CN105732895A - Conjugated diene-vinyl aromatic hydrocarbon copolymer and rubber composition - Google Patents
Conjugated diene-vinyl aromatic hydrocarbon copolymer and rubber composition Download PDFInfo
- Publication number
- CN105732895A CN105732895A CN201510929257.XA CN201510929257A CN105732895A CN 105732895 A CN105732895 A CN 105732895A CN 201510929257 A CN201510929257 A CN 201510929257A CN 105732895 A CN105732895 A CN 105732895A
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- CN
- China
- Prior art keywords
- conjugated diene
- construction unit
- weight
- aromatic hydrocarbon
- vinyl aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 115
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 86
- 229920001971 elastomer Polymers 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 150000001993 dienes Chemical class 0.000 claims abstract description 78
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 25
- 238000010276 construction Methods 0.000 claims description 112
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 48
- 229930195733 hydrocarbon Natural products 0.000 claims description 38
- 239000004215 Carbon black (E152) Substances 0.000 claims description 37
- 150000002430 hydrocarbons Chemical class 0.000 claims description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 23
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 20
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 9
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 claims description 3
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 2
- APPOKADJQUIAHP-UHFFFAOYSA-N hexa-2,4-diene Chemical class CC=CC=CC APPOKADJQUIAHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 description 23
- 238000005299 abrasion Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000470 constituent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 239000003595 mist Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 150000005002 naphthylamines Chemical class 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
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- ODNRTOSCFYDTKF-UHFFFAOYSA-N 1,3,5-Trimethyl-cyclohexan Natural products CC1CC(C)CC(C)C1 ODNRTOSCFYDTKF-UHFFFAOYSA-N 0.000 description 1
- LQWSBXWILISUST-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane Chemical compound CC1[CH]C(C)CC(C)C1 LQWSBXWILISUST-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PCPYTNCQOSFKGG-UHFFFAOYSA-N 1-chlorobuta-1,3-diene Chemical compound ClC=CC=C PCPYTNCQOSFKGG-UHFFFAOYSA-N 0.000 description 1
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- JIQZSDHJQKWGGN-UHFFFAOYSA-N C(CCC)C1=CC=CC2=C1N=C(S2)SN.S2C(=NC1=C2C=CC=C1)SNCCCC Chemical compound C(CCC)C1=CC=CC2=C1N=C(S2)SN.S2C(=NC1=C2C=CC=C1)SNCCCC JIQZSDHJQKWGGN-UHFFFAOYSA-N 0.000 description 1
- OMBCWOUMFUPNDK-UHFFFAOYSA-N C1(CCCCC1)C1=CC=CC2=C1N=C(S2)SN.C2(CCCCC2)C2=CC=CC1=C2N=C(S1)SN Chemical compound C1(CCCCC1)C1=CC=CC2=C1N=C(S2)SN.C2(CCCCC2)C2=CC=CC1=C2N=C(S1)SN OMBCWOUMFUPNDK-UHFFFAOYSA-N 0.000 description 1
- WLMKWWZFXJSVRO-UHFFFAOYSA-N C1(CCCCC1)C=1C=CC2=C(N=C(S2)SN)C1C1CCCCC1.C1(CCCCC1)C=1C=CC2=C(N=C(S2)SN)C1C1CCCCC1 Chemical compound C1(CCCCC1)C=1C=CC2=C(N=C(S2)SN)C1C1CCCCC1.C1(CCCCC1)C=1C=CC2=C(N=C(S2)SN)C1C1CCCCC1 WLMKWWZFXJSVRO-UHFFFAOYSA-N 0.000 description 1
- FSPIGXNLDXWYKZ-UHFFFAOYSA-N CCO[Si](CCC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CCC[Si](OCC)(OCC)OCC)(OCC)OCC Chemical compound CCO[Si](CCC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CCC[Si](OCC)(OCC)OCC)(OCC)OCC FSPIGXNLDXWYKZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YKYMGFHOJJOSEB-UHFFFAOYSA-N butan-1-ol;potassium Chemical compound [K].CCCCO YKYMGFHOJJOSEB-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
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- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- FUGIIBWTNARRSF-UHFFFAOYSA-N decane-5,6-diol Chemical compound CCCCC(O)C(O)CCCC FUGIIBWTNARRSF-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- GJGSXVBJZVLVSE-UHFFFAOYSA-N pentan-1-ol;potassium Chemical compound [K].CCCCCO GJGSXVBJZVLVSE-UHFFFAOYSA-N 0.000 description 1
- NSHQEUFMYDDCJR-UHFFFAOYSA-N pentan-1-ol;sodium Chemical compound [Na].CCCCCO NSHQEUFMYDDCJR-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a conjugated diene-vinyl aromatic hydrocarbon copolymer and a rubber composition, which comprises a conjugated diene structural unit and a vinyl aromatic hydrocarbon structural unit, wherein the conjugated diene structural unit accounts for 40-54 wt%, and the vinyl aromatic hydrocarbon structural unit accounts for 46-60 wt%. The content of the block composed of four linked or more than four linked vinyl aromatic hydrocarbon structural units is 12 to 15.7% of the total amount of the vinyl aromatic hydrocarbon structural units in the conjugated diene-vinyl aromatic hydrocarbon copolymer. The weight average molecular weight of the conjugated diene-vinyl aromatic hydrocarbon copolymer is 15-18.5 ten thousand, the conjugated diene-vinyl aromatic hydrocarbon copolymer can be applied to the preparation of rubber compositions, the rubber compositions have good wear resistance and transparency, and the conjugated diene-vinyl aromatic hydrocarbon copolymer can also be applied to the sole rubber of sports shoes.
Description
Technical field
The invention relates to a kind of olefin polymer, and in particular to a kind of conjugated diene-vinyl aromatic hydrocarbon copolymer and rubber composition.
Background technology
In recent years, science and technology progress rapidly, material and culture, quality of the life constantly promote, and CRUX is movable luxuriant for agitation.Therefore, along with CRUX agitation is more universal, for the performance requirement also rapid increase of various sport shoes.
It is said that in general, the primer of sport shoes is based on rubber.For the transparency of primer and the abrasion performance of lifter motion footwear, in the primer raw material of sport shoes, generally add the packing material of the classes such as Silicon stone (Silica).But, the affinity between Silicon stone and rubber is not good, and therefore Silicon stone is not easy to be dispersed in rubber, and has the not good problem of abrasion resistance and the transparency.
Summary of the invention
In view of this, the present invention provides a kind of conjugated diene-vinyl aromatic hydrocarbon copolymer and rubber composition, and it can be applicable to prepare rubber composition, and the abrasion resistance of this rubber composition and excellent transparency, also can be used in the primer of sport shoes.
The present invention provides a kind of conjugated diene-vinyl aromatic hydrocarbon copolymer, it includes conjugated diene construction unit and vinylaromatic hydrocarbon construction unit, wherein conjugated diene construction unit is 40 weight %～54 weight %, and vinylaromatic hydrocarbon construction unit is 46 weight %～60 weight %.Be connected by four or total amount that the content of block that the vinylaromatic hydrocarbon construction unit connected more than four forms is vinylaromatic hydrocarbon construction unit in conjugated diene-vinyl aromatic hydrocarbon copolymer 12%～15.7%.The weight average molecular weight of conjugated diene-vinyl aromatic hydrocarbon copolymer is 15 ten thousand to 18.5 ten thousand.
In one embodiment of the invention, the Buddhist nun's viscosity that rubs of above-mentioned conjugated diene-vinyl aromatic hydrocarbon copolymer is 30MU～45MU.
In one embodiment of this invention, above-mentioned conjugated diene construction unit includes the construction unit containing the carbon-carbon double bond group shown in formula (1).The content of the construction unit containing the carbon-carbon double bond group shown in formula (1) is in conjugated diene-vinyl aromatic hydrocarbon copolymer the 27%～34% of the total amount of conjugated diene construction unit.
In formula (1), R1For hydrogen atom, methyl, ethyl, phenyl or chlorine atom；R2And R3Each stand alone as hydrogen atom or methyl.
In one embodiment of this invention, the glass transition temperature of above-mentioned conjugated diene-vinyl aromatic hydrocarbon copolymer is-25 DEG C～-12 DEG C.
In one embodiment of this invention, conjugated diene construction unit is 42 weight %～50 weight %, and vinylaromatic hydrocarbon construction unit is 50 weight %～58 weight %.
In one embodiment of this invention, above-mentioned conjugated diene construction unit is using butadiene structural units as the first construction unit, and vinylaromatic hydrocarbon construction unit is using styrol structural unit as the second construction unit.Conjugated diene-vinyl aromatic hydrocarbon copolymer also includes the 3rd construction unit, and wherein the 3rd construction unit is selected from the conjugated diene construction unit except butadiene structural units and styrol structural unit and vinylaromatic hydrocarbon construction unit.3rd construction unit is more than 0 weight % and less than or equal to 8 weight %.
In one embodiment of this invention, above-mentioned conjugated diene construction unit is from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, chlorbutadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 4-methyl isophthalic acid, 3-pentadiene, 2,4-hexadienes or combinations of the above.Vinylaromatic hydrocarbon construction unit is from styrene, α-methyl styrene, 4-tributyl styrene or combinations of the above.
The present invention separately provides a kind of rubber composition, it includes above-mentioned conjugated diene-vinyl aromatic hydrocarbon copolymer and conjugated diene polymer, wherein with the total amount of conjugated diene-vinyl aromatic hydrocarbon copolymer and conjugated diene polymer for 100 parts by weight, conjugated diene-vinyl aromatic hydrocarbon copolymer is 20 weight portion～40 weight portions, and conjugated diene polymer is 60 weight portion～80 weight portions.Conjugated diene polymer includes the butadiene structural units of 95 weight %～100 weight % and the 4th construction unit of 0 weight %～5 weight %.4th construction unit is selected from the conjugated diene construction unit except this butadiene structural units.
In one embodiment of this invention, above-mentioned rubber composition also includes inorganic filler, and wherein with the total amount of conjugated diene-vinyl aromatic hydrocarbon copolymer and conjugated diene polymer for 100 parts by weight, inorganic filler is 15 weight portion～45 weight portions.
In one embodiment of this invention, above-mentioned rubber composition visible ray penetrance under 3mm thickness is more than 76%.
Based on above-mentioned, the present invention proposes a kind of content by controlling the block that conjugated diene construction unit forms with the content of vinylaromatic hydrocarbon construction unit, vinylaromatic hydrocarbon construction unit and weight average molecular weight prepares conjugated diene-vinyl aromatic hydrocarbon copolymer.This conjugated diene-vinyl aromatic hydrocarbon copolymer can be applicable to prepare rubber composition, and the abrasion resistance of this rubber composition and excellent transparency, also can be used in the primer of sport shoes.
For the features described above of the present invention and advantage can be become apparent, special embodiment below is described in detail below.
Detailed description of the invention
<conjugated diene-vinyl aromatic hydrocarbon copolymer>
Conjugated diene-vinyl aromatic hydrocarbon copolymer is to be formed by conjugate diene monomer and vinyl aromatic hydrocarbon monomer combined polymerization, and therefore conjugated diene-vinyl aromatic hydrocarbon copolymer includes conjugated diene construction unit and vinylaromatic hydrocarbon construction unit.
Conjugated diene construction unit includes the construction unit (hereinafter referred to as " construction unit containing carbon-carbon double bond ") containing the carbon-carbon double bond group shown in formula (1).
In formula (1), R1For hydrogen atom, methyl, ethyl, phenyl or chlorine atom；R2And R3Each stand alone as hydrogen atom or methyl.
The content of the construction unit containing carbon-carbon double bond is in conjugated diene-vinyl aromatic hydrocarbon copolymer the 27%～34% of the total amount of conjugated diene construction unit.When the content of the construction unit containing carbon-carbon double bond is more than 27%, it is possible to the glass transition temperature of raising conjugated diene-vinyl aromatic hydrocarbon copolymer and the abrasion resistance of prepared rubber composition are good.
Conjugated diene construction unit is from conjugate diene monomer such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentylene, 4-methyl isophthalic acid, 3-pentadiene, 2,4-hexadiene or combinations of the above.
Conjugated diene construction unit is 40 weight %～54 weight %, it is advantageous to be 42 weight %～50 weight %.
Vinylaromatic hydrocarbon construction unit is from vinyl aromatic hydrocarbon monomer such as styrene, α-methyl styrene, 4-tributyl styrene or combinations of the above.
Vinylaromatic hydrocarbon construction unit is 46 weight %～60 weight %, it is advantageous to be 50 weight %～58 weight %.When the content of vinylaromatic hydrocarbon construction unit is more than 46 weight %, it is possible to effectively reduce the molding shrinkage of conjugated diene-vinyl aromatic hydrocarbon copolymer.
Be connected by four or total amount that the content of block that the vinylaromatic hydrocarbon construction unit connected more than four forms is vinylaromatic hydrocarbon construction unit in conjugated diene-vinyl aromatic hydrocarbon copolymer 12%～15.7%, it is advantageous to be 12.4%～15.7%.When the content of block is less than 12%, prepared rubber composition will be unable to provide enough abrasion resistances, and cannot use stripping (Stripping) in the purification of conjugated diene-vinyl aromatic hydrocarbon copolymer, and its stripping operation is not good.When the content of block is more than 15.7%, the Buddhist nun's viscosity that rubs of conjugated diene-vinyl aromatic hydrocarbon copolymer is too high and affects dispersibility when rubber kneading and operability is not good.
Additionally, when conjugated diene construction unit is using butadiene structural units as the first construction unit, when vinylaromatic hydrocarbon construction unit is using styrol structural unit as the second construction unit, conjugated diene-vinyl aromatic hydrocarbon copolymer can also include the 3rd construction unit.3rd construction unit is selected from the conjugated diene construction unit except butadiene structural units and styrol structural unit and at least one in vinylaromatic hydrocarbon construction unit.3rd construction unit is more than 0 weight % and less than or equal to 8 weight %.
The weight average molecular weight of conjugated diene-vinyl aromatic hydrocarbon copolymer can be 15 ten thousand to 18.5 ten thousand, it is advantageous to is 15 ten thousand to 16.5 ten thousand, is more preferred from 15.3 ten thousand to 16.3 ten thousand.
The Buddhist nun's viscosity that rubs of conjugated diene-vinyl aromatic hydrocarbon copolymer is 30MU～45MU, it is advantageous to for 36MU～45MU.Rub Buddhist nun's viscosity lower than 30MU time, conjugated diene-vinyl aromatic hydrocarbon copolymer can become sol shape when air stripping and cannot become blob of viscose and separate with solvent, and will be unable to dry, again through common, the moisture content being also had in blob of viscose when processing procedure removes air stripping, therefore stripping operation is not good.When the Buddhist nun's viscosity that rubs is higher than 45MU, mist degree can be deteriorated.
The glass transition temperature of conjugated diene-vinyl aromatic hydrocarbon copolymer is-25 DEG C～-12 DEG C, it is advantageous to for-20 DEG C～-5 DEG C.
<synthetic method of conjugated diene-vinyl aromatic hydrocarbon copolymer>
Any existing method making conjugate diene monomer and vinyl aromatic hydrocarbon monomer generation polyreaction can carry out synthesis of conjugate diene-vinyl aromatic hydrocarbon copolymer.For example, it is possible to make conjugate diene monomer be polymerized formation conjugated diene-vinyl aromatic hydrocarbon copolymer with vinyl aromatic hydrocarbon monomer under the existence of initiator.The concrete example of conjugate diene monomer and vinyl aromatic hydrocarbon monomer is not as it was noted above, repeat separately at this.
Conjugate diene monomer, because the relation of polyreaction, can carry out the Isosorbide-5-Nitrae structure that Isosorbide-5-Nitrae is polymerized, it is possible to carrying out 1,21,2 structure being polymerized, Isosorbide-5-Nitrae structure and 1,2 structure can coexist in a part chain.Wherein, Isosorbide-5-Nitrae structure can be further separated into cis and trans two kinds；And 1,2 structures are the carbon-carbon double bond structures at side chain.If that is, carry out 1,2 polymerization, then the aforementioned construction unit containing carbon-carbon double bond can be formed.
Initiator can be organic alkali metal compound, for instance ethyl-lithium, n-pro-pyl lithium, isopropyl lithium, n-BuLi, n-pentyl lithium, phenyl lithium, tolyl lithium or combinations of the above.
The polyreaction of conjugate diene monomer and vinyl aromatic hydrocarbon monomer can carry out in the presence of the solvent.For example, solvent can include the non-polar solven of saturated hydrocarbons, aromatic hydrocarbon etc. or combinations of the above, for instance the aliphatic hydrocarbons such as pentane, hexane, heptane；The clicyclic hydrocarbons such as Pentamethylene., hexamethylene, methyl cyclopentane, hexahydrotoluene；Aromatic hydrocarbons such as benzene,toluene,xylene and comprise the hydrocarbon of such mixture, are so not limited to this.
The polyreaction of conjugate diene monomer and vinyl aromatic hydrocarbon monomer also can carry out under the existence of micro structure regulator.Use micro structure regulator can make conjugate diene monomer and vinyl aromatic hydrocarbon monomer random copolymerization.Micro structure regulator can be polar compound and as ethylene agent (vinylatingagent).
Micro structure regulator can include the ethers such as oxolane, diethyl ether, dioxanes, glycol dimethyl ether, butyl cellosolve, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, dimethoxy benzene, double; two (2-tetrahydrofuran base) propane of 2,2-；The tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinine pyridine (quinuclidine)；The alkali metal alkanolates compounds such as the 3rd amylalcohol potassium, the 3rd butanol potassium, the 3rd sodium butoxide, the 3rd amylalcohol sodium；The phosphine compounds such as triphenylphosphine；Alkyl or aryl sulfoacid compounds etc., are so not limited to this.Above-mentioned polar compound can be used alone or combine multiple use.
The consumption that makes of micro structure regulator can select according to purpose and effect.Generally, micro structure regulator is essentially 0.01～100 mole relative to initiator 1 mole.According to the desired construction unit quantity containing carbon-carbon double bond, and this kind of polar compound (ethylene agent) can be used in right amount to be used as the micro structure regulator of polymer diene portions.
In an embodiment, conjugated diene-vinyl aromatic the hydrocarbon copolymer prepared can add the poor solvent of this copolymer, alcohols (such as methanol, ethanol or isopropanol) etc. is such as used to make polymer precipitate out, or with the hot water higher than solvent temperature or with water vapour removal solvent, and isolate this copolymer.The present invention can also allow the dispersion of the conjugated diene of upgrading-between vinyl aromatic hydrocarbon copolymer and inorganic filler be more uniformly distributed by the use of modification agent, and then increase transparency and reduce mist degree.Wherein the method for used modification agent or upgrading is such as but not limited to TaiWan, China patent the I453224th, No. I413648, No. I428357, No. I432466, the content of I462939 and No. 201422643.
<rubber composition>
The present invention separately provides a kind of rubber composition.Rubber composition visible ray penetrance under 3mm thickness is more than 76%.
Rubber composition is to be obtained by conjugated diene-vinyl aromatic hydrocarbon copolymer and conjugated diene polymer kneading, and can add inorganic filler and other additives if desired.
With the total amount of conjugated diene-vinyl aromatic hydrocarbon copolymer and conjugated diene polymer for 100 parts by weight, conjugated diene-vinyl aromatic hydrocarbon copolymer is 20 weight portion～40 weight portions, it is advantageous to be 25 weight portion～35 weight portions.
The concrete example of conjugated diene construction unit is identical with the concrete example of the conjugated diene construction unit in aforementioned conjugated diene-vinyl aromatic hydrocarbon copolymer, does not repeat separately at this.
Conjugated diene polymer is preferably butadiene structural units.When conjugated diene polymer includes butadiene structural units, conjugated diene polymer may also include the 4th construction unit.4th construction unit is selected from the conjugated diene construction unit except this butadiene structural units.With conjugated diene polymer for 100 weight %, butadiene structural units is 95 weight %～100 weight %, it is advantageous to be 97 weight %～100 weight %.With conjugated diene polymer for 100 weight %, the 4th construction unit is 0 weight %～5 weight %, it is advantageous to be 0 weight %～3 weight %.
With the total amount of conjugated diene-vinyl aromatic hydrocarbon copolymer and conjugated diene polymer for 100 parts by weight, conjugated diene polymer is 60 weight portion～80 weight portions, it is advantageous to be 75 weight portion～65 weight portions.
It addition, rubber composition can also include inorganic filler.Inorganic filler includes silica solids or by the silica inorganic filler of surfaction, silicates, metal hydroxides, metal-oxide, metal carbonate, metal sulfate, metal powder, carbon black or above-mentioned combination.Inorganic filler is preferably the smoked silicon (fumedsilica) in silica solids, and its particle diameter is 0.01 μm～150 μm, and average dispersed particle diameter is preferably 0.05 μm～1 μm, and the best is 0.05 μm～0.5 μm.
With the total amount of conjugated diene-vinyl aromatic hydrocarbon copolymer and conjugated diene polymer for 100 parts by weight, inorganic filler is 15 weight portion～45 weight portions.
Additive in rubber composition is such as antioxidant, coupling agent, vulcanization reaction activator (vulcanization aid/zinc oxide, stearic acid), vulcanization accelerator, vulcanizing agent, age resistor, operation wet goods.
Antioxidant can be the phenol based compound having at least a hindered phenol (hinderedphenol) functional group, for instance: the Ix-1076 that CIBA manufactures.Or Sanya di(2-ethylhexyl)phosphate alkylbenzene ester type (dialkylphenyltriphosphite) antioxidant；Amination antioxidant selected from naphthylamines (naphthylamines), diphenylamines (diphenylamines) and p-phenylenediamine (p-phenylenediamines)；Phenol antioxidant selected from trialkyl phenol (trialkylphenols), hydroquinone (hydroquinones) and polyphenol.With rubber composition for 100 parts by weight, antioxidant consumption can be 0.2 to 1 weight portion.
nullCoupling agent is such as double; two-3-(triethoxysilylpropyltetrasulfide) tetrasulfides (bis-(3-triethoxysilylpropyl) tetrasulfide)、Double; two-3-(triethoxysilylpropyltetrasulfide) disulphide (bis-(3-triethoxysilylpropyl) di-sulfide)、Double; two-2-(triethoxysilylethyl) tetrasulfide (bis-(2-triethoxysilylethyl) tetrasulfide)、3-Mercaptopropyltriethoxysilane (3-mercaptopropyltriethoxysilane)、3-triethoxysilylpropyltetrasulfide-N,N-dimethyl thio amido formacyl tetrasulfide (3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide)、3-triethoxysilylpropyltetrasulfide benzothiazole tetrasulfide (3-triethoxysilylpropylbenzothiazoletetrasulfide) etc..With rubber composition for 100 parts by weight, coupling agent consumption can be 1 to 15 weight portion, is preferred with 5 to 10 weight portions.
Vulcanization reaction activator is such as zinc oxide, stearic acid etc..
Vulcanization accelerator can be mercaptobenzothiazoler (mercapto-benzthiazoles), sulfenamide (sulfenamides), guanidine (guanidines), dithiocarbamate ester (dithiocarbamates), thiourea (thioureas) and sulfocarbonate (thiocarbonates).Vulcanization accelerator is preferably use sulfenamide vulcanization accelerator (sulfenamideaccelerators), such as: cyclohexylbenzothiazole sulfenamide (cyclohexylbenzothiazole-sulfenamide) and/or dicyclohexylbenzothiazole sulfenamide (dicyclohexylbenzothiazole-sulfenamide) and/or butyl benzo thiazolesulfenamide (butylbenzo-thiazolesulfenamide).Vulcanization accelerator is more preferred from n-cyclohexyl-2-[4-morpholinodithio sulfenamide (n-cyclohexyl-2-benzothiazolesulphen-amide, CBS) and diphenylguanidine (DiphenylGuanidine, DPG).
Vulcanizing agent such as sulfur or organic sulfur supplier.With rubber composition for 100 parts by weight, above vulcanization reaction accelerator and sulfur consumption can be 0.1 to 15 weight portion, are preferred with 0.5 to 5 weight portion.
Age resistor is such as 6PPD, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine).With rubber composition for 100 parts by weight, aging inhibitor dosage can be 1 to 10 weight portion.
The present invention will be described further with regard to following example, however, it should be noted that such embodiment is only and illustrates, and be not necessarily to be construed as restriction of the invention process.
[synthesis example of conjugated diene-vinyl aromatic hydrocarbon copolymer]
Synthesis example 1
First, the hexamethylene of 800 grams are added in reactive tank and is used as solvent, and maintain constant temperature 45 DEG C.Then, 2,2-double; two (2-tetrahydrofuran base) propane (2,2-ditetrahydrofurylpropane, DTHFP) taking 0.105 gram add in reactive tank as micro structure regulator.Then, the n-BuLi (n-butyllithium) taking 0.287 gram adds the initiator reacted in reactive tank as polymer polymerizing.It is substantially about 2:1 relative to the mole ratio of initiator in this micro structure regulator.Then, take the styrene of 193.2 grams (1.86 moles) as vinyl aromatic hydrocarbon monomer and 168.3 grams of (3.11 moles) 1,3-butadiene carries out polyreaction as in conjugate diene monomer addition reactive tank, after continuous pan feeding carries out polyreaction in 35 minutes, after now solvent is removed in sampling, copolymer A-1 can be obtained.Utilizing NMR to measure the content of the construction unit containing carbon-carbon double bond in copolymer A-1 in copolymer A-1 the 46.3% of the total amount of conjugated diene construction unit, vinylaromatic hydrocarbon construction unit is 53.7 weight %.Finally, use steam to carry out air stripping and remove solvent and terminate reaction, obtain conjugated diene-vinyl aromatic hydrocarbon copolymer after drying.The evaluation method of copolymer A-1 and evaluation result are as be described hereinafter.
Synthesis example 2 to synthesis example 5
Synthesis example 2 to synthesis example 5 is to prepare copolymer A-2 respectively to copolymer A-5 with the step identical with synthesis example 1, and it is same using styrene as vinyl aromatic hydrocarbon monomer, with 1,3-butadiene as conjugate diene monomer, using n-BuLi as initiator, with cyclohexane give be solvent, with 2, double; two (2-tetrahydrofuran base) propane of 2-is as micro structure regulator, but different place is in that: change initiator make consumption, micro structure regulator make consumption (as shown in table 1).It addition, utilize the content (as shown in table 2) that the NMR content measuring in copolymer the construction unit containing carbon-carbon double bond is the ratio of the total amount of conjugated diene construction unit in copolymer and vinylaromatic hydrocarbon construction unit.Copolymer A-2 is to the evaluation method of copolymer A-5 and evaluation result as be described hereinafter.
Relatively synthesis example 1 is to comparing synthesis example 8
Relatively synthesis example 1 is prepare copolymer B-1 to copolymer B-8 respectively with the step identical with synthesis example 1 to comparing synthesis example 8, and it is same using styrene as vinyl aromatic hydrocarbon monomer, with 1, 3-butadiene is as conjugate diene monomer, using n-BuLi as initiator, with cyclohexane give for solvent, with 2, double, two (2-tetrahydrofuran base) propane of 2-is as micro structure regulator, but different places are in that: what change initiator makes consumption, the kind of modification agent and make consumption, micro structure regulator make consumption (as shown in table 1), after continuous pan feeding carries out polyreaction in 35 minutes, add little molecular pattern 3-glycidoxypropyltrimewasxysilane (KBM-403, manufactured by chemical industrial company of SHIN-ETSU HANTOTAI, as modification agent).It addition, utilize the content (as shown in table 2) that the NMR content measuring in copolymer the construction unit containing carbon-carbon double bond is the ratio of the total amount of conjugated diene construction unit in copolymer and vinylaromatic hydrocarbon construction unit.The evaluation method of copolymer B-1 to copolymer B-8 and evaluation result are as be described hereinafter.
In table 1 and table 2, it is called for short corresponding meaning as follows:
[embodiment of rubber thing constituent]
Embodiment 1
First, take high-cis butadiene (the model KIBOPOLPR-040S of the copolymer A-1 of 30 weight portions, 70 weight portions, by strange U.S. industry manufacture) and following material carry out kneading in Li Nashi (kneader) mixer, with prepared rubber composition.Copolymer A-1 and high-cis butadiene add the smoked silicon (AEROSIL200 of 50 weight portions, manufactured by EVONIK company), the Polyethylene Glycol (polyethyleneglycol of 4 weight portions, PEG, produced by Tao Shi), IX-1520 (the model IX-1520 of 0.1 weight portion, manufactured by CIBA company) and IX-1076 (the model IX-1076 of 0.1 weight portion, manufactured by CIBA company) mixing, dnockout discharging after 10 minutes, aging 24 hours of room temperature.Mixed glue after discharging adds the 1 of 0.5 weight portion in rolling (roll) formula mixer, double; two tributyl peroxidating-3 of 1-, 3,5-trimethyl-cyclohexane (model Lupersol231, manufactured by gloomy Dihua, Shanghai work) vulcanize, with the rubber thing constituent of prepared embodiment 1.The evaluation method of the rubber thing constituent of embodiment 1 and evaluation result are as be described hereinafter.
Embodiment 2-5 and comparative example 1-8
The rubber thing constituent of embodiment 2-5 and comparative example 1-8 is to prepare with the step identical with embodiment 1.But, different part is in that: change the kind (as shown in table 3) of rubber thing constituent.The result being evaluated by obtained rubber thing constituent is as shown in table 3.The evaluation method of the rubber thing constituent of embodiment 2-5 and comparative example 1-8 and evaluation result are as be described hereinafter.
[evaluation method]
It is used for evaluating copolymer A-1 as follows to copolymer A-5, copolymer B-1 to the method for the rubber thing constituent of copolymer B-8, embodiment 2-5 and comparative example 1-8:
A, the percentage ratio (C=C%) of construction unit containing carbon-carbon double bond, block ethylene base aromatic hydrocarbon construction unit percentage ratio (block SM)
The data that nuclear magnetic resonance analyser (BRUKER-NMR400MHz) will be utilized to record, measure the copolymer A-1 percentage ratio to copolymer A-5 and the percentage when block ethylene base aromatic hydrocarbon construction unit of the construction unit containing carbon-carbon double bond of copolymer B-1 to copolymer B-8.
B, rub Buddhist nun's viscosity
According to ASTMD-1646, with the machine of AlphaTechnology company model MV-2000 measurement copolymer A-1 to copolymer A-5 and copolymer B-1 to copolymer B-8.Measuring temperature condition is 100 DEG C, and the measurement time is 1+4 minute (preheat 1 minute, test 4 minutes).The numerical value of Buddhist nun's viscosity of rubbing is more low, represents that finished product viscosity is more low, more easily processes.
C, glass transition temperature (Tg, DEG C)
Differential Scanning Calorimeter instrument (DSC2910, TAInstrumentsInc.) is used to measure the copolymer A-1 glass transition temperature to copolymer A-5 and copolymer B-1 to copolymer B-8.
D, weight average molecular weight, number mean molecule quantity and molecular weight dispersity
Weight average molecular weight (Mw) and number mean molecule quantity (Mn) are to utilize the calibration curve that known available standard styrene is made to try to achieve, gel permeation chromatograph (GPC, water generation (Waters) company manufactures) to have the detection of differential tortuosity ratio and two functions of scattering measuring measures.Molecular weight dispersity (polydispersityindex is called for short PDI) obtains divided by number mean molecule quantity (Mw/Mn) for weight average molecular weight.
E, visible ray penetrance (T, %)
According to ASTMD-1003 testing standard, test by the test piece that the 3mm obtained by the rubber thing constituent of embodiment 1-5 and comparative example 1-8 is thick.
F, mist degree
Ibid, according to ASTMD-1003 testing standard, the rubber thing constituent of embodiment 1-5 and comparative example 1-8 being measured through the test piece that the 3mm obtained by ejection formation is thick, wherein the more high expression transparency of haze value is more poor.
G, abrasion
According to DIN53516, measuring the test piece prepared by the rubber thing constituent of embodiment 1-5 and comparative example 1-8 with abrasion performance testing machine GT-7012-D, wherein test piece is sized to 29cm (diameter) × 12.5mm (thickness).Abrasion values unit is gram.
[evaluation result]
Refer to table 2 and table 3, vinylaromatic hydrocarbon structural unit content be 46 weight %～60 weight %, block ethylene base aromatic hydrocarbon construction unit percentage ratio be 12%～15.7%, and when weight average molecular weight is with 150,000～18.5 ten thousand time (copolymer A-1 to copolymer A-5), prepared rubber thing constituent (embodiment 1-5) can not only obtain high visible ray penetrance, abrasion resistance and processability have certain balance concurrently, and mist degree is also at tolerance interval.In conjugated diene-vinyl aromatic hydrocarbon copolymer, vinylaromatic hydrocarbon structural unit content be 46 weight %～60 weight %, block ethylene base aromatic hydrocarbon construction unit percentage ratio be 12%～15.7%, weight average molecular weight with 150,000～18.5 ten thousand time, the Buddhist nun's viscosity that rubs of conjugated diene-vinyl aromatic hydrocarbon copolymer is that 30MU～45MU is preferred.Being speculated by result, the percentage ratio of higher block ethylene base aromatic hydrocarbon construction unit can reduce abrasion performance；Higher glass transition temperature represents the random number degree of alignment higher (more chaotic) of butadiene structural units and styrol structural unit, thereby can improve wear intensity；But the structural unit content (i.e. contents of ethylene) of the carbon-carbon double bond group of higher proportion also can improve glass transition temperature simultaneously, and then improve and rub Buddhist nun's viscosity and affect follow-up processability.The consumption increasing irregular agent can improve the percentage ratio of the butadiene structural units random scheduling degree with styrol structural unit and the construction unit containing carbon-carbon double bond simultaneously, thus while increase random scheduling degree can improve wearability, but the percentage ratio (i.e. contents of ethylene) of the construction unit containing carbon-carbon double bond is too high or too low that mist degree all can be made to be deteriorated.Embodiment 1-5 promoting penetration, maintain the balance of the physical property such as mist degree and abrasion performance preferably.In comparison, copolymer B-4 is higher with the percentage ratio higher (contents of ethylene) of the construction unit containing carbon-carbon double bond of the rubber thing constituent (comparative example 4, comparative example 5) prepared by copolymer B-5 and glass transition temperature, therefore prepared rubber thing constituent (comparative example 4, comparative example 5) obtains higher abrasion performance, but because the too high transparency causing that relatively low penetration and higher mist degree make comparative example 5 of its Buddhist nun's viscosity that rubs is not good.Copolymer B-1 to the rubber thing constituent (comparative example 1-8) prepared by copolymer B-8 although having part to obtain higher penetrance but causing that because mist degree is too high overall transparency is not good.In addition, copolymer (such as embodiment 1-5) as not modified in this case is by controlling molecular configuration, content such as the block that conjugated diene construction unit is 40 weight %～54 weight % with the content of vinylaromatic hydrocarbon construction unit is 46 weight %～60 weight %, vinylaromatic hydrocarbon construction unit composition be 12%～15.7% and weight average molecular weight be 15 ten thousand to 18.5 ten thousand etc., it might even be possible to obtain the balance than physical property such as the copolymer (such as comparative example 1-3,7-8) processed through modification agent penetration more preferably, mist degree and abrasion performances.It follows that the rubber composition prepared by the conjugated diene of the present invention-vinyl aromatic hydrocarbon copolymer has abrasion resistance and the transparency concurrently, the primer of sport shoes also can be used in.
In sum, the present invention propose a kind of by control the content of the block that conjugated diene construction unit is 40 weight %～54 weight % with the content of vinylaromatic hydrocarbon construction unit is 46 weight %～60 weight %, vinylaromatic hydrocarbon construction unit composition be 12%～15.7% and weight average molecular weight be 15 ten thousand to 18.5 ten thousand prepare conjugated diene-vinyl aromatic hydrocarbon copolymer.This conjugated diene-vinyl aromatic hydrocarbon copolymer can be applicable to prepare rubber composition, and the abrasion resistance of this rubber composition and excellent transparency, also can be used in the primer of sport shoes.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit；Although the present invention being described in detail with reference to foregoing embodiments, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or wherein some or all of technical characteristic is carried out equivalent replacement；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. conjugated diene-vinyl aromatic hydrocarbon copolymer, it is characterised in that including:
Conjugated diene construction unit and vinylaromatic hydrocarbon construction unit；
Wherein said conjugated diene construction unit is 40 weight %～54 weight %, and described vinylaromatic hydrocarbon construction unit is 46 weight %～60 weight %；
Be connected by four or total amount that the content of block that the described vinylaromatic hydrocarbon construction unit connected more than four forms is described vinylaromatic hydrocarbon construction unit in described conjugated diene-vinyl aromatic hydrocarbon copolymer 12%～15.7%；
The weight average molecular weight of described conjugated diene-vinyl aromatic hydrocarbon copolymer is 15 ten thousand to 18.5 ten thousand.
2. conjugated diene according to claim 1-vinyl aromatic hydrocarbon copolymer, it is characterised in that the Buddhist nun's viscosity that rubs of described conjugated diene-vinyl aromatic hydrocarbon copolymer is 30MU～45MU.
3. conjugated diene according to claim 1-vinyl aromatic hydrocarbon copolymer, it is characterised in that described conjugated diene construction unit includes the construction unit containing the carbon-carbon double bond group shown in formula (1),
In formula (1), R1For hydrogen atom, methyl, ethyl, phenyl or chlorine atom；R2And R3Each stand alone as hydrogen atom or methyl,
The content of the described construction unit containing the carbon-carbon double bond group shown in formula (1) is described in described conjugated diene-vinyl aromatic hydrocarbon copolymer the 27%～34% of the total amount of conjugated diene construction unit.
4. conjugated diene according to claim 1-vinyl aromatic hydrocarbon copolymer, it is characterised in that the glass transition temperature of described conjugated diene-vinyl aromatic hydrocarbon copolymer is-25 DEG C～-12 DEG C.
5. conjugated diene according to claim 1-vinyl aromatic hydrocarbon copolymer, it is characterised in that described conjugated diene construction unit is 42 weight %～50 weight %, described vinylaromatic hydrocarbon construction unit is 50 weight %～58 weight %.
6. conjugated diene according to claim 1-vinyl aromatic hydrocarbon copolymer, it is characterized in that, described conjugated diene construction unit is using butadiene structural units as the first construction unit, described vinylaromatic hydrocarbon construction unit is using styrol structural unit as the second construction unit, described conjugated diene-vinyl aromatic hydrocarbon copolymer also includes the 3rd construction unit, described 3rd construction unit is selected from the described conjugated diene construction unit except described butadiene structural units and described styrol structural unit and described vinylaromatic hydrocarbon construction unit
Described 3rd construction unit is more than 0 weight % and less than or equal to 8 weight %.
7. conjugated diene according to claim 1-vinyl aromatic hydrocarbon copolymer, it is characterized in that, described conjugated diene construction unit is from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 4-methyl isophthalic acid, 3-pentadiene, 2,4-hexadienes or combinations of the above, described vinylaromatic hydrocarbon construction unit is from styrene, α-methyl styrene, 4-tributyl styrene or combinations of the above.
8. a rubber composition, it is characterised in that including:
Conjugated diene according to any one of claim 1 to 7-vinyl aromatic hydrocarbon copolymer；And
Conjugated diene polymer；
Wherein with the total amount of described conjugated diene-vinyl aromatic hydrocarbon copolymer and described conjugated diene polymer for 100 parts by weight, described conjugated diene-vinyl aromatic hydrocarbon copolymer is 20 weight portion～40 weight portions, and described conjugated diene polymer is 60 weight portion～80 weight portions；
Described conjugated diene polymer includes the butadiene structural units of 95 weight %～100 weight % and the 4th construction unit of 0 weight %～5 weight %, and described 4th construction unit is selected from the conjugated diene construction unit except described butadiene structural units.
9. rubber composition according to claim 8, it is characterised in that also include inorganic filler,
Wherein with the total amount of described conjugated diene-vinyl aromatic hydrocarbon copolymer and described conjugated diene polymer for 100 parts by weight, described inorganic filler is 15 weight portion～45 weight portions.
10. rubber composition according to claim 8, it is characterised in that described rubber composition visible ray penetrance under 3mm thickness is more than 76%.
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