
本発明で用いる成分（Ｉ）及び成分（ＩＩ）は、ビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体又はその水添物であって、成分（Ｉ）及び成分（ＩＩ）は、その組成において異なる。
ａ）工程
［成分（Ｉ）］
本発明の成分（Ｉ）のビニル芳香族炭化水素含有量は８５〜９５重量％であり、好ましくは８８〜９２重量％の範囲であり、共役ジエンの含有量は５〜１５重量％であり、好ましくは８〜１２重量％の範囲である。成分（Ｉ）の２５℃の貯蔵弾性率は１．５×１０9〜２．８×１０9Ｐａであり、好ましくは１．７×１０9〜２．８×１０9Ｐａであり、より好ましくは２．０×１０9〜２．８×１０9Ｐａの範囲である。
成分（Ｉ）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるピーク分子量は３万〜１００万であり、好ましくは５万〜８５万であり、より好ましくは８万〜７０万である。
さらに、成分（Ｉ）の分子量分布は、３万〜２０万の範囲と、２０万を越え１００万以下の範囲に各々少なくとも１つのピーク分子量を有するものが好ましい。
Component (I) and component (II) used in the present invention are a block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene or a hydrogenated product thereof, wherein component (I) and component (II) are: It differs in its composition.
a) Step [Component (I)]
The vinyl aromatic hydrocarbon content of component (I) of the present invention is 85 to 95% by weight, preferably in the range of 88 to 92% by weight, and the conjugated diene content is 5 to 15% by weight, Preferably it is the range of 8-12 weight%. The storage elastic modulus at 25 ° C. of the component (I) is 1.5 × 10 9 to 2.8 × 10 9 Pa, preferably 1.7 × 10 9 to 2.8 × 10 9 Pa, more preferably. Is in the range of 2.0 × 10 9 to 2.8 × 10 9 Pa.
The peak molecular weight of the component (I) measured by gel permeation chromatography (GPC) is 30,000 to 1,000,000, preferably 50,000 to 850,000, and more preferably 80,000 to 700,000.
Furthermore, the molecular weight distribution of component (I) preferably has at least one peak molecular weight in the range of 30,000 to 200,000 and in the range of more than 200,000 and less than 1,000,000.
本発明の成分（Ｉ）は、ビニル芳香族炭化水素単独重合体及び／又はビニル芳香族炭化水素と共役ジエンとを含む共重合体から構成されるセグメントを少なくとも1つと、共役ジエン単独重合体及び／又はビニル芳香族炭化水素と共役ジエンとを含む共重合体から構成されるセグメントを少なくとも1つ有する。成分（Ｉ）のポリマー構造は特に制限は無いが、例えば、一般式：
（Ａ−Ｂ）n、Ａ−（Ｂ−Ａ）n、Ｂ−（Ａ−Ｂ）n+1
［（Ａ−Ｂ）k］m+1−Ｘ、［（Ａ−Ｂ）k−Ａ］m+1−Ｘ
［（Ｂ−Ａ）k］m+1−Ｘ、［（Ｂ−Ａ）k−Ｂ］m+1−Ｘ
（上式において、セグメントＡはビニル芳香族炭化水素単独重合体及び／又はビニル芳香族炭化水素と共役ジエンとを含む共重合体、セグメントＢは共役ジエン単独重合体及び／又はビニル芳香族炭化水素と共役ジエンとを含む共重合体である。Ｘは、例えば、四塩化ケイ素、四塩化スズ、１，３−ビス（Ｎ，Ｎ−グリシジルアミノメチル）シクロヘキサン、エポキシ化大豆油等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。ｎ、ｋ及びｍは１以上の整数、一般的には１〜５の整数である。また、Ｘに複数結合しているポリマー鎖の構造は同一でも、異なっていてもよい。）で表される線状ブロック共重合体やラジアルブロック共重合体、或いはこれらのポリマー構造の任意の混合物が使用できる。また、上記一般式で表されるラジアルブロック共重合体において、更にＡ及び／又はＢが少なくとも一つＸに結合していてもよい。
Component (I) of the present invention comprises at least one segment composed of a vinyl aromatic hydrocarbon homopolymer and / or a copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene, a conjugated diene homopolymer, and And / or having at least one segment composed of a copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene. The polymer structure of component (I) is not particularly limited, but for example, the general formula:
(AB) n , A- (BA) n , B- (AB) n + 1
[(A−B) k ] m + 1 −X, [(A−B) k −A] m + 1 −X
[(B−A) k ] m + 1 −X, [(B−A) k −B] m + 1 −X
(In the above formula, segment A is a vinyl aromatic hydrocarbon homopolymer and / or a copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene, and segment B is a conjugated diene homopolymer and / or a vinyl aromatic hydrocarbon. And X is a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil, etc. Or a residue of an initiator such as a polyfunctional organolithium compound, where n, k and m are integers of 1 or more, generally an integer of 1 to 5. The structures of the polymer chains may be the same or different.), And a linear block copolymer or a radial block copolymer represented by the following formula, or any mixture of these polymer structures can be used. In the radial block copolymer represented by the above general formula, at least one A and / or B may be bonded to X.
本発明の成分（Ｉ）において、セグメントＡ、セグメントＢにおけるビニル芳香族炭化水素と共役ジエンとの共重合体中のビニル芳香族炭化水素は均一に分布していても、テーパー（漸減）状に分布していてもよい。また、該共重合体中には、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セグメント中にそれぞれ複数個共存してもよい。セグメントＡ中のビニル芳香族炭化水素含有量（｛セグメントＡ中のビニル芳香族炭化水素／（セグメントＡ中のビニル芳香族炭化水素＋共役ジエン）｝×１００）とセグメントＢ中のビニル芳香族炭化水素含有量（｛セグメントＢ中のビニル芳香族炭化水素／（セグメントＢ中のビニル芳香族炭化水素＋共役ジエン）｝×１００）との関係は、セグメントＡにおけるビニル芳香族炭化水素含有量のほうが、セグメントＢにおけるビニル芳香族炭化水素含有量より大である。セグメントＡとセグメントＢの好ましいビニル芳香族炭化水素含有量の差は５重量％以上であることが好ましい。 In the component (I) of the present invention, the vinyl aromatic hydrocarbon in the copolymer of the vinyl aromatic hydrocarbon and the conjugated diene in the segment A and the segment B is tapered (gradually reduced) even if it is uniformly distributed. It may be distributed. In the copolymer, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed may coexist in the segment. Vinyl aromatic hydrocarbon content in segment A ({vinyl aromatic hydrocarbon in segment A / (vinyl aromatic hydrocarbon in segment A + conjugated diene)} × 100) and vinyl aromatic carbon in segment B The relationship between the hydrogen content ({vinyl aromatic hydrocarbon in segment B / (vinyl aromatic hydrocarbon in segment B + conjugated diene)} × 100) is greater with the vinyl aromatic hydrocarbon content in segment A. , Greater than the vinyl aromatic hydrocarbon content in segment B. The difference in the preferred vinyl aromatic hydrocarbon content between segment A and segment B is preferably 5% by weight or more.
［成分（ＩＩ）］
本発明の成分（ＩＩ）のビニル芳香族炭化水素含有量は２５重量％以上、８５重量％未満、好ましくは３０〜８０重量％であり、より好ましくは３５重量％〜７５重量％未満の範囲である。一方、本発明の成分（ＩＩ）の共役ジエンの含有量は、１５重量％以上、７５重量％未満であり、好ましくは２０〜７０重量％であり、より好ましくは２５重量％〜６５重量％の範囲である。成分（ＩＩ）の２５℃の貯蔵弾性率は０．１×１０9Ｐａ以上、１．５×１０9Ｐａ未満であり、好ましくは０．１×１０9〜１．０×１０9Ｐａであり、より好ましくは０．１×１０9〜０．７×１０9Ｐａの範囲である。
成分（ＩＩ）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるピーク分子量は３万〜１００万であり、好ましくは５万〜８５万であり、より好ましくは８万〜７０万である。
[Component (II)]
The vinyl aromatic hydrocarbon content of the component (II) of the present invention is 25 wt% or more and less than 85 wt%, preferably 30 to 80 wt%, more preferably 35 wt% to less than 75 wt%. is there. On the other hand, the content of the conjugated diene of the component (II) of the present invention is 15 wt% or more and less than 75 wt%, preferably 20 to 70 wt%, more preferably 25 wt% to 65 wt%. It is a range. The storage elastic modulus at 25 ° C. of component (II) is 0.1 × 10 9 Pa or more and less than 1.5 × 10 9 Pa, preferably 0.1 × 10 9 to 1.0 × 10 9 Pa. , more preferably from 0.1 × 10 9 ~0.7 × 10 9 Pa.
The peak molecular weight of the component (II) measured by gel permeation chromatography (GPC) is 30,000 to 1,000,000, preferably 50,000 to 850,000, and more preferably 80,000 to 700,000.
本発明の成分（ＩＩ）は、ビニル芳香族炭化水素単独重合体及び／又はビニル芳香族炭化水素と共役ジエンとを含む共重合体から構成されるセグメントを少なくとも1つと、共役ジエン単独重合体及び／又はビニル芳香族炭化水素と共役ジエンとを含む共重合体から構成されるセグメントを少なくとも1つ有する。成分（ＩＩ）のポリマー構造は特に制限は無いが、例えば、一般式：
（Ａｂ−Ｂｂ）n、Ａｂ−（Ｂｂ−Ａｂ）n、Ｂｂ−（Ａｂ−Ｂｂ）n+1
（上式において、ｎは１以上の整数、一般的には１〜５である。）で表される線状ブロ
ック共重合体、或いは一般式；
［（Ａｂ−Ｂｂ）k］m+1−Ｘ、［（Ａｂ−Ｂｂ）k−Ａｂ］m+1−Ｘ、
［（Ｂｂ−Ａｂ）k］m+1−Ｘ、［（Ｂｂ−Ａｂ）k−Ｂｂ］m+1−Ｘ
（上式において、Ａｂはビニル芳香族炭化水素を主体とする重合体ブロックであり、Ｂｂは共役ジエンを主体とする重合体である。ＡｂブロックとＢｂ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。Ｘは、例えば、四塩化ケイ素、四塩化スズ、１，３−ビス（Ｎ，Ｎ−グリシジルアミノメチル）シクロヘキサン、エポキシ化大豆油等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。ｋ及びｍは１〜５の整数である。）で表されるラジアルブロック共重合体、或いはこれらのブロック共重合体の任意のポリマー構造の混合物が使用できる。本発明の成分（ＩＩ）において、セグメントＡｂ、セグメントＢｂにおけるビニル芳香族炭化水素と共役ジエンとの共重合体中のビニル芳香族炭化水素は均一に分布していても、テーパー（漸減）状に分布していてもよい。また、該共重合体中には、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セグメント中にそれぞれ複数個共存してもよい。セグメントＡｂ中のビニル芳香族炭化水素含有量（｛セグメントＡｂ中のビニル芳香族炭化水素／（セグメントＡｂ中のビニル芳香族炭化水素＋共役ジエン）｝×１００）とセグメントＢｂ中のビニル芳香族炭化水素含有量（｛セグメントＢｂ中のビニル芳香族炭化水素／（セグメントＢｂ中のビニル芳香族炭化水素＋共役ジエン）｝×１００）との関係は、セグメントＡｂにおけるビニル芳香族炭化水素含有量のほうが、セグメントＢｂにおけるビニル芳香族炭化水素含有量より大である。セグメントＡｂとセグメントＢｂの好ましいビニル芳香族炭化水素含有量の差は５重量％以上であることが好ましい。
Component (II) of the present invention comprises at least one segment composed of a vinyl aromatic hydrocarbon homopolymer and / or a copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene, a conjugated diene homopolymer, and And / or having at least one segment composed of a copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene. The polymer structure of component (II) is not particularly limited, but for example, the general formula:
(Ab-Bb) n , Ab- (Bb-Ab) n , Bb- (Ab-Bb) n + 1
(Wherein n is an integer of 1 or more, generally 1 to 5), or a linear block copolymer represented by the general formula;
[(Ab−Bb) k ] m + 1 −X, [(Ab−Bb) k −Ab] m + 1 −X,
[(Bb−Ab) k ] m + 1 −X, [(Bb−Ab) k −Bb] m + 1 −X
(In the above formula, Ab is a polymer block mainly composed of vinyl aromatic hydrocarbons, and Bb is a polymer mainly composed of conjugated dienes. The boundary between the Ab block and the Bb block is not always clearly distinguished. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil, or polyfunctional organolithium. A residue of an initiator such as a compound, k and m are integers of 1 to 5), or a mixture of arbitrary polymer structures of these block copolymers. it can. In the component (II) of the present invention, the vinyl aromatic hydrocarbon in the copolymer of the vinyl aromatic hydrocarbon and the conjugated diene in the segment Ab and the segment Bb has a taper (gradual decrease) even if the vinyl aromatic hydrocarbon is uniformly distributed. It may be distributed. In the copolymer, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where tapes are distributed may coexist in the segment. Vinyl aromatic hydrocarbon content in segment Ab ({vinyl aromatic hydrocarbon in segment Ab / (vinyl aromatic hydrocarbon in segment Ab + conjugated diene)} × 100) and vinyl aromatic carbonization in segment Bb The relationship between the hydrogen content ({vinyl aromatic hydrocarbon in segment Bb / (vinyl aromatic hydrocarbon in segment Bb + conjugated diene)} × 100) is greater for the vinyl aromatic hydrocarbon content in segment Ab. , Greater than the vinyl aromatic hydrocarbon content in segment Bb. The difference in the preferred vinyl aromatic hydrocarbon content between segment Ab and segment Bb is preferably 5% by weight or more.
本発明に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、１，１−ジフェニルエチレン、Ｎ，Ｎ−ジメチル−ｐ−アミノエチルスチレン、Ｎ，Ｎ−ジエチル−ｐ−アミノエチルスチレンなどが挙げられ、スチレンが好ましい。これらは１種のみならず２種以上混合使用してもよい。 Examples of the vinyl aromatic hydrocarbon used in the present invention include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1 , 1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like, and styrene is preferable. These may be used alone or in combination of two or more.
本発明に用いる共役ジエンとしては、１対の共役二重結合を有するジオレフィンを用いることができ、例えば、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挙げられ、１，３−ブタジエン、イソプレンなどが好ましい。これらは１種のみならず２種以上混合使用してもよい。 As the conjugated diene used in the present invention, a diolefin having a pair of conjugated double bonds can be used. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like are mentioned, and 1,3-butadiene, isoprene and the like are preferable. These may be used alone or in combination of two or more.
本発明の成分（Ｉ）と成分（ＩＩ）において、（イ）イソプレンと１，３−ブタジエンとを含む共重合体ブロック、（ロ）イソプレンとビニル芳香族炭化水素とを含む共重合体ブロック、及び（ハ）イソプレンと１，３−ブタジエンとビニル芳香族炭化水素とを含む共重合体ブロックの（イ）〜（ハ）の群から選ばれる少なくとも１つの重合体ブロックが組み込まれていてもよく、ブタジエンとイソプレンの重量比が３／９７〜９０／１０であり、好ましくは５／９５〜８５／１５であり、より好ましくは１０／９０〜８０／２０である。なお、ブタジエンとイソプレンの重量比が３／９７〜９０／１０のブロック共重合体とを含む水添ブロック共重合体は、水添率が５０重量％以下にあっては熱成形・加工等におけるゲル生成が少ない。 In component (I) and component (II) of the present invention, (a) a copolymer block containing isoprene and 1,3-butadiene, (b) a copolymer block containing isoprene and a vinyl aromatic hydrocarbon, And (c) at least one polymer block selected from the group (a) to (c) of a copolymer block containing isoprene, 1,3-butadiene and vinyl aromatic hydrocarbon may be incorporated. The weight ratio of butadiene to isoprene is 3/97 to 90/10, preferably 5/95 to 85/15, more preferably 10/90 to 80/20. A hydrogenated block copolymer containing a block copolymer having a weight ratio of butadiene to isoprene of 3/97 to 90/10 is suitable for thermoforming and processing when the hydrogenation ratio is 50% by weight or less. Less gel formation.
本発明の成分（Ｉ）と成分（ＩＩ）は、例えば、炭化水素溶媒中で有機アルカリ金属化合物等の開始剤を用いてアニオンリビング重合により得られる。炭化水素溶媒としては、例えば、ｎ−ブタン、イソブタン、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン等の脂肪族炭化水素類；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、シクロヘプタン、メチルシクロヘプタン等の脂環式炭化水素類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素等が使用できる。これらは１種のみならず２種以上混合使用してもよい。 Component (I) and component (II) of the present invention can be obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclohexane Alicyclic hydrocarbons such as heptane and methylcycloheptane; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can be used. These may be used alone or in combination of two or more.
また、重合開始剤としては、一般的に共役ジエン及びビニル芳香族化合物に対しアニオン重合活性があることが知られている脂肪族炭化水素アルカリ金属化合物、芳香族炭化水素アルカリ金属化合物、有機アミノアルカリ金属化合物等を用いることができる。アルカリ金属としてはリチウム、ナトリウム、カリウム等が挙げられ、好適な有機アルカリ金属化合物としては、炭素数１から２０の脂肪族及び芳香族炭化水素リチウム化合物であって、１分子中に１個のリチウムを含む化合物や１分子中に複数のリチウムを含むジリチウム化合物、トリリチウム化合物、テトラリチウム化合物が挙げられる。具体的には、ｎ−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、イソプレニルジリチウム、ジイソプロペニルベンゼンとｓｅｃ−ブチルリチウムの反応生成物、さらにジビニルベンゼンとｓｅｃ−ブチルリチウムと少量の１，３−ブタジエンとの反応生成物等が挙げられる。さらに、米国特許第５，７０８，０９２号明細書、英国特許第２，２４１，２３９号明細書、米国特許第５，５２７，７５３号明細書等に開示されている有機アルカリ金属化合物も使用することができる。これらは１種のみならず２種以上混合使用してもよい。 In addition, as polymerization initiators, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, organic amino alkalis generally known to have anionic polymerization activity for conjugated dienes and vinyl aromatic compounds. A metal compound or the like can be used. Examples of the alkali metal include lithium, sodium, potassium, and the like. Suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, and one lithium per molecule. And dilithium compounds, trilithium compounds, and tetralithium compounds containing a plurality of lithium atoms in one molecule. Specifically, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, diisopropenylbenzene and sec-butyl lithium In addition, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene can be used. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to. These may be used alone or in combination of two or more.
本発明において、水添前のブロック共重合体を製造する際の重合温度は、一般的には、−１０℃〜１５０℃であり、好ましくは４０℃〜１２０℃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１０時間以内であり、特に好適には０．５〜５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などをもって置換するのが望ましい。重合圧力は、上記重合温度範囲でモノマー及び溶媒を液層に維持するに充分な圧力の範囲で行えばよく、特に制限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、例えば水、酸素、炭酸ガス等が混入しないよう留意する必要がある。 In the present invention, the polymerization temperature for producing the block copolymer before hydrogenation is generally -10 ° C to 150 ° C, preferably 40 ° C to 120 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 10 hours, particularly preferably 0.5 to 5 hours. The polymerization atmosphere is preferably replaced with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is carried out within a range of pressure sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range. Furthermore, care must be taken not to mix impurities, such as water, oxygen, carbon dioxide, etc., that inactivate the catalyst and living polymer into the polymerization system.
本発明の成分（Ｉ）と成分（ＩＩ）のブロック共重合体の水添物は、上記で得られた水添前のブロック共重合体を水素添加することにより得られる。水添触媒としては、特に制限されず、従来から公知である（１）Ｎｉ、Ｐｔ、Ｐｄ、Ｒｕ等の金属をカーボン、シリカ、アルミナ、ケイソウ土等に担持させた担持型不均一系水添触媒；（２）Ｎｉ、Ｃｏ、Ｆｅ、Ｃｒ等の有機酸塩又はアセチルアセトン塩などの遷移金属塩と有機アルミニウム等の還元剤とを用いる、いわゆるチーグラー型水添触媒；（３）Ｔｉ、Ｒｕ、Ｒｈ、Ｚｒ等の有機金属化合物等のいわゆる有機金属錯体等の均一系水添触媒が用いられる。具体的な水添触媒としては、特公昭４２−８７０４号公報、特公昭４３−６６３６号公報、特公昭６３−４８４１号公報、特公平１−３７９７０号公報、特公平１−５３８５１号公報、特公平２−９０４１号公報に記載された水添触媒を使用することができる。好ましい水添触媒としてはチタノセン化合物及び／又は還元性有機金属化合物との混合物が挙げられる。チタノセン化合物としては、特開平８−１０９２１９号公報に記載された化合物が使用できるが、具体例としては、ビスシクロペンタジエニルチタンジクロライド、モノペンタメチルシクロペンタジエニルチタントリクロライド等の（置換）シクロペンタジエニル骨格、インデニル骨格あるいはフルオレニル骨格を有する配位子を少なくとも１つ以上もつ化合物が挙げられる。また、還元性有機金属化合物としては、有機リチウム等の有機アルカリ金属化合物、有機マグネシウム化合物、有機アルミニウム化合物、有機ホウ素化合物あるいは有機亜鉛化合物等が挙げられる。 The hydrogenated product of the block copolymer of components (I) and (II) of the present invention can be obtained by hydrogenating the block copolymer before hydrogenation obtained above. The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. (2) So-called Ziegler-type hydrogenation catalyst using a transition metal salt such as an organic acid salt such as Ni, Co, Fe, Cr or an acetylacetone salt and a reducing agent such as organic aluminum; (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh or Zr is used. Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Utility Model Publication No. 2-9041 can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound. As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
水添反応は、一般的には、０〜２００℃であり、より好ましくは３０〜１５０℃の温度範囲で実施される。水添反応に使用される水素の圧力は０．１〜１５ＭＰａであり、好ましくは０．２〜１０ＭＰａであり、より好ましくは０．３〜７ＭＰａである。また、水添反応時間は、通常３分〜１０時間であり、好ましくは１０分〜５時間である。水添反応は、バッチプロセス、連続プロセス、或いはそれらの組み合わせのいずれでも用いることができる。 The hydrogenation reaction is generally performed at a temperature of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 7 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
本発明のブロック共重合体の水添物において、共役ジエンに基づく不飽和二重結合の水素添加率は、目的に合わせて任意に選択でき、特に限定されない。熱安定性及び耐候性の良好な水添ブロック共重合体を得る場合、水添ブロック共重合体中の共役ジエン化合物に基づく不飽和二重結合の７０％を超える、好ましくは７５％以上であり、より好ましくは８５％以上、特に好ましくは９０％以上が水添されている。また、熱安定性の良好な水添ブロック共重合体を得る場合、水素添加率は３〜７０％であり、或いは５〜６５％であり、特に好ましくは１０〜６０％である。なお、水添ブロック共重合体中のビニル芳香族炭化水素に基づく芳香族二重結合の水添率については特に制限はないが、水添率を５０％以下、好ましくは３０％以下、より好ましくは２０％以下にすることが好ましい。水添率は、核磁気共鳴装置（ＮＭＲ）により知ることができる。 In the hydrogenated product of the block copolymer of the present invention, the hydrogenation rate of the unsaturated double bond based on the conjugated diene can be arbitrarily selected according to the purpose and is not particularly limited. When obtaining a hydrogenated block copolymer having good thermal stability and weather resistance, it exceeds 70% of the unsaturated double bond based on the conjugated diene compound in the hydrogenated block copolymer, preferably 75% or more. More preferably, 85% or more, particularly preferably 90% or more is hydrogenated. Moreover, when obtaining a hydrogenated block copolymer with favorable thermal stability, a hydrogenation rate is 3 to 70%, or 5 to 65%, Most preferably, it is 10 to 60%. The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the hydrogenated block copolymer is not particularly limited, but the hydrogenation rate is 50% or less, preferably 30% or less, more preferably Is preferably 20% or less. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).
本発明において、水添ブロック共重合体の共役ジエン部分のミクロ構造（シス、トランス、ビニルの比率）は、前述の極性化合物等の使用により任意に変えることができ、特に制限はない。一般に、ビニル結合量は５〜９０％であり、好ましくは１０〜８０％であり、より好ましくは１５〜７５％の範囲で設定できる。なお、本発明においてビニル結合量とは、１，２−ビニル結合と３，４−ビニル結合の合計量（但し、共役ジエンとして１，３−ブタジエンを使用した場合には、１，２−ビニル結合量）である。ビニル結合量は、核磁気共鳴装置（ＮＭＲ）により求めることができる。 In the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene portion of the hydrogenated block copolymer can be arbitrarily changed by the use of the aforementioned polar compound or the like, and is not particularly limited. In general, the vinyl bond content is 5 to 90%, preferably 10 to 80%, more preferably 15 to 75%. In the present invention, the amount of vinyl bonds means the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, 1,2-vinyl bonds are used. Binding amount). The amount of vinyl bonds can be determined by a nuclear magnetic resonance apparatus (NMR).
ここで、成分（Ｉ）と成分（ＩＩ）の２５℃の貯蔵弾性率を制御する方法の例を以下に示す。ビニル芳香族炭化水素を単独重合させ、重合完結後、ビニル芳香族炭化水素と共役ジエンの混合物を一度に仕込んで重合を続行させるとビニル芳香族炭化水素・共役ジエン比が次第に変化するビニル芳香族炭化水素・共役ジエン共重合体部をもつビニル芳香族炭化水素−共役ジエンブロック共重合体を得ることができる。また、ビニル芳香族炭化水素と共役ジエンの均一な混合物を連続的に仕込むとビニル芳香族炭化水素・共役ジエン比の均一なビニル芳香族炭化水素・共役ジエン共重合体部をもつビニル芳香族炭化水素−共役ジエンブロック共重合体を得ることができる。ビニル芳香族炭化水素・共役ジエン比が次第に変化するビニル芳香族炭化水素・共役ジエン共重合体部をもつブロック共重合体の貯蔵弾性率の挙動は漸減的であるのに対して、ビニル芳香族炭化水素・共役ジエン比の均一なビニル芳香族炭化水素・共役ジエン共重合体部をもつブロック共重合体の貯蔵弾性率の挙動は急激に変化する。そこで、ビニル芳香族炭化水素を単独重合させてからビニル芳香族炭化水素と共役ジエンの混合物を仕込んで重合を続行させる方法と、ビニル芳香族炭化水素と共役ジエンの均一な混合物を連続的に仕込む方法とを適宜採用し、ブロック共重合体のビニル芳香族炭化水素含有量も併せて調整することによって、成分（Ｉ）と成分（ＩＩ）が任意の２５℃の貯蔵弾性率を持つポリマーを得ることが可能となる。 Here, the example of the method of controlling the storage elastic modulus of 25 degreeC of a component (I) and a component (II) is shown below. When vinyl aromatic hydrocarbons are homopolymerized and the polymerization is completed, a mixture of vinyl aromatic hydrocarbon and conjugated diene is charged at once and polymerization is continued. Vinyl aromatic hydrocarbon / conjugated diene ratio gradually changes. A vinyl aromatic hydrocarbon-conjugated diene block copolymer having a hydrocarbon / conjugated diene copolymer portion can be obtained. In addition, when a uniform mixture of vinyl aromatic hydrocarbon and conjugated diene is continuously charged, vinyl aromatic carbon having a vinyl aromatic hydrocarbon / conjugated diene copolymer part with a uniform ratio of vinyl aromatic hydrocarbon / conjugated diene. A hydrogen-conjugated diene block copolymer can be obtained. The storage elastic modulus behavior of block copolymer with vinyl aromatic hydrocarbon / conjugated diene copolymer part with gradually changing vinyl aromatic hydrocarbon / conjugated diene ratio is gradual, whereas vinyl aromatic The behavior of storage modulus of block copolymer with vinyl aromatic hydrocarbon / conjugated diene copolymer part with uniform hydrocarbon / conjugated diene ratio changes rapidly. Therefore, after homopolymerizing vinyl aromatic hydrocarbons, a mixture of vinyl aromatic hydrocarbon and conjugated diene is charged and polymerization is continued, and a uniform mixture of vinyl aromatic hydrocarbon and conjugated diene is continuously charged. By appropriately adopting the method and adjusting the vinyl aromatic hydrocarbon content of the block copolymer together, a polymer having components (I) and (II) having an arbitrary storage elastic modulus of 25 ° C. is obtained. It becomes possible.
本発明の成分（Ｉ）は、２５℃の貯蔵弾性率が１．５×１０9〜２．８×１０9Ｐａの範囲であり、好ましくは１．７×１０9〜２．６×１０9Ｐａ範囲であり、より好ましくは１．８×１０9〜２．４×１０9Ｐａ範囲である。また、本発明の成分（ＩＩ）は、２５℃の貯蔵弾性率が０．１×１０9Ｐａ以上、１．５×１０9Ｐａ未満の範囲であり、好ましくは０．１×１０9Ｐａ以上、１．３×１０9Ｐａ範囲であり、より好ましくは０．１×１０9Ｐａ以上、１．０×１０9Ｐａ範囲である。 Component (I) of the present invention has a storage elastic modulus at 25 ° C. in the range of 1.5 × 10 9 to 2.8 × 10 9 Pa, preferably 1.7 × 10 9 to 2.6 × 10 9. a Pa range, more preferably from 1.8 × 10 9 ~2.4 × 10 9 Pa range. Further, component (II) of the present invention, 25 ° C. of storage modulus 0.1 × 10 9 Pa or more, a range of less than 1.5 × 10 9 Pa, preferably 0.1 × 10 9 Pa or more 1.3 × 10 9 Pa, more preferably 0.1 × 10 9 Pa or more and 1.0 × 10 9 Pa.
（ｂ）工程
本工程は、ブロック共重合体又はその水添物の活性重合体溶液に、反応停止剤を添加する工程であり、反応停止剤は、重合器中へ添加することが好ましい。本工程は、最終的に得られるブロック共重合体又はその水添物に混在するゲルの減少に有効である。反応停止剤としては、活性水素を有する化合物；有機ハロゲン化物；無機ハロゲン化物等が挙げられる。活性水素を有する化合物としては、水、アルコール、チオール、アミン、無機酸、有機酸等が、有機ハロゲン化物又は無機ハロゲン化物としてはハロゲン化アルキル化合物、ハロゲン化珪素、ハロゲン化錫等があり、好適な反応停止剤は水、アルコールである。少量の水とアルコールを反応停止剤として使用することにより、溶媒と共に排出されて重合器中に残存せず、次の重合系に影響を及ぼさない。特に、水と炭素数１〜３のアルコールは沸点が低く揮散性に優れ、脱溶媒したブロック共重合体又はその水添物に残存しないため、臭気がない点で好ましい。
(B) Process This process is a process of adding a reaction terminator to the active polymer solution of the block copolymer or its hydrogenated product, and it is preferable to add the reaction terminator into the polymerization vessel. This step is effective for reducing the gel mixed in the finally obtained block copolymer or its hydrogenated product. Examples of the reaction terminator include compounds having active hydrogen; organic halides; inorganic halides and the like. Examples of the compound having active hydrogen include water, alcohol, thiol, amine, inorganic acid, and organic acid, and examples of the organic halide or inorganic halide include halogenated alkyl compound, silicon halide, and tin halide. Suitable reaction terminators are water and alcohol. By using a small amount of water and alcohol as a reaction terminator, they are discharged together with the solvent and do not remain in the polymerization vessel, and do not affect the next polymerization system. In particular, water and alcohol having 1 to 3 carbon atoms are preferable in that they have no odor because they have a low boiling point and excellent volatility and do not remain in the desolvated block copolymer or its hydrogenated product.
（ｃ）工程
前記反応停止剤を添加したブロック共重合体又はその水添物の溶液の製造に用いられる開始剤は、有機リチウム化合物を用い、そのポリマー溶液は強塩基である。このような状態でフェノール系酸化防止剤等の安定剤をポリマー溶液に添加した場合、多くの安定剤は塩基性条件下で好ましくない変質を起こすため、ポリマーの色調悪化、熱安定性の低下等が発生する。本工程では炭酸ガスと有機酸の少なくとも１種を用いて溶液のＰＨを調整することによって、優れた品質を有するブロック共重合体又はその水添物を得ることができる。ＰＨの調整は、重合器中、移送先である貯蔵槽への移送配管途中、又は貯蔵槽内で行うことができる。本発明において使用する炭酸ガス、有機酸の添加量は、溶液のＰＨが６．０〜９．５の範囲内になるように所定量添加する。溶液のＰＨが９．５を超える場合は色調に劣り、６．０未満としても色調の向上はなく、ブロック共重合体又はその水添物溶液中に炭酸ガス、有機酸がそのまま存在するため、設備の腐食等が発生する可能性もあり好ましくない。ここで溶液のＰＨとは、溶液の一部を採取し、該溶液と同重量の蒸留水（ＰＨ７．０±０．５のもの）を該溶液と充分混合した後、静置して二層分離した水層のＰＨを表示するものとする。ＰＨは、ガラス電極式水素イオン濃度計（ＰＨメーター）を用いて測定できる。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、スルフィン酸、フェノール等の化合物が挙げられるが、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、炭素数８以上の脂肪酸、芳香族カルボン酸が好ましい。本発明で好適に用いられる脂肪酸の具体例としては、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、ベヘン酸又はこれらの混合物等が挙げられる。芳香族カルボン酸としては、安息香酸、クロロ安息香酸、アミノ安息香酸、ケイ皮酸、フェニル酢酸又はこれらの混合物等が挙げられる。使用する炭酸ガスは、ガス状でも固体状とであってもよく、水俣は溶媒に溶解させた状態で添加することもできる。
(C) Process The initiator used for manufacture of the solution of the block copolymer which added the said reaction terminator, or its hydrogenated product uses an organic lithium compound, The polymer solution is a strong base. When stabilizers such as phenolic antioxidants are added to the polymer solution in such a state, many stabilizers cause undesirable alteration under basic conditions, so the color tone of the polymer deteriorates, the thermal stability decreases, etc. Will occur. In this step, a block copolymer having excellent quality or a hydrogenated product thereof can be obtained by adjusting the pH of the solution using at least one of carbon dioxide and organic acid. The pH can be adjusted in the polymerization vessel, in the middle of the transfer piping to the storage tank that is the transfer destination, or in the storage tank. Carbon dioxide gas and organic acid used in the present invention are added in predetermined amounts so that the pH of the solution is in the range of 6.0 to 9.5. When the pH of the solution exceeds 9.5, the color tone is inferior, and even if it is less than 6.0, there is no improvement in color tone, and carbon dioxide gas and organic acid are present as they are in the block copolymer or its hydrogenated solution. There is a possibility that the equipment may be corroded, which is not preferable. Here, the pH of the solution means that a part of the solution is sampled and distilled water having the same weight as the solution (with a pH of 7.0 ± 0.5) is sufficiently mixed with the solution and then left to stand to form two layers. The pH of the separated water layer shall be displayed. PH can be measured using a glass electrode type hydrogen ion concentration meter (PH meter). 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, phenol, and the like, preferably an organic compound containing a carboxyl group, A fatty acid having 8 or more and an aromatic carboxylic acid are preferred. Specific examples of fatty acids preferably used in the present invention include octylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, and mixtures thereof. Examples of the aromatic carboxylic acid include benzoic acid, chlorobenzoic acid, aminobenzoic acid, cinnamic acid, phenylacetic acid, and mixtures thereof. The carbon dioxide gas to be used may be gaseous or solid, and the starch syrup can be added in a state dissolved in a solvent.
（ｄ）工程
前記の炭酸ガス及び／又は有機酸を添加して混合した後、成分（Ｉ）の溶液と成分（ＩＩ）の溶液を配管途中に設けた連続混合機を用いて同時に供給して混合後、フェノール系安定剤の１種以上を添加する、或いは前記成分（Ｉ）と成分（ＩＩ）の溶液にフェノール系安定剤の１種以上を添加後、配管途中に設けた連続混合機を用いて同時に供給して混合する工程である。
本発明に使用するフェノール系安定剤を添加することがブロック共重合体又はその水添物の酸化劣化等による変質を防止する上で必要である。
本発明では、２００℃の蒸気圧が５ｍｍＨｇ以下のフェノール系安定剤を用いることが、次工程の脱溶媒時におけるフェノール系安定剤の揮散を防止し、添加量に見合った効果を発揮する。逆に、２００℃の蒸気圧が５ｍｍＨｇを超えるフェノール系安定剤を用いた場合は、フェノール系安定剤の揮散が著しいため熱安定性の低下が大きく、好ましくない。本発明で用いるフェノール系安定剤は、２００℃の蒸気圧が５ｍｍＨｇ以下の従来公知のフェノール系安定剤が使用でき、これらはそのまま溶液に添加しても、また炭化水素溶媒に溶解して添加してもよい。好適なフェノール系安定剤としては、２−〔１−（２−ヒドロキシ−３，５−ジ−ｔ−ペンチルフェニル）エチル〕−４，６−ジ−ｔ−ペンチルフェニルアクリレート、２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート、ｎ−オクタデシル３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、テトラキス〔メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）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−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、２，４−ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジン等が挙げられる。前記フェノール系安定剤は、２種以上組み合わせて使用することもできる。これらのフェノール系安定剤はブロック共重合体又はその水添物１００重量部に対して０．０５〜３重量部、好ましくは０．１〜２重量部の範囲で使用される。フェノール系安定剤の使用量が０．０５重量部未満の場合には安定性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外の効果が発揮されない。
Step (d) After adding and mixing the carbon dioxide gas and / or organic acid, the solution of component (I) and the solution of component (II) are simultaneously supplied using a continuous mixer provided in the middle of the piping. After mixing, one or more phenolic stabilizers are added, or after adding one or more phenolic stabilizers to the solution of component (I) and component (II), a continuous mixer provided in the middle of the pipe It is the process of supplying and mixing simultaneously using.
The addition of the phenol-based stabilizer used in the present invention is necessary for preventing the block copolymer or its hydrogenated product from being deteriorated due to oxidative degradation or the like.
In the present invention, use of a phenol stabilizer having a vapor pressure of 200 ° C. of 5 mmHg or less prevents volatilization of the phenol stabilizer at the time of desolvation in the next step, and exhibits an effect commensurate with the amount added. On the other hand, when a phenol-based stabilizer having a vapor pressure at 200 ° C. exceeding 5 mmHg is used, volatilization of the phenol-based stabilizer is remarkable, resulting in a large decrease in thermal stability. As the phenol-based stabilizer used in the present invention, conventionally known phenol-based stabilizers having a vapor pressure at 200 ° C. of 5 mmHg or less can be used, and these can be added as they are to a solution or dissolved in a hydrocarbon solvent. May be. Suitable phenolic stabilizers include 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2-t-butyl. -6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl -4-hydroxybenzyl) benzene, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like. It is below. Two or more kinds of the phenol-based stabilizers can be used in combination. These phenolic stabilizers are used in an amount of 0.05 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the block copolymer or its hydrogenated product. When the amount of the phenol-based stabilizer used is less than 0.05 parts by weight, the effect of improving the stability is not recognized. Conversely, when the amount exceeds 3 parts by weight, the effects other than the scope of the present invention are not exhibited.
本工程の配管途中に設けた連続混合機は、混合能力がＥＳＰ（ＫＷｈ／ｋｇ）≧１×１０-6、好ましくはＥＳＰ＝５×１０-6、より好ましくはＥＳＰ＝１０×１０-6であるスタティックミキサー、及び／又は、Ｐ／Ｖ値（ＫＷ／ｍ3）≧１０3、好ましくはＰ／Ｖ値≧３×１０3、より好ましくはＰ／Ｖ値≧５×１０3、（Ｐ：混合機の動力（ＫＷ）、Ｖ：混合部の空間容積（ｍ3））の連続混合式の乳化分散機を使用することが好ましい。連続混合機の混合能力がＥＳＰ＝１０×１０-6、Ｐ／Ｖ値≧１０3にあっては、組成の異なる２種類から構成されるビニル芳香族炭化水素と共役ジエンとを含むブロック共重合体又はその水添物の混合物を、均一混合を維持した状態で溶媒を脱溶媒することができる。スタティックミキサーのＥＳＰは、ＥＳＰ＝ΔＰ×Ｖ[m3/sec]／（ρＶ[kg/sec]）であり、ＥＳＰ（ＫＷｈ／ｋｇ）＝ΔＰ×２７×１０-6／ρとして計算される。ここで、ΔＰは圧力損失（ｋｇ／ｃｍ2）、ρは密度（ｇ／ｍｌ）であり、ΔＰを変動させることによって、ＥＳＰを制御することができる。成分（Ｉ）の溶液と成分（ＩＩ）の溶液を、連続混合機を使用せずに、同一の槽内で混合、貯蔵する場合は、溶液が分離して均一混合状態とならないため好ましくない。 The continuous mixer provided in the middle of the piping of this step has a mixing capacity of ESP (KWh / kg) ≧ 1 × 10 −6 , preferably ESP = 5 × 10 −6 , more preferably ESP = 10 × 10 −6 . A static mixer and / or P / V value (KW / m 3 ) ≧ 10 3 , preferably P / V value ≧ 3 × 10 3 , more preferably P / V value ≧ 5 × 10 3 , (P: It is preferable to use a continuous mixing type emulsifying disperser having a power (KW) of the mixer, V: space volume of the mixing section (m 3 )). When the mixing capacity of the continuous mixer is ESP = 10 × 10 −6 and P / V value ≧ 10 3 , the block co-polymer containing vinyl aromatic hydrocarbons composed of two different compositions and conjugated dienes The solvent can be removed from the mixture or a mixture of hydrogenated products while maintaining uniform mixing. The ESP of the static mixer is ESP = ΔP × V [m 3 / sec] / (ρV [kg / sec]), and is calculated as ESP (KWh / kg) = ΔP × 27 × 10 −6 / ρ. Here, ΔP is a pressure loss (kg / cm 2 ), ρ is a density (g / ml), and ESP can be controlled by changing ΔP. When the solution of component (I) and the solution of component (II) are mixed and stored in the same tank without using a continuous mixer, it is not preferable because the solution does not separate and become a uniform mixed state.
（ｅ）工程
本工程は、次工程の多段ベント押出機で脱溶媒と、ペレット化する前にフラッシュ型濃縮器で溶媒の一部をフラッシュ蒸発させ、濃縮する工程である。フラッシュする方法は、特に限定されるものではなく、ポリマー溶液に適用される一般的な方法で行うことができる。例えば、揮発成分が揮発するのに十分な熱量を与えた後に、フラッシュバルブを介して圧力を制御したフラッシュドラムにフイードする方法や、特開昭６１−９７３０２号公報、特開昭６１−２２８０１２号公報に記載されているように、フラッシュドラムに直接接続したプレートフイン型熱交換器や竪型の多管式熱交換器にポリマー溶液をフイードして、加熱しつつ揮発分を発泡させて予熱させる方法、或いは特開２００１−４００３１号公報に記載されているようにポリマー溶液から、揮発成分をフラッシュ濃縮するに際して、該揮発成分の揮発に必要な熱量を与えた後、気相部のジャケット温度をフラッシュ後の液相部の滞留ポリマー溶液温度より高く保持し、かつ、液相部のジャケット温度をフラッシュ後の滞留ポリマー溶液温度より低く保持したフラッシュドラムに導入しフラッシュ濃縮して該揮発成分除去する方法等がある。本工程における濃縮された混合溶液のポリマー濃度は４０〜７０重量％とすることが好ましい。
(E) Process This process is a process of desolvating with the multistage vent extruder of the next process, and flash-evaporating a part of solvent with a flash-type concentrator before pelletizing. The flashing method is not particularly limited, and can be performed by a general method applied to a polymer solution. For example, a method of feeding a flash drum having a controlled pressure through a flash valve after applying a sufficient amount of heat to volatilize a volatile component, or JP-A-61-97302 and JP-A-61-228012. As described in the official gazette, the polymer solution is fed into a plate fin type heat exchanger directly connected to the flash drum or a vertical multi-tubular heat exchanger, and the volatile components are foamed and preheated while heating. When the volatile component is flash-concentrated from the polymer solution as described in the method or JP-A-2001-40031, the amount of heat necessary for volatilization of the volatile component is given, and then the jacket temperature of the gas phase part is set. Hold higher than the temperature of the staying polymer solution in the liquid phase part after flushing, and set the jacket temperature of the liquid phase part to the temperature of the staying polymer solution after flushing. There is low retained method in which volatiles components removed by introducing flushed concentrated to a flash drum. The polymer concentration of the concentrated mixed solution in this step is preferably 40 to 70% by weight.
（ｆ）工程
本工程は、前述のように濃縮された混合溶液から溶媒を分離すると共に、ペレット状の形態を得る工程である。本工程では２軸エンドレススクリューと後方排気ゾーンを有する押出機に１３０〜１８０℃のブロック共重合体又はその水添物の溶液をエンドレススクリューの供給ホッパーに導入して供給ゾーンで除圧を生じさせ、溶媒の７５〜９５重量％を供給ゾーンで除去する。この除圧はエンドレススクリューに供給するラインに配置した制御弁によって調整される。ブロック共重合体又はその水添物の最終的に得られるペレット中の好ましい残存溶媒量は１０００ｐｐｍ以下である。次に、後方排気ゾーンでポリマー温度が相当低下するため、前方に位置した排気ゾーンのポリマー温度を１５０〜２６０℃の温度になるように再加熱し、バレル内でのスクリューの前進運動と共に排気ゾーン間の少なくとも１箇所に０．５〜２重量％の水の注入によって段階的に漸次、残りの溶媒の５〜２５重量％を除去する。前方排気ゾーンのポリマー温度が２６０℃を越えるとポリマー分子鎖の切断と架橋が顕著に起きるため好ましくない。本工程では、前方に位置した排気ゾーンの少なくとも１ゾーンのポリマー温度が２００℃を越え、２６０℃以下にすることが、高押出量で低残存溶媒量を実現するのに有効であり、好ましい。ブロック共重合体又はその水添物に対して０．５〜２重量％の水を添加することで、より溶剤除去効率を高めることができる。本工程の２軸ベント押出機は、スクリュー先端部と吐出ダイ部との間にギアポンプを有する構造のものが好ましい。これによって、スクリュー回転数を上げても、スムーズな吐出が可能であるため、ブロック共重合体又はその水添物の圧力上昇が抑制されポリマー温度の上昇を防止し、熱安定性の向上に寄与する。
(F) Process This process is a process of obtaining a pellet form while separating the solvent from the mixed solution concentrated as described above. In this process, a 130-180 ° C block copolymer or its hydrogenated solution is introduced into an endless screw supply hopper into an extruder having a twin-screw endless screw and a rear exhaust zone to cause pressure reduction in the supply zone. 75 to 95% by weight of the solvent is removed in the feed zone. This depressurization is adjusted by a control valve arranged in a line supplying the endless screw. A preferable residual solvent amount in the finally obtained pellet of the block copolymer or its hydrogenated product is 1000 ppm or less. Next, since the polymer temperature drops considerably in the rear exhaust zone, the polymer temperature in the exhaust zone located at the front is reheated to a temperature of 150 to 260 ° C., and the exhaust zone moves with the forward movement of the screw in the barrel. Gradually, 5-25% by weight of the remaining solvent is removed by injecting 0.5-2% by weight of water in at least one place in between. If the polymer temperature in the front exhaust zone exceeds 260 ° C., the polymer molecular chain is severely broken and crosslinked, which is not preferable. In this step, it is effective and preferable to achieve a high amount of extrusion and a low residual solvent amount in which the polymer temperature in at least one of the exhaust zones located in the front exceeds 200 ° C. and is 260 ° C. or less. The solvent removal efficiency can be further increased by adding 0.5 to 2% by weight of water to the block copolymer or its hydrogenated product. The twin-screw vent extruder in this step preferably has a structure having a gear pump between the screw tip portion and the discharge die portion. As a result, smooth discharge is possible even if the number of screw rotations is increased, and the pressure increase of the block copolymer or its hydrogenated product is suppressed, preventing an increase in the polymer temperature and contributing to an improvement in thermal stability. To do.
本工程で用いる多段ベント押出機のダイは、アンダーウォーターカット用又はホットカット用のものとし、カッターは必要なペレットサイズに合わせて、２〜６枚刃のものを用いる。本工程の２軸ベント押出機は、排気用のベントゾーンを２〜５個有し、Ｌ／Ｄ＝３０〜６０（Ｌはスクリューの長さ、Ｄはスクリューの外径を示す。）のもので、かみ合い型同方向２軸ベント押出機が好ましい。 The die of the multistage vent extruder used in this step is for underwater cutting or hot cutting, and the cutter has 2 to 6 blades according to the required pellet size. The biaxial vent extruder of this process has 2 to 5 vent zones for exhaust, and L / D = 30 to 60 (L is the length of the screw and D is the outer diameter of the screw). Therefore, a meshing type same-direction biaxial vent extruder is preferable.
本発明の方法によって得られたブロック共重合体又はその水添物の混合物には、目的に応じて種々の添加剤を添加することができる。例えば、オイル等の軟化剤、難燃剤、酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、可塑剤、顔料、ガラス繊維，ガラスビーズ，シリカ，炭カル，タルク等の無機補強剤、有機繊維，クマロンインデン樹脂等の有機補強剤、他の熱可塑性樹脂等が添加剤として使用できる。 Various additives can be added to the block copolymer obtained by the method of the present invention or a mixture of hydrogenated products according to the purpose. For example, softeners such as oil, flame retardants, antioxidants, UV absorbers, antistatic agents, lubricants, plasticizers, pigments, glass fibers, glass beads, silica, charcoal, talc and other inorganic reinforcing agents, organic fibers Organic reinforcing agents such as coumarone indene resin and other thermoplastic resins can be used as additives.
以下、本発明を実施例により詳細に説明する。但し、本発明は以下の実施例によって限
定を受けるものではない。実施例に示す測定値及び評価は、下記の方法によって行った。
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following examples. The measured values and evaluations shown in the examples were performed by the following methods.
（１）動的粘弾性：
加熱プレスで圧縮成形した厚さ約１ｍｍの試験片を、株式会社ユービーエム製粘弾性測定解析装置ＤＶＥ−Ｖ４を用い、振動周波数３５Ｈｚ、昇温速度３℃／ｍｉｎの条件で温度−５０℃〜１５０℃の範囲を測定し、２５℃の貯蔵弾性率を求めた。
(1) Dynamic viscoelasticity:
Using a viscoelasticity measuring / analyzing apparatus DVE-V4 manufactured by UBM Co., Ltd., a test piece compression-molded by a heating press was used at a temperature of −50 ° C. to a vibration frequency of 35 Hz and a heating rate of 3 ° C./min. The range of 150 ° C. was measured, and the storage elastic modulus at 25 ° C. was determined.
（２）水添率：
ブロック共重合体水添物を用い，核磁気共鳴装置（装置名：ＤＰＸ−４００；ドイツ国、ＢＲＵＫＥＲ社製）で測定した。
(2) Hydrogenation rate:
A block copolymer hydrogenated product was used and measured with a nuclear magnetic resonance apparatus (device name: DPX-400; manufactured by BRUKER, Germany).
（３）ＰＨ：
炭酸ガスを添加混合した後の重合体溶液の一部をサンプリングし、その溶液１００ｇとＰＨ７．０の蒸留水１００ｇとを充分混合した後、静置して二層分離した水層部分をＰＨメーター（岩城硝子株式会社製、ガラス電極式水素イオン濃度計）で測定した。
(3) PH:
A portion of the polymer solution after the addition of carbon dioxide gas was sampled, and 100 g of the solution and 100 g of distilled water having a pH of 7.0 were sufficiently mixed, and then allowed to stand to separate the two water layers into a PH meter. It was measured by (Iwaki Glass Co., Ltd., glass electrode type hydrogen ion concentration meter).
（４）色調：
日本電色工業株式会社製ＮＤ−Ｖ６Ｂ型総合視覚測定機を用いてペレットのｂ値を測定した。ｂ値が大きい程みかけの黄色度が大きい。
(4) Color tone:
The b value of the pellet was measured using a ND-V6B type comprehensive visual measuring machine manufactured by Nippon Denshoku Industries Co., Ltd. The larger the b value, the larger the apparent yellowness.
（５）フィッシュアイ：
２０ｍｍシート押出機（押出温度２００℃）で作成した厚み０．１ｍｍ、幅８ｃｍ、長さ１５ｍシートの目視判定によるフィッシュアイサイズ０．２ｍｍ以上の個数により評価した。個数が少ない程ゲルが形成されにくい。
(5) Fisheye:
Evaluation was made based on the number of fish eye sizes of 0.2 mm or more by visual judgment of a sheet having a thickness of 0.1 mm, a width of 8 cm, and a length of 15 m prepared by a 20 mm sheet extruder (extrusion temperature 200 ° C.). The smaller the number, the harder the gel is formed.
（６）均一混合性：
脱溶媒スタート直後ペレットと脱溶媒最終ペレットのスチレン含量の差を均一混合性とした。均一混合性が良好なものは差が小さく、均一混合性に劣るものは差が大きい。評価基準は以下の通りである。
○：スタート直後ペレットと最終ペレットのスチレン含量の差が１％以下
△：スタート直後ペレットと最終ペレットのスチレン含量の差が１％を越え、５％未満
×：スタート直後ペレットと最終ペレットのスチレン含量の差が５％以上
なお、スチレン含量は核磁気共鳴装置（装置名：ＤＰＸ−４００；ドイツ国、ＢＲＵＫＥＲ社製）で測定した。
(6) Uniform mixing property:
The difference in styrene content between the pellet immediately after the start of solvent removal and the final pellet of solvent removal was defined as uniform mixing. Those having good uniform mixing properties have small differences, and those having poor uniform mixing properties have large differences. The evaluation criteria are as follows.
○: Difference in styrene content between pellet immediately after start and final pellet is 1% or less Δ: Difference in styrene content between pellet immediately after start and final pellet exceeds 1% and less than 5% ×: Styrene content in pellet immediately after start and final pellet The styrene content was measured with a nuclear magnetic resonance apparatus (device name: DPX-400; manufactured by BRUKER, Germany).
[製造例１]
［成分Ｉ−１の製造］
窒素ガス雰囲気下において、スチレン２０重量部を含むシクロヘキサン溶液にテトラメチルエチレンジアミン０．０６重量部とｎ−ブチルリチウムを０．０５５重量部添加し、７５℃で２５分間重合した後、更に１，３−ブタジエン８重量部とスチレン５２重量部を含むシクロヘキサンを連続的に添加して７５℃で５０分間重合した。次に、スチレン２０重量部を含むシクロヘキサン溶液を添加し、７５℃で２５分間重合して活性重合体溶液を得た。本発明の成分（Ｉ）として、該溶液中の重合体は、スチレン含有量９２重量％のＡ−Ｂ−Ａ構造のブロック共重合体であった。
[Production Example 1]
[Production of Component I-1]
Under a nitrogen gas atmosphere, 0.06 part by weight of tetramethylethylenediamine and 0.055 part by weight of n-butyllithium were added to a cyclohexane solution containing 20 parts by weight of styrene and polymerized at 75 ° C. for 25 minutes. -Cyclohexane containing 8 parts by weight of butadiene and 52 parts by weight of styrene was continuously added and polymerized at 75 ° C for 50 minutes. Next, a cyclohexane solution containing 20 parts by weight of styrene was added and polymerized at 75 ° C. for 25 minutes to obtain an active polymer solution. As component (I) of the present invention, the polymer in the solution was a block copolymer having an ABA structure having a styrene content of 92% by weight.
[製造例２]
［成分Ｉ−２の製造］
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テトラメチルエチレンジアミン０．０６重量部とｎ−ブチルリチウムを０．０６２重量部添加し、７５℃で１５分間重合した後、更に１，３−ブタジエン１１重量部とスチレン５４重量部を含むシクロヘキサンを連続的に添加して７５℃で５０分間重合した。次にスチレン２５重量部を含むシクロヘキサン溶液を添加し、７５℃で３０分間重合した。次に、上記で得られたブロック共重合体を特開昭５９−１３３２０３号公報記載のＴｉ系水添触媒で水添し、本発明の成分（Ｉ）として、ブタジエン部の水添率が７４％のＡ−Ｂ−Ａ構造の水添ブロック共重合体を得た。
[Production Example 2]
[Production of Component I-2]
Under a nitrogen gas atmosphere, 0.06 part by weight of tetramethylethylenediamine and 0.062 part by weight of n-butyllithium were added to a cyclohexane solution containing 10 parts by weight of styrene and polymerized at 75 ° C. for 15 minutes. -Cyclohexane containing 11 parts by weight of butadiene and 54 parts by weight of styrene was continuously added and polymerized at 75 ° C for 50 minutes. Next, a cyclohexane solution containing 25 parts by weight of styrene was added and polymerized at 75 ° C. for 30 minutes. Next, the block copolymer obtained above was hydrogenated with a Ti-based hydrogenation catalyst described in JP-A-59-133203, and as a component (I) of the present invention, the hydrogenation rate of the butadiene portion was 74. % Of a hydrogenated block copolymer having an ABA structure was obtained.
[製造例３]
［成分ＩＩ−１の製造］
窒素ガス雰囲気下において、スチレン２０重量部を含むシクロヘキサン溶液にテトラメチルエチレンジアミン０．０６重量部とｎ−ブチルリチウムを０．０７２重量部添加し、７５℃で２５分間重合した後、更に１，３−ブタジエン３０重量部とスチレン２０重量部を含むシクロヘキサンを連続的に添加して７５℃で４５分間重合した。次にスチレン３０重量部を含むシクロヘキサン溶液を添加し、７５℃で３５分間重合して活性重合体溶液を得た。本発明の成分（ＩＩ）として、該溶液中の重合体は、スチレン含有量７０重量％のＡ−Ｂ−Ａ構造のブロック共重合体であった。
[Production Example 3]
[Production of Component II-1]
Under a nitrogen gas atmosphere, 0.06 part by weight of tetramethylethylenediamine and 0.072 part by weight of n-butyllithium were added to a cyclohexane solution containing 20 parts by weight of styrene, and polymerized at 75 ° C. for 25 minutes. -Cyclohexane containing 30 parts by weight of butadiene and 20 parts by weight of styrene was continuously added and polymerized at 75 ° C for 45 minutes. Next, a cyclohexane solution containing 30 parts by weight of styrene was added and polymerized at 75 ° C. for 35 minutes to obtain an active polymer solution. As component (II) of the present invention, the polymer in the solution was a block copolymer having an ABA structure having a styrene content of 70% by weight.
[製造例４]
［成分ＩＩ−２の製造］
窒素ガス雰囲気下において、スチレン３０重量部を含むシクロヘキサン溶液にテトラメチルエチレンジアミン０．０３重量部とｎ−ブチルリチウムを０．０８３重量部添加し、７５℃で２５分間重合した後、更に１，３−ブタジエン３８重量部とスチレン２重量部を含むシクロヘキサンを連続的に添加して７５℃で４０分間重合した。次にスチレン３０重量部を含むシクロヘキサン溶液を添加し、７５℃で３０分間重合した。次に、上記で得られたブロック共重合体を特開昭５９−１３３２０３号公報記載のＴｉ系水添触媒で水添し、本発明の成分（ＩＩ）として、ブタジエン部の水添率が３８％のＡ−Ｂ−Ａ構造の水添ブロック共重合体を得た。
[Production Example 4]
[Production of Component II-2]
Under a nitrogen gas atmosphere, 0.03 part by weight of tetramethylethylenediamine and 0.083 part by weight of n-butyllithium were added to a cyclohexane solution containing 30 parts by weight of styrene and polymerized at 75 ° C. for 25 minutes. -Cyclohexane containing 38 parts by weight of butadiene and 2 parts by weight of styrene was continuously added and polymerized at 75 ° C for 40 minutes. Next, a cyclohexane solution containing 30 parts by weight of styrene was added and polymerized at 75 ° C. for 30 minutes. Next, the block copolymer obtained above was hydrogenated with a Ti-based hydrogenation catalyst described in JP-A-59-133203, and the hydrogenation rate of the butadiene part was 38 as component (II) of the present invention. % Of a hydrogenated block copolymer having an ABA structure was obtained.
[製造例５]
［成分ＩＩ−３の製造］
窒素ガス雰囲気下において、スチレン２０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０．０７８重量部添加し、７５℃で２０分間重合した後、更に１，３−ブタジエン６０重量部を含むシクロヘキサンを連続的に添加して７５℃で７０分間重合した。次にスチレン２０重量部を含むシクロヘキサン溶液を添加し、７５℃で２０分間重合して活性重合体溶液を得た。本発明の成分（ＩＩ）として、該溶液中の重合体は、スチレン含有量４０重量％のＡ−Ｂ−Ａ構造のブロック共重合体であった。
[Production Example 5]
[Production of Component II-3]
Under a nitrogen gas atmosphere, 0.078 parts by weight of n-butyllithium was added to a cyclohexane solution containing 20 parts by weight of styrene, polymerized at 75 ° C. for 20 minutes, and then cyclohexane containing 60 parts by weight of 1,3-butadiene was further added. The polymer was continuously added and polymerized at 75 ° C. for 70 minutes. Next, a cyclohexane solution containing 20 parts by weight of styrene was added and polymerized at 75 ° C. for 20 minutes to obtain an active polymer solution. As component (II) of the present invention, the polymer in the solution was a block copolymer having an ABA structure having a styrene content of 40% by weight.
[実施例１]
製造例１で得た成分Ｉ−１と製造例３で得た成分ＩＩ−１の活性重合体溶液に、エタノールをｎ−ブチルリチウムに対して０．９倍当量、重合器中で添加して反応を停止した。その後、重合溶液を重合器から他の各々異なる貯蔵槽へ移送する間に水を重合体１００重量部に対して０．０２重量部加えた後、炭酸ガスを加えて表２に示した溶液のＰＨに調整した。前記溶液を各々異なる貯蔵槽から移送配管で合流させ、その下流に設けたスタティックミキサーで混合した後、安定剤を添加してフラッシュ型濃縮器に送液した。ここで使用したスタティックミキサーは内径２７ｍｍ、エレメント数６（１モジュールあたり）、全長１１００ｍｍ（４セット）であり、スタティックミキサー混合条件は溶液温度６０℃、流速は２６Ｌ／分、圧力損失は０．４１ｋｇ／ｃｍ2、溶液密度は０．８ｇ／ｍｌであった。スタティックミキサーの混合能力は圧力損失を制御することで調整でき、圧力損失を大きくすることで混合能力は大きくなり、逆に圧力損失を小さくすることで混合能力も小さくなった。フラッシュ型濃縮器への送液は、フラッシュ型濃縮器へ入る途中に設けられた熱交換器を通して重合体溶液の温度を１７０℃に昇温し、フラッシュ型濃縮器で溶媒の一部をフラッシュ蒸発させた。濃縮器出口での温度は、１００℃に低下し、濃度は５０重量％であった。濃縮された重合体溶液を、熱交換器を通して再度１６０℃に加熱し、２軸ベント押出機にフィードして脱溶媒を行った。使用した押出機は後方排気ゾーンを有するスクリュー外径６５ｍｍ、Ｌ／Ｄ＝４０のかみ合い型同方向２軸３段ベント押出機であり、スクリュー先端とダイの間に、ギアポンプを取り付けたものである。運転条件はスクリュー回転数１５０ｒｐｍ、ポリマー押出量は１２０Ｋｇ／時間で行った。本発明のブロック共重合体は各成分が均一であり、色調及びフィシュアイが良好で、残存溶媒も１０４０ｐｐｍと少ない量であった。
[Example 1]
To the active polymer solution of Component I-1 obtained in Production Example 1 and Component II-1 obtained in Production Example 3, ethanol was added 0.9 times equivalent to n-butyllithium in a polymerization vessel. The reaction was stopped. Thereafter, 0.02 part by weight of water is added to 100 parts by weight of the polymer while the polymerization solution is transferred from the polymerization vessel to each of the different storage tanks, and then carbon dioxide is added to the solution shown in Table 2. Adjusted to PH. The solutions were combined from different storage tanks by transfer pipes, mixed by a static mixer provided downstream thereof, added with a stabilizer, and fed to a flash type concentrator. The static mixer used here has an inner diameter of 27 mm, the number of elements is 6 (per module) and the total length is 1100 mm (4 sets). The static mixer mixing conditions are a solution temperature of 60 ° C., a flow rate of 26 L / min, and a pressure loss of 0.41 kg. / Cm 2 , and the solution density was 0.8 g / ml. The mixing ability of the static mixer can be adjusted by controlling the pressure loss, and the mixing ability is increased by increasing the pressure loss. Conversely, the mixing ability is reduced by reducing the pressure loss. The liquid sent to the flash-type concentrator is heated to 170 ° C through a heat exchanger installed on the way to the flash-type concentrator, and a part of the solvent is flash-evaporated with the flash-type concentrator. I let you. The temperature at the outlet of the concentrator was lowered to 100 ° C. and the concentration was 50% by weight. The concentrated polymer solution was again heated to 160 ° C. through a heat exchanger and fed to a twin-screw vent extruder to remove the solvent. The used extruder is a mesh type bi-directional three-stage vent extruder with a screw outer diameter of 65 mm and L / D = 40 having a rear exhaust zone, with a gear pump attached between the screw tip and the die. . The operating conditions were a screw rotation speed of 150 rpm and a polymer extrusion rate of 120 kg / hour. In the block copolymer of the present invention, each component was uniform, the color tone and fisheye were good, and the residual solvent was a small amount of 1040 ppm.
[実施例２〜４]
表２に示した成分から構成されるブロック共重合体をスタティックミキサーの混合条件を変化させた以外は実施例１と同様に製造した。結果を表２に示した。本発明のブロック共重合体は各成分が均一であり、色調及びフィシュアイが良好であった。
[Examples 2 to 4]
A block copolymer composed of the components shown in Table 2 was produced in the same manner as in Example 1 except that the mixing conditions of the static mixer were changed. The results are shown in Table 2. Each component of the block copolymer of the present invention was uniform, and the color tone and fisheye were good.
[実施例５]
表２に示した成分から構成されるブロック共重合体を連続混合機として連続混合式の乳化分散機を用いた以外は実施例１と同様に製造した。連続混合式の乳化分散機はキャビトロン１０１０型（ユーロテック（株）社、空間容量４ｍＬ）に滞留時間０．０７秒で通過させた。この時のキャビトロン１０１０の運転条件はローター回転数が３０００ｒｐｍ、Ｐ／Ｖ値（ＫＷ／ｍ3）が１０×１０3であった。結果を表２に示した。本発明のブロック共重合体は各成分が均一であり、色調及びフィシュアイが良好であった。
[Example 5]
It was produced in the same manner as in Example 1 except that a block copolymer composed of the components shown in Table 2 was used as a continuous mixer and a continuous mixing emulsion disperser was used. The continuous mixing type emulsifying disperser was passed through Cavitron 1010 (Eurotech Co., Ltd., space capacity 4 mL) with a residence time of 0.07 seconds. The operating conditions of the Cavitron 1010 at this time were a rotor rotational speed of 3000 rpm and a P / V value (KW / m 3 ) of 10 × 10 3 . The results are shown in Table 2. Each component of the block copolymer of the present invention was uniform, and the color tone and fisheye were good.
[比較例１]
製造例１で得た成分Ｉ−１と製造例３で得た成分ＩＩ−１の活性重合体溶液に、エタノールをｎ−ブチルリチウムに対して０．９倍当量、重合器中で添加して反応を停止した。その後、重合溶液を重合器から同一の貯蔵槽へ移送する間に水を重合体１００重量部に対して０．０２重量部加えた後、炭酸ガスを加えて表２に示した溶液のＰＨに調整した。同一の貯蔵槽に約２時間貯蔵後、安定剤を添加して実施例１と同様にフラッシュ型濃縮器への送液し、２軸ベント押出機で脱溶媒してペレットを得た。結果を表２に示した。本発明とは異なり、同一の貯蔵槽に貯蔵し、連続混合機を使用しない製造方法では、本発明で規定した複数成分を同一貯蔵槽で貯蔵した際に２層分離するため、均一混合性に劣る結果であった。
[Comparative Example 1]
To the active polymer solution of Component I-1 obtained in Production Example 1 and Component II-1 obtained in Production Example 3, ethanol was added 0.9 times equivalent to n-butyllithium in a polymerization vessel. The reaction was stopped. Thereafter, 0.02 part by weight of water was added to 100 parts by weight of the polymer while the polymerization solution was being transferred from the polymerization vessel to the same storage tank, and then carbon dioxide was added to the pH of the solution shown in Table 2. It was adjusted. After storing in the same storage tank for about 2 hours, a stabilizer was added and the mixture was fed to a flash-type concentrator in the same manner as in Example 1 and desolvated with a twin-screw vent extruder to obtain pellets. The results are shown in Table 2. Unlike the present invention, in a production method that stores in the same storage tank and does not use a continuous mixer, when the multiple components defined in the present invention are stored in the same storage tank, two layers are separated, so that uniform mixing is achieved. The result was inferior.
[比較例２]
表２に示した安定剤処方以外は実施例１と同様に製造した。結果を表２に示した。本発明で規定したフェノール系安定剤ではなく、２００℃の蒸気圧が約１２０ｍｍＨｇである２，６−ジ−ｔ−ブチル−４−メチルフェノールを添加したブロック共重合体はフィシュアイが多くなり、好ましくない。
[Comparative Example 2]
Except for the stabilizer formulation shown in Table 2, it was produced in the same manner as in Example 1. The results are shown in Table 2. The block copolymer to which 2,6-di-tert-butyl-4-methylphenol having a vapor pressure at 200 ° C. of about 120 mmHg instead of the phenol-based stabilizer defined in the present invention has an increased fisheye, It is not preferable.
[比較例３]
表２に示した溶液のＰＨ以外は実施例１と同様に製造した。結果を表２に示した。本発明で規定した溶液のＰＨではないため、色調が黄色で、着色製品とした場合に所定の着色ができないため、好ましくない。
[Comparative Example 3]
Except for the pH of the solutions shown in Table 2, it was produced in the same manner as in Example 1. The results are shown in Table 2. Since it is not PH of the solution prescribed | regulated by this invention, when a color tone is yellow and it is set as a colored product, since predetermined coloring cannot be performed, it is unpreferable.
本発明のブロック共重合体又はその水添物の製造方法は、組成の異なる複数成分の均一混合を維持した状態で脱溶媒が可能であり、ペレット中のゲルが少なく、色調及び透明性に優れ、残留溶媒量が少ないブロック共重合体又はその水添物の混合物を得ることができる。 The method for producing a block copolymer or a hydrogenated product thereof according to the present invention can be desolvated while maintaining uniform mixing of a plurality of components having different compositions, has less gel in the pellet, and has excellent color tone and transparency. Thus, a block copolymer having a small amount of residual solvent or a mixture of hydrogenated products thereof can be obtained.
Claims (8)
下記（ａ）〜（ｆ）の工程；
（ａ）ビニル芳香族炭化水素含有量が８５〜９５重量％及び共役ジエン含有量が５〜１５重量％である前記第１のブロック共重合体又はその水添物（成分（Ｉ））と、ビニル芳香族炭化水素含有量が２５重量％以上８５重量％未満及び共役ジエン含有量が１５重量％を越え７５重量％以下である前記第２のブロック共重合体又はその水添物（成分（ＩＩ））とを、各々個別に重合する工程と、
（ｂ）前記成分（Ｉ）と前記成分（ＩＩ）の活性重合体溶液に反応停止剤を添加する工程と、
（ｃ）前記成分（Ｉ）と前記成分（ＩＩ）の溶液に、炭酸ガス及び／又は有機酸の少なくとも１種を添加し、溶液のＰＨを６．０〜９．５の範囲に調整する工程と、
（ｄ）前記成分（Ｉ）の溶液と前記成分（ＩＩ）の溶液を配管途中に設けた連続混合機を用いて同時に供給して混合後、フェノール系安定剤の１種以上を添加する、或いは前記成分（Ｉ）の溶液と前記成分（ＩＩ）の溶液に、フェノール系安定剤の１種以上を添加後、配管途中に設けた連続混合機を用いて同時に供給して混合する工程と、
（ｅ）前記成分（Ｉ）と前記成分（ＩＩ）の混合溶液をフラッシュ型濃縮器で溶媒の一部をフラッシュ蒸発させる工程と、
（ｆ）前記成分（Ｉ）と前記成分（ＩＩ）の混合溶液を２軸エンドレススクリューと後方排気ゾーンを有する多段ベント押出機で、脱溶媒する工程と、
を含む混合物の製造方法。 A first block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene or a hydrogenated product thereof, and a vinyl aromatic hydrocarbon and a conjugated diene containing the first block copolymer or a hydrogenated product thereof And a second block copolymer having a different composition or a hydrogenated product thereof, and a method for producing a mixture comprising:
The following steps (a) to (f);
(A) the first block copolymer having a vinyl aromatic hydrocarbon content of 85 to 95% by weight and a conjugated diene content of 5 to 15% by weight or a hydrogenated product thereof (component (I)); The second block copolymer having a vinyl aromatic hydrocarbon content of 25% by weight or more and less than 85% by weight and a conjugated diene content of more than 15% by weight and 75% by weight or less, or a hydrogenated product thereof (component (II )) And polymerizing each individually,
(B) adding a reaction terminator to the active polymer solution of component (I) and component (II);
(C) adding at least one of carbon dioxide and / or organic acid to the solution of the component (I) and the component (II) to adjust the pH of the solution to a range of 6.0 to 9.5. When,
(D) The solution of the component (I) and the solution of the component (II) are simultaneously supplied and mixed using a continuous mixer provided in the middle of the pipe, and then one or more phenol-based stabilizers are added, or A step of adding and mixing one or more phenolic stabilizers to the solution of component (I) and the solution of component (II), and simultaneously supplying and mixing them using a continuous mixer provided in the middle of the piping;
(E) flash evaporating a part of the solvent of the mixed solution of the component (I) and the component (II) with a flash-type concentrator;
(F) Desolvating the mixed solution of the component (I) and the component (II) with a multistage vent extruder having a twin-screw endless screw and a rear exhaust zone;
The manufacturing method of the mixture containing this.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011057827A (en) * | 2009-09-09 | 2011-03-24 | Asahi Kasei Chemicals Corp | Resin composition for plane-luminous body, molded product for plane-luminous body and plane-luminous body |
| KR101104741B1 (en) * | 2008-12-30 | 2012-01-11 | 티에스알시 코포레이션 | Method for manufacturing hydrogenated block copolymer |
| KR20170101209A (en) | 2014-12-25 | 2017-09-05 | 주식회사 쿠라레 | Process for producing aromatic vinyl/conjugated diene copolymer and product of hydrogenation thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124728A (en) * | 1995-10-31 | 1997-05-13 | Asahi Chem Ind Co Ltd | Method for recovering block copolymer |
| JPH11171949A (en) * | 1997-12-11 | 1999-06-29 | Asahi Chem Ind Co Ltd | Production of block copolymer |
| JP2006143944A (en) * | 2004-11-24 | 2006-06-08 | Denki Kagaku Kogyo Kk | Block copolymer mixture and molded article |
| JP2008231372A (en) * | 2007-03-23 | 2008-10-02 | Asahi Kasei Chemicals Corp | Method for producing mixture containing block copolymers having different compositions |
-
2007
- 2007-03-23 JP JP2007077076A patent/JP5059459B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124728A (en) * | 1995-10-31 | 1997-05-13 | Asahi Chem Ind Co Ltd | Method for recovering block copolymer |
| JPH11171949A (en) * | 1997-12-11 | 1999-06-29 | Asahi Chem Ind Co Ltd | Production of block copolymer |
| JP2006143944A (en) * | 2004-11-24 | 2006-06-08 | Denki Kagaku Kogyo Kk | Block copolymer mixture and molded article |
| JP2008231372A (en) * | 2007-03-23 | 2008-10-02 | Asahi Kasei Chemicals Corp | Method for producing mixture containing block copolymers having different compositions |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101104741B1 (en) * | 2008-12-30 | 2012-01-11 | 티에스알시 코포레이션 | Method for manufacturing hydrogenated block copolymer |
| JP2011057827A (en) * | 2009-09-09 | 2011-03-24 | Asahi Kasei Chemicals Corp | Resin composition for plane-luminous body, molded product for plane-luminous body and plane-luminous body |
| KR20170101209A (en) | 2014-12-25 | 2017-09-05 | 주식회사 쿠라레 | Process for producing aromatic vinyl/conjugated diene copolymer and product of hydrogenation thereof |
| US10000585B2 (en) | 2014-12-25 | 2018-06-19 | Kuraray Co., Ltd. | Process for producing aromatic vinyl/conjugated diene copolymer and product of hydrogenation thereof |
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