CN100390213C - Star-shaped solution-polymerized conjugated diene/monovinylarene copolymer rubber with high vinyl content and preparation method thereof - Google Patents
Star-shaped solution-polymerized conjugated diene/monovinylarene copolymer rubber with high vinyl content and preparation method thereof Download PDFInfo
- Publication number
- CN100390213C CN100390213C CNB2005100522286A CN200510052228A CN100390213C CN 100390213 C CN100390213 C CN 100390213C CN B2005100522286 A CNB2005100522286 A CN B2005100522286A CN 200510052228 A CN200510052228 A CN 200510052228A CN 100390213 C CN100390213 C CN 100390213C
- Authority
- CN
- China
- Prior art keywords
- conjugated diene
- raffinate
- ether
- monovinylarene
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 229920001577 copolymer Polymers 0.000 title claims abstract description 39
- 150000001993 dienes Chemical class 0.000 title claims abstract description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 10
- 239000002879 Lewis base Substances 0.000 claims abstract description 9
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 28
- 239000003921 oil Substances 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 20
- -1 cyclic ether compound Chemical class 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 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 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 10
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000001979 organolithium group Chemical group 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 4
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical group CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- XZKRXPZXQLARHH-XVNBXDOJSA-N [(1e)-buta-1,3-dienyl]benzene Chemical compound C=C\C=C\C1=CC=CC=C1 XZKRXPZXQLARHH-XVNBXDOJSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 4
- 150000003440 styrenes Chemical class 0.000 claims 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims 2
- 150000008378 aryl ethers Chemical class 0.000 claims 2
- 229910052697 platinum Inorganic materials 0.000 claims 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical group CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims 1
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation Methods 0.000 claims 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims 1
- JNUKOTUICJZAIB-UHFFFAOYSA-N hexa-1,2,3,4-tetraene Chemical compound CC=C=C=C=C JNUKOTUICJZAIB-UHFFFAOYSA-N 0.000 claims 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005096 rolling process Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000006073 displacement reaction Methods 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 241001120493 Arene Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QWHNJUXXYKPLQM-UHFFFAOYSA-N 1,1-dimethylcyclopentane Chemical compound CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- RIRARCHMRDHZAR-UHFFFAOYSA-N 1,2-dimethylcyclopentane Chemical compound CC1CCCC1C RIRARCHMRDHZAR-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- QWOLVDBEENYDEO-UHFFFAOYSA-N NCC1=C(C=CC=C1)[Li] Chemical compound NCC1=C(C=CC=C1)[Li] QWOLVDBEENYDEO-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000002989 phenols Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 150000003527 tetrahydropyrans Chemical class 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种星型高乙烯基含量的溶聚共轭二烯烃/单乙烯基芳烃共聚物橡胶及其制备方法。本发明以复合添加剂(路易斯碱、阴离子表面活性剂和抽余油的混合物)为结构调节剂，使共轭二烯烃和单乙烯基芳烃发生共聚反应，经偶联反应后即得产品。该方法的反应时间短，例如为10分钟左右，生产效率和设备利用率高，所得产品的乙烯基结构含量达到60%以上，同时偶联效率达到70%以上，具备高抗湿滑性和低滚动阻力，特别适合于制造轮胎胎面。The invention relates to a star-shaped solution-polymerized conjugated diene/monovinylarene copolymer rubber with high vinyl content and a preparation method thereof. The invention uses composite additives (a mixture of Lewis base, anionic surfactant and raffinate oil) as a structure regulator to make conjugated diolefins and monovinylarenes undergo copolymerization reactions, and obtain products after coupling reactions. The reaction time of this method is short, such as about 10 minutes, and the production efficiency and equipment utilization rate are high. The vinyl structure content of the obtained product reaches more than 60%, and the coupling efficiency reaches more than 70%. Rolling resistance, especially suitable for making tire treads.
Description
Invention field
The present invention relates to a kind of method for preparing novel conjugated-diolefin/uni-vinyl-arene copolymer rubber, more particularly, relate to the new copolymer rubber and the application thereof of a kind of method of the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber for preparing star high-vinyl-content and preparation thus.
Background of invention
The current rubber of tread rubber of automobile tires that is applicable to not only will have good abrasion resistance, also will have high wet-sliding resistant and low-rolling-resistance, could satisfy demand energy-conservation and safety traffic like this.And these two kinds of performance demands of low-rolling-resistance and high wet-sliding resistant are conflicting, and the rubber of single variety is difficult to satisfy simultaneously this two kinds of requirements.Method with blend just makes two kinds of performances improve to some extent two kinds of blend rubbers that have low-rolling-resistance and high wet-sliding resistant respectively, is difficult to obtain the ideal product.For improving the anti-slippery and the rolling resistance of rubber item, attempt mainly to reach with divinyl rubber or the styrene-butadiene rubber(SBR) that organic lithium initiator obtains by modification.For example, by Molecular Structure Design, can synthesize multipolymer and homopolymer with low-rolling-resistance and high wet-sliding resistant.The rolling resistance of rubber item and anti-slippery can be characterized by the tan δ value of 60 ℃ and 0 ℃ in its viscoelastic spectra usually, and the value of the tan δ in the time of 60 ℃ is low more, and the rolling resistance of rubber is more little, and the tan δ value in the time of 0 ℃ is high, and the anti-slippery of rubber is good more.
US 4,367, and 325 and US4, mentioned a kind of method that adopts the solution polymerized butadiene styrene rubber of the synthetic high-vinyl-content of anionoid polymerization in 139,690, it is the composite structure conditioning agent that this method adopts ethers and anion surfactant, because of initiation reaction at low temperatures, long reaction time.
US 5, also mentioned a kind of method that adopts the solution polymerized butadiene styrene rubber of the synthetic star high-vinyl-content of anionoid polymerization in 008,343, this method is the activator and the structure regulator of reaction with the asymmetrical ether, because the complex ability of asymmetrical ether is poor, so long reaction time; And the method that this patent relates to will be carried out removing of reaction heat, polymerization technique complexity when reaction reaches a high temperature.
US 4,397, also mentioned a kind of method that adopts the solution polymerized butadiene styrene rubber of the synthetic star high-vinyl-content of anionoid polymerization in 994, this method adopts cyclic ethers (THF) as structure regulator, initiation reaction at low temperatures, this method running cost height, long reaction time are unfavorable for suitability for industrialized production.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the styrene-butadiene rubber(SBR) field, a kind ofly not only has good abrasion resistance in the hope of developing, but also has the styrene-butadiene rubber(SBR) of high wet-sliding resistant and low-rolling-resistance.Found that by in divinyl and cinnamic polymerization process, using specific structure regulator and being used in combination to raffinate oil and be solvent, can at room temperature cause and carry out polyreaction, when reaction high temperature, need not remove reaction heat, and produce the solution polymerized butadiene styrene rubber product of the star high-vinyl-content that satisfies above-mentioned performance requriements thus.The present invention just is being based on this discovery and is being accomplished.
General purpose of the present invention is to provide a kind of novel method for preparing conjugated-diolefin/uni-vinyl-arene copolymer rubber, this method at room temperature causes and carries out polyreaction, reaction heat need not be removed during polyreaction high temperature, technological process is simple, reaction times is short, production efficiency and plant factor height.
A comparatively concrete purpose of the present invention is to provide a kind of method for preparing the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of star high-vinyl-content, comprise making conjugated diene and monovinylarene, carry out coupling and termination then as carrying out copolymerization at organic lithium initiator and Lewis base, anion surfactant and the mixture of raffinating oil in the presence of as composite additive in the raffinating oil of solvent.
Another object of the present invention is to provide the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber product of the new star high-vinyl-content of a class, especially styrene-butadiene rubber(SBR) product, this series products has high moisture resistance and low-rolling-resistance, be particularly suitable for making tire tread, can use separately, also can use with other rubber mix.
Therefore, one aspect of the present invention provides a kind of method for preparing the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of star high-vinyl-content, comprises the steps:
1) adopting organolithium under inert gas environment is initiator, is composite additive with Lewis base, anion surfactant and the mixture of raffinating oil, as the copolymerization of carrying out conjugated diene and monovinylarene in the raffinating oil of solvent;
2) after finishing, polyreaction adds coupling agent;
3) after linked reaction is finished, add terminator and anti-aging agent, condense in the usual way then and drying.
The present invention provides the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of the new star high-vinyl-content of a class on the other hand, and therein ethylene base content is 60% or higher.
Further aspect of the present invention provides the goods based on the soluble poly-conjugated-diolefin/uni-vinyl-arene copolymer rubber of above-mentioned star high-vinyl-content, as tire.
Implement best mode of the present invention
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, operable conjugated diene is meant any monomer that has conjugated double bond in its molecule, as C
4～C
12Conjugated diene monomer, preferred C
4～C
8Conjugated diene monomer, its specific examples comprise 1,3-butadiene, isoprene, 1,3-pentadiene, 1, the 1,3-pentadiene of 3-hexadiene, replacement or the 1,3-butadiene of replacement, and as 2,3-dimethyl-1,3-butadiene or 1-phenyl-1,3-butadiene.Conjugated diene monomer can use separately, also can mix use.Preferably select 1,3-butadiene or isoprene for use, because these two kinds monomeric rate of polymerization height help suitability for industrialized production.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, operable mono vinyl arenes monomer is meant the aromatic monomer that has a vinyl substituted base on its aromatic ring, as contains C
8～C
20Monovinylarene, preferred C
8-C
12Monovinylarene, its specific examples comprises vinylbenzene, C
1-C
6The vinylbenzene that alkyl replaces, as-vinyl toluene, p-methylstyrene or right-t-butyl styrene, or have substituent styrene derivatives on the vinyl, as alpha-methyl styrene.Mono vinyl arenes monomer can use separately, also can mix use.Consider from obtaining the complexity aspect, preferably use vinylbenzene and p-methylstyrene, most preferably use vinylbenzene.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, the consumption of conjugated diene monomer is a 25-95% weight based on the monomer total amount, preferred 50-90% weight; Correspondingly, the consumption of mono vinyl arenes monomer is a 5-75% weight based on the monomer total amount, preferred 10-50% weight.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, should make monomer concentration as the consumption of raffinating oil of solvent is 2～70g total monomer/100ml solvent, preferred 5-50g/ total monomer/100ml solvent, most preferably 10-25g total monomer/100ml solvent.
According to the present invention, preferred raffinating oil of using is meant that boiling range is the hydrogenated gasoline that 60～90 ℃ platformate raffinate or boiling range are 60～90 ℃.Boiling range is that 60-90 ℃ platformate raffinate is meant from platformate raffinate and extracts remaining that part of oil behind the aromatic hydrocarbons, and main component is:
Component concentration (volume %)
2-methylpropane 0.43
Normal butane 0.10
2-methylbutane 4.55
Skellysolve A 7.10
Pentamethylene 4.24
2,3-methyl cyclobutane 3.84
2-methylpentane 14.94
3-methylpentane 11.30
Normal hexane 22.53
Methylcyclopentane 8.44
Benzene 0.38
Hexanaphthene 1.28
2-methyl hexane 6.38
1,1-dimethylcyclopentane 2.5
2,3-dimethylcyclopentane 2.5
3-methyl hexane 5.55
Suitable-1,2-dimethylcyclopentane 1.14
Instead-1,3-dimethylcyclopentane 0.46
3,3-dimethylpentane 0.72
Instead-1,2-dimethylcyclopentane 0.72
Normal heptane 0.79
C
8On a small quantity
Generally can be used for polymer solvent raffinate oil or the specification of hydrogenated gasoline as follows:
Boiling range: 60～140 ℃, be preferably 60～90 ℃
Iodine number :≤0.4g/100g
Water-content: do not have
Water-soluble soda acid: neutrality
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, used composite additive is Lewis base, anion surfactant and the mixture of raffinating oil in the polymerization process.Various Lewis base compounds can be selected for use, preferably select for use ether compound or tertiary amine compound as polar additive and structure regulator, can select tetrahydrofuran (THF), tetrahydropyrans or 1,4-dioxane for use as cyclic ether compounds; Aliphatic monoether can be selected Anaesthetie Ether or dibutyl ether for use; The optional spent glycol dme of aliphatic polyether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diglyme, diethyl carbitol or diethylene glycol dibutyl ether; Aromatic oxide can be selected diphenyl ether, methyl-phenoxide or similar ether for use; Tertiary amine compound can be selected triethylamine, tripropyl amine, Tributylamine or other compound such as N, N, N ' for use, N '-Tetramethyl Ethylene Diamine, N, N-Diethyl Aniline, pyridine or quinoline etc., its consumption is 10～30% weight based on the composite additive total amount, preferred 15～25% weight; Anion surfactant is selected the Sulfonates compound of the alkyl that contains 4～20 carbon atoms for use, and as Sodium dodecylbenzene sulfonate or Potassium dodecylbenzenesulfonate, its consumption is 3～15% weight based on the composite additive total amount, preferred 5～12% weight; Raffinating oil and selecting boiling range for use is the hydrogenated gasoline that 60～90 ℃ platformate raffinate or boiling range are 60～90 ℃, and wherein boiling range is that 60-90 ℃ platformate raffinate is meant from platformate raffinate and extracts remaining that part of oil behind the aromatic hydrocarbons.In composite additive, the consumption of raffinating oil is 55～87% weight based on the composite additive total amount, preferred 65～80% weight.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, the consumption of composite additive should make that the weight ratio of itself and organic lithium initiator is 1～40, preferred 10～30.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, used organic lithium initiator is commonly used those in anionoid polymerization field in the polymerization process, the preferred organic single-lithium that uses, those shown in the formula RLi for example, wherein R is the C of straight or branched
1-C
7Alkyl, C
3-C
6Cycloalkyl or C
6-C
12Aryl as lithium ethide, propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium, naphthyl lithium etc., but is preferably selected n-Butyl Lithium or s-butyl lithium for use.The consumption of initiator depends on the size of design molecular weight in the polymerization process.General initiator amount is that every 100g monomer need add 0.3～2.5mmol.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, operable rare gas element is commonly used those in this area, as nitrogen, argon gas or helium etc.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, operable coupling agent is many vinyl compounds, halogenide, ether, aldehyde, ketone, ester etc., as Vinylstyrene, tetrem thiazolinyl silane, tetrachloromethane, silicon tetrachloride, tin tetrachloride, dimethyl terephthalate (DMT) etc.Coupling agent is Vinylstyrene, silicon tetrachloride or tin tetrachloride etc. preferably.It is 0.1～2 that the consumption of coupling agent should make the mol ratio of coupling agent and organic lithium initiator.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, operable terminator is water or alcohols, as being methyl alcohol, ethanol, Virahol etc., preferably selects Virahol for use.It is 0.1～1 that the consumption of terminator should make the mol ratio of terminator and organic lithium initiator.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, operable anti-aging agent can be normally used phenols or amine, be preferably 2,6-ditertbutylparacresol (abbreviation antioxidant 264), tert-butyl catechol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol) (abbreviation antioxidant 2246) etc.The add-on of anti-aging agent is 0.5～2% weight based on polymkeric substance generally.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, the polymeric reaction temperature in step 1) is generally 0～150 ℃, and preferred 20～110 ℃, most preferably 30～90 ℃.
In the preparation method of conjugated-diolefin/uni-vinyl-arene copolymer rubber of the present invention, the polymerization pressure in step 1) is generally 0.1～0.8MPa, preferred 0.1～0.4MPa, most preferably 0.1～0.3MPa.
According to the present invention, carry out the copolymerization of conjugated diene and monovinylarene as solvent by using specific composite additive also to use to raffinate oil as structure regulator, can be at short notice, for example in 5-30 minute, especially in 7-20 minute, finish polyreaction, so production efficiency and plant factor are all very high.In addition, it is 60% or higher copolymer rubber that the method according to this invention can obtain contents of ethylene, and coupling efficiency reaches more than 70% simultaneously, and described copolymer rubber has high wet-sliding resistant and low-rolling-resistance, is particularly suitable for making tire tread.
Embodiment
Describe the present invention in detail by embodiment and Comparative Examples below, but scope of the present invention is not limited to these embodiment.
Initiator concentration records with two volumetrys in an embodiment; The molecular weight of polymkeric substance and coupling efficiency are tested with gel permeation chromatograph (mobile phase solvent is THF for day island proper Tianjin LC-10Atvp of company series, normal temperature mensuration); Vinyl structure content infrared spectrometer in styrene content and the divinyl chain (U.S. FTS3000 of BIO-RAD company type infrared spectrometer, normal temperature is measured, the liquid pool method, solvent is CS
2, scanning times 32 times) and test; (measure by U.S. TA-DMA2980 viscoelastic spectrometer with viscoelastic spectrometer for the tan δ value of rubber unvulcanizate.Frequency 2Hz, 5 ℃/min of temperature rise rate ,-120 ℃～+ 100 ℃, batten size: 40mm*5mm*1mm) test.
Embodiment 1
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60～90 ℃ a the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 200 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Embodiment 2
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60～90 ℃ a the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 250 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 750 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Embodiment 3
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60～90 ℃ a the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 150 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 850 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Embodiment 4
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60～90 ℃ a the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 200 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 10: 70) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 40 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Embodiment 5
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60～90 ℃ a the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 200 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and raffinate oil (boiling range is 60～90 ℃ a platformate raffinate) successively; weight ratio is 20: 5: 75) 15g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.Polyreaction is in the time of 10 minutes, and transformation efficiency reaches 100%, adds silicon tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Comparative Examples 6
Test is carried out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds hexanaphthene 7000ml, vinylbenzene 200 grams, structural additives THF 18g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 3 hours, transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Comparative Examples 7
Test is carried out in 10 liters of polymeric kettles, under the high pure nitrogen protection, adds mixed solvent (hexanaphthene and normal hexane, volume ratio 9: 1) 7000ml, vinylbenzene 200 grams, structural additives THF 18g successively in still, and paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 800 grams, reacting liquid temperature reduced to 10 ℃, add n-Butyl Lithium 0.53g, carry out copolyreaction then by cooling.Reaction pressure is 0.1～0.3MPa.After the polyreaction 5 hours, transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
Comparative Examples 8
Test is carried out in 10 liters of polymeric kettles; under the high pure nitrogen protection; in still, add (boiling range is 60～90 ℃ a the platformate raffinate) 7000ml that raffinates oil, vinylbenzene 250 grams, the composite additive GSA (mixture of glycol dimethyl ether, Sodium dodecylbenzene sulfonate and hexanaphthene/normal hexane (volume ratio is 90: 1) successively; weight ratio is 20: 10: 70) 16g, paradigmatic system is through high-purity N
2After the displacement deoxidation, add divinyl 750 grams, n-Butyl Lithium 0.53g, carry out copolyreaction then.The polymerization kick off temperature is 30 ℃, and reaction pressure is 0.1～0.3MPa.After the polyreaction 1.5 hours, transformation efficiency reaches 100%, adds tin tetrachloride 0.5g again in polymeric kettle, proceeds linked reaction.Linked reaction adds terminator Virahol 0.5g and antioxidant 2246 10g after finishing once more, carries out termination reaction, after glue condenses through water vapor, obtains the solution polymerized butadiene styrene rubber product of star high-vinyl-content.The structure and the performance data that record copolymer product see Table 1.
The structure of table 1 copolymer product and performance data
| Embodiment number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Mn (ten thousand) | 12.0 | 11.9 | 12.0 | 12.1 | 11.8 | 12.3 | 12.1 | 14.2 |
| CE％ | 75 | 76 | 75 | 76 | 80 | 55 | 50 | 55 |
| St％ | 20 | 25 | 15 | 20 | 20 | 20 | 20 | 25 |
| Bv％ | 70 | 69 | 70 | 60 | 69 | 50 | 54 | 65 |
| Ct％ | 20 | 19 | 19 | 26 | 20 | 33 | 32 | 18 |
| Cc％ | 10 | 12 | 11 | 14 | 11 | 17 | 14 | 17 |
| tanδ(0℃) | 1.012 | 1.083 | 0.9665 | 0.8141 | 0.8199 | 0.4007 | 0.4431 | 0.8350 |
| Tanδ(60 ℃) | 0.1060 | 0.1035 | 0.1096 | 0.1101 | 0.0986 | 0.1114 | 0.1082 | 0.1128 |
Annotate:
Mn (ten thousand) is basic number-average molecular weight; CE% is a coupling efficiency; St% is a styrene content; Bv% is 1, the 2-structural content; Cc% is suitable-1,4 structural content; Ct% is anti--1,4 structural content; Cure conditions:
Rubber: 200g; SULPHUR POWDER: 3.4g; Stearic acid: 4g; Anti-aging agent (N-Phenyl beta naphthylamine): 2g; Carbon black: 90g; Promotor (N-cyclohexyl-2-[4-morpholinodithio base sulphenamide): 2g; Zinc oxide: 10g; Curing time: 50 minutes; Curing temperature: 145～150 ℃.
Claims (25)
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| US20150065647A1 (en) * | 2013-08-28 | 2015-03-05 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
| CN106632928B (en) * | 2015-10-28 | 2019-04-19 | 中国石油化工股份有限公司 | Star-like butadiene-styrene block copolymer and its preparation method and application |
| JP7273623B2 (en) * | 2019-06-13 | 2023-05-15 | 株式会社ブリヂストン | Rubber composition and tire |
| CN113583197B (en) * | 2020-04-30 | 2024-02-13 | 中国石油化工股份有限公司 | Low-heat-generation integrated rubber and synthetic method and application thereof |
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2005
- 2005-01-31 CN CNB2005100522286A patent/CN100390213C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367325A (en) * | 1980-04-22 | 1983-01-04 | Japan Synthetic Rubber Co., Ltd. | Styrene-butadiene random copolymer and process for the production thereof |
| CN1039036A (en) * | 1989-08-17 | 1990-01-24 | 北京燕山石油化工公司研究院 | The manufacture method of atactic butadiene styrene copolymer |
| CN1089272A (en) * | 1992-12-26 | 1994-07-13 | 中国石油化工总公司 | The method of contents of ethylene in control dienite and the multipolymer |
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