JP2005533151A - カップリングしたスチレン性ブロックコポリマーおよびそれを調製する方法 - Google Patents
カップリングしたスチレン性ブロックコポリマーおよびそれを調製する方法 Download PDFInfo
- Publication number
- JP2005533151A JP2005533151A JP2004521737A JP2004521737A JP2005533151A JP 2005533151 A JP2005533151 A JP 2005533151A JP 2004521737 A JP2004521737 A JP 2004521737A JP 2004521737 A JP2004521737 A JP 2004521737A JP 2005533151 A JP2005533151 A JP 2005533151A
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- alkyl
- polymer
- styrenic block
- metal compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006132 styrene block copolymer Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- -1 alkyl metal compound Chemical class 0.000 claims abstract description 19
- 239000004568 cement Substances 0.000 claims abstract description 7
- 239000010426 asphalt Substances 0.000 claims description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 12
- 150000005690 diesters Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011414 polymer cement Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 claims 1
- 229920001195 polyisoprene Polymers 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 17
- 238000010168 coupling process Methods 0.000 abstract description 16
- 230000008878 coupling Effects 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract 1
- 229920001400 block copolymer Polymers 0.000 description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-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
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-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
- ZKSADANYBSWZAB-UHFFFAOYSA-N CCCCCC[Mg]CCCCCC Chemical compound CCCCCC[Mg]CCCCCC ZKSADANYBSWZAB-UHFFFAOYSA-N 0.000 description 1
- QQTGJVBUIOTPGZ-UHFFFAOYSA-N CCC[Zn]CCC Chemical compound CCC[Zn]CCC QQTGJVBUIOTPGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000004796 dialkyl magnesium compounds Chemical class 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- UKOVZLWSUZKTRL-UHFFFAOYSA-N naphthalid Chemical class C1=CC(C(=O)OC2)=C3C2=CC=CC3=C1 UKOVZLWSUZKTRL-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- ABIAVOPWHAWUGT-UHFFFAOYSA-N zinc;2-methanidylpropane Chemical compound [Zn+2].CC(C)[CH2-].CC(C)[CH2-] ABIAVOPWHAWUGT-UHFFFAOYSA-N 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
式中、Rは1〜約20個の炭素原子を有する脂肪族、脂環式、芳香族またはアルキル置換芳香族炭化水素基であり、nは1〜4である。有機リチウム開始剤は高い温度における安定性が高いので比較的高い温度における重合に好ましい。
ジブロックポリマーアニオンであるS−B−Liは以下のようにして調製される。157kgのシクロヘキサンおよび11.7kgのスチレンが反応器に仕込まれる。色が検知されるまで少しずつsec−ブチルリチウムを加えることによって不純物が除去され、スチレンの重合を開始するために451mLのsec−ブチルリチウム溶液(8.8重量%BuLi、0.56モル)が加えられる。スチレンの重合に引き続き、ブタジエンが反応器に加えられる。合計31.1kgのブタジエンが加えられ、固形分含有率(製造されたポリマーの重量%)21%となる。約92%のブタジエンの添加に続いて415gの25重量%トリエチルアルミニウム(TEA)のシクロヘキサン溶液が添加される。観測されるスチレンブロックの分子量および仕込まれるスチレンの量がリビングポリマーのモル数を計算するのに使用される。その値に基づいて、リビング鎖1モル当たり約1.0モルのTEAが存在する。ブタジエンの添加速度はTEAの添加の直前に温度が約95℃に達するように調節される。ブタジエンの残りの重合中は温度は100℃〜110℃に保持される。ブタジエンの重合の完結に続いて、25gのアジピン酸ジメチル(DMA)が添加される(DMA:PLi約0.26)。約30分後に重合がメタノールによって停止される。生成物はゲルパーミエーションクロマトグラフィー(GPC)を使用して分析される。カップリングの前に、スチレンブロックは分子量約22,000ダルトンであり、ブタジエンブロックは分子量約55,000ダルトンである。UV検出器を使用して検出される様々な種に帰属されるピークの面積が以下の表1に報告される。カップリング効率も報告される。UV検出器はスチレンの繰り返し単位にのみ感度を有し、またスチレンの重量百分率はすべてのカップリングした種において同じなので、これらの面積は本質的にそれぞれの種のモル分率を表している。それぞれの種の分子量を使用して重量%に転換可能である。本明細書の実施例においては重量百分率は本質的にUV面積と等しい。
実施例2の生成物は、TEA:Li比が0.98に下げられることを除き、実質的に実施例1と同様に調製される。
実施例3の生成物は、TEAがブタジエンの約99.5%重合後に加えられることを除き、実質的に実施例1と同様に調製される。TEA:Liの比は0.99である。
実施例4の生成物は、ブタジエンの約72%の重合後に加えられ、TEA:Li比が約1.03に上げられることを除き、実質的に実施例1と同様に調製される。
実施例5の生成物は、モノマーの仕込みが少し増やされ、重合後の固形分濃度が22%となり、TEAがブタジエンの約72%の重合後に加えられ、TEA:Li比が約0.96に下げられることを除き、実質的に実施例1と同様に調製される。
比較例6の生成物は、TEAが添加されないことを除き実質的に実施例1と同様に調製される。
変成した瀝青12重量%の本発明のポリマーを相溶性瀝青、具体的にはアスファルト含有率約13%であり、商品名B−180のベネズエラ瀝青と混合して調製される。この混合物はSILVERSONL4R高剪断ミキサを使用して約180℃で約45分間ブレンドしてさらに調製される。このサンプルは以下の試験に供される。ASTMD−5による25℃における針入度;ASTMD−36によるリングとボール軟化点(℃);ASTMD−4402による180℃における粘度(Pa・s);ASTMD−5147によるコールド曲げ試験(℃);DIN52123によるDINフロー(℃)。結果は下記表2において報告される。
KRATON POLYMERS LLCから入手可能な商品名D1184の従来のブロックコポリマーが使用されることを除いて実質的に同様にして実施例7の手順が繰り返される。
瀝青が、プロパン瀝青とブライトフルフラール抽出物の67/33の比の混合物から調製され商品名PX−200の非相溶性瀝青であることを除き、実質的に同様にして、実施例7の手順が繰り返される。
KRATON POLYMER SLLCから入手可能な商品名D1184の従来のブロックコポリマーが使用されることを除いて実質的に同様にして実施例9の手順が繰り返される。
Claims (9)
- 一般式(AB)nXを有する放射状スチレン性ブロックコポリマーまたはその水素化された誘導体。
[上記式において
(i)Aはスチレンのブロックであり、
(ii)Bはジエンのブロックであり、
(iii)Xはジエステルカップリング剤の残基であり、
(iv)nはジエステルカップリング剤残基に結合した、スチレン性ブロックコポリマーのアームの数であり、
(v)スチレン性ブロックコポリマーアーム(AB)の分子量は2,000ダルトン〜300,000ダルトンであり、
(vi)nが5以上であるポリマーの重量百分率は8%未満である] - nが5以上であるポリマーの重量百分率が6%未満、好ましくは5%未満であり、あるいはnが2であるポリマーの重量百分率が5%未満であり、あるいはnが2と5以上であるポリマーの重量百分率が12%未満である請求項1に記載の放射状スチレン性ブロックコポリマー。
- スチレンのブロック(A)がポリスチレンであり、かつ/またはジエンのブロック(B)がポリブタジエン、ポリイソプレン、およびその混合物から選択される請求項1または2に記載の放射状スチレン性ブロックコポリマー。
- ジエステルカップリング剤の残基がアジピン酸ジメチル、アジピン酸ジエチル、テレフタル酸ジメチル、テレフタル酸ジエチル、およびそれらの混合物から選択されたジエステルの残基である請求項1から4のいずれか一項に記載の放射状スチレン性ブロックコポリマー。
- (a)スチレンのモノマーとジエンのモノマーを、適当な溶媒中で有機置換アルカリ金属化合物であるアニオン重合開始剤と接触させてリビングポリマーセメントを形成すること、
(b)前記セメントに、重合中または重合後に、アルキル金属化合物のアルキル基がリビングポリマー連鎖末端と交換しないように選択され、アルキル金属化合物がアルキル置換基当たり1〜20個の炭素原子を有するアルキルアルミニウム、アルキル亜鉛、およびアルキルマグネシウムから選択されたアルキル金属化合物をリビングポリマー連鎖末端1当量当たり0.01〜1.5当量加えること、
(c)前記セメントにリビングポリマーをカップリングするのに十分な反応条件下でジエステルカップリング剤を加えること、ならびに場合によっては
(d)ステップ(c)において得られた生成物を、好ましくは選択的な水素化方法を使用して水素化すること
を含む請求項1から4のいずれか一項に記載の放射状スチレン性ブロックコポリマーを調製する方法。 - 前記セメントにリビングポリマー連鎖末端1当量当たり0.9〜1.1当量のアルキル金属化合物を加える請求項5に記載の方法。
- アルキル金属化合物がトリアルキルアルミニウム化合物、好ましくはトリエチルアルミニウムである請求項5または6に記載の方法。
- ステップ(b)において、モノマーの転化率70%以後、好ましくは90%以後にアルキル金属化合物を加える請求項5から7のいずれか一項に記載の方法。
- 請求項1から4のいずれか一項に記載の放射状スチレン性ブロックコポリマーまたは請求項5から8のいずれか一項に記載の方法の生成物と瀝青との混合物を含む改質した瀝青。
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JPWO2015111669A1 (ja) * | 2014-01-23 | 2017-03-23 | 旭化成株式会社 | ブロック共重合体組成物及び粘接着剤組成物 |
KR101838832B1 (ko) | 2014-01-23 | 2018-03-14 | 아사히 가세이 가부시키가이샤 | 블록 공중합체 조성물 및 점접착제 조성물 |
EA033260B1 (ru) * | 2014-01-23 | 2019-09-30 | Асахи Касеи Кабусики Кайся | Блок-сополимерная композиция и клеевая композиция |
US10472514B2 (en) | 2014-01-23 | 2019-11-12 | Asahi Kasei Kabushiki Kaisha | Block copolymer composition and adhesive composition |
Also Published As
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KR20050021458A (ko) | 2005-03-07 |
KR100626442B1 (ko) | 2006-09-20 |
EP1532185B1 (en) | 2008-06-04 |
ATE397632T1 (de) | 2008-06-15 |
WO2004007581A1 (en) | 2004-01-22 |
EP1532185A1 (en) | 2005-05-25 |
EA200500161A1 (ru) | 2005-08-25 |
JP4368303B2 (ja) | 2009-11-18 |
DE60321467D1 (de) | 2008-07-17 |
CN1675272A (zh) | 2005-09-28 |
US7009000B2 (en) | 2006-03-07 |
AU2003249169A1 (en) | 2004-02-02 |
EA008191B1 (ru) | 2007-04-27 |
CN1302036C (zh) | 2007-02-28 |
BR0312603B1 (pt) | 2012-12-11 |
US20040054090A1 (en) | 2004-03-18 |
BR0312603A (pt) | 2005-05-31 |
ES2307979T3 (es) | 2008-12-01 |
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