CN115785525B - Structure regulator composition, liquid terpolymer, preparation method and application thereof - Google Patents
Structure regulator composition, liquid terpolymer, preparation method and application thereof Download PDFInfo
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- CN115785525B CN115785525B CN202111062105.6A CN202111062105A CN115785525B CN 115785525 B CN115785525 B CN 115785525B CN 202111062105 A CN202111062105 A CN 202111062105A CN 115785525 B CN115785525 B CN 115785525B
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- terpolymer
- anionic surfactant
- styrene
- formula
- ether
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- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 229920001897 terpolymer Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 title claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 90
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003607 modifier Substances 0.000 claims abstract description 34
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 31
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- -1 alkyl tetrahydrofurfuryl ether Chemical compound 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 74
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 44
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 230000000977 initiatory effect Effects 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 125000001979 organolithium group Chemical group 0.000 claims description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 14
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 13
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical group OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 230000008878 coupling Effects 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005227 alkyl sulfonate group Chemical group 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052700 potassium Chemical group 0.000 claims description 3
- 239000011591 potassium Chemical group 0.000 claims description 3
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010057 rubber processing Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- XWBRTYSASIVIKP-UHFFFAOYSA-N 1,3-dibutyl-5-ethenylbenzene Chemical compound CCCCC1=CC(CCCC)=CC(C=C)=C1 XWBRTYSASIVIKP-UHFFFAOYSA-N 0.000 claims description 2
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-UHFFFAOYSA-N 0.000 claims description 2
- HVOKBODBWQEEGI-UHFFFAOYSA-N 1-ethenyl-3,5-diethylbenzene Chemical compound CCC1=CC(CC)=CC(C=C)=C1 HVOKBODBWQEEGI-UHFFFAOYSA-N 0.000 claims description 2
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 241001120493 Arene Species 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 24
- 239000005060 rubber Substances 0.000 abstract description 24
- 238000002156 mixing Methods 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 10
- 239000010692 aromatic oil Substances 0.000 description 10
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 10
- 241001441571 Hiodontidae Species 0.000 description 9
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 description 2
- KOJGQOMKJLGGPI-UHFFFAOYSA-N 2-(propoxymethyl)oxolane Chemical compound CCCOCC1CCCO1 KOJGQOMKJLGGPI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-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
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- XQOZFAAKQVWOCE-UHFFFAOYSA-N [Li]C1=CC=CC=C1C Chemical compound [Li]C1=CC=CC=C1C XQOZFAAKQVWOCE-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- TVKQVMQEOOKKMN-UHFFFAOYSA-N [Li]CCC[Li] Chemical compound [Li]CCC[Li] TVKQVMQEOOKKMN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001151 other effect Effects 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
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention discloses a structure regulator composition, a liquid terpolymer, a preparation method and application thereof. The structure modifier composition comprises tetrahydrofuran, asymmetric ether and an anionic surfactant; and 1 to 10mmol of the asymmetric ether and 0.1 to 1mmol of the anionic surfactant relative to 1mL of tetrahydrofuran; the asymmetric ether is alkyl tetrahydrofurfuryl ether shown in a formula (1); r is C 1 ‑C 20 An alkyl group; the preparation method of the structure regulator composition comprises the following steps: under the heating and stirring conditions, tetrahydrofuran and an anionic surfactant are mixed, and the mixture is contacted with asymmetric ether to obtain a structure regulator composition; the terpolymer can improve the processability of rubber in the mixing process, and can further improve the wet skid resistance of the rubber.
Description
Technical Field
The invention relates to the technical field of application of a structure regulator, in particular to a structure regulator composition, a liquid terpolymer and a preparation method and application thereof.
Background
With the development of the automobile industry, the requirements on environmental protection applicable to all aspects of rubber products are higher and higher, and the rubber products have good use performance and certain environmental protection, including environmental protection of the products in the processing process and raw materials.
The processing of rubber materials requires a number of compounding agents, of which aromatic oils are one of the important components, to promote the mutual fusion of the rubber with the filler and other compounding agents.
CN106467762B discloses a preparation method of environment-friendly rubber filling oil, which comprises the following steps: the high aromatic oil is placed in an extraction tower for solvent extraction, the solvent is recovered from the product obtained from the top of the extraction tower to obtain environment-friendly rubber filling oil, and the solvent is recovered from the product obtained from the bottom of the extraction tower to obtain extraction oil; and (3) hydrotreating the extracted oil to obtain hydrotreated oil, returning the hydrotreated oil to be mixed with the high aromatic oil, and then extracting the solvent, thus recycling. The filling oil obtained by the method has high aromatic hydrocarbon content, good compatibility with rubber and excellent processability.
CN102311784B discloses a method for producing environment-friendly aromatic oil, which comprises the steps of producing environment-friendly aromatic oil through hydrotreatment, and sequentially passing raw oil and hydrogen through a hydro-upgrading region and a hydrofining reaction region under the condition of hydrotreatment to obtain environment-friendly aromatic oil with the content of polycyclic aromatic hydrocarbon less than 3% and the content of aromatic hydrocarbon higher than 20%.
Both processes are extremely complex and costly.
Therefore, research and development of a structure regulator for anionic polymerization, which can replace the effect of environment-friendly aromatic hydrocarbon oil, has important significance.
Disclosure of Invention
The invention aims to solve the defect that aromatic hydrocarbon oil is used to improve the processability of rubber in the processing process of the prior art, and particularly, the environment-friendly aromatic hydrocarbon oil used at present is more in variety, the component compositions are not the same due to different obtaining processes, and the composition has no other effect except improving the processability of the rubber.
In order to achieve the above object, the present invention provides in a first aspect a structure modifier composition, wherein the structure modifier composition comprises tetrahydrofuran, an asymmetric ether, and an anionic surfactant; and 1 to 10mmol of the asymmetric ether and 0.1 to 1mmol of the anionic surfactant relative to 1mL of tetrahydrofuran; wherein the asymmetric ether is an alkyl tetrahydrofurfuryl ether having the formula (1);
wherein in formula (1), R is C 1 -C 20 An alkyl group;
the preparation method of the structure regulator composition comprises the following steps: tetrahydrofuran and anionic surfactant are mixed under heating and stirring conditions to obtain a mixture, and the mixture is contacted with asymmetric ether to continuously mix to obtain the structure regulator composition.
In a second aspect, the present invention provides a method for preparing a liquid terpolymer, wherein the method comprises:
(1) Under the condition of anion polymerization, adding an organic lithium initiator into a hydrocarbon solvent, and then adding the structure regulator composition and mixing to obtain an initiation regulation system premix;
(2) Contacting a first conjugated olefin, a second conjugated olefin, and a monovinylarene in the hydrocarbon solvent in the presence of the initiation conditioning system premix to perform a terpolymerization reaction;
(2) And adding a coupling agent or a terminator to terminate the living polymer chain after the ternary polymerization reaction is completed.
In a third aspect, the present invention provides a liquid terpolymer prepared by the method of preparation described above.
In a fourth aspect, the present invention provides the use of a liquid terpolymer as hereinbefore described in rubber processing.
Through the technical scheme, the invention adopts the compound structure regulator, and under the polymerization condition, the copolymerization of the first conjugated olefin, the second conjugated olefin and the monovinylarene can be effectively regulated, the vinyl content of the terpolymer is controlled at a medium level and a low level, the number average molecular weight of the prepared terpolymer is 0.05-5 ten thousand, and the molecular weight distribution is 1.1-1.2, so that the purpose of improving the rubber processability and simultaneously improving the dynamic mechanical property of the terpolymer is achieved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present invention provides in a first aspect a structure modifier composition, wherein the structure modifier composition comprises tetrahydrofuran, an asymmetric ether, and an anionic surfactant; and 1 to 10mmol of the asymmetric ether and 0.1 to 1mmol of the anionic surfactant relative to 1mL of tetrahydrofuran;
wherein the asymmetric ether is an alkyl tetrahydrofurfuryl ether having the formula (1);
wherein in formula (1), R is C 1 -C 20 An alkyl group;
the preparation method of the structure regulator composition comprises the following steps: tetrahydrofuran and anionic surfactant are mixed under heating and stirring conditions to obtain a mixture, and the mixture is contacted with asymmetric ether to continuously mix to obtain the structure regulator composition.
In the present invention, the inventors of the present invention found that: mixing tetrahydrofuran and the anionic surfactant under heating and stirring conditions to obtain a mixture, and then contacting the mixture with the asymmetric ether to obtain a structure regulator composition; thus, tetrahydrofuran, asymmetric ether and anionic surfactant are compounded, and under a specific content ratio, the microstructure of the polymer can be effectively controlled, and the wet skid resistance of the rubber product in use can be improved. In addition, the technical process for preparing the environment-friendly aromatic oil in the prior art is extremely complex and has higher cost; based on the above, the inventor of the present invention has found that it is very convenient to obtain a liquid polymer by a one-step simple chemical synthesis method to replace the aromatic hydrocarbon oil.
According to the present invention, each component of the structure modifier composition is stored separately prior to use.
According to the present invention, preferably, the asymmetric ether is 1 to 5mmol and the anionic surfactant is 0.1 to 0.5mmol with respect to 1mL of tetrahydrofuran; more preferably, the asymmetric ether is 1.09 to 4.59mmol and the anionic surfactant is 0.14 to 0.44mmol relative to 1mL of tetrahydrofuran, and specifically, for example, the asymmetric ether may be 1.09mmol, 1.7mmol, 1.82mmol, 2.18mmol, 3.36mmol, 4.17mmol, 4.59mmol relative to 1mL of tetrahydrofuran; the anionic surfactant may be 0.14mmol, 0.18mmol, 0.23mmol, 0.28mmol, 0.31mmol, 0.43mmol, 0.44mmol, and any value in the range of any two of these point values.
According to the invention, the molar ratio of the asymmetric ether to the anionic surfactant is (1-5): 0.14, preferably (1-2): 0.14, more preferably (1.09-1.36): 0.14.
in the invention, tetrahydrofuran, asymmetric ether and anionic surfactant are compounded within the specific range, so that the prepared ternary rubber copolymer has high wear resistance, high wet skid resistance and low rolling resistance.
According to the invention, in formula (1), R is C 1 -C 10 Alkyl, preferably C 1 -C 6 Alkyl, more preferably C 2 -C 3 Alkyl, more preferably C 2 An alkyl group; in the present invention, when R is C 2 Alkyl (C) 2 H 5 ) When the asymmetric ether is tetrahydrofurfuryl alcohol diethyl ether (alias, ethyl tetrahydrofurfuryl ether or 2- (ethoxymethyl) tetrahydrofuran, the molecular formula is C 7 H 14 O 2 The method comprises the steps of carrying out a first treatment on the surface of the When R is C 3 In the case of alkyl, the asymmetric ether is tetrahydrofurfuryl alcohol propyl ether (alias, propyl tetrahydrofurfuryl ether or 2- (propoxymethyl) tetrahydrofuran); alternatively, tetrahydrofurfuryl alcohol ethyl ether and tetrahydrofurfuryl alcohol propyl ether are commercially available, in the present invention from carbofuran (which is also self-made).
According to the present invention, the anionic surfactant is an alkyl sulfonate having the formula (2);
R 1 -C 6 H 4 -SO 3 m, formula (2);
wherein in formula (2), M is sodium or potassium, R 1 Is C 4 -C 20 Is a hydrocarbon group.
According to the present invention, preferably, the anionic surfactant is sodium dodecylbenzenesulfonate and/or potassium dodecylbenzenesulfonate.
According to the present invention, in the preparation method of the structure-adjusting agent composition, the preparation method comprises: mixing tetrahydrofuran and the anionic surfactant under heating and stirring at 25-45 ℃ to obtain a mixture, and then contacting the mixture with the asymmetric ether for continuous mixing to obtain the structure regulator composition.
In the present invention, the stirring conditions include: the stirring rate is 60-150 rpm.
In the present invention, preferably, the heating conditions include: 30-50 ℃.
In the present invention, the mixing time is 5 to 10min, preferably 5 to 6min; the contact time is 5-10min, preferably 5-6min.
In a second aspect, the present invention provides a method for preparing a liquid terpolymer, wherein the method comprises:
(1) Under the condition of anion polymerization, adding an organic lithium initiator into a hydrocarbon solvent, and then adding the structure regulator composition and mixing to obtain an initiation regulation system premix;
(2) Contacting a first conjugated olefin, a second conjugated olefin, and a monovinylarene in the hydrocarbon solvent in the presence of the initiation conditioning system premix to perform a terpolymerization reaction;
(3) And adding a coupling agent or a terminator to terminate the living polymer chain after the ternary polymerization reaction is completed.
According to the invention, the molar ratio of tetrahydrofuran to the organolithium initiator is (0.01-10): 1, preferably (0.1-1): 1, more preferably (01.—0.5): 1.
according to the invention, the molar ratio of the asymmetric ether to the organolithium initiator is (0.002-0.2): 1, preferably (0.002-0.1): 1, more preferably (0.002-0.02): 1.
according to the invention, the molar ratio of the anionic surfactant to the organolithium initiator is (0.001-0.2): 1, preferably (0.001-0.06): 1, more preferably (0.001-0.004): 1.
according to the present invention, the amount of the hydrocarbon solvent is controlled so that the monovinylarene concentration is 5 to 50wt%, preferably 15 to 40wt%, more preferably 21 to 30wt%.
According to the present invention, the hydrocarbon solvent is selected from one or more of cycloalkanes, arenes and isoparaffins having 5 to 7 carbon atoms; preferably, the hydrocarbon solvent is selected from one or more of benzene, toluene, hexane, cyclohexane, pentane, heptane, hexane/cyclohexane mixtures.
According to the present invention, the first conjugated olefin and the second conjugated olefin are the same or different and are each selected from one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene; preferably, the first conjugated diene and the second conjugated diene are butadiene and isoprene.
According to the invention, the monovinylarenes are styrene and/or alkyl-substituted styrene; preferably, the monovinylarene is selected from one or more of styrene, vinyl toluene, alpha-methylstyrene, 4-t-butylstyrene, 4-methylstyrene, 3, 5-diethylstyrene, 3, 5-di-n-butylstyrene, 4-n-propylstyrene and 4-dodecylstyrene; more preferably, the monovinylarene is selected from one or more of styrene, vinyl toluene and alpha-methyl styrene; still more preferably, the monovinylarene is styrene.
In the preparation of the polymer according to the present invention, the initiator may be various existing initiators capable of initiating polymerization of the monovinylarene, the first conjugated diene and the second conjugated diene, and for example, may be organolithium initiators. The organolithium initiator may be various organolithium initiators capable of initiating anionic polymerization known to those skilled in the art, for example, the organolithium initiator may be a mono-organolithium initiator of formula RLi wherein R is a linear or branched alkyl, cycloalkyl or aryl group; in particular, the mono-organolithium initiator may be selected from one or more of ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, amyl lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, methylphenyl lithium and naphthyl lithium, preferably n-butyl lithium and/or sec-butyl lithium. In addition, the present invention may also employ a dilithium initiator such as trimethylene dilithium and/or tetramethylene dilithium. The amount of the initiator used in the present invention is not particularly limited and may be appropriately selected according to the molecular weight of the design. It will be readily appreciated by those skilled in the art that when it is desired to prepare a polymer of greater molecular weight, the amount of initiator used can be reduced, but the rate of polymerization will be correspondingly reduced; when it is desired to prepare a polymer having a smaller molecular weight, the amount of the initiator may be increased, but the polymerization rate may be increased accordingly. Thus, considering the polymerization rate in combination with the molecular weight of the polymer obtained, the initiator is preferably used in an amount of 2 to 200mmol, based on 100g of the total weight of the monomers (for example, monovinylarenes, first conjugated dienes or second conjugated olefins).
In general, according to the invention, the anionic polymerization system does not have a significant termination and transfer reaction, and the active sites remain after the complete monomer consumption. Thus, after the polymerization reaction is completed, the resulting polymer solution should be contacted with a terminator to inactivate the active center. The amount of the terminator may be appropriately selected depending on the amount of the initiator used for the prepared terpolymer, and in general, the molar ratio of the terminator to the organolithium initiator used for the prepared terpolymer may be (0.1-1): 1. The terminating agent may be any existing agent capable of inactivating the anionic active center, and may be selected from one or more of water, methanol, ethanol, n-isopropyl alcohol and isopropyl alcohol, preferably isopropyl alcohol.
According to the invention, during the preparation of the terpolymer, after the polymerization reaction has been completed, before the addition of the terminating agent, a coupling agent may optionally be added to couple the living copolymer chains formed, the coupling agent being used in an amount such as to ensure that 20 to 100% of the segments are coupled, preferably with a coupling efficiency of 50 to 90%. In the present invention, the coupling agent that can be used is one or more of polyvinyl compounds, halides, ethers, aldehydes, ketones, and esters; preferably, the coupling agent is selected from one or more of divinylbenzene, tetravinylsilane, tetrachloromethane, silicon tetrachloride, tin tetrachloride and dimethyl terephthalate; more preferably, the coupling agent is selected from one or more of divinylbenzene, silicon tetrachloride and tin tetrachloride. In the present invention, the coupling agent is used in such an amount that the molar ratio of the coupling agent to the organolithium initiator is (0.1-2): 1.
according to the invention, the terminating agent can be directly added to terminate the reaction after the coupling, or a tin-containing compound can be added to partially or completely terminate the uncoupling portion after the coupling, and the terminating reaction operation can be performed after the termination. The blocking agents used are the conventional blocking agents in the rubber synthesis field, such as trialkyltin chlorides, in which the alkyl groups contain 1 to 8 carbon atoms, such as trimethyltin chloride, triethyltin chloride, tributyltin chloride. The molar ratio of capping agent to uncoupled moiety is (0.2-1.0): 1, preferably (0.5-1.0): 1.
according to the invention, the terpolymer of the invention may optionally be treated with an anti-ageing agent, for example by adding the anti-ageing agent to the gum solution prior to drying. Possible antioxidants are generally phenols or amines, including Irganox 1520 (Switzerland vapor company), pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (i.e., 1010)/tris (2, 4-di-tert-butylphenyl) phosphite (i.e., 168)) composite antioxidants (wherein the content of 168 is not more than 50% by weight), octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (i.e., 1076)/tris (2, 4-di-tert-butylphenyl) phosphite (i.e., 168) composite antioxidants (wherein the content of 168 is not more than 50% by weight), 2, 6-di-tert-butyl-p-cresol (abbreviated as antioxidant 264), tert-butyl catechol, 2' -methylene-bis (4-methyl-6-tert-butylphenol) (abbreviated as antioxidant 2246), and the like. The amount of the antioxidant added is generally 0.005 to 2% by weight based on the terpolymer. After the anti-aging agent is added, the terpolymer gum solution can be precipitated and separated from the solvent in a similar way such as alcoholization precipitation, centrifugal separation, filtration, decantation, hot water condensation and the like, and the volatile organic solvent in the copolymer can be separated out in a steam stripping way.
In the preparation method of the terpolymer, the temperature is controlled at 35-80 ℃, preferably 40-50 ℃ when the initiator is added; controlling the polymerization temperature to be 80-110 ℃, preferably 85-90 ℃; the pressure is between 0.05MPa and 0.5MPa, preferably between 0.1MPa and 0.3 MPa; the reaction time is 0.5-3h.
In a third aspect, the present invention provides a liquid terpolymer prepared by the method of preparation described above.
According to the invention, the terpolymer has the following characteristics:
(1) The monovinylarene content is 40-80wt%, preferably 45-80wt%;
(2) The first conjugated diene is present in an amount of 5 to 50wt%, preferably 10 to 35wt%;
(3) The content of the second conjugated diene is 5 to 50wt%, preferably 10 to 35wt%;
(4) The vinyl structure content of the terpolymer is 2-20wt%, preferably 3-15wt%;
(5) The structural content of the propenyl group of the terpolymer is 2-20wt%, preferably 3-15wt%;
(6) The content of the styrene block of the terpolymer is 10-50wt%;
(7) The terpolymer has a number average molecular weight of 0.05 to 5 ten thousand, preferably 0.1 to 1.5 ten thousand, and a molecular weight distribution of 1.1 to 1.2 prior to coupling.
According to the invention, the coupling efficiency is 20 to 100%, preferably 50 to 90%.
In a preferred embodiment of the present invention, it is preferable to use three monomers of Styrene (ST), isoprene (IP) and Butadiene (BD) as comonomers, wherein the content of ST is 40 to 80wt%, preferably 40 to 60wt%; the IP content is 5-85wt%, preferably 20-60wt%; the BD content is 5 to 85wt%, preferably 20 to 60wt%. The microstructure of the resulting terpolymer was: the 1,2-BD structure content is 8-50wt%, preferably 10-30wt%; the 3,4-IP structure content is 8-50wt%, preferably 10-30wt%.
In a fourth aspect, the present invention provides the use of a liquid terpolymer as hereinbefore described in rubber processing.
According to the present invention, the liquid terpolymer can be used in a rubber kneading process of a shoe material or the like.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the microstructure of the synthesized terpolymer is measured by adopting an AVANCE DRX400MHz nuclear magnetic resonance spectrometer of Bruker company, switzerland, and the solvent is deuterated chloroform;
molecular weight and coupling efficiency were measured using an ALLIANCE2690 Gel Permeation Chromatograph (GPC) from water company, USA, THF as mobile phase, narrow-distribution polystyrene as standard, and temperature 25 ℃;
the glass transition temperature is measured by a American TA company MDSC2910 type Differential Scanning Calorimeter (DSC) for 60s, the modulation amplitude is +/-1.5 ℃, the heating rate is 10 ℃/min, the nitrogen protection is adopted, and the flow rate is 50mL/min;
the dynamic mechanical properties are measured by a DMA-2980 type viscoelastometer of the company TA of America, the frequency is 2Hz, the heating rate is 5 ℃/min, the temperature is between 120 ℃ below zero and 100 ℃, and the size of a sample is 40mm multiplied by 5mm multiplied by 1mm;
mixing raw rubber at a roller temperature of 50+/-5 ℃ by an open mill; vulcanization conditions: vulcanizing at 145 ℃ under a pressure of more than 10MPa for 35min; vulcanizing the basic formula, and carrying out SSBR2305:100g; terpolymer: 15g; carbon black: 45g; sulfur: 1g; and (3) an accelerator: 1g; stearic acid: 2g; anti-aging agent: 1g; zinc oxide: 5g.
The physical properties of the vulcanized rubber are measured by a Japanese SHIMADZU AG-20KNG tensile machine according to GB/T528-1998;
mooney viscosity was measured in accordance with GB/T1232-92 using a SHIMADZU SMV-300 tester of Japan.
Example 1
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: under the condition of stirring speed of 60 revolutions per minute and temperature of 40 ℃,0.6mL of tetrahydrofuran and 0.19mmol of Sodium Dodecyl Benzene Sulfonate (SDBS) are mixed for 5min under the protection of nitrogen, and then 2.02mmol of tetrahydrofurfuryl alcohol diethyl ether is added for contact for 5min, so that the structure regulator composition S1 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 40.5mmol of n-butyllithium and the structure-modifying agent composition S1 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 25℃for 10 minutes to obtain an initiation-modifying premix;
(2) 1500g cyclohexane, 233.8g styrene, 37.2g isoprene and 37.7g butadiene were added under high purity nitrogen protection in a 5 liter stainless steel stirred tank, and the initiation adjusting premix was added at 35℃for 120min;
(3) Then, 3.1mmol of tin tetrachloride was added to the autoclave, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was 1.1 ten thousand, the molecular weight distribution was 1.2, the bound styrene mass content was 75.7%, the block styrene content was 45.3%, the bound butadiene mass content was 12.1%, the bound isoprene mass content was 12.2%, the vinyl mass content was 4.42%, and the propenyl mass content was 4.03%.
Example 2
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: under the condition of stirring speed of 90 revolutions per minute and temperature of 30 ℃, 0.8mL of tetrahydrofuran and 0.35mmol of Sodium Dodecyl Benzene Sulfonate (SDBS) are mixed for 5min under the protection of nitrogen, and then 3.67mmol of tetrahydrofurfuryl alcohol butyl ether is added for contact for 5min, so that the structure regulator composition S2 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 30.6mmol of n-butyllithium and the structure-modifying agent composition S2 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 25℃for 10 minutes to obtain an initiation-modifying premix;
(2) 1500g cyclohexane, 144.2g styrene, 96.0g isoprene and 79.8g butadiene were added under high purity nitrogen protection in a 5 liter stainless steel stirred tank, and the initiation adjusting premix S2 was added at 35℃for 40 minutes;
(3) Then, 2.1mmol of tin tetrachloride was added to the autoclave, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was found to be 0.6 ten thousand, the molecular weight distribution was 1.2, the combined styrene mass content was 45.1%, the block styrene mass content was 14.4%, the combined butadiene mass content was 24.9%, the combined isoprene mass content was 30.0%, the vinyl mass content was 9.5%, and the propenyl mass content was 11.4%.
Example 3
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: under the condition of stirring speed of 100 revolutions per minute and temperature of 50 ℃, 0.3mL of tetrahydrofuran and 0.13mmol of Sodium Dodecyl Benzene Sulfonate (SDBS) are mixed for 5min under the protection of nitrogen, and then 1.25mmol of tetrahydrofurfuryl alcohol propyl ether is added for contact for 5min, so that the structure regulator composition S3 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 13.6mmol of n-butyllithium and the structure-modifying agent composition S3 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 30℃for 10 minutes to obtain an initiation-modifying premix;
(2) 1500g cyclohexane, 145g styrene, 80g isoprene and 96g butadiene are added into a 5 liter stainless steel stirred tank under the protection of high-purity nitrogen, and the initiation adjusting premix is added under the condition of 60 ℃ to react for 40 minutes;
(3) 2.8mmol of tin tetrachloride was then added to the autoclave, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was measured to be 0.3 ten thousand, the molecular weight distribution was 1.2, the structure was 45.2% by mass of bound styrene, wherein the block styrene content was 12.2% by mass, the bound butadiene content was 29.9% by mass, the bound isoprene content was 24.9% by mass, the vinyl content was 9.3% by mass, and the propenyl content was 7.7% by mass.
Example 4
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: 1mL of tetrahydrofuran and 0.14mmol of sodium dodecyl benzene sulfonate are mixed for 5min under the protection of nitrogen at the stirring speed of 70 r/min and the temperature of 35 ℃, and then 1.09mmol of tetrahydrofurfuryl alcohol diethyl ether is added for contact for 5min, so that the structure regulator composition S4 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 15.4mmol of n-butyllithium and the structure-modifying agent composition S4 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 30℃for 10 minutes to obtain an initiation-modifying premix;
(2) 1500g cyclohexane, 192g styrene, 64g isoprene and 64g butadiene were added under high purity nitrogen protection in a 5 liter stainless steel stirred tank, and the initiation adjusting premix was added at 40℃for 40 minutes;
(3) 2.8mmol of tin tetrachloride was then added to the autoclave, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was measured to be 0.8 ten thousand, the molecular weight distribution was 1.2, the bound styrene mass content was 60%, the block styrene content was 25.1%, the bound butadiene mass content was 20%, the bound isoprene mass content was 20%, the vinyl mass content was 6.9%, and the propenyl mass content was 6.6%.
Example 5
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: under the condition of stirring speed of 60 revolutions per minute and temperature of 45 ℃,0.6mL of tetrahydrofuran and 0.14mmol of sodium dodecyl benzene sulfonate are mixed for 5min under the protection of nitrogen, and then 1.09mmol of tetrahydrofurfuryl alcohol diethyl ether is added for contact for 5min, so that the structure regulator composition S5 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 16.3mmol of n-butyllithium and the structure-modifying agent composition S5 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 25℃for 10 minutes to obtain an initiation-modifying premix;
(2) 1508g cyclohexane, 224g styrene, 48g isoprene and 48g butadiene, 0.6mL tetrahydrofuran are added under high purity nitrogen protection in a 5 liter stainless steel stirred tank, and the initiation adjusting premix is added under 55 ℃ to react for 40 minutes;
(3) 2.8mmol of tin tetrachloride was then added to the autoclave, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was measured to be 0.9 ten thousand, the molecular weight distribution was 1.2, the bound styrene mass content was 70%, the block styrene content was 46.3%, the bound butadiene mass content was 15%, the bound isoprene mass content was 15%, the vinyl mass content was 4.8%, and the propenyl mass content was 4.5%.
Example 6
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: under the condition of stirring speed of 90 r/min and temperature of 40 ℃, 0.8mL of tetrahydrofuran and 0.14mmol of sodium dodecyl benzene sulfonate are mixed for 5min under the protection of nitrogen, and then 1.36mmol of tetrahydrofurfuryl alcohol diethyl ether is added for contact for 5min, so that the structure regulator composition S6 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 17.6mmol of n-butyllithium and the structure-modifying agent composition S6 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 25℃for 10 minutes to obtain an initiation-modifying premix;
(2) In a 5 liter stainless steel stirring kettle, under the protection of high-purity nitrogen, 1588g of cyclohexane, 256g of styrene, 32g of isoprene and 32g of butadiene are added, and the initiation adjusting premix is added at 50 ℃ for reaction for 40 minutes;
(3) 2.8mmol of tin tetrachloride was then added to the autoclave, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was measured to be 0.8 ten thousand, the molecular weight distribution was 1.2, the bound styrene mass content was 80%, the block styrene content was 49.5%, the bound butadiene mass content was 10%, the bound isoprene mass content was 10%, the vinyl mass content was 3.1%, and the propenyl mass content was 3.0%.
Example 7
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: under the condition of stirring speed of 60 revolutions per minute and temperature of 35 ℃, 0.5mL of tetrahydrofuran and 0.14mmol of sodium dodecyl benzene sulfonate are mixed for 5min under the protection of nitrogen, and then 1.09mmol of tetrahydrofurfuryl alcohol diethyl ether is added for contact for 5min, so that the structure regulator composition S7 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 12.7mmol of n-butyllithium and the structure-modifying agent composition S7 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 25℃for 10 minutes to obtain an initiation-modifying premix;
(2) In a 5 liter stainless steel stirring kettle, under the protection of high-purity nitrogen, 1588g of cyclohexane, 256g of styrene, 32g of isoprene and 32g of butadiene are added, and the initiation adjusting premix is added at 60 ℃ for reaction for 40 minutes;
(3) 2.4mmol of tin tetrachloride was then added to the reaction vessel, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was 1.5 ten thousand, the molecular weight distribution was 1.2, the bound styrene mass content was 80%, the block styrene content was 48.3%, the bound butadiene mass content was 10%, the bound isoprene mass content was 10%, the vinyl mass content was 2.9%, and the propenyl mass content was 2.7%.
Example 8
This example illustrates the preparation of a liquid terpolymer using the structure modifier composition of the present invention.
Preparation of a structure modifier composition: 1mL of tetrahydrofuran and 0.14mmol of sodium dodecyl benzene sulfonate are mixed for 5min under the protection of nitrogen at the stirring speed of 60 revolutions per minute and the temperature of 35 ℃, and then 1.09mmol of tetrahydrofurfuryl alcohol diethyl ether is added for contact for 5min, so that the structure regulator composition S8 is prepared.
Preparation of a terpolymer in liquid form:
(1) 150ml of cyclohexane, 12.4mmol of n-butyllithium and the structure-modifying agent composition S8 were added to a 300ml three-necked flask under nitrogen protection, and stirred and mixed at 25℃for 10 minutes to obtain an initiation-modifying premix;
(2) 1508g cyclohexane, 160g styrene, 82g isoprene and 78g butadiene were added under high purity nitrogen protection in a 5 liter stainless steel stirred tank, and the initiation conditioning premix was added at 35 ℃ to react for 40 minutes;
(3) 2.4mmol of tin tetrachloride was then added to the reaction vessel, and after 70 minutes, 0.5g of isopropyl alcohol was added to terminate the reaction, thereby obtaining a terpolymer (star-shaped terpolymer).
The number average molecular weight of the terpolymer was measured to be 0.2 ten thousand, the molecular weight distribution was 1.2, the bound styrene mass content was 50%, the block styrene content was 30.5%, the bound butadiene mass content was 25.6%, the bound isoprene mass content was 24.4%, the vinyl mass content was 8.2%, and the propenyl mass content was 7.8%.
Application example
Vulcanized rubbers were prepared using the terpolymers prepared in examples 1-8.
The vulcanization basic formula comprises: raw rubber SSBR2305 (styrene content 25wt%, vinyl content 30 wt%): 100g; terpolymers prepared in examples 1-8: 15g; reinforcing agent carbon black: 45g; vulcanizing agent sulfur: 1g; vulcanization accelerator TBBS:1g; activator stearic acid: 2g; anti-aging agent 4010:1g; activator zinc oxide: 5g. The performance parameters of the vulcanizates are shown in Table 1.
Comparative example 1
The terpolymer was replaced with an equivalent amount of the environmentally friendly aromatic oil in the vulcanized base formulation of comparative example 1, i.e., the vulcanized base formulation comprises: raw rubber SSBR2305 (styrene content 25wt%, vinyl content 30 wt%): 100g; environment-friendly aromatic oil TDAE:15g; reinforcing agent carbon black: 45g; vulcanizing agent sulfur: 1g; vulcanization accelerator TBBS:1g; activator stearic acid: 2g; anti-aging agent 4010:1g; activator zinc oxide: 5g. The performance parameters of the vulcanizates are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the examples 1 to 8 according to the present invention can obtain good processability, i.e., good caking property, when added to the rubber kneading process, and have better processability, compared with the environment-friendly aromatic oil used in comparative example 1, as shown by a lower Mooney relaxation area A during the rubber kneading process; in table 1, a mooney relaxation t 70 S is the time for a 70 percent decrease in mooney; t is t 80 S is the time for which the Mooney drop is 80 percent; t is t 90 S is the time for 90 percent of the mooney drop; the intercept K is a Mooney value at the moment of 1 second of Mooney relaxation, and can reflect the initial contractility of the material; slope a is the slope of the Mooney stress relaxation line, reflecting the rate of stress relaxation; the area A is the area under the relaxation straight line, and is the performance of comprehensively reflecting the Mooney relaxation.
While being beneficial for improving the wet skid resistance of the rubber, i.e., the Tan (0 ℃) values of examples 1-8 are all higher than comparative example 1, which is beneficial for improving the skid resistance of the rubber (e.g., shoe material); in addition, the Tan (60 ℃) values of examples 1 to 8 are lower than those of comparative example 1, and the rolling resistance is reduced, which is slightly helpful for improving the comprehensive dynamic performance.
In table 1, the hardness, tear strength, permanent set, elongation and 300% elongation were substantially the same as those of comparative example 1, so that the physical and mechanical properties were not affected by the technique of the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (25)
1. A structure modifier composition, characterized in that the structure modifier composition comprises tetrahydrofuran, an asymmetric ether, and an anionic surfactant; and 1 to 10mmol of the asymmetric ether and 0.1 to 1mmol of the anionic surfactant relative to 1mL of tetrahydrofuran;
wherein the asymmetric ether is an alkyl tetrahydrofurfuryl ether having the formula (1);
formula (1);
wherein in formula (1), R is C 1 -C 20 An alkyl group;
the preparation method of the structure regulator composition comprises the following steps: tetrahydrofuran and anionic surfactant are mixed under heating and stirring conditions to obtain a mixture, and the mixture is contacted with asymmetric ether to continuously mix to obtain the structure regulator composition.
2. The structure modifier composition according to claim 1, wherein the asymmetric ether is 1 to 5mmol and the anionic surfactant is 0.1 to 0.5mmol with respect to 1mL of tetrahydrofuran.
3. The structure modifier composition of claim 2, wherein the molar ratio of the asymmetric ether to the anionic surfactant is (1-5): 0.14.
4. a structure modifier composition according to claim 3, wherein the molar ratio of the asymmetric ether to the anionic surfactant is (1-2): 0.14.
5. the structure-modifier composition according to claim 2, wherein in formula (1), R is C 1 -C 10 An alkyl group.
6. The structure-modifying agent composition according to claim 5, wherein in the formula (1), R is C 1 -C 6 An alkyl group.
7. The structure-modifying agent composition according to claim 5 or 6, wherein in the formula (1), R is C 2 -C 3 An alkyl group.
8. The structure modifier composition of claim 2, wherein the asymmetric ether is tetrahydrofurfuryl alcohol diethyl ether.
9. The structure regulator composition according to any one of claims 1 to 6 or 8, wherein the anionic surfactant is an alkyl sulfonate having the formula (2);
R 1 -C 6 H 4 -SO 3 m, formula (2);
wherein in formula (2), M is sodium or potassium, R 1 Is C 4 -C 20 Is a hydrocarbon group.
10. The structure modifier composition according to claim 9, wherein the anionic surfactant is sodium dodecyl benzene sulfonate and/or potassium dodecyl benzene sulfonate.
11. The structure modifier composition according to claim 7, wherein the anionic surfactant is an alkyl sulfonate having formula (2);
R 1 -C 6 H 4 -SO 3 m, formula (2);
wherein in formula (2), M is sodium or potassium, R 1 Is C 4 -C 20 Is a hydrocarbon group.
12. The structure modifier composition according to claim 11, wherein the anionic surfactant is sodium dodecyl benzene sulfonate and/or potassium dodecyl benzene sulfonate.
13. A process for preparing a terpolymer in liquid form, said process comprising:
(1) Under the condition of anionic polymerization, adding an organolithium initiator into a hydrocarbon solvent, and then adding the structure regulator composition according to any one of claims 1-12 to mix to obtain an initiation regulation system premix;
(2) Contacting a first conjugated olefin, a second conjugated olefin, and a monovinylarene in the hydrocarbon solvent in the presence of the initiation conditioning system premix to perform a terpolymerization reaction;
(3) And adding a coupling agent or a terminator to terminate the living polymer chain after the ternary polymerization reaction is completed.
14. The preparation method according to claim 13, wherein a molar ratio of tetrahydrofuran to the organolithium initiator in the structure-adjusting agent composition is (0.01-10): 1.
15. the method of claim 13, wherein the molar ratio of asymmetric ether to organolithium initiator in the structure modifier composition is (0.002-0.2): 1.
16. the preparation method according to claim 13, wherein a molar ratio of the anionic surfactant to the organolithium initiator in the structure-modifier composition is (0.001-0.2): 1.
17. the production process according to claim 13, wherein the amount of the hydrocarbon solvent is controlled so that the monovinylarene concentration is 5 to 50wt%.
18. The preparation method according to claim 13, wherein a molar ratio of the coupling agent to the organolithium initiator is (0.1-2): 1.
19. the production process according to any one of claims 13 to 18, wherein the first conjugated olefin and the second conjugated olefin are the same or different and are each selected from one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene.
20. The process of claim 19, wherein the monovinylarene is styrene and/or alkyl-substituted styrene.
21. The process according to claim 19, wherein the monovinylarene is selected from one or more of styrene, vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-methyl styrene, 3, 5-diethyl styrene, 3, 5-di-n-butyl styrene, 4-n-propyl styrene and 4-dodecyl styrene.
22. The production process according to claim 19, wherein the hydrocarbon solvent is selected from one or more of cycloalkanes, arenes and isoparaffins having 5 to 7 carbon atoms.
23. A liquid terpolymer prepared by the preparation method of any one of claims 13 to 22.
24. The liquid terpolymer of claim 23, wherein the liquid terpolymer has the following characteristics:
(1) The content of the monovinylarene is 40-80wt%;
(2) The first conjugated diene is present in an amount of 5 to 50wt%;
(3) The content of the second conjugated diene is 5-50wt%;
(4) The vinyl structure content of the terpolymer is 2-20wt%;
(5) The propylene-based structure content of the terpolymer is 2-20wt%;
(6) The content of the styrene block of the terpolymer is 10-50wt%;
(7) The terpolymer has a number average molecular weight of 0.05-5 ten thousand and a molecular weight distribution of 1.1-1.2 prior to coupling.
25. Use of a liquid terpolymer according to claim 23 or 24 in rubber processing.
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| CN106928415A (en) * | 2015-12-30 | 2017-07-07 | 中国石油化工股份有限公司 | Composite coupler and application and monovinylarene-conjugated diene copolymer composition and preparation method and tire |
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| US5231153A (en) * | 1992-04-06 | 1993-07-27 | The Goodyear Tire & Rubber Company | Anionic polymerization of conjugated dienes modified with alkyltetrahydrofurfuryl ethers |
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