CN115521467B - Polybutadiene-styrene grafted polyisoprene graft polymer, preparation method thereof and vulcanized rubber - Google Patents
Polybutadiene-styrene grafted polyisoprene graft polymer, preparation method thereof and vulcanized rubber Download PDFInfo
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- CN115521467B CN115521467B CN202110713014.8A CN202110713014A CN115521467B CN 115521467 B CN115521467 B CN 115521467B CN 202110713014 A CN202110713014 A CN 202110713014A CN 115521467 B CN115521467 B CN 115521467B
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 86
- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004636 vulcanized rubber Substances 0.000 title abstract description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000009826 distribution Methods 0.000 claims abstract description 28
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 85
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 66
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 64
- 239000012295 chemical reaction liquid Substances 0.000 claims description 50
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 30
- 238000007334 copolymerization reaction Methods 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 21
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- -1 alkyl lithium Chemical compound 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical group C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 claims description 4
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 claims description 2
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 claims description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 23
- 239000005060 rubber Substances 0.000 abstract description 23
- 229920000642 polymer Polymers 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 47
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 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 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 150000002910 rare earth metals Chemical class 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012916 structural analysis Methods 0.000 description 6
- 229920005683 SIBR Polymers 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 5
- 229920003049 isoprene rubber Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 1
- HHRAWPICZKGGFQ-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethylidene)cyclohex-2-en-1-ol Chemical compound C(CCCCCCC)SC=C1C(C(=CC(C1)=CSCCCCCCCC)C)O HHRAWPICZKGGFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JBSODNBBAKNHEU-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] propanoate Chemical compound CCC(=O)OCC(CO)(CO)CO JBSODNBBAKNHEU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
- C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of grafted polymers, and discloses a polybutadiene-styrene grafted polyisoprene grafted polymer, a preparation method thereof and vulcanized rubber. In the graft polymer, the content of butadiene-styrene structural units in the graft polymer is 10-50wt% and the content of isoprene structural units in the graft polymer is 50-90wt% based on the total weight of the graft polymer; the number average molecular weight of the graft polymer is 10-100 g/mol, and the molecular weight distribution index is 3-6; the content of cis 1, 4-structure is more than or equal to 95wt% based on the total amount of the isoprene structural units. The preparation method of the invention is simple and easy to control, and can simultaneously, efficiently and accurately control the composition and the molecular weight of the prepared polymer. The vulcanized rubber prepared from the polymer has excellent tensile property, and is a new tire rubber variety with wide market application and development prospect.
Description
Technical Field
The invention relates to the field of grafted polymers, in particular to a polybutadiene-styrene grafted polyisoprene grafted polymer and a preparation method thereof, and vulcanized rubber obtained from the polybutadiene-styrene grafted polyisoprene grafted polymer.
Background
Isoprene rubber is a general purpose synthetic rubber with excellent comprehensive properties, and is mainly used for producing tires. The initiation/catalysis systems commonly used for the synthesis of isoprene rubber include lithium-based initiators, titanium-based catalysts, and rare earth catalysts. In recent years, rare earth isoprene rubber has a good wet skid resistance and a low rolling resistance, and wear resistance can still be kept at a good level, so that the rare earth isoprene rubber is of great interest to tire enterprises in the world.
Chemical "tailoring" of the branching and grafting structures of synthetic rubbers is an effective way to control the polymer structure while improving its processability, while also improving compatibility with other gum types when used in combination. In recent years, studies on branched modified diene rubbers have also been frequently carried out in the relevant patent and literature reports.
CN1705687a discloses a synthetic branched polyisoprene and a preparation method thereof. The method comprises the steps of catalyzing isoprene by a catalytic system to polymerize, and adding SnCl after the active chain end in the later period of polymerization reaction 4 And the like, and branched polyisoprene with high cis-1, 4 bond content and almost no gel can be obtained, and the branched polyisoprene has excellent mechanical properties.
CN1884328A discloses that a molybdenum-based catalyst can be used to prepare a branched high vinyl polybutadiene rubber with controllable structure, and the branched properties, length, distribution, branching degree and the like of the branched chains are controllable within a certain range, and the processability and physical and mechanical properties are excellent.
The rubber SIBR synthesized by chemically copolymerizing three monomers of styrene, isoprene and butadiene is an integrated rubber, integrates the excellent performances of a plurality of rubbers such as polybutadiene rubber, styrene-butadiene rubber, polyisoprene rubber and the like, and has soft Bd and Ip component chain segments and rigid St component chain segments in a molecular chain. The rigid chain segment can increase the wet skid resistance of the rubber, the flexible chain segment can improve the wear resistance of the rubber, reduce the rolling resistance, and the hard and soft combined chain segment structure endows the rubber with excellent comprehensive performance. Meanwhile, the chemical bonding between the rigid chain segment and the flexible chain segment solves the problem of unfused two phases, and ensures the stability of rubber performance. Early SIBR is prepared by an anionic polymerization method, and the product can meet the requirements of high-performance tire tread rubber. Compared with anionic polymerization, coordination polymerization has better regioselectivity and stereoselectivity, and the sequence structure and the stereospecificity of the polymer are more convenient to regulate and control, so that the performance of rubber is regulated. For example, "Chain-Shuttling Polymerization at Two Different Scandium Sites: regio-and Stereospecific" One-dot "Block Copolymerization of Styrene, isoprene, and Butadiene" (Hou Zhaomin et al, angew.chem.Int.Ed.2011,50, 12012-12015) discloses that St/Ip/Bd terpolymers (Sc-SIBR) containing syndiotactic polystyrene (sPS) segments, cis 1,4-Ip and cis 1,4-Bd segments, wherein the sPS segments have a degree of syndiotactic of greater than 99% and the conjugated diene components have a cis 1,4-Ip and cis 1,4-Bd structure content of greater than 97%, were achieved using scandium-based rare earth metallocene catalysts, exhibiting excellent stereoselectivity. But Sc-SIBR is a multi-block structure, and has a regular structure and stronger crystallization property, so that the polymer hardly has rubber characteristics.
CN102786621B adopts neodymium catalyst to realize terpolymer with high styrene content and narrow distribution, but compared with polybutadiene rubber (rare earth butadiene rubber) and polyisoprene rubber (rare earth isoprene rubber) prepared by adopting rare earth catalytic system, the cis-1, 4-structure content of the terpolymer is obviously lower.
Disclosure of Invention
The invention aims to solve the problems of low content of isoprene chain segment, low content of cis-1, 4-structure and low tensile strength of vulcanized rubber in the existing rubber containing styrene, butadiene and isoprene, and provides a polybutadiene-styrene grafted polyisoprene graft polymer, a preparation method thereof and vulcanized rubber.
In order to achieve the above object, an aspect of the present invention provides a graft polymer of polybutadiene-styrene graft polyisoprene, wherein the content of butadiene-styrene structural unit in the graft polymer is 10 to 50wt% and the content of isoprene structural unit is 50 to 90wt% based on the total weight of the graft polymer; the number average molecular weight of the graft polymer is 10-100 g/mol, and the molecular weight distribution index is 3-6; the content of cis 1, 4-structure is more than or equal to 95wt% based on the total amount of the isoprene structural units.
In another aspect, the present invention provides a method for preparing a graft polymer of polybutadiene-styrene grafted polyisoprene, comprising the steps of:
(1) Carrying out a first reaction on polyisoprene, a polar additive and first alkyl lithium in a first organic solvent to obtain an active reaction liquid 1;
(2) In the presence of second alkyl lithium and optional additives, carrying out copolymerization reaction on butadiene and styrene in a second organic solvent to obtain a reaction solution containing a styrene-butadiene copolymer; then slowly adding the reaction liquid into the coupling agent in batches, and fully mixing the reaction liquid with the coupling agent to obtain an active reaction liquid 2;
(3) And carrying out a second reaction on the active reaction liquid 1 and the active reaction liquid 2 to obtain the graft polymer.
In another aspect, the invention also provides a polybutadiene-styrene grafted polyisoprene graft polymer prepared by the method.
In another aspect, the invention also provides a vulcanized rubber obtained from the polybutadiene-styrene grafted polyisoprene graft polymer.
Through the technical scheme, the preparation method is simple and easy to control, the composition and the number average molecular weight of the prepared graft polymer can be controlled simultaneously, efficiently and accurately, and the graft polymer has good structural regularity and excellent physical and mechanical properties.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a graft polymer of polybutadiene-styrene grafted polyisoprene, wherein the content of butadiene-styrene structural units in the graft polymer is 10 to 50wt% and the content of isoprene structural units is 50 to 90wt%, based on the total weight of the graft polymer;
the number average molecular weight of the graft polymer is 10-100 g/mol, and the molecular weight distribution index is 3-6; the content of cis 1, 4-structure is more than or equal to 95wt% based on the total amount of the isoprene structural units.
In some embodiments of the invention, it is preferred that the graft polymer have a number average molecular weight of 20 to 80 thousand g/mol and a molecular weight distribution index of 3.5 to 5.5.
In some embodiments of the invention, preferably, the content of cis 1, 4-structure in the isoprene structural units is not less than 97.5 wt.% based on the total amount of the isoprene structural units.
In some embodiments of the present invention, preferably, the graft polymer has a butadiene-styrene structural unit content of 20 to 40wt% and an isoprene structural unit content of 60 to 80wt%.
In some embodiments of the present invention, preferably, the weight ratio of butadiene structural units to styrene structural units in the butadiene-styrene structural units is 1.5:1 to 5:1, preferably 2:1 to 4:1.
The invention can provide the graft polymer with the physical parameters, which contains a styrene structural unit, a butadiene structural unit and an isoprene structural unit, and has more isoprene structural unit content and more cis-1, 4-structure content, and finally the tensile strength of the prepared vulcanized rubber can reach more than 21.6MPa.
In a second aspect, the present invention provides a process for preparing a graft polymer of polybutadiene-styrene grafted polyisoprene, comprising the steps of:
(1) Carrying out a first reaction on polyisoprene, a polar additive and first alkyl lithium in a first organic solvent to obtain an active reaction liquid 1;
(2) In the presence of second alkyl lithium and optional additives, carrying out copolymerization reaction on butadiene and styrene in a second organic solvent to obtain a reaction solution containing a styrene-butadiene copolymer; then slowly adding the reaction liquid into the coupling agent in batches, and fully mixing the reaction liquid with the coupling agent to obtain an active reaction liquid 2;
(3) And carrying out a second reaction on the active reaction liquid 1 and the active reaction liquid 2 to obtain the graft polymer.
In order to obtain the graft polymer provided by the invention, the graft polymer can be obtained by using the conditions defined by the invention on the preparation steps and the materials adopted.
In some embodiments of the present invention, preferably, in step (1), the polar additive is N, N' -tetramethyl ethylenediamine (abbreviated as TMEDA); can play a role in reducing the association of alkyl lithium in a solvent and improving the reactivity. To better function in obtaining the graft polymer of the invention, it is preferred that the molar ratio of the polar additive to butyllithium is between 1.5 and 3.5:1, preferably 2-3:1. further, the weight ratio of the polar additive to the polyisoprene is 1:8-80.
In some embodiments of the invention, the polyisoprene has defined physical properties that enable better achievement of the graft polymer of the invention. Preferably, in step (1), the content of cis 1, 4-structures in the polyisoprene is greater than or equal to 95wt%, preferably greater than or equal to 97.5wt%, based on the total amount of the polyisoprene.
In some embodiments of the invention, the polyisoprene preferably has a number average molecular weight of 6 to 80, preferably 12 to 64, and a molecular weight distribution index of 2.5 to 5, preferably 3 to 4.5.
In some embodiments of the present invention, preferably, the polyisoprene may be prepared by catalytic polymerization of isoprene monomers in the presence of a rare earth catalytic system; but no anti-aging agent is added in the later stage of the reaction.
In some embodiments of the invention, preferably, in step (1), the first reaction is performed in an inert atmosphere. The inert atmosphere refers to any gas or gas mixture that does not chemically react with the reactants and products, such as nitrogen and one or more of the gases of group zero of the periodic table of elements, preferably nitrogen.
In some embodiments of the present invention, preferably, the conditions of the first reaction include: the first reaction temperature is room temperature-70deg.C, the first reaction pressure is 0.1-0.4MPa, and the first reaction time is 2-12hr; preferably, the first reaction temperature is 40-60 ℃, the first reaction pressure is 0.2-0.3MPa, and the first reaction time is 4-8hr.
In some embodiments of the present invention, preferably, in step (2), the additive is tetrahydrofuran (THF for short) or N, N' -tetramethyl ethylenediamine. The use of said additives enables the regulation of the action of the polymerization environment.
In some embodiments of the invention, the additives are further defined to be more advantageous in preparing the microstructure-tunable styrene-butadiene polymer. Preferably, the molar ratio of the additive to butyllithium is between 0 and 200:1, preferably 1.5-150:1. More specifically, THF: n-buli=0-200:1, preferably THF: n-buli=50-150:1; or TMEDA: n-buli=0-3.5:1, preferably TMEDA: n-buli=1.5-3:1.
In some embodiments of the invention, step (2) performs a copolymerization of butadiene with styrene. Preferably, the molar ratio of the total amount of butadiene and styrene to butyllithium is 100:0.3-3, preferably 100:0.5-2. Further, the molar ratio of styrene to butadiene is 1:2-10, preferably 1:4-8.
In some embodiments of the present invention, preferably, in step (2), the coupling agent is dimethyldichlorosilane or dimethyltin dichloride; the reaction solution is slowly added into the coupling agent in batches, so that the coupling agent and Li at the tail end of the polymer react according to the mol ratio of 1:1 to generate the reaction solution 2 containing the required activity.
Preferably, the molar ratio of the coupling agent to butyllithium is 1-1.1:1, preferably 1.02-1.08:1.
in some embodiments of the present invention, preferably, in step (2), the copolymerization is performed in an inert atmosphere. As mentioned above, the inert atmosphere refers to any gas or mixture of gases that does not chemically react with the reactants and products, such as nitrogen and one or more of the gases of group zero of the periodic Table of the elements, preferably nitrogen.
In some embodiments of the present invention, preferably, the copolymerization reaction temperature is 0℃to room temperature, the copolymerization reaction pressure is 0.1 to 0.4MPa, and the copolymerization reaction time may be 1 to 3hr; preferably, the copolymerization reaction temperature is 5-15 ℃, the copolymerization reaction pressure is 0.2-0.3MPa, and the copolymerization reaction time is 1.5-2hr.
In some embodiments of the present invention, preferably, the first alkyl lithium and the second alkyl lithium are each independently selected from one or more of methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, and are each preferably n-butyl lithium.
In some embodiments of the present invention, preferably, in the step (3), the weight ratio of the polyisoprene contained in the active reaction liquid 1 to the styrene-butadiene copolymer contained in the active reaction liquid 2 is 60 to 80:20-40. Wherein the weight of polyisoprene contained in the active reaction liquid 1 is based on the amount of polyisoprene added in step (1). The weight of the styrene-butadiene copolymer contained in the active reaction liquid 2 can be measured by the following method: the weight of the active reaction liquid 2 is m 1 From which a small amount by weight of m is taken 2 Is dried in vacuo at 50℃to a constant weight m 3 The weight of the styrene-butadiene copolymer in the active reaction liquid 2 is m 1 *m 3 /m 2 。
In some embodiments of the present invention, preferably, a molar ratio of active Li contained in the active reaction liquid 1 to active chlorine contained in the active reaction liquid 2 is 1.4 to 1:1, preferably 1.5-1:1. the molar amount of active Li in the active reaction liquid 1 is the amount of the substance of alkyl lithium in step (1). The molar amount of active chlorine in the active reaction liquid 2 is 2 times the amount of the substance of the coupling agent in the step (2) minus the amount of the substance of the alkyllithium in the step (2). The molar ratio of the active Li to the active chlorine is limited in the invention, so that the active Li and the active chlorine can react according to the molar ratio of 1:1, and the graft polymer of the invention is ensured to be obtained.
In some embodiments of the invention, preferably, in step (3), the second reaction is carried out in an inert atmosphere, as described above, which refers to any gas or mixture of gases that does not react chemically with the reactants and products, such as one or more of nitrogen and a gas of group zero of the periodic table of elements, preferably nitrogen. The second reaction temperature is room temperature-70deg.C, the second reaction pressure is 0.1-0.4MPa, and the second reaction time is 2-12hr; preferably, the second reaction temperature is 40-60deg.C, the second reaction pressure is 0.2-0.3MPa, and the second reaction time is 4-8hr.
In some embodiments of the present invention, the first organic solvent and the second organic solvent may be organic solvents commonly used in the art and capable of acting as a reaction medium, so long as the first organic solvent and the second organic solvent are liquid under the reaction conditions and do not participate in the polymerization reaction or chemically interact with the polymer. Preferably, the first solvent and the second solvent are C 5 -C 10 Saturated alkane, C 5 -C 10 At least one of cycloalkanes (C). In general, the first and second organic solvents may each be independently selected from one or more of pentane and its isomers (e.g., n-pentane and isopentane), hexane and its isomers (e.g., n-hexane), heptane and its isomers (e.g., n-heptane), octane and its isomers (e.g., n-octane), cyclohexane, and raffinate oil. Preferably at least one of hexane, methylcyclopentane, 2-methylpentane, 3-methylpentane, cyclohexane, heptane and octane.
The amounts of the first organic solvent and the second organic solvent may be selected conventionally in the art, and are not particularly limited. In general, the first organic solvent may be used in an amount such that the concentration of polyisoprene is 1X 10 -4 -4×10 -4 The second organic solvent is used in an amount such that the total concentration of butadiene and styrene is 1-2mol/L, which not only enables the polymerization reaction to proceed smoothly, but also enables higher production efficiency to be obtained.
In some embodiments of the present invention, after the second reaction is completed, the reactive polymer chains may be deactivated by the addition of a terminator-anti-aging agent to terminate the reaction while preventing subsequent gum preparationAnd aging deterioration during storage. The terminator-antioxidant may be used in the form of a terminator solution containing an antioxidant at a certain mass concentration. The antioxidants are, for example, 2, 6-di-tert-butyl-p-methylphenol (264 for short), 2-sec-butyl-4, 6-dinitrophenol, 2, 4-di (n-octylthiomethylene) -6-methylphenol, trisnonylated phenylphosphite, tetrakis [ beta- (3 ',5 ') -di-tert-butyl-4 ' -hydroxyphenyl ]]At least one of pentaerythritol propionate, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 2,2' -methylenebis- (4-methyl-6-tert-butylphenol), and the mass concentration of the anti-aging agent may be 1-5 wt%. The kind of the terminator is not particularly limited as long as the terminator can inactivate the polymer active chain. Typically, the terminating agent may be water, C 1 -C 6 Aliphatic alcohols, C 4 -C 12 At least one of an aliphatic carboxylic acid and an aryl polyol. The aryl polyhydroxy compound refers to a compound formed by substituting at least two hydrogen atoms on a benzene ring with hydroxyl groups. Preferably, the terminator is at least one of water, methanol, ethanol and isopropanol.
The amount of the terminator is not particularly limited in the present invention, so long as the amount of the terminator can inactivate active species in the polymerization product, and will not be described in detail herein.
The polymerization apparatus for the polymerization reaction is not particularly limited, and may be selected conventionally in the art, and may be, for example, a polymerization tube or a batch reactor.
In a third aspect, the present invention provides a graft polymer of polybutadiene-styrene grafted polyisoprene obtained by the above preparation method. The graft polymer has the features described above and will not be described in detail.
In a fourth aspect, the present invention provides a vulcanizate obtained from the graft polymer of polybutadiene-styrene grafted polyisoprene described above.
The vulcanized rubber can be prepared by adding a vulcanizing agent into the grafted polymer and performing a vulcanization process.
The kind and amount of the vulcanizing agent and the specific operation and condition of vulcanization are not particularly limited in the present invention, and may be appropriately selected according to the specific application of the vulcanized rubber and the conventional knowledge in the art. For example, when the vulcanized rubber is used in the field of automobile tires, the total amount of the vulcanizing agent may be 0.5 to 2.5 parts by weight, preferably 0.6 to 2.5 parts by weight, relative to 100 parts by weight of the graft polymer. The sulfiding agent may be selected from one or more of sulfur, selenium, tellurium, benzoyl peroxide, urethane and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
The vulcanization process may also be carried out in the presence of at least one vulcanization accelerator. The vulcanization accelerator may be various vulcanization accelerators commonly used in the art, and may be at least one selected from zinc oxide, magnesium oxide, and stearic acid, for example. The amount of the vulcanization accelerator may be appropriately selected according to the kind of the vulcanizing agent, and will not be described in detail herein.
In the invention, various additives such as an anti-aging agent and a filler which are commonly used can be added into the vulcanized rubber according to the specific application field so as to improve the performance of the vulcanized rubber or endow the vulcanized rubber with various performances or functions. For example, an anti-aging agent may be added to give the resulting vulcanized rubber good aging resistance. The types and amounts of the additives may be selected as is conventional in the art and are not described in detail herein.
The present invention will be described in detail by examples.
In the following examples and comparative examples, the parameters involved were measured by the following methods:
the number average molecular weight (Mn) and the molecular weight distribution index (pdi=mw/Mn) of the polyisoprene, styrene-butadiene grafted polyisoprene were characterized by Gel Permeation Chromatography (GPC) (Waters company) and standard curves were prepared with polystyrene standards;
the microstructure content and composition of the polymer were characterized by using a Bruker 400MHz NMR apparatus, germany, and the solvent was deuterated chloroform.
Examples 1-7 illustrate the graft polymers provided by the present invention and methods of making the same.
Example 1
In a reaction flask which had been evacuated, baked under heating and replaced three times with high-purity nitrogen gas, 500mL of n-hexane and 30g of polyisoprene (number average molecular weight: 38.2 g/mol, molecular weight distribution index: 3.73) were then added, respectively, and the polyisoprene was dissolved with stirring. Then, 0.42g of TMEDA (3.62 mmol) and 0.90mL of a 1.6mol/L hexane solution of nBuLi (1.44 mmol) were sequentially added, and the first reaction was carried out at 60℃for 5hr to obtain an active reaction solution 1-1.
To the reaction tube, which was evacuated, baked with heat and replaced three times with high purity nitrogen, 100mL of n-hexane, 2.5g of styrene (24.0 mmol) and 7.5g of butadiene (138.9 mmol) were successively added. After mixing uniformly, 0.32g of TMEDA (2.76 mmol) and 0.70mL of 1.6mol/L nBuLi (1.12 mmol) in hexane were added, and copolymerization was performed at 10℃for 2hr. The reaction mixture was then added slowly in portions to 0.15g of dimethyldichlorosilane (1.16 mmol) and maintained in intimate admixture with the coupling agent to give active reaction mixture 2-1.
Adding the active reaction liquid 2-1 into the active reaction liquid 1-1 under the protection of nitrogen, and performing a second reaction at 60 ℃ for 6hr. After the completion of the second reaction, the termination reaction was carried out with an ethanol solution having a 2, 6-di-t-butyl-p-methylphenol content of 1% by weight, and the resulting polymer solution was precipitated, washed and dried to obtain 37.2g of a graft polymer, which was designated JZ-1.
The number average molecular weight of the graft polymer was 47.2 ten thousand g/mol as measured by GPC, and the molecular weight distribution index was 3.85.
The results of the structural analysis of the graft polymer are as follows: the content of butadiene-styrene structural unit was 23.6wt% and the content of isoprene structural unit was 76.4wt% based on 100% by weight of the graft polymer. Wherein the weight ratio of butadiene structural units to styrene structural units is 2.92:1, a step of; the content of cis-1, 4-structure was 98.3% by weight based on 100% by weight of the isoprene structural unit.
Example 2
In a reaction flask which had been evacuated, baked under heating and replaced three times with high-purity nitrogen gas, 420mL of n-hexane and 25g of polyisoprene (number average molecular weight: 23.9 g/mol, molecular weight distribution index: 3.92) were then added, respectively, and the polyisoprene was dissolved with stirring. Then, 0.46g of TMEDA (3.97 mmol) and 1.00mL of 1.6mol/L nBuLi (1.60 mmol) in hexane were sequentially added, and the first reaction was performed at 60℃for 6hr to obtain an active reaction solution 1-2.
To the reaction tube, which was evacuated, baked with heat and replaced three times with high purity nitrogen, 100mL of n-hexane, 2.8g of styrene (26.9 mmol) and 7.2g of butadiene (133.3 mmol) were successively added. After mixing uniformly, 0.24g of TMEDA (2.06 mmol) and 0.80mL of 1.6mol/L nBuLi (1.28 mmol) in hexane were added, and copolymerization was performed at 10℃for 2hr. The reaction mixture was then added slowly in portions to 0.17g of dimethyldichlorosilane (1.32 mmol) and maintained in intimate admixture with the coupling agent to give active reaction mixture 2-2.
Adding the active reaction liquid 2-2 into the active reaction liquid 1-2 under the protection of nitrogen, and performing a second reaction at 50 ℃ for 7hr. After the completion of the second reaction, the termination reaction was carried out with an ethanol solution having a 2, 6-di-t-butyl-p-methylphenol content of 1% by weight, and the obtained polymer solution was precipitated, washed and dried to obtain 32.0g of a graft polymer, which was designated JZ-2.
The number average molecular weight of the graft polymer was 30.5 ten thousand g/mol as measured by GPC, and the molecular weight distribution index was 4.37.
The results of the structural analysis of the graft polymer are as follows: the content of butadiene-styrene structural unit was 26.9wt% and the content of isoprene structural unit was 73.1wt% based on 100% by weight of the graft polymer. Wherein the weight ratio of butadiene structural units to styrene structural units is 2.47:1, a step of; the content of cis-1, 4-structure was 98.0% by weight based on 100% by weight of the isoprene structural unit.
Example 3
In a reaction flask which had been evacuated, baked under heating and replaced three times with high-purity nitrogen gas, 340mL of n-hexane and 20g of polyisoprene (number average molecular weight: 44.7 g/mol, molecular weight distribution index: 3.58) were then added, respectively, and the polyisoprene was dissolved with stirring. Then, 0.56g of TMEDA (4.83 mmol) and 1.30mL of 1.6mol/L nBuLi (2.08 mmol) in hexane were sequentially added, and the first reaction was performed at 60℃for 5hr to obtain an active reaction solution 1-3.
To the reaction tube, which was evacuated, baked with heat and replaced three times with high purity nitrogen, 100mL of n-hexane, 3.0g of styrene (28.8 mmol) and 7.0g of butadiene (129.6 mmol) were successively added. After mixing uniformly, 11.52g of THF (160 mmol) and 1.00mL of 1.6mol/L nBuLi (1.60 mmol) in hexane were added, and copolymerization was performed at 5℃for 2hr. The reaction mixture was then slowly added in portions to 0.36g of dimethyltin dichloride (1.64 mmol) and maintained in intimate admixture with the coupling agent to give active reaction mixture 2-3.
Adding the active reaction liquid 2-3 into the active reaction liquid 1-3 under the protection of nitrogen, and performing a second reaction at 60 ℃ for 6hr. After the completion of the second reaction, the termination reaction was carried out with an ethanol solution having a 2wt% content of 2, 6-di-t-butyl-p-methylphenol, and the resulting polymer solution was precipitated, washed and dried to obtain 27.0g of a graft polymer, which was designated JZ-3.
The number average molecular weight of the graft polymer was 74.9 ten thousand g/mol as measured by GPC, and the molecular weight distribution index was 4.53.
The results of the structural analysis of the graft polymer are as follows: the content of butadiene-styrene structural unit was 30.3wt% and the content of isoprene structural unit was 69.7wt% based on 100% by weight of the graft polymer. Wherein the weight ratio of butadiene structural units to styrene structural units is 2.26:1, a step of; the content of cis-1, 4-structure was 98.4% by weight based on 100% by weight of the isoprene structural unit.
Example 4
In a reaction flask which had been evacuated, baked under heating and replaced three times with high-purity nitrogen gas, 310mL of n-hexane and 18g of polyisoprene (number average molecular weight: 15.8 g/mol, molecular weight distribution index: 4.10) were then added, respectively, and the polyisoprene was dissolved with stirring. Then, 0.56g of TMEDA (4.83 mmol) and 1.90mL of 1.6mol/L nBuLi (3.04 mmol) in hexane were sequentially added, and the first reaction was performed at 60℃for 5hr to obtain an active reaction solution 1-4.
To the reaction tube, which was evacuated, baked with heat and replaced three times with high purity nitrogen, were successively added 120mL of n-hexane, 2.4g of styrene (23.1 mmol) and 9.6g of butadiene (177.8 mmol). After mixing uniformly, 0.49g of TMEDA (4.22 mmol) and 1.50mL of 1.6mol/L nBuLi (2.40 mmol) in hexane were added, and copolymerization was performed at 5℃for 2hr. The reaction mixture was then added slowly in portions to 0.32g of dimethyldichlorosilane (2.48 mmol) and maintained in intimate admixture with the coupling agent to give active reaction mixture 2-4.
Adding the active reaction liquid 2-4 into the active reaction liquid 1-4 under the protection of nitrogen, and performing a second reaction at 60 ℃ for 6hr. After the completion of the second reaction, the termination reaction was carried out with an ethanol solution having a 2, 6-di-t-butyl-p-methylphenol content of 1% by weight, and the resulting polymer solution was precipitated, washed and dried to obtain 27.1g of a graft polymer, which was designated JZ-4.
The number average molecular weight of the graft polymer was 23.8 g/mol as measured by GPC, and the molecular weight distribution index was 5.35.
The results of the structural analysis of the graft polymer are as follows: the content of butadiene-styrene structural unit was 38.1wt% and the content of isoprene structural unit was 61.9wt% based on 100% by weight of the graft polymer. Wherein the weight ratio of butadiene structural units to styrene structural units is 3.84:1, a step of; the content of cis-1, 4-structure was 97.8% by weight based on 100% by weight of the isoprene polymer.
Example 5
In a reaction flask which had been evacuated, baked under heating and replaced three times with high-purity nitrogen gas, 500mL of n-hexane and 30g of polyisoprene (number average molecular weight: 38.2 g/mol, molecular weight distribution index: 3.73) were then added, respectively, and the polyisoprene was dissolved with stirring. Then, 0.98g of TMEDA (8.45 mmol) and 2.20mL of 1.6mol/L nBuLi (3.52 mmol) in hexane were sequentially added, and the first reaction was carried out at 60℃for 5hr to obtain an active reaction solution 1-5.
To the reaction tube, which was evacuated, baked with heat and replaced three times with high purity nitrogen, 180mL of n-hexane, 5.4g of styrene (51.8 mmol) and 12.6g of butadiene (233.3 mmol) were successively added. After mixing uniformly, 20.74g of THF (288 mmol) and 1.80mL of 1.6mol/L nBuLi (2.88 mmol) in hexane were added, and copolymerization was performed at 5℃for 2hr. The reaction mixture was then slowly added in portions to 0.65g of dimethyltin dichloride (2.95 mmol) and maintained in intimate admixture with the coupling agent to give active reaction mixture 2-5.
And adding the active reaction liquid 2-5 into the active reaction liquid 1-5 under the protection of nitrogen. The second reaction was carried out at 50℃for 6hr. After the completion of the second reaction, the termination reaction was carried out with an ethanol solution having a 2, 6-di-t-butyl-p-methylphenol content of 1% by weight, and the resulting polymer solution was precipitated, washed and dried to obtain 45.1g of a graft polymer, which was designated JZ-5.
The number average molecular weight of the graft polymer was 53.2 ten thousand g/mol as measured by GPC, and the molecular weight distribution index was 4.68.
The results of the structural analysis of the graft polymer are as follows: the content of butadiene-styrene structural unit was 35.4wt% and the content of isoprene structural unit was 64.6wt% based on 100% by weight of the graft polymer. Wherein the weight ratio of butadiene structural units to styrene structural units is 2.20:1, a step of; the content of cis-1, 4-structure was 98.0% by weight based on 100% by weight of the isoprene structural unit.
Example 6
In a reaction flask which had been evacuated, baked under heating and replaced three times with high-purity nitrogen gas, 310mL of n-hexane and 18g of polyisoprene (number average molecular weight: 15.8 g/mol, molecular weight distribution index: 4.10) were then added, respectively, and the polyisoprene was dissolved with stirring. Then, 0.53g of TMEDA (4.58 mmol) and 1.1mL of 1.6mol/L nBuLi (1.76 mmol) in hexane were sequentially added, and the first reaction was carried out at 60℃for 5hr to obtain an active reaction liquid 1-6.
To the reaction tube, which was evacuated, baked with heat and replaced three times with high purity nitrogen, 120mL of n-hexane, 3.0g of styrene (28.8 mmol) and 9.0g of butadiene (166.7 mmol) were successively added. After mixing uniformly, 0.38g of TMEDA (3.31 mmol) and 0.84mL of a 1.6mol/L nBuLi (1.34 mmol) hexane solution were added, and copolymerization was performed at 10℃for 2hr. The reaction mixture was then added slowly in portions to 0.18g of dimethyldichlorosilane (1.39 mmol) and maintained in intimate admixture with the coupling agent to give active reaction mixtures 2-6.
Adding the active reaction liquid 2-6 into the active reaction liquid 1-6 under the protection of nitrogen, and performing a second reaction at 60 ℃ for 6hr. After the completion of the second reaction, the termination reaction was carried out with an ethanol solution having a 2, 6-di-t-butyl-p-methylphenol content of 1% by weight, and the resulting polymer solution was precipitated, washed and dried to obtain 28.2g of a graft polymer, designated JZ-6.
The number average molecular weight of the graft polymer was 24.6 g/mol as measured by GPC, and the molecular weight distribution index was 4.77.
The results of the structural analysis of the graft polymer are as follows: the content of butadiene-styrene structural unit was 37.6 wt% and the content of isoprene structural unit was 62.4wt% based on 100% by weight of the graft polymer. Wherein the weight ratio of butadiene structural units to styrene structural units is 2.86:1, a step of; the content of cis-1, 4-structure was 97.9% by weight based on 100% by weight of the isoprene structural unit.
Example 7
In a reaction flask which had been evacuated, baked under heating and replaced three times with high-purity nitrogen gas, 500mL of n-hexane and 30g of polyisoprene (number average molecular weight: 15.8 g/mol, molecular weight distribution index: 4.10) were then added, respectively, and the polyisoprene was dissolved with stirring. Then, 0.37g of TMEDA (3.20 mmol) and 0.85mL of 1.6mol/L nBuLi (1.36 mmol) in hexane were sequentially added, and the first reaction was carried out at 60℃for 5hr to obtain an active reaction liquid 1-7.
To the reaction tube, which was evacuated, baked with heat and replaced three times with high purity nitrogen, 100mL of n-hexane, 2.5g of styrene (24.0 mmol) and 7.5g of butadiene (138.9 mmol) were successively added. After mixing uniformly, 0.32g of TMEDA (2.76 mmol) and 0.70mL of 1.6mol/L nBuLi (1.12 mmol) in hexane were added, and copolymerization was performed at 10℃for 2hr. The reaction mixture was then added slowly in portions to 0.15g of dimethyldichlorosilane (1.39 mmol) and maintained thoroughly mixed with the coupling agent to give active reaction mixture 2-7.
Adding the active reaction liquid 2-7 into the active reaction liquid 1-7 under the protection of nitrogen, and performing a second reaction at 60 ℃ for 6hr. After the completion of the second reaction, the termination reaction was carried out on an ethanol solution having a 2, 6-di-t-butyl-p-methylphenol content of 1% by weight, and the obtained polymer solution was precipitated, washed and dried to obtain 37.2g of a graft polymer, which was designated JZ-7.
The number average molecular weight of the graft polymer was 69.3 ten thousand g/mol as measured by GPC, and the molecular weight distribution index was 4.38.
The results of the structure analysis of the graft polymer are as follows: the content of butadiene-styrene structural unit was 23.4wt% and the content of isoprene structural unit was 76.6wt% based on 100% by weight of the graft polymer. Wherein the weight ratio of butadiene structural units to styrene structural units is 2.84:1, a step of; the content of cis-1, 4-structure was 98.4% by weight based on 100% by weight of the isoprene structural unit.
Comparative example 1
Styrene-isoprene-butadiene terpolymer rubber, designated DJZ-1, was synthesized with reference to "Integrated rubber properties with different sequence distributions" (synthetic rubber industry, 2014,4, 280-283), and had a number average molecular weight of 20.5 g/mol, a molecular weight distribution index of 2.08, and an isoprene structural unit content of 40.2 wt.%.
Test case
The JZ-1 to JZ-7 obtained in the above examples 1 to 7 and the DJZ-1 of comparative example 1 were prepared as vulcanized gums.
Mixing at 50+/-5 deg.c in an open mill and vulcanizing; the vulcanization conditions include: the temperature was 145℃and the vulcanization time was 20min.
The vulcanization basic formula comprises: 100phr of raw rubber; 50phr of carbon black; 1.75phr of sulfur; 1phr of accelerator NS;1phr of stearic acid; 3phr of zinc oxide; 1phr of anti-ageing agent D. The raw rubber is JZ-1 to JZ-7 and DJZ-1 respectively. phr is parts by weight.
The mechanical properties of the obtained vulcanized rubber were tested by preparing a 1-type sample according to the method specified in GB/T528-1998. The physical and mechanical properties of the vulcanizates are shown in Table 1.
TABLE 1
As can be seen from Table 1, the vulcanizates prepared from the graft polymers JZ-1 to JZ-7 prepared in examples 1 to 7 as raw rubber have higher tensile strength than the vulcanizates prepared from the DJZ-1 graft polymer of comparative example 1 as raw rubber. It can also be seen that the tensile strength tends to increase with increasing isoprene structural unit content.
Comparing JZ-1 with JZ-7, the content of isoprene structural units was 76.4wt% and 76.6wt%, respectively, and the tensile strengths of the vulcanized rubbers further prepared as raw rubber were 24.8MPa and 24.2MPa, respectively. Comparing JZ-4 and JZ-6, the content of isoprene structural units was 61.9wt% and 62.4wt%, respectively, and the tensile strengths of the vulcanized rubbers further prepared as raw rubber were 22.2MPa and 21.6MPa, respectively. It can be seen that the tensile strength tends to increase with increasing cis 1, 4-structure content in the isoprene structural unit.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (25)
1. A graft polymer of polybutadiene-styrene grafted polyisoprene, characterized in that the content of butadiene-styrene structural units in the graft polymer is 10-50wt% and the content of isoprene structural units is 50-90wt%, based on the total weight of the graft polymer;
the number average molecular weight of the graft polymer is 10-100 g/mol, and the molecular weight distribution index is 3-6; the content of cis 1, 4-structure is more than or equal to 95wt% based on the total amount of the isoprene structural units.
2. The graft polymer according to claim 1, wherein the number average molecular weight of the graft polymer is 20 to 80 thousand g/mol and the molecular weight distribution index is 3.5 to 5.5;
and/or, based on the total amount of the isoprene structural units, the content of cis 1, 4-structure in the isoprene structural units is not less than 97.5wt%;
and/or, in the graft polymer, the content of butadiene-styrene structural units is 20 to 40wt% and the content of isoprene structural units is 60 to 80wt%.
3. The graft polymer of claim 1 or 2, wherein the weight ratio of butadiene structural units to styrene structural units in the butadiene-styrene structural units is 1.5:1-5:1.
4. The graft polymer of claim 3, wherein the weight ratio of butadiene structural units to styrene structural units in the butadiene-styrene structural units is from 2:1 to 4:1.
5. The process for preparing a graft polymer of polybutadiene-styrene-grafted polyisoprene according to any of claims 1 to 4, which comprises the steps of:
(1) Carrying out a first reaction on polyisoprene, a polar additive and first alkyl lithium in a first organic solvent to obtain an active reaction liquid 1;
(2) In the presence of second alkyl lithium and optional additives, carrying out copolymerization reaction on butadiene and styrene in a second organic solvent to obtain a reaction solution containing a styrene-butadiene copolymer; then slowly adding the reaction liquid into the coupling agent in batches, and fully mixing the reaction liquid with the coupling agent to obtain an active reaction liquid 2;
(3) And carrying out a second reaction on the active reaction liquid 1 and the active reaction liquid 2 to obtain the graft polymer.
6. The process according to claim 5, wherein in the step (1), the polar additive is N, N, N ', N' -tetramethyl ethylenediamine;
and/or the molar ratio of the polar additive to the first alkyl lithium is 1.5-3.5:1, a step of;
and/or the weight ratio of the polar additive to the polyisoprene is 1:8-80.
7. The method of claim 6, wherein the molar ratio of the polar additive to the first alkyllithium is 2-3:1.
8. the process according to any one of claims 5 to 7, wherein in step (1), the content of cis 1, 4-structure in the polyisoprene is not less than 95% by weight based on the total amount of the polyisoprene;
the number average molecular weight of the polyisoprene is 6-80 ten thousand g/mol, and the molecular weight distribution index of the polyisoprene is 2.5-5.
9. The process according to claim 7, wherein in the step (1), the content of cis 1, 4-structure in the polyisoprene is not less than 97.5% by weight based on the total amount of the polyisoprene;
the number average molecular weight of the polyisoprene is 12-64 ten thousand g/mol, and the molecular weight distribution index of the polyisoprene is 3-4.5.
10. The production method according to any one of claims 5 to 7, wherein in step (1), the first reaction is performed in an inert atmosphere;
and/or, the conditions of the first reaction include: the first reaction temperature is room temperature-70deg.C, the first reaction pressure is 0.1-0.4MPa, and the first reaction time is 2-12hr.
11. The method of preparation of claim 10, wherein the conditions of the first reaction comprise: the first reaction temperature is 40-60deg.C, the first reaction pressure is 0.2-0.3MPa, and the first reaction time is 4-8hr.
12. The production process according to any one of claims 5 to 7, wherein in the step (2), the additive is tetrahydrofuran or N, N' -tetramethyl ethylenediamine;
and/or the molar ratio of the additive to the second alkyl lithium is 0-200:1, a step of;
and/or the molar ratio of the total amount of butadiene and styrene to the second alkyllithium is 100:0.3-3;
and/or the molar ratio of styrene to butadiene is 1:2-10.
13. The method of claim 12, wherein the molar ratio of the additive to the second alkyllithium is 1.5-150:1;
and/or the molar ratio of the total amount of butadiene and styrene to the second alkyllithium is 100:0.5-2;
and/or the molar ratio of styrene to butadiene is 1:4-8.
14. The production process according to any one of claims 5 to 7, wherein in the step (2), the coupling agent is dimethyldichlorosilane or dimethyltin dichloride;
and/or the molar ratio of the coupling agent to the second alkyl lithium is 1-1.1:1.
15. the method of claim 14, wherein the molar ratio of the coupling agent to the second alkyllithium is 1.02-1.08:1.
16. the production process according to any one of claims 5 to 7, wherein in the step (2), the copolymerization is carried out in an inert atmosphere; the copolymerization reaction temperature is 0-room temperature, the copolymerization reaction pressure is 0.1-0.4MPa, and the copolymerization reaction time is 1-3hr.
17. The process according to claim 16, wherein the copolymerization reaction temperature is 5 to 15 ℃, the copolymerization reaction pressure is 0.2 to 0.3MPa, and the copolymerization reaction time is 1.5 to 2hr.
18. The production method according to any one of claims 5 to 7, wherein the first alkyllithium and the second alkyllithium are each independently selected from one or more of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and n-hexyllithium.
19. The method of claim 18, wherein the first and second alkyl lithium are each independently n-butyl lithium.
20. The production process according to any one of claims 5 to 7, wherein in the step (3), the weight ratio of the polyisoprene contained in the active reaction liquid 1 to the styrene-butadiene copolymer contained in the active reaction liquid 2 is 60 to 80:20-40 parts;
and/or the molar ratio of the active Li contained in the active reaction liquid 1 to the active chlorine contained in the active reaction liquid 2 is 1.4-1:1.
21. the production method according to claim 20, wherein a molar ratio of active Li contained in the active reaction liquid 1 to active chlorine contained in the active reaction liquid 2 is 1.5 to 1:1.
22. the production method according to any one of claims 5 to 7, wherein in step (3), the second reaction is performed in an inert atmosphere; the second reaction temperature is room temperature-70deg.C, the second reaction pressure is 0.1-0.4MPa, and the second reaction time is 2-12hr.
23. The production process according to claim 22, wherein the second reaction temperature is 40 to 60 ℃, the second reaction pressure is 0.2 to 0.3MPa, and the second reaction time is 4 to 8hr.
24. A graft polymer of polybutadiene-styrene grafted polyisoprene obtained by the process according to any of claims 5 to 23.
25. A vulcanizate obtained from a graft polymer of polybutadiene-styrene grafted polyisoprene according to any of claims 1 to 4 and 24.
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| CN101817911A (en) * | 2009-02-26 | 2010-09-01 | 中国石油化工股份有限公司 | Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof |
| CN103374109A (en) * | 2012-04-24 | 2013-10-30 | 中国石油天然气股份有限公司 | Star-shaped isoprene-styrene copolymer and preparation method thereof |
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