CN1675272A - 偶联的苯乙烯嵌段共聚物及其制备方法 - Google Patents
偶联的苯乙烯嵌段共聚物及其制备方法 Download PDFInfo
- Publication number
- CN1675272A CN1675272A CNA038197987A CN03819798A CN1675272A CN 1675272 A CN1675272 A CN 1675272A CN A038197987 A CNA038197987 A CN A038197987A CN 03819798 A CN03819798 A CN 03819798A CN 1675272 A CN1675272 A CN 1675272A
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- CN
- China
- Prior art keywords
- styrene block
- block copolymer
- alkyl
- polymkeric substance
- diester
- 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 26
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000010426 asphalt Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000004568 cement Substances 0.000 claims abstract description 9
- -1 alkyl compound Chemical class 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 12
- 150000005690 diesters Chemical group 0.000 claims description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003505 polymerization initiator 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 229920013730 reactive polymer Polymers 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 125000002897 diene group Chemical group 0.000 claims description 3
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 150000001399 aluminium compounds Chemical class 0.000 claims description 2
- 230000001808 coupling effect Effects 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
- XHEDLZYGAQSNTR-UHFFFAOYSA-N ethene;hexanedioic acid Chemical compound C=C.C=C.OC(=O)CCCCC(O)=O XHEDLZYGAQSNTR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims 1
- 230000009466 transformation Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 17
- 238000010168 coupling process Methods 0.000 abstract description 15
- 230000008878 coupling Effects 0.000 abstract description 14
- 238000005859 coupling reaction Methods 0.000 abstract description 14
- 230000006872 improvement Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- 239000011295 pitch Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000011414 polymer cement Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 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
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 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
- 239000003999 initiator Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 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
- 239000003921 oil Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical group COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 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
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical compound CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-UHFFFAOYSA-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
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- ZKSADANYBSWZAB-UHFFFAOYSA-N CCCCCC[Mg]CCCCCC Chemical compound CCCCCC[Mg]CCCCCC ZKSADANYBSWZAB-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 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
- 240000000233 Melia azedarach Species 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
- 241001597008 Nomeidae Species 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
- 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
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004796 dialkyl magnesium compounds Chemical class 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 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
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UKOVZLWSUZKTRL-UHFFFAOYSA-N naphthalid Chemical compound 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 230000008569 process Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Substances C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 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
- 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
- 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
- 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
- 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)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Materials For Medical Uses (AREA)
Abstract
公开了制备偶联的苯乙烯嵌段共聚物的方法的改进，其中在聚合之中或之后，以每当量活性聚合物链端计，添加约0.01－约1.5当量的金属烷基化合物到胶浆中，从而改进偶联效率。所得星形苯乙烯嵌段共聚物其有降低含量的5+臂低聚物，这在一些应用，如改性沥青中，是非常理想的。
Description
技术领域
本发明涉及苯乙烯嵌段共聚物及其制备方法。本发明特别地涉及偶联的苯乙烯嵌段共聚物及其制备方法。
背景技术
嵌段共聚物的制备是公知的。在合成方法中，使用引发剂化合物引发一种单体的聚合。允许反应进行，一直到所有单体被消耗，从而导致活性均聚物。向这种活性均聚物中添加化学上不同于第一种的第二种单体。第一聚合物的活性端充当继续聚合的位点，从而将第二种单体作为不同的嵌段掺入到线型聚合物内。如此生长的嵌段聚合物是活性的，一直到被终止。
终止使嵌段共聚物的活性端基转化成非生长的物质，从而使得聚合物对其余单体不反应。如此终止的聚合物常被称为二嵌段共聚物。或者，活性嵌段共聚物可与常被称为偶联剂的多官能团缩合剂反应。活性端基的偶联导致具有至少两个支链的星形聚合物，其中在本领域中支链常被称为“臂”。
尽管所得嵌段共聚物可具有至少两条臂，但对于一些应用来说，它们优选具有3、4或甚至更多的臂。例如，沥青是在各种各样的应用中使用的成本有效的热塑性材料。然而，特别地在更加复杂的应用中，常规沥青的性能性质具有的缺点是对温度非常敏感。沥青常常在低温下太硬且脆，而在炎热的气候条件下太软。
将具有三和四或更多条臂的嵌段共聚物掺入到沥青中，既通过改进沥青的估计寿命，又通过降低维护要求，从而可显著提高沥青在道路、通道、跑道和屋顶应用中的性能。将这种嵌段共聚物加入到沥青中，给改性沥青引入显著优异的性能。例如，这种改性沥青可在高和低温下具有大得多的弹性。
尽管在沥青中使用这种嵌段共聚物的优点是公知的，但使用这种嵌段共聚物有麻烦。例如，在偶联工艺中，所产生的臂数没有限制到3或4条，而是可继续包括5条或更多。为了本发明的目的，术语“5条或更多”和“大于或等于5条”用术语5+表示。当嵌段共聚物的臂数超过4(或＝5+)时，则在沥青内包括嵌段共聚物以改进其物理和特性性能的优点可开始被所得加工难度抵消。例如，5臂聚合物比3臂聚合物产生显著更大的沥青粘度增加。
本发明的一个目的是提供生产具有增加的3和4臂含量和降低的5和更高臂含量的嵌段共聚物的方法。进一步的目的是提供可在沥青改性之类方法中使用以改进改性沥青的物理性能，且没有引起显著加工难度的组合物。
发明概述
一方面，本发明涉及具有通式(AB)nX的星形苯乙烯嵌段共聚物，其中(i)A是苯乙烯嵌段，(ii)B是二烯烃嵌段，(iii)X是二酯偶联剂残基，(iv)n是键合到二酯偶联剂残基上的苯乙烯嵌段共聚物臂的数目，(v)苯乙烯嵌段共聚物臂(AB)的分子量为约2000道尔顿-约300000道尔顿，和(vi)其中n＝5+的聚合物的重量百分数小于约8％。
另一方面，本发明涉及制备星形苯乙烯嵌段共聚物的方法，该方法包括：(a)使苯乙烯和二烯烃单体与阴离子聚合引发剂在合适的溶剂内接触，形成活性聚合物胶浆(polymer cement)，其中所述阴离子聚合引发剂是有机取代的碱金属化合物；(b)在聚合之中或之后，以每当量活性聚合物链端计，添加约0.01-约1.5当量的烷基金属化合物到胶浆中，其中如此选择烷基金属化合物中的烷基，以便它们不与活性聚合物链端交换，和烷基金属化合物选自每一烷基取代基上具有1-20个碳原子的烷基铝、锌和镁；(c)在足以偶联活性聚合物的反应条件下，添加二酯偶联剂到胶浆中。
再一方面，本发明涉及改性沥青，所述改性沥青包括具有通式(AB)nX的星形苯乙烯嵌段共聚物和沥青的混合物，其中：(i)A是苯乙烯嵌段，(ii)B是二烯烃嵌段，(iii)X是二酯偶联剂残基，(iv)n是键合到二酯偶联剂残基上的苯乙烯嵌段共聚物臂的数目，(v)苯乙烯嵌段共聚物链(AB)的分子量为约2000道尔顿-约300000道尔顿，和(vi)其中n＝5+的聚合物的重量百分数小于约8％。
优选实施方案
本发明的嵌段共聚物是具有通式AB)nX的星形嵌段共聚物。在该通式中，A表示乙烯基芳族聚合物嵌段；B表示共轭二烯烃聚合物嵌段，其被任选地氢化；X表示偶联剂残基；n大于1，优选是2-10，更优选2-5，最优选2-4。
本发明的嵌段共聚物可具有递变的嵌段结构。每一嵌段应当主要含有仅仅一种组分，A或B。除主要的一种组分以外的其它组分的存在应当小于5wt％，更优选小于2wt％。最优选每一嵌段含有仅仅一种或基本上仅仅一种组分，A或B。
使用溶液阴离子聚合技术制备本发明的嵌段共聚物。利用该方法，通过使待聚合的单体同时或按序与阴离子聚合引发剂如第IA族金属、它们的烷基化物、酰胺、硅烷醇化物、萘基金属、联苯或蒽衍生物接触，从而制备共聚物。优选使用在约-150℃-约150℃的温度范围内，优选在约-70℃-约100℃的温度范围内在合适溶剂中的有机碱金属(如锂或钠或钾)化合物。特别有效的阴离子聚合引发剂是具有通式RLin的有机锂化合物，其中R是具有1-约20个碳原子的脂族、脂环族、芳族或烷基取代的芳烃基和n为整数1-4。对于在较高温度下的聚合来说，优选有机锂引发剂，因为其在升高的温度下稳定性增加。
优选在添加于烃溶剂内的烷基金属之前，在20℃-90℃的温度下进行本发明的聚合方法。合适的溶剂包括直链和支链烃如戊烷、己烷、辛烷和类似物，以及它的烷基取代的衍生物；脂环族烃如环戊烷、环己烷、环庚烷和类似物，以及它的烷基取代的衍生物；它的芳基和烷基取代的衍生物；芳基和烷基取代的芳烃衍生物如苯、萘、甲苯、二甲苯和类似物；氢化芳烃如1，2，3，4-四氢化萘、十氢化萘和类似物；直链和环状醚如二甲醚、甲乙醚、二乙醚、四氢呋喃和类似物。
在以上所述的阴离子聚合方法中，产生活性聚合物链、溶剂、副产物等的混合物，下文将其称为聚合物胶浆。本发明包括在聚合之中或之后，以每当量活性聚合物链端计，添加约0.01-约1.5当量，更优选约0.9∶1-约1.1∶1当量的烷基金属化合物到胶浆中。还优选在二烯烃聚合的后期阶段添加烷基金属，因为这是聚合物胶浆粘度可能成为重要问题的点。优选在二烯烃的聚合完成50％之后，更优选在70％之后和最优选在二烯烃的聚合完成90％之后添加烷基金属。在给定温度下，添加烷基金属降低聚合速度，但也相当显著地降低热终止反应的速度。结果，优选在至少90℃的温度下，优选100℃-120℃进行剩下的聚合。在优选的方法中，允许就在添加烷基金属之前，升高聚合温度到约90-100℃。
在本发明方法的实践中，优选选择烷基金属化合物中的烷基，以便它们不与活性聚合物链端交换。为此，从每一烷基取代基具有1-20个碳原子的烷基铝、锌和镁中选择烷基金属化合物。烷基金属优选选自三烷基铝、二烷基镁和二烷基锌化合物。优选的三烷基铝化合物是三乙基铝、三甲基铝、三正丙基铝、三正丁基铝、三异丁基铝、三正己基铝和三辛基铝。最优选三乙基铝。优选的二烷基镁化合物是丁基乙基镁、二正丁基镁和二正己基镁。优选的二烷基锌化合物是二甲基锌、二乙基锌、二正丙基锌、二异丁基锌和二正丁基锌。
在这些嵌段共聚物的制备中，这些材料的使用是Willis等的美国专利No.6391981的主题。此处公开了使用这种材料可显著降低同时形成的聚合物胶浆的粘度。聚合物胶浆中的这种粘度下降可提供制备优点。本发明涉及使用这些烷基金属材料制备的偶联的嵌段共聚物在偶联效率和性能上的一些改进。
在嵌段共聚物的合成中，偶联效率最重要，其中通过连接技术制备所述共聚物。在典型的阴离子聚合物合成中，在偶联反应之前，未连接的臂可具有仅仅一个硬嵌段，典型地为聚苯乙烯。在嵌段共聚物内要求两条硬嵌段，若它将有助于材料的强度机制。未偶联的臂可稀释削弱材料本身的嵌段共聚物的强度形成网络。
在诸如制备改性沥青之类的应用中，本发明所实现的非常高的偶联效率是特别重要的。偶联的苯乙烯嵌段共聚物改性的沥青相对于未改性的沥青的一个优点是更好的高低温性能，和认为这是由于偶联的苯乙烯嵌段共聚物的网络形成性能所致。存在于嵌段共聚物内的未偶联的嵌段共聚物低聚物每单位重量至少在相同程度上不如偶联的嵌段共聚物低聚物的贡献大。
为了本发明的目的，根据GPC曲线，使用下式计算偶联效率：((全部测量面积的百分数-未偶联的嵌段面积的百分数)/全部测量面积的百分数)×100。也可使用面积百分数来计算偶联效率(也标记为C/E)：(((n＝1+n＝2...n＝5+)-(n＝1))/(n＝1，n＝2，...n＝5+))×100并以百分数来表达。C/E为100的嵌段共聚物将不存在或通过GPC可检测的n＝1。
尽管在技术上没有以上所定义的偶联效率的量度，但本发明的聚合物具有改进的性能，其特征在于相对于常规聚合物，n＝2和n＝5+低聚物的百分数之和的数值低。甚至在其中聚合条件使得偶联效率接近常规值的本发明的聚合物中，n＝2和n＝5+低聚物的百分数之和也显著低于常规聚合物。
本发明的嵌段共聚物优选具有3和4条臂的形式作为主要的低聚物且通过一起偶联共聚物分子AB来制备，其中已使用如上所述的烷基金属来制备该共聚物分子。偶联剂可以是任何二酯。二酯优选选自己二酸二甲酯、己二酸二乙酯、对苯二甲酸二甲酯、对苯二甲酸二乙酯及其混合物。为了促进偶联反应，可使用促进剂。这些试剂通常是极性化合物和基本上是非质子化合物。这些试剂的实例包括芳族醚、直链烷基醚和环烷基醚。特别优选的促进剂是邻二甲氧基苯、甘醇二甲醚和二甘醇二甲醚。当使用这些促进剂时，基于全部溶液的用量，以在约100-1000ppm范围内的用量添加促进剂。优选在约200-500ppm范围内的用量。
可用于本发明的合适的乙烯基芳族化合物包括具有8-20个碳原子的那些和包括苯乙烯、邻甲基苯乙烯、对甲基苯乙烯、对叔丁基苯乙烯、2，4-二甲基苯乙烯、α-甲基苯乙烯、乙烯基萘、乙烯基甲苯、乙烯基二甲苯及其混合物。优选的单乙烯基芳族化合物是苯乙烯、α-甲基苯乙烯和对甲基苯乙烯，其中最优选苯乙烯。为了本发明的目的，苯乙烯嵌段共聚物是用合适的乙烯基芳族化合物制备的任何嵌段共聚物聚合物。
可用于本发明的合适的共轭二烯烃包括具有4-8个碳原子的那些，例如，1，3-丁二烯、2-甲基-1，3-丁二烯(异戊二烯)、2，3-二甲基-1，3-丁二烯、1，3-戊二烯和1，3-己二烯。也可使用这种二烯烃的混合物。优选的共轭二烯烃是1，3-丁二烯和异戊二烯。
本发明的偶联的苯乙烯嵌段共聚物中各自的总的平均分子量优选在约2000-约300000道尔顿范围内。更优选数均分子量为约3000-约150000道尔顿，和最优选约30000-100000道尔顿。
可用凝胶渗透色谱(GPC)，使用聚苯乙烯校正标准物，测量在本说明书和权利要求中所指的数均分子量，如根据ASTM 3536进行。GPC是其中根据分子尺寸分离聚合物的公知方法，其中最大的分子首先洗脱出来。使用商购的聚苯乙烯分子量标准物校正色谱图。其它(嵌段)聚合物的分子量以苯乙烯的等价分子量形式表达。所使用的检测器优选紫外检测器。
本发明的嵌段共聚物是支化的，具有通式(AB)nX。正如已经定义的，n是支化数。本发明的聚合物不同于常规聚合物在于，本发明方法的较高偶联效率产生其中n＝5或更大(n＝5+)的低聚物含量较低的聚合物。这种聚合物在其中使用聚合物改性沥青的应用中是高度所需的。本发明的聚合物可赋予在沥青性能方面相同的有利改进和显著降低的沥青粘度增加，从而改进沥青的加工条件。
存在于本发明沥青组合物内的沥青组分可以是天然存在的沥青或者衍生于矿物油。此外，通过裂解工艺获得的石油沥青和煤焦油以及各种沥青材料的共混物可用作沥青组分。合适的组分的实例包括蒸馏或直馏沥青、沉淀沥青，例如丙烷沥青、吹制沥青，例如催化吹制沥青或“Multiphalte”及其混合物。其它合适的沥青组分包括一种或多种这些沥青与增量剂(稀释剂)如石油提取物，例如芳烃提取物、馏出液或残渣的混合物，或与油的混合物。合适的沥青组分(或者“直馏沥青”或者“稀释沥青”)是在25℃下的针入度在50-250dmm范围内的那些。优选使用针入度在60-170dmm范围内的沥青。可使用相容或者不相容的沥青。
本发明的聚合物，当用作沥青改性剂时，基于总的沥青组合物，以约1-约15wt％，更优选约2-约12wt％的用量范围存在于沥青组合物内。沥青组合物也可任选地含有其它成分如所预计的最终用途可能要求的那些成分。当然，如果有利的话，除了本发明的聚合物以外，其它聚合物改性剂也可包括在沥青组合物内。
在制备之后，可氢化本发明的偶联的苯乙烯嵌段共聚物。可使用现有技术已知的任何方法完成这种氢化。氢化优选是其中芳族不饱和度未被氢化的选择氢化。
本发明的聚合物也可任选地含有各种添加剂，如抗氧剂、紫外吸收剂、光稳定剂或着色剂。以每100重量份嵌段共聚物计，存在于聚合物组合物内的这些添加剂的用量优选不大于5重量份。
实施例
提供下述实施例阐述本发明。实施例不打算限制本发明的范围和它们不应当被如此解释。除非另有说明，用量以重量份或重量百分数计。
实施例1
如下所述制备二嵌段聚合物阴离子S-B-Li：将157kg环己烷和11.7kg苯乙烯引入到反应器中。通过添加较小递增量的仲丁基锂一直到检测到颜色，从而除去杂质，和添加451ml仲丁基锂溶液(8.8wt％BuLi，0.56mol)，以引发苯乙烯的聚合。在苯乙烯的聚合之后，将丁二烯加入到反应器中。添加总计31.1kg丁二烯，从而导致21％的固体内容物(所生产聚合物的重量百分数)。在添加约92％的丁二烯之后添加415g在环己烷内的25wt％的三乙基铝(TEA)。使用苯乙烯嵌段所观察到的分子量和所引入的苯乙烯的量来计算活性聚合物的摩尔数。基于该数值，存在约1.0molTEA/mol活性链。调节丁二烯的添加速度，使就在TEA的添加之前温度达到约95℃。对于剩余丁二烯的聚合来说，维持约100-110℃的温度。在丁二烯的聚合完成之后，添加25g己二酸二甲酯(DMA)(DMA∶PLi约0.26)。在30分钟以后用甲醇终止聚合。使用凝胶渗透色谱(GPC)分析产物。在偶联之前，苯乙烯嵌段的分子量为约22000道尔顿，和丁二烯嵌段的分子量为约55000道尔顿。下表1报道了使用UV检测器，相应于所测定的各种物质的峰值面积。还报道了偶联效率。由于UV检测器仅对苯乙烯重复单元敏感和苯乙烯的重量分数在所有偶联的物质内相同，因此这些区域基本上代表各物质的摩尔分数。使用各物质的分子量，将这些数值转化成重量百分数。对于本发明的实施例，重量分数基本上与UV面积相同。
实施例2
基本上与实施例1相同地制备实施例2的产物，所不同的是TEA∶Li的比降低到0.98。
实施例3
基本上与实施例1相同地制备实施例3的产物，所不同的是在约99.5％的丁二烯聚合之后添加TEA。TEA∶Li之比为0.99。
实施例4
基本上与实施例1相同地制备实施例4的产物，所不同的是在约72％的丁二烯聚合之后添加TEA，和TEA∶Li之比增加到约1.03。
实施例5
基本上与实施例1相同地制备实施例5的产物，所不同的是略微增加单体的进料，从而导致在聚合最后22％的固体含量，在约72％的丁二烯聚合之后添加TEA，和降低TEA∶Li之比到约0.96。
对比例6
基本上与实施例1相同地制备对比例6的产物，所不同的是不添加TEA。
表1
| 实施例 | n＝1 | n＝2 | n＝3 | n＝4 | n＝5+ | C/E(％) |
| 1 | 10.2 | 6.1 | 22.8 | 55.4 | 5.3 | 89.8 |
| 2 | 6.6 | 4.4 | 23.9 | 62.6 | 2.6 | 93.4 |
| 3 | 5.2 | 4.8 | 21.5 | 63.9 | 4.6 | 94.8 |
| 4 | 18.3 | 7.5 | 25.9 | 44.5 | 3.8 | 81.7 |
| 5 | 16.6 | 8.5 | 33.7 | 37.8 | 3.4 | 83.4 |
| 对比例6 | 15.5 | 8.6 | 14.8 | 49.8 | 12.1 | 84.6 |
结果是使用UV检测器基于GPC值的面积百分数。
实施例7a-d
通过混合12wt％本发明的聚合物与相容沥青，具体地是沥青质含量为约13％且商品牌号为B-180的Venezuelan沥青，从而制备改性沥青。通过使用SILVERSON L4R高剪切混合机，在约180℃下共混约45分钟，进一步制备混合物。使用ASTM D-5，测试样品在25℃下的针入度；使用ASTM D-36，测试环球软化点(℃)；使用ASTM D-4402，测试在180℃下的粘度(Pa.s)；使用ASTM D-5147，测试冷弯曲温度(℃)；和使用DIN 52123测试DIN流动(℃)。下表2报道了结果。
对比例8
基本上相同地重复实施例7的步骤，所不同的是使用获自于KRATONPOLYMERS LLC商品牌号为D 1184的常规嵌段共聚物。
实施例9a-d
基本上相同地重复实施例7的步骤，所不同的是沥青为由丙烷沥青和透明的糠醛提取物以67/33的比例的混合物制备的且商品牌号为PX-200的不相容沥青。
对比例10
基本上相同地重复实施例9的步骤，所不同的是使用获自于KRATONPOLYMERS LLC商品牌号为D 1184的常规嵌段共聚物。
表2
| 样品ID | 7a | 7b | 7c | 7d | 对比例8 |
| n＝1 | 13.8％ | 17.5％ | 9.8％ | 8.4％ | 16.7％ |
| n＝2+n＝3 | 77.6％ | 78.1％ | 82.1％ | 86.2％ | |
| n＝5+ | 3.2％ | 2.6％ | 2.7％ | 2.2％ | 8.5 |
| n＝4峰值分子量 | 409K | 445K | 402K | 401K | 422K |
| 偶联效率 | 85.5％ | 82.7％ | 89.6％ | 91.4％ | 82.7％ |
| 沥青 | B-180 | B-180 | B-180 | B-180 | B-180 |
| 在25℃下的针入度，dmm | 56 | 51 | 54 | 45 | 46 |
| 环球软化点，℃ | 123 | 124 | 122 | 125 | 123 |
| 在180℃下的粘度，Pa.s | |||||
| 剪切速度20s-1 | 2.5 | 2.6 | 2.8 | 2.1 | 2.3 |
| 剪切速度100s-1 | 1.7 | 1.9 | 1.9 | 1.9 | 1.9 |
| 冷弯曲温度，合格℃ | -20 | -25 | -35 | -35 | -25 |
| DIN流动，合格℃ | 100 | 100 | 105 | 100 | 95 |
| 样品ID | 9a | 9b | 9c | 9d | 对比例10 |
| n＝1 | 13.8％ | 16.9％ | 9.8％ | 5.3％ | 16.7％ |
| n＝3+n＝4 | 77.6％ | 80.7％ | 82.1％ | 87.7％ | |
| n＝5+ | 3.2％ | 1.3％ | 2.7％ | 4.2％ | 8.5 |
| n＝4峰值分子量 | 409K | 465K | 402K | 424K | 422K |
| 偶联效率 | 85.5％ | 84.6％ | 89.6％ | 93.7％ | 82.7％ |
| 沥青 | PX-200 | PX-200 | PX-200 | PX-200 | PX-200 |
| 在25℃下的针入度，dmm | 62 | 66 | 55 | 40 | 51 |
| 环球软化点，℃ | 121 | 120 | 120 | 127 | 123 |
| 在180℃下的粘度，Pa.s | |||||
| 剪切速度20s-1 | 2.6 | 3.6 | 3.1 | 3.4 | 3.5 |
| 剪切速度100s-1 | 2.5 | 3.6 | 2.6 | 2.8 | 3.4 |
| 冷弯曲温度，合格℃ | -30 | -25 | -35 | -25 | -25 |
| DIN流动，合格℃ | 95 | 95 | 100 | 95 | 95 |
Claims (9)
1.一种具有通式(AB)nX的星形苯乙烯嵌段共聚物或其氢化衍生物，其中：
(i)A是苯乙烯嵌段，
(ii)B是二烯烃嵌段，
(iii)X是二酯偶联剂残基，
(iv)n是键合到二酯偶联剂残基上的苯乙烯嵌段共聚物臂的数目，
(v)苯乙烯嵌段共聚物臂(AB)的分子量为2000道尔顿至300000道尔顿，和
(vi)其中n为至少5的聚合物的重量百分数小于8％。
2.权利要求1的星形苯乙烯嵌段共聚物，其中n为至少5的聚合物的重量百分数小于6％，优选小于5％，或其中n为2的聚合物的重量百分数小于5％，或其中n为2和n为至少5的聚合物的重量百分数小于12％。
3.权利要求1或2的星形苯乙烯嵌段共聚物，其中苯乙烯嵌段(A)是聚苯乙烯和/或其中二烯烃嵌段(B)选自聚丁二烯、聚异戊二烯及其混合物。
4.权利要求1-4任何一项的星形苯乙烯嵌段共聚物，其中二酯偶联剂残基选自己二酸二甲酯、己二酸二乙酯、对苯二甲酸二甲酯、对苯二甲酸二乙酯及其混合物的二酯的残基。
5.制备权利要求1-4任何一项的星形苯乙烯嵌段共聚物的方法，该方法包括：
(a)使苯乙烯和二烯烃单体与阴离子聚合引发剂在合适的溶剂内接触，形成活性聚合物胶浆，其中所述阴离子聚合引发剂是有机取代的碱金属化合物；
(b)在聚合之中或之后，以每当量活性聚合物链端计，添加0.01-1.5当量的烷基金属化合物到所述胶浆中，其中选择烷基金属化合物中的烷基使它们不与活性聚合物链端交换，和烷基金属化合物选自每一烷基取代基上具有1-20个碳原子的烷基铝、锌和镁；
(c)在足以偶联活性聚合物的反应条件下，添加二酯偶联剂到所述胶浆中；和任选地
(d)优选通过使用选择氢化方法，氢化步骤(c)中获得的产物。
6.权利要求5的方法，其中以每当量活性聚合物链端计，添加0.9-1.1当量的烷基金属化合物到所述胶浆中。
7.权利要求5或6的方法，其中烷基金属化合物是三烷基铝化合物，优选三乙基铝。
8.权利要求5-7任何一项的方法，其中在单体的转化率为70％之时或之后，优选90％之时或之后，在步骤(b)中添加烷基金属化合物。
9.一种改性沥青，其包含权利要求1-4任何一项的星形苯乙烯嵌段共聚物或权利要求5-8任何一项的方法的产品与沥青的混合物。
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| US (1) | US7009000B2 (zh) |
| EP (1) | EP1532185B1 (zh) |
| JP (1) | JP4368303B2 (zh) |
| KR (1) | KR100626442B1 (zh) |
| CN (1) | CN1302036C (zh) |
| AT (1) | ATE397632T1 (zh) |
| AU (1) | AU2003249169A1 (zh) |
| BR (1) | BR0312603B1 (zh) |
| DE (1) | DE60321467D1 (zh) |
| EA (1) | EA008191B1 (zh) |
| ES (1) | ES2307979T3 (zh) |
| WO (1) | WO2004007581A1 (zh) |
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| CN105764970A (zh) * | 2013-10-11 | 2016-07-13 | 科腾聚合物美国有限责任公司 | 烯键式不饱和星型苯乙烯类嵌段共聚物和改进的不含硫化剂的胶乳 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101925624B (zh) * | 2007-11-28 | 2014-08-20 | 戴纳索尔伊莱斯托米罗斯公司 | 星形多嵌段共聚物 |
| CN102844339A (zh) * | 2010-04-21 | 2012-12-26 | 日本曹达株式会社 | 星形聚合物及其制法 |
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| CN102844339B (zh) * | 2010-04-21 | 2015-05-20 | 日本曹达株式会社 | 星形聚合物及其制法 |
| CN105764970A (zh) * | 2013-10-11 | 2016-07-13 | 科腾聚合物美国有限责任公司 | 烯键式不饱和星型苯乙烯类嵌段共聚物和改进的不含硫化剂的胶乳 |
| CN105764970B (zh) * | 2013-10-11 | 2019-06-11 | 科腾聚合物美国有限责任公司 | 烯键式不饱和星型苯乙烯类嵌段共聚物和改进的不含硫化剂的胶乳 |
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| Publication number | Publication date |
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| KR100626442B1 (ko) | 2006-09-20 |
| EP1532185A1 (en) | 2005-05-25 |
| KR20050021458A (ko) | 2005-03-07 |
| DE60321467D1 (de) | 2008-07-17 |
| BR0312603B1 (pt) | 2012-12-11 |
| JP2005533151A (ja) | 2005-11-04 |
| US20040054090A1 (en) | 2004-03-18 |
| WO2004007581A1 (en) | 2004-01-22 |
| EP1532185B1 (en) | 2008-06-04 |
| EA200500161A1 (ru) | 2005-08-25 |
| CN1302036C (zh) | 2007-02-28 |
| AU2003249169A1 (en) | 2004-02-02 |
| US7009000B2 (en) | 2006-03-07 |
| JP4368303B2 (ja) | 2009-11-18 |
| ES2307979T3 (es) | 2008-12-01 |
| BR0312603A (pt) | 2005-05-31 |
| ATE397632T1 (de) | 2008-06-15 |
| EA008191B1 (ru) | 2007-04-27 |
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