CN103848948B - Partially hydrogenated terpolymer, and preparation method and application thereof - Google Patents
Partially hydrogenated terpolymer, and preparation method and application thereof Download PDFInfo
- Publication number
- CN103848948B CN103848948B CN201210505927.1A CN201210505927A CN103848948B CN 103848948 B CN103848948 B CN 103848948B CN 201210505927 A CN201210505927 A CN 201210505927A CN 103848948 B CN103848948 B CN 103848948B
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- Prior art keywords
- isoprene
- butadiene
- construction unit
- hydrogenation
- weight
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- 229920001897 terpolymer Polymers 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 247
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 239
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 172
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 119
- 238000010276 construction Methods 0.000 claims description 154
- 238000000034 method Methods 0.000 claims description 122
- 239000003999 initiator Substances 0.000 claims description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 49
- 229920001577 copolymer Polymers 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 38
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 34
- 150000001336 alkenes Chemical class 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 21
- 238000005859 coupling reaction Methods 0.000 claims description 18
- 229910052756 noble gas Inorganic materials 0.000 claims description 17
- 150000002835 noble gases Chemical class 0.000 claims description 17
- -1 isoamyl Diene Chemical class 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 150000001993 dienes Chemical class 0.000 claims description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 9
- 150000005671 trienes Chemical class 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003440 styrenes Chemical class 0.000 claims description 8
- 238000012660 binary copolymerization Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 235000014121 butter Nutrition 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 150000005672 tetraenes Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002466 imines Chemical group 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical group C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical group [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 claims 1
- 238000005096 rolling process Methods 0.000 abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 241001120493 Arene Species 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 50
- 229920001971 elastomer Polymers 0.000 description 45
- 239000005060 rubber Substances 0.000 description 45
- 229910052744 lithium Inorganic materials 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000032683 aging Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 125000000129 anionic group Chemical group 0.000 description 11
- 238000003483 aging Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005987 sulfurization reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 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 5
- 125000001979 organolithium group Chemical group 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Chemical group 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- LDAIXGYVPYQKJN-UHFFFAOYSA-N CCCCCCCCCC.[Li].[Li] Chemical compound CCCCCCCCCC.[Li].[Li] LDAIXGYVPYQKJN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001441571 Hiodontidae Species 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
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PVFQZIGCPRBYPZ-UHFFFAOYSA-N [Li].[Li].CCCC Chemical compound [Li].[Li].CCCC PVFQZIGCPRBYPZ-UHFFFAOYSA-N 0.000 description 1
- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000003872 feeding technique Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000004845 hydriding Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011787 zinc oxide 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a partially hydrogenated terpolymer, and a preparation method and application thereof. According to the terpolymer, the hydrogenation degree of a structural unit derived from 1,3-butadiene is 5-90%; the hydrogenation degree of a structural unit derived from 1,3-butandiene in a 1,2-polymerizatino manner is 60-95%, and the hydrogenation degree of a structural unit derived from 1,3-butandiene in a 1,4-polymerization manner is 2-20%; the hydrogenation degree of a structural unit derived from isoprene is 5-90%; the hydrogenation degree of a structural unit derived from isoprene in a 3,4-polymerization manner is 10-40%, and the hydrogenation degree of a structural unit derived from isoprene in a 1,4-polymerization manner is 2-30%; and the hydrogenation degree of a structural unit derived from monovinyl arenes is less than 5%. The terpolymer disclosed by the invention reaches a relatively good balance among high slippery resistance, low rolling resistance and high wear resistance. The structural formula of the terpolymer is shown in the specification.
Description
Technical field
The present invention relates to a kind of partially hydrogenated terpolymer and its preparation method and application, the copolymer can be widely
In for various rubbers, it is particularly suited for tire tread glue.
Background technology
With the development increasingly of auto industry, the requirement to the rubber each side suitable for tread rubber of automobile tires is increasingly
Height, will not only have good anti-wear performance, will also have high wet-sliding resistant and low-rolling-resistance, could so meet safety traffic
And the demand of energy-conservation.In general, the performance of rubber can be showed by its dynamic viscoelasticity spectrum curve.It is well known that tool
The rubber for having wider Dynamic Viscoelastic spectral peak can possess excellent combination property, and such as high anti-skidding, low-heat-generation, reduction dynamic are generated
Rolling resistance, high-wearing feature etc..Improve in rubber articles Quality Research, in order to balance high wet-sliding resistant in past numerous trials
Property, the contradiction between low-rolling-resistance and high abrasion, be applied in tread rubber of automobile tires using the mixture of different rubber more,
But the different structure of the copolymer microcell different with the presentation that chemical property causes blend, in order that different rubber reach it is micro-
Unification in sight, Nordsiek propose and the structural chain with different rubber are incorporated on a strand, i.e. integrated rubber
Concept（Referring to K.H.Nordsiek, The " integral rubber " concept-an approach to an ideal
Tire tread rubber, Kautschuk Gummi Kunststoffe, 1985,38（3）：178-185）, this is a kind of dynamic
State viscoelastic spectra has styrene, butadiene and the isoprene terpolymer rubber of broad peak distribution, as which has isoamyl simultaneously
The structural chain forging of rubber, polybutadiene rubber and butadiene-styrene rubber, so it will combine in one the advantage of these three general purpose rubbers
Body, while with good high wet-sliding resistant, low-rolling-resistance and high-wearing feature.
US4,673,709 report the rubber composition that a kind of Dynamic Viscoelastic spectrogram is presented broad peak distribution, and it is by two kinds
Different rubber are formed by physical mixed, and one of which rubber is that 1,3-butadiene is obtained by ziegler catalysed ones, and
1,2- polymerized unit is less than or equal to 10% weight, and another kind of rubber is that styrene, butadiene and isoprene pass through anionic polymerisation
Obtain SIB-SB-B triblock copolymers.The rubber composition is particularly suitable as tire tread glue, but this rubber composition
Obtained by physical mixed, there is no the rubber polymer mix homogeneously that chemical reaction is obtained, it is impossible to give full play to respective rubber
Superiority.In addition when SIB-SB-B triblock copolymers are prepared by anionic polymerisation using condition gradual change technique, this bar
Part gradual change process conditions are difficult accurately to control in industrialization, make the finished product colloid amount of every batch unstable, so as to affect product
Performance.
US4,814,386 is reported and is obtained tri-block of the Dynamic Viscoelastic spectrogram in broad peak distribution by Multistep feeding technique
Copolymer, as tire tread glue.It can be seen that the rubber of the dynamic viscoelasticity spectrum with wide distribution possesses good combination property, suitably
As tire tread glue.But this technique judges next step by controlling first step monomer conversion and feeds, difficult in industrialization
To realize, and purity requirement of the Multistep feeding to solvent and monomer is high, if improper very to impurity treatment in solvent and monomer
Middle transition product is produced easily so as to have a negative impact to final products performance.
Gawai etc.（Yuichi Kita Gawai etc. write. and Wang Mingdong is compiled, and tire is with new polymerss [J]. tire work
Industry, 1997,6 (17):353-356.）A kind of high-performance novel polymer of fuel-economizing is developed, it is in solution polymerized butadiene styrene rubber
On the basis of introduce new construction unit.This new construction unit is by the 1,2- construction units in polybutadiene segments
Carry out 1-butylene obtained from selective hydrogenation.The vulcanizate of this new polymerss has preferable viscoelasticity, also
It is that its hysteresis loss is less at high temperature, and it is larger at low temperature, and ageing-resistant performance is also preferable.But due in the polymer
Only two kinds of construction units of styrene and butadiene, no isoprene structures unit have to the structure regulating power of polymer
Limit, although causing its low temperature hysteresis loss to increased before being relatively hydrogenated with, low temperature hysteresis loss is still less, uses the polymer
Safety when making tire tread glue is still somewhat limited.
With the development of rubber industry especially tire industry, tyre rubber material is put forward higher requirement, this
Wet-sliding resistant performance, low rolling while kind of the Dynamic Viscoelastic spectrogram with wide distribution, under the ageing-resistant performance that has concurrently, low temperature
The rubber of resistance is the research and development direction of tire tread glue.
The content of the invention
It is an object of the invention to the terpolymer provided in overcoming prior art is present under ageing-resistant performance, low temperature
The deficiency of wet-sliding resistant performance, low-rolling-resistance deviation, there is provided a kind of partially hydrogenated terpolymer and preparation method thereof and should
With the terpolymer is can be widely used in various rubbers, is particularly suited for tire tread glue.
Based on prior art above-mentioned condition, if it was found by the inventors of the present invention that to containing conjugated diene and cinnamic
The construction unit derived from conjugated diene in copolymer is all hydrogenated, and can produce following adverse effect：（1）Can in copolymer
Double bond for sulfuration seldom or does not almost have, and is unfavorable for the copolymer as sulfuration during rubber；（2）With 1 in copolymer,
The construction unit that 4- polymerization methodses are formed is changed into polyethylene after hydrogenating completely, and the presence of longer polyethylene block can make copolymer
Easily separate out from copolymer solution in hydriding process, affect being normally carried out for hydrogenation reaction, and longer polyethylene
The elasticity when presence of block can also make copolymer be used as rubber is deteriorated, and makes the penalty of copolymer.The present inventor
It was found that the content of the specific construction unit derived from conjugated diene and cinnamic construction unit, the molecule of specific copolymer
Amount, with reference to the specific content derived from the specific micro- block of cinnamic construction unit, specific 1,3- fourths two in copolymer
The amount of the construction unit that the amount and isoprene of the construction unit that alkene is formed with 1,2- polymerization methodses is formed with 3,4- polymerization methodses,
In conjunction with specific copolymer degree of hydrogenation when, copolymer combination property is optimal.
Find based on more than, inventor is by being used using relatively mild hydrogenation process conditions and relatively low hydrogenation catalyst
Amount, the construction unit that 1,3-butadiene is formed with 1,2- polymerization methodses in main hydrogenated copolymer, and isoprene are poly- with 3,4-
The amount of the construction unit that conjunction mode is formed, and 1.3- butadiene is not substantially hydrogenated with the construction unit of Isosorbide-5-Nitrae-polymerization methodses formation
And the construction unit that isoprene is formed with Isosorbide-5-Nitrae polymerization methodses, and member-retaining portion is used for the double bond of sulfuration in copolymer chain.
1,3- butadiene obtains the vitrification point ratio hydrogenation of construction unit after hydrogenating with the construction unit that 1,2- polymerization methodses are formed before
1,2- construction units vitrification point it is low, the structure after the construction unit hydrogenation that isoprene is formed with 3,4- polymerization methodses
Unit vitrification point is low compared with the vitrification point of the 3,4- construction units before hydrogenation.The glass of present copolymer is allowed for so
Glass temperature is reduced, and wearability is improved, while part hydrogenation also improves the ageing-resistant performance of copolymer.Copolymerization of the present invention in addition
Thing selective hydration can also make the microstructure of copolymer and aggregated structure change, and before hydrogenation is kept, copolymer has
While high wet-sliding resistant and low-rolling-resistance, make the hysteresis loss under copolymer low temperature further increase i.e. wet-sliding resistant performance and enter
One step is improved, and the hysteresis loss under high temperature further reduces i.e. rolling resistance and further reduces, and wearability is further improved, and is reached
Preferably balance between high wet-sliding resistant, low-rolling-resistance and high-wearing feature three.So by present copolymer structure
Adjustment and belong to the selective hydrogenation of unsaturated bond to chain and obtained the new copolymer with brand new, so as to copolymer can be made
Combination property is improved.Study based on more than, the present inventor adopts and is first respectively synthesized isoprene rubber, polybutadiene rubber, fourth
Benzene rubber or styrene and isoprene copolymer and the ternary polymerization rubber being made up of styrene, butadiene and isoprene
Glue, in the case of the mix homogeneously segment represented by different performance are coupled together, and synthesize viscous with wide distribution dynamic
Play spectrogram ter-polymers, then by the present invention derived from 1,3-butadiene construction unit and derived from isoprene
Construction unit carries out targetedly part and hydrogenates, i.e. the structure list for mainly being formed with 1,2- polymerization methodses to 1,3-butadiene
Unit's hydrogenation, is hydrogenated with the construction unit that 3,4- polymerization methodses are formed to isoprene, control hydrogenation of polymer degree, guarantee one
The thermal-oxidative aging property of polymer on the basis of determining double bond content, can be improved, while the microstructure of polymer can be changed
And aggregated structure, the Dynamic Viscoelastic spectrogram being distributed with width when being used for rubber so as to the partially hydrogenated copolymer for making to obtain
While the wet-sliding resistant performance in a low temperature of more preferably, low-rolling-resistance performance can be had concurrently.
The present invention provides a kind of partially hydrogenated terpolymer, the structure such as formula of the partially hydrogenated terpolymer
（I）It is shown：
Formula（I）
Formula（I）In, A is partially hydrogenated 1,3-butadiene homopolymerization section, B is isoprene homopolymerization section；C is partially hydrogenated
Styrene and 1,3- butadiene binary copolymerization sections or partially hydrogenated styrene and isoprene binary copolymerization section；D is part
The styrene of hydrogenation, 1,3- butadiene and isoprene ternary polymerization section；X is the residue of multifunctional coupling agent, and,
Wherein, e, f, g, j are respectively the arm number of A, B, C, D, and respectively more than or equal to zero, and one of them is when being zero, its
Its three is respectively more than or equal to the quantity of the residue that 1, m-e-f-g-j is multifunctional coupling agent, and m-e-f-g-j >=0,3≤e
+ f+g+j≤25,
Wherein, the degree of hydrogenation of the construction unit derived from 1,3-butadiene is 5-90%, wherein, 1,3-butadiene is with 1,2-
The degree of hydrogenation of the construction unit that polymerization methodses are formed is 60-95%, and 1,3-butadiene is with the construction unit of Isosorbide-5-Nitrae-polymerization methodses formation
Degree of hydrogenation be 2-20%；
The degree of hydrogenation of the construction unit derived from isoprene is 5-90%, and isoprene formed with 3,4- polymerization methodses
The degree of hydrogenation of construction unit is 10-40%, and the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-30%；
The degree of hydrogenation of the construction unit derived from monovinylarene is less than 5%.
The present invention also provides a kind of preparation method of partially hydrogenated terpolymer, and the method is comprised the following steps：
（1）In the presence of the first noble gases, under the first alkene anionic polymerization conditions, in the first reactor, will
1,3-butadiene is contacted in the first solvent with the first initiator, so that 1,3-butadiene is polymerized, obtains the activity of A
Chain；
In the presence of the second noble gases, under the second alkene anionic polymerization conditions, in the second reactor, by isoamyl
Diene is contacted in the second solvent with the second initiator, so that isoprene is polymerized, obtains the living chain of B；
In the presence of the 3rd noble gases, under alkatrienes anionic polymerization conditions, in the 3rd reactor, by benzene second
Alkene is contacted with the 3rd initiator in the 3rd solvent with 1,3-butadiene or isoprene so that styrene and 1,3-butadiene or
Isoprene is polymerized, and obtains the living chain of C；
In the presence of the 4th noble gases, under alkatetraenes anionic polymerization conditions, in the 4th reactor, by benzene second
Alkene, 1,3-butadiene and isoprene are contacted in the 4th solvent with the 4th initiator, so that styrene, 1,3-butadiene and different
Pentadiene is polymerized, and obtains the living chain of D；
（2）By step（1）In add multiple functionalized coupling agent to enter after tetra- kinds of living chain mix homogeneously of A, B, C and D for obtaining
Row is coupled, and coupling reaction adds terminator terminating reaction after terminating, and obtains copolymer solution to be hydrogenated with；
（3）Under hydrogenation conditions, in the presence of a hydrogenation catalyst, make step（2）Treating after middle terminating reaction is hydrogenated with
Copolymer solution and hydrogen contact, to obtain meeting the partially hydrogenated terpolymer of following condition：
The degree of hydrogenation of the construction unit derived from 1,3-butadiene is 5-90%, wherein, 1,3-butadiene is with 1,2- polymerization sides
The degree of hydrogenation of the construction unit that formula is formed is 60-95%, and 1,3-butadiene is with the hydrogenation of the construction unit of Isosorbide-5-Nitrae-polymerization methodses formation
Spend for 2-20%；
The degree of hydrogenation of the construction unit derived from isoprene is 5-90%, and isoprene formed with 3,4- polymerization methodses
The degree of hydrogenation of construction unit is 10-40%, and the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-30%；
The degree of hydrogenation of the construction unit derived from monovinylarene is less than 5%.
Invention further provides application of the above-mentioned ter-polymers in tire tread glue.
The terpolymer that the present invention is provided, while ensureing that polymer has wide distribution dynamic viscoelastic spectrogram, makes to gather
Hysteresis loss under compound low temperature further increases, i.e., wet-sliding resistant performance is further improved；Hysteresis loss under high temperature is further
Reduce, i.e., rolling resistance further reduces；Wearability is further improved, and reaches high wet-sliding resistant, low-rolling-resistance and high abrasion
Property three between preferably balance, improve the polymer as tire tread rubber when combination property.
Specific embodiment
The partially hydrogenated terpolymer that the present invention is provided, the structure such as formula of the partially hydrogenated terpolymer（I）
It is shown：
Formula（I）
Formula（I）In, A is partially hydrogenated 1,3-butadiene homopolymerization section, B is isoprene homopolymerization section；C is partially hydrogenated
The binary copolymerization section or partially hydrogenated styrene and isoprene binary copolymerization section of styrene and 1,3- butadiene；D is portion
Divide styrene, 1,3- butadiene and the isoprene ternary polymerization section of hydrogenation；X is the residue of multifunctional coupling agent, and,
Wherein, e, f, g, j are respectively the arm number of A, B, C, D, and respectively more than or equal to zero, and one of them is when being zero, its
Its three is respectively more than or equal to the quantity of the residue that 1, m-e-f-g-j is multifunctional coupling agent, and m-e-f-g-j >=0,3≤e
+ f+g+j≤25,
Wherein, the degree of hydrogenation of the construction unit derived from 1,3-butadiene is 5-90%, wherein, 1,3-butadiene is with 1,2-
The degree of hydrogenation of the construction unit that polymerization methodses are formed is 60-95%, and 1,3-butadiene is with the construction unit of Isosorbide-5-Nitrae-polymerization methodses formation
Degree of hydrogenation be 2-20%；The degree of hydrogenation of the construction unit derived from isoprene is 5-90%, and isoprene is with 3,4- polymerization sides
The degree of hydrogenation of the construction unit that formula is formed is 10-40%, and isoprene is with the degree of hydrogenation of the construction unit of Isosorbide-5-Nitrae-polymerization methodses formation
For 2-30%；The degree of hydrogenation of the construction unit derived from monovinylarene is less than 5%.
Under preferable case, according to the partially hydrogenated terpolymer that the present invention is provided, wherein, m-e-f-g-j>0,3≤e
+f+g+j≤22；It is preferred that 3≤e+f+g+j≤20；Still more preferably 4≤e+f+g+j≤18, then still more preferably 4≤e+f
+ g+j≤15, most preferably 4≤e+f+g+j≤12.In one embodiment of the invention, e+f+g+j can be 3 or 4, preferably
For 4.
X is many vinyl-arenes, polyfunctional epoxide, group with imine moiety, aldehyde, ketone, acid anhydride, ester, polyisocyanates
With the residue of one or more in polyhalide；Preferably divinylbenzene, tetravinyl silane, tetrachloromethane, four chlorinations
The residue of one or more in silicon, butter of tin and dimethyl terephthalate (DMT)；More preferably Silicon chloride. and/or four
The residue of stannic chloride.
According to the present invention, it is contemplated that the combination property of partially hydrogenated terpolymer, it is preferable that derived from 1,3- fourths two
The degree of hydrogenation of the construction unit of alkene be 10-60%, wherein, the construction unit that 1,3-butadiene is formed with 1,2- polymerization methodses add
Hydrogen degree is 70-90%, and the degree of hydrogenation of the construction unit that 1,3-butadiene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-18%；Further preferably
Ground, the degree of hydrogenation of the construction unit derived from 1,3-butadiene is 37-42%, and 1,3-butadiene is formed with 1,2- polymerization methodses
The degree of hydrogenation of construction unit be 75-85%, the degree of hydrogenation of the construction unit that 1,3-butadiene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 5-
15%；The degree of hydrogenation of the construction unit derived from isoprene is 12-20%, and the knot that isoprene is formed with 3,4- polymerization methodses
The degree of hydrogenation of structure unit is 20-30%, and the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 5-15%；Spread out
The degree of hydrogenation for being conigenous the construction unit of monovinylarene is less than 2%.
In the present invention, the degree of hydrogenation of each construction unit adopts proton nmr spectra（1H-NMR）Absorb spectrogram to measure.
According to the partially hydrogenated terpolymer that the present invention is provided, it is preferable that the A is partially hydrogenated 1,3- fourths two
Polyamino alkenyl section, the number-average molecular weight of the A is 5000-500000, preferably 30000-180000, more preferably 50000-
120000；And the structural unit content that formed with 1,2- polymerization methodses of the 1,3-butadiene in A is 8-80 weight %, preferably 8-
50 weight %, more preferably 10-30 weight %.
According to the partially hydrogenated terpolymer that the present invention is provided, it is preferable that the B is partially hydrogenated isoprene
Homopolymerization section, the number-average molecular weight of the B is 5000-500000, preferably 30000-180000, more excellent to select 50000-
120000；And the structural unit content that isoprene is formed with 3,4- polymerization methodses in B is 7-80 weight %, preferably 8-70 weights
Amount %, more preferably 8-60 weight %.
According to the present invention provide partially hydrogenated terpolymer, it is preferable that the C be partially hydrogenated styrene and
The copolymerization section of 1,3-butadiene or styrene and isoprene, wherein, it is 5-50 weights derived from cinnamic structural unit content
Amount %, the content derived from 1,3-butadiene or the construction unit of isoprene is 50-95 weight %, is preferably derived from cinnamic
Structural unit content is 15-40 weight %, and the content derived from 1,3-butadiene or the construction unit of isoprene is 60-85 heavy
Amount %；Number-average molecular weight is 20000-500000, preferably 50000-250000, more preferably 80000-180000；Wherein, with
On the basis of the weight of the construction unit derived from 1,3-butadiene, the construction unit that 1,3-butadiene is formed with 1,2- polymerization methodses
Content is 8-95 weight %, preferably 20-75 weight %, more preferably 25-55 weight %；With the structure list derived from isoprene
On the basis of the weight of unit, the structural unit content that isoprene is formed with 3,4- polymerization methodses is 8-95 weight %, preferably 20-
75 weight %, more preferably 25-55 weight %.
According to the present invention provide partially hydrogenated terpolymer, it is preferable that the D be partially hydrogenated styrene,
Butadiene and isoprene ternary polymerization section, and the content derived from cinnamic construction unit is 5-50 weight %, derived from 1,
The content of the construction unit of 3- butadiene is 5-85 weight %, and the content of the construction unit derived from isoprene is 5-85 weights
Amount %, the content for being preferably derived from cinnamic construction unit are 15-40 weight %, the construction unit derived from 1,3-butadiene
Content is 10-75 weight %, and the content of the construction unit derived from isoprene is 10-75 weight %；The number-average molecular weight of the D
For 20000-500000, more preferably preferably 50000-250000,80000-180000；Wherein, with derived from 1,3- fourths two
On the basis of the gross weight of the construction unit of alkene and the construction unit derived from isoprene, 1,3-butadiene is with 1,2- polymerization methodses
The structural unit content sum that the construction unit and isoprene of formation is formed with 3,4- polymerization methodses is 8-95 weight %, preferably
For 20-75 weight %, more preferably 30-55 weight %.
According to the partially hydrogenated terpolymer that the present invention is provided, it is preferable that the partially hydrogenated terpolymer
Coupling efficiency be 20-100%, preferably 30-80%, more preferably 40-70%.
In the present invention, remaining conjugated diene polymer after the content for being coupled the polymer for being formed and coupling
Content（That is, coupling efficiency）It is to be determined using gel permeation chromatography method.Specifically method of testing is：The mixing that coupling is obtained
Thing carries out gpc analysis, the peak area and idol of the polymer formed with coupling corresponding to the peak area for being coupled the polymer for being formed
After connection, the ratio of the peak area sum of remaining conjugated diene polymer is exactly the content for being coupled the polymer for being formed, i.e. even
The number for coupled strand that connection efficiency is measured accounts for the percentage by weight of the total number of strand.
The preparation method of ter-polymers of the invention, the method are comprised the following steps：
（1）In the presence of the first noble gases, under the first alkene anionic polymerization conditions, in the first reactor, will
1,3-butadiene is contacted in the first solvent with the first initiator, so that 1,3-butadiene is polymerized, obtains the activity of A
Chain；
In the presence of the second noble gases, under the second alkene anionic polymerization conditions, in the second reactor, by isoamyl
Diene is contacted in the second solvent with the second initiator, so that isoprene is polymerized, obtains the living chain of B；
In the presence of the 3rd noble gases, under alkatrienes anionic polymerization conditions, in the 3rd reactor, by benzene second
Alkene is contacted with the 3rd initiator in the 3rd solvent with 1,3-butadiene or isoprene so that styrene and 1,3-butadiene or
Isoprene is polymerized, and obtains the living chain of C；
In the presence of the 4th noble gases, under alkatetraenes anionic polymerization conditions, in the 4th reactor, by benzene second
Alkene, 1,3-butadiene and isoprene are contacted in the 4th solvent with the 4th initiator, so that styrene, 1,3-butadiene and different
Pentadiene is polymerized, and obtains the living chain of D；
（2）By step（1）In add multiple functionalized coupling agent to be coupled after four kinds of living chain mix homogeneously obtaining, it is even
Connection reaction adds terminator terminating reaction after terminating, and obtains copolymer solution to be hydrogenated with；
（3）Under hydrogenation conditions, in the presence of a hydrogenation catalyst, make step（2）Treating after middle terminating reaction is hydrogenated with
Copolymer solution and hydrogen contact, to obtain the terpolymer of the selective hydration for meeting following condition：
The degree of hydrogenation of the construction unit derived from 1,3-butadiene is 5-90%, wherein, 1,3-butadiene is with 1,2- polymerization sides
The degree of hydrogenation of the construction unit that formula is formed is 60-95%, and 1,3-butadiene is with the hydrogenation of the construction unit of Isosorbide-5-Nitrae-polymerization methodses formation
Spend for 2-20%；
The degree of hydrogenation of the construction unit derived from isoprene is 5-90%, and isoprene formed with 3,4- polymerization methodses
The degree of hydrogenation of construction unit is 10-40%, and the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-30%；
The degree of hydrogenation of the construction unit derived from monovinylarene is less than 5%.
According to the preparation method that the present invention is provided, it is preferable that the degree of hydrogenation of the construction unit derived from 1,3-butadiene is
10-60%, wherein, the degree of hydrogenation of the construction unit that 1,3-butadiene is formed with 1,2- polymerization methodses is 70-90%, 1,3-butadiene
The degree of hydrogenation of the construction unit formed with 1,4- polymerization methodses is as 2-18%；It is further preferred that the knot derived from 1,3-butadiene
The degree of hydrogenation of structure unit is 37-42%, and the degree of hydrogenation of construction unit that 1,3-butadiene is formed with 1,2- polymerization methodses is 75-
85%, the degree of hydrogenation of the construction unit that 1,3-butadiene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 5-15%；Knot derived from isoprene
The degree of hydrogenation of structure unit is 12-20%, and the degree of hydrogenation of construction unit that isoprene is formed with 3,4- polymerization methodses is 20-
30%, the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 5-15%；Derived from monovinylarene
The degree of hydrogenation of construction unit is less than 2%.
The degree of hydrogenation of the construction unit derived from isoprene is 12-20%, and isoprene formed with 3,4- polymerization methodses
The degree of hydrogenation of construction unit be 20-30%, the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 5-
15%；
The degree of hydrogenation of the construction unit derived from monovinylarene is less than 2%.
The present invention is not particularly limited for the species of the hydrogenation catalyst, can be the conventional selection of this area.It is excellent
Selection of land, the hydrogenation catalyst are the mixture of major catalyst and promoter, and major catalyst is the VIIIth race of periodic table of elements gold
Category compound and/or coordination compound, promoter is alkyl metal cpd；It is preferred that the major catalyst of the hydrogenation catalyst is ring
Alkanoic acid nickel and/or nickel octoate, the promoter of the hydrogenation catalyst are triisobutyl aluminium, triethyl aluminum, n-BuLi and secondary
One or more in butyl lithium, more preferably triisobutyl aluminium and/or triethyl aluminum.The hydrogenation catalyst agent composition
Middle aluminum is 1-7 with the mol ratio of nickel:1, preferably 3-6:1.
In accordance with the present invention it is preferred that, the hydrogenation catalyst consumption treats hydrogenated copolymer for 0.01-0.08gNi/100g,
Preferably 0.02-0.06gNi/100g treats hydrogenated copolymer.
In accordance with the present invention it is preferred that, the hydrogenation conditions include：Reaction temperature is 30-120 DEG C, preferably 40-70
℃；Reaction pressure 0.1-4.0MPa, preferably 0.2-3.0MPa；Response time is 2-180 minutes, preferably 5-60 minutes.
Polymerization of the invention, from the angle for being easy to describe, by the alkene anion in the first reactor
Polymerizing condition is referred to as " the first alkene anionic polymerization conditions ", and the alkene anionic polymerization conditions in the second reactor are referred to as
" the second alkene anionic polymerization conditions ", the alkene anionic polymerization conditions in the 3rd reactor are referred to as " alkatrienes it is cloudy from
Alkene anionic polymerization conditions in 4th reactor are referred to as " alkatetraenes anionic polymerization conditions " by sub- polymerizing condition ".This
The polymerization of invention is for the first alkene anionic polymerization conditions, the second alkene anionic polymerization conditions, described
Alkatrienes anionic polymerization conditions and the alkatetraenes anionic polymerization conditions are not particularly limited, and can be respectively ability
The conventional selection in domain, as long as the monomer polymerization enabled in each step polymerization is complete.
Preferably, the first alkene anionic polymerization conditions include：Temperature be 20-100 DEG C, preferably 40-70 DEG C, when
Between be 10-120 minutes, preferably 30-60 minutes；The second alkene anionic polymerization conditions include：Temperature is 20-100 DEG C,
Preferably 40-70 DEG C, the time is 10-120 minutes, preferably 30-60 minutes；The alkatrienes anionic polymerization conditions bag
Include：Temperature is 30-100 DEG C, and preferably 40-80 DEG C, the time is 30-120 minutes, preferably 30-90 minutes.The alkatrienes
Anionic polymerization conditions include：Temperature be 30-100 DEG C, preferably 40-80 DEG C, the time be 30-120 minutes, preferably 30-90
Minute.
According to the present invention, noble gases refer to any gas for being not involved in polymer reaction, such as nitrogen, helium etc..
The first noble gases, the second noble gases, the 3rd noble gases and the 4th noble gases in the present invention can with identical or different,
It is each independently selected from nitrogen and/helium.
Preparation in accordance with the present invention, from the angle for being easy to describe, the solvent used in the first reactor is claimed
For " the first solvent ", the solvent used in the second reactor is referred to as into " the second solvent ", by the solvent used in the 3rd reactor
Referred to as " the 3rd solvent ", the solvent used in the 4th reactor is referred to as into " the 4th solvent ".First solvent, the second solvent,
3rd solvent and the 4th solvent can be various non-polar hydrocarbon series solvents commonly used in the art, as long as the non-polar hydrocarbon series solvent exists
It is liquid under polymerizing condition, and both cannot participate in polyreaction also chemical interaction will not occur with polymer.Typically
Ground, the solvent selected by the present invention can be anionic polymerisation solvent disclosed in prior art, wherein, the first solvent, second
Solvent, the 3rd solvent and the 4th solvent can be each independently the cycloalkane containing 5-7 carbon atom, virtue with identical or different
One or more in hydrocarbon and isoparaffin；At least one preferably in benzene, toluene, hexamethylene, pentane and heptane.At each
In reactor, the consumption of preferably each solvent causes monomer concentration in 5-30 weight %, preferably in the range of 8-20 weight %, so
Polyreaction is steadily carried out, but also be obtained in that higher production efficiency.
Polymerization of the invention, from the angle for being easy to describe, by the initiator used in the first reactor
Referred to as " the first initiator ", the initiator used in the second reactor is referred to as into " the second initiator ", will be made in the 3rd reactor
Initiator is referred to as " the 3rd initiator ", and the initiator used in the 4th reactor is referred to as " the 4th initiator ".Described
One initiator, the second initiator, the 3rd initiator and the 4th initiator can cause mono-vinyl for commonly used in the art
Aromatic hydrocarbons and conjugated diene carry out the organo-lithium compound of anionic polymerisation, are not particularly limited.Selected by the present invention first
Initiator, the second initiator, the 3rd initiator and the 4th initiator can be using anionic polymerisations disclosed in prior art with drawing
Agent is sent out, and organolithium is preferably used as initiator.The organic lithium initiator can be organic single-lithium, organic pair of lithium or organic many
Lithium.In polymerization process, the consumption of initiator depends on the size of design molecular weight.General initiator amount is that every 100g monomers are needed
Add 0.05-20mmol.
Disclosed in prior art, anionic polymerisation organic single-lithium initiator is used equally to the present invention, and they are preferably C1-C6
Lithium alkylide, C6-C12Aryl lithium, C7-C14Aralkyl lithium, C3-Cl2Cycloalkyl lithium, more preferably ethyl-lithium, isopropyl lithium, normal-butyl
Lithium, s-butyl lithium, tert-butyl lithium, t-octyl lithium, AI3-28404 base lithium, phenyl lithium, 2- naphthyl lithiums, 4- butyl phenyl lithiums, 4- first
One or more in phenyl lithium, cyclohexyl lithium and 4- butylcyclohexyl lithiums, most preferably n-BuLi and/or s-butyl lithium,
Especially n-BuLi.
Anionic polymerisation disclosed in prior art is used equally to the present invention with organic Dilithium initiator, and they are preferably two lithiums
One or more in methane, bis- lithium butane of 1,4-, bis- lithium hexamethylene of bis- lithium decane of 1,10- and 1,4-.
Initiator used in the present invention can also be any multifunctional lithium initiator disclosed in prior art, and they are excellent
Elect the mixture of single multifunctional lithium initiator or several multifunctional lithium initiators, such as RLi asn、T（RLi）n, wherein：R is that carbon is former
Alkyl of the subnumber for 4-20, R can be alkyl or aryl, and T is metallic atom, generally stannum Sn, silicon Si, lead Pb, titanium Ti, germanium Ge
Deng metallic element, n is initiator degree of functionality, and n is generally the integer of 3-150 more than or equal to 3, n, preferably the integer of 3-50, most
The preferably integer of 3-10.Multifunctional lithium initiator RLin can also be multi-chelate organolithium initiator, such as GB2124228A,
The divinylbenzene mentioned in the patents such as US3280084, EP0573893A2, CN1197806A（DVB）Obtain with lithium alkylide reaction
Various multi-chelate organolithium initiators, aforementioned documents are specially incorporated herein by reference.Multifunctional lithium initiator can also be
Multifunctional organic lithium initiator T (RLi) containing above-mentioned metaln, multifunctional lithium initiator T (RLi)nIt is selected generally from stanniferous Sn classes many
Sense organolithium causes Sn (RLi)n, the multifunctional organic lithium initiator Sn of the stanniferous Sn classes such as mentioned in patent CN1148053A
(RLi)4.Multifunctional lithium initiator can also be that other can be used in causing butadiene, isoprene equiconjugate alkadienes and benzene
Multifunctional organic lithium initiator of the degree of functionality of vinyl monomer not less than 3, such as mentions in patent US5262213, US5595951
Various multifunctional organic lithium initiator, aforementioned documents are specially incorporated herein by reference.
Preparation in accordance with the present invention, in a kind of specific embodiment, the first alkene anionic polymerisation, second
Alkene anionic polymerisation, alkatrienes anionic polymerisation and alkatetraenes anionic polymerisation independently of one another can be in structural conditions
In the presence of carry out, from be easy to describe angle, by the structure regulator used in the first reactor be referred to as " first structure
Structure regulator used in second reactor is referred to as " the second structure regulator ", used in the 3rd reactor by regulator "
Structure regulator be referred to as " the 3rd structure regulator ", by the structure regulator used in the 4th reactor be referred to as " the 4th structure
Regulator ".The first structure regulator, the second structure regulator, the 3rd structure regulator and the 4th structure regulator can be with
For the material of the commonly used in the art microstructure that can adjust polymer, it is not particularly limited.Selected by the present invention first
Structure regulator, the second structure regulator, the 3rd structure regulator and the 4th structure regulator can be disclosed in prior art
The polar modifier of anionic polymerisation, including nitrogenous, sulfur-bearing and phosphorous etc. compound and their mixture, the present invention
In, the example of the first structure regulator, the second structure regulator, the 3rd structure regulator and the 4th structure regulator can be with
For but be not limited to：Ether, butyl oxide, tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, dioxy six
Ring, crown ether, triethylamine, tetramethylethylenediamine, HMPA, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkylbenzene
One or more in potassium sulfonate and sodium alkyl benzene sulfonate.Preferably, the first structure regulator, the second structure regulator,
3rd structure regulator and the 4th structure regulator are respectively tetrahydrofuran.
The consumption of structure regulator is not particularly limited in the preparation process in accordance with the present invention, is tied according to designed polymer
Depending on structure, in the case of obtaining same polymer structure, the consumption of different adjustment agent is also different, it is preferable that step（1）In, with
Weight meter, the concentration of the first structure regulator, the second structure regulator, the 3rd structure regulator and the 4th structure regulator
For 1-1000ppm, preferably 50-200ppm.
The present invention is not specially required for the weight ratio of tetra- kinds of living chains of A, B, C and D, from partially hydrogenated ternary polymerization
The combination property of thing considers, it is preferable that the weight ratio of tetra- kinds of living chains of A, B, C and D can be 1：0.1-10：0.2-10：0.2-
10, more preferably 1：0.3-3：0.5-5：0.5-3.
Multifunctional coupling agent selected by the present invention can be anionic polymerisation coupling agent disclosed in prior art, be coupled
So that tetra- kinds of living chain 20-100% of A, B, C and D are coupled, preferred 30-80% is coupled for the consumption of agent.
The present invention is not particularly limited for the species of the coupling agent, can be carried out suitably according to expected application scenario
Selection.When the synthetic rubber for preparing is used to prepare tire, the coupling agent can be many vinyl-arenes, polyfunctional ring
One or more in oxygen compound, group with imine moiety, aldehyde, ketone, acid anhydride, ester, polyisocyanates and polyhalide；Preferably diethyl
One kind or many in alkenyl benzene, tetravinyl silane, tetrachloromethane, Silicon chloride., butter of tin and dimethyl terephthalate (DMT)
Kind；One or more more preferably in divinylbenzene, Silicon chloride. and butter of tin；Most preferably Silicon chloride. and/or
Butter of tin.
Preparation in accordance with the present invention, by the condition are coupled by tetra- kinds of living chain coupling agents of A, B, C and D can be
The conventional selection of this area, reacted can tetra- kinds of living chains of the coupling agent and A, B, C and D, so as to form coupling
Product is defined.Usually, the temperature that tetra- kinds of living chains of described A, B, C and D contact to be coupled with the coupling agent can be
20-120 DEG C, preferably 60-100 DEG C；Time can be 5-90 minutes, preferably 10-60 minutes.
Preparation in accordance with the present invention, step（2）After the completion of middle coupling reaction, can adopt commonly used in the art various
Living polymer chains are inactivated by method.For example：Can be by adding polymerization terminator in the mixture that obtains to coupling reaction
To make living polymer chains lose activity.Terminator selected by the present invention can select the conventional termination in anionic polymerisation field
Agent, available terminator mostly are water or alcohols, such as water, methanol, ethanol, positive isopropanol, isopropanol etc..Preferably use isopropyl
Alcohol is used as terminator.It is 0.1-1 with the mol ratio of organolithium that the consumption of terminator should make terminator.
Preparation in accordance with the present invention, the condition terminated by the mixing agent after coupling reaction can be this area
Conventional selection, it is preferable that step（2）Middle terminating reaction temperature is 0-100 DEG C, and preferred 40-70 DEG C, terminating reaction pressure is
0.005-1MPa gauge pressures, preferably 0.1-0.3MPa gauge pressures, terminating reaction time are 5-60 minutes, preferably 10-30 minutes.
Preparation in accordance with the present invention, can also add various additives and/or auxiliary agent according to specific use requirement,
To give the terpolymer with various performances or function.Preferably, the method according to the invention can also add age resistor, with
Make the terpolymer and the material formed by the terpolymer of the present invention of the present invention that there is good ageing resistace.
Age resistor selected by the present invention is the conventional age resistor of anionic polymerisation, includes but are not limited to Irganox1520
(Ciba of Switzerland), four [3- (3,5- di-tert-butyl-hydroxy phenyls) propanoic acid] pentaerythritol ester (i.e. 1010)/phosphorous acid three
(2,4- di-tert-butyl-phenyls) ester (i.e. 168)) compound age resistor (wherein 168 content is not higher than 50 weight %), 3- (3,5-
Di-tert-butyl-hydroxy phenyl) ester is (i.e. for propanoic acid stearyl (i.e. 1076)/phosphorous acid three (2,4- di-tert-butyl-phenyls)
168) compound age resistor (wherein 168 content is not higher than 50 weight %).Addition age resistor such as Irganox 1520 is to prevent altogether
Double bond in yoke diene polymer strand and oxygen etc. contact after under certain condition, produce under such as heat effect it is bad after
Really, the such as reaction such as crosslinking, degraded, increases gel content of the rubber in toluene solution.
The present invention is not particularly limited for the consumption of the age resistor, can be the conventional selection of this area.Preferably,
On the basis of the weight of terpolymer described in 100 weight portions, the consumption of the age resistor is 0.05-2 weight portions.
Finally, terpolymer can be by refining the similar fashions such as precipitation, centrifugation, filtration, decantation, hot water cohesion
The Precipitation from solvent, it would however also be possible to employ the volatile organic solvent in copolymer is separated by stripping mode.
Terpolymer is hydrogenated according to the part that said method is prepared.
Ter-polymer rubber is hydrogenated by part prepared by synthetic method of the present invention to can be used for preparing various rubbers,
It is especially suitable for making tire tread glue use.
Method of testing according to the present invention is as follows：
1st, the microstructure of polymer（That is, conjugated diene monomer is formed with 1,2- polymerization methodses and 3,4- polymerization methodses
Construction unit amount, with 1,4- polymerization methodses formed construction unit amount）Using commercially available from Nicolet companies of the U.S. 560
Type fourier transform infrared spectroscopy is determined, and solvent is CS2.Wherein, St% represents containing derived from cinnamic construction unit
Amount, Isosorbide-5-Nitrae-Bd% represent the content of the construction unit that butadiene is formed in the way of Isosorbide-5-Nitrae-polymerization, and Isosorbide-5-Nitrae-Ip% represents isoprene
The content of the construction unit formed in the way of Isosorbide-5-Nitrae-polymerization, what the mode that 1,2-Bd% represents butadiene is polymerized with 1,2- was formed
The content of construction unit, the content of the construction unit that the mode that 3,4-Ip% represent isoprene is polymerized with 3,4- is formed, side base knot
The structure list that construction unit and the isoprene that structure % is represented butadiene and formed with 1,2- polymerization methodses is formed with 3,4- polymerization methodses
The total content of unit.
2nd, molecular weight, molecular weight distribution and coupling efficiency adopt U.S.'s WATERS companies 150C type chromatograph of gel permeation
(GPC) determine, THF is mobile phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C, wherein, coupling efficiency refers to coupled
Strand number account for strand total number percentage by weight.
3rd, degree of hydrogenation adopts Switzerland's BRUKER DRX400 type nmr determination proton nmr spectras（1H-NMR）Absorb
Spectrogram, with deuterochloroform（CDCl3）For solvent, polymer samples are made into into 1-2% at normal temperatures（w/v）Solution, with tetramethyl
Radical siloxane（TMS）For internal standard.1H-NMR operating frequencies：400.13MHz, spectrum width：8012.82Hz, data point 32K, pulse angle
45 degree, 6 μ s of pulse width, pulse daley 5s, sampling number 64, wherein,
Degree of hydrogenation=（Degree of unsaturation after degree of unsaturation-hydrogenation before hydrogenation）Degree of unsaturation × 100% before/hydrogenation,
The degree of hydrogenation of the construction unit derived from 1,3- butadiene=（Construction unit derived from 1,3- butadiene before hydrogenation
Degree of unsaturation-hydrogenation after the construction unit derived from 1,3- butadiene degree of unsaturation）Derived from 1,3- butadiene before/hydrogenation
Construction unit degree of unsaturation × 100%；
The degree of hydrogenation of the construction unit that 1,3- butadiene is formed with 1,2- polymerization methodses=（Front 1,3- butadiene is hydrogenated with 1,
The degree of unsaturation that 1,3- butadiene is formed with 1,2- polymerization methodses after degree of unsaturation-hydrogenation that 2- polymerization methodses are formed）Before/hydrogenation
Degree of unsaturation × 100% that 1,3- butadiene is formed with 1,2- polymerization methodses；
The degree of hydrogenation of the construction unit that 1,3- butadiene is formed with 1,4- polymerization methodses=（Front 1,3- butadiene is hydrogenated with 1,
The degree of unsaturation that 1,3- butadiene is formed with 1,4- polymerization methodses after degree of unsaturation-hydrogenation that 4- polymerization methodses are formed）Before/hydrogenation
Degree of unsaturation × 100% that 1,3- butadiene is formed with 1,4- polymerization methodses；
The degree of hydrogenation of the construction unit derived from isoprene=（The front construction unit derived from isoprene of hydrogenation is not
The degree of unsaturation of the construction unit derived from isoprene after saturation-hydrogenation）Structure list derived from isoprene before/hydrogenation
Degree of unsaturation × 100% of unit；
The degree of hydrogenation of the construction unit that isoprene is formed with 3,4- polymerization methodses=（Before hydrogenation, isoprene is poly- with 3,4-
The degree of unsaturation that isoprene is formed with 3,4- polymerization methodses after degree of unsaturation-hydrogenation that conjunction mode is formed）Isoamyl two before/hydrogenation
Degree of unsaturation × 100% that alkene is formed with 3,4- polymerization methodses；
The degree of hydrogenation of the construction unit that isoprene is formed with 1,4- polymerization methodses=（Before hydrogenation, isoprene is poly- with 1,4-
The degree of unsaturation that isoprene is formed with 1,4- polymerization methodses after degree of unsaturation-hydrogenation that conjunction mode is formed）Isoamyl two before/hydrogenation
Degree of unsaturation × 100% that alkene is formed with 1,4- polymerization methodses.
4th, glass transition temperature is determined using U.S. TA companies MDSC2910 type differential scanning calorimetry (DSC) instrument, is adjusted
Cycle processed is 60 seconds, modulated amplitude ± 1.5 DEG C, 10 DEG C/min of heating rate, nitrogen protection, flow velocity 50mL/min.
5th, dynamic mechanical is determined using U.S.'s TA companies DMA-2980 types viscoelastic spectrometer, frequency 2Hz, heating rate 5
DEG C/min, -120 DEG C to 100 DEG C of temperature, sample size 40mm × 5mm × 1mm.
6th, elastomeric mechanical property is pressed using the XLL250 type rubber puller systems commercially available from four factory of Shanghai chemical machinery
Determine according to method specified in GB/T528-1998.
7th, vulcanizating glue physical performance presses GB/T528-1998 measure using XLL250 type rubber puller systems；Mooney viscosity is adopted
Japanese SHIMADZU Mooney viscosities instrument presses GB/T1232-92, wherein, use big specified in GB/T1232-92 during test
Rotor.
In following examples and comparative example, the sample for determining fissipation factor and mechanical property is according to GB/T8656-
A series formula in 1998 is vulcanized and is prepared, and conditions of vulcanization includes：Rubber adopts mill mixing, is 50 in roller temperature
Kneaded at ± 5 DEG C；The temperature of sulfuration is 145 DEG C, and pressure is more than 10MPa, and cure time is 35 minutes.
Embodiment 1
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
（1）Under high pure nitrogen protection, hexamethylene 720g, 1,3-butadiene 80g are added in reactors of the 2L with stirring,
0.9mL tetrahydrofurans, are heated to 60 DEG C, add 2.2mL concentration to be 0.5mol/L n-BuLis, are polymerized 50 minutes, form activity
1,3- butadiene homopolymerization sections A.
（2）Under high pure nitrogen protection, hexamethylene 610g, isoprene 40g are added in reactors of the 2L with stirring, plus
Heat is added 1.0mL concentration to be 0.5mol/L n-BuLis, is polymerized 50 minutes, form the homopolymerization section of active isoprene to 60 DEG C
B。
（3）Under high pure nitrogen protection, hexamethylene 1500g, styrene 40g, 1 are added in reactors of the 3L with stirring,
3- butadiene 160g, 4.4mL tetrahydrofurans are heated to 50 DEG C, add 2.9mL concentration for 0.5mol/L n-BuLis, polymerization 50
Minute, form the binary copolymerization section of active styrene and 1,3-butadiene.
（4）Under high pure nitrogen protection, hexamethylene 720g, styrene 16g, 1,3- are added in reactors of the 2L with stirring
Butadiene 32g, isoprene 32g, 1.5mL tetrahydrofurans are heated to 50 DEG C, add 0.96mL concentration to be 0.5mol/L normal-butyls
Lithium, is polymerized 50 minutes, forms active styrene, 1,3-butadiene and isoprene ternary polymerization section D.
（5）Active A, B, C and D polymeric segment is proceeded to into reactors of the 7L with stirring under high pure nitrogen protection together,
50 DEG C are heated to, are mixed 30 minutes, add 0.43mmol butters of tin to be coupled, kept for 50 DEG C be coupled 30 minutes, add 1.9mmol
Isopropanol terminating reaction, obtains polymer solution to be hydrogenated with.
（6）Hydrogenation catalyst is added in the polymer solution to be hydrogenated with after above-mentioned termination under agitation, hydrogen is then passed to
Gas carries out hydrogenation reaction, is hydrogenated with the mixture that used catalyst is nickel octoate and triethyl aluminum, and wherein Al/Ni mol ratios are 4：1,
Catalyst amount treats hydrogenated polymers for 0.03gNi/100g, and hydrogenation reaction temperature is 60 DEG C, and hydrogenation reaction pressure is 1.0MPa,
Response time is 20 minutes.Glue after hydrogenation adds 0.4g age resistor Irganox 1520.
With reference to United States Patent (USP) US3 after hydrogenation, in 780.138, the method removing hydrogenation catalyst of embodiment 1, makes polymerization
Remaining nickel content in thing is less than 5ppm, and remaining Al content is less than 10ppm.The polymer of hydrogenation catalyst is removed after this is hydrogenated
Dry in 80 DEG C of vacuum drying oven after solution devaporation standby to constant weight.Polymer（Ternary before and after part hydrogenates is common
Polymers）Structure is shown in Table 1.
The part hydrogenation terpolymer of embodiment 1 is carried out carrying out sulfur according to the A series formula in GB/T8656-1998
Change and prepare, conditions of vulcanization includes：Rubber adopts mill mixing, is to be kneaded at 50 ± 5 DEG C in roller temperature；The temperature of sulfuration
Spend for 145 DEG C, pressure is more than 10MPa, and cure time is 35 minutes.Obtain vulcanite performance and be shown in Table 2.
Embodiment 2
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, step（1）In be added without tetrahydrofuran, and concentration be 0.5mol/L just
The addition of butyl lithium be 3.2mL, step（5）Middle addition 0.45mmol silicon tetrachlorides.Polymer（Before and after part hydrogenates
Terpolymer）Structure is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 3
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
Remaining repeats embodiment 1 substantially, except that, step（1）In structure regulator and initiator species and
Consumption is adjusted to：1.6mL tetrahydrofurans, and concentration is 1.2mL for the addition of 0.5mol/L n-BuLis.Polymer（Part
Terpolymer before and after hydrogenation）Structure is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 4
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, 40g butadiene and 0.2mL tetrahydrofurfuryl alcohol ether are added in step (2),
Step（3）Middle addition 30g styrene, step（4）Middle addition 27g styrene.Polymer（Ternary polymerization before and after the hydrogenation of part
Thing）Structure is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 5
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, it is 0.5mol/L n-BuLis that step (2) adds 1.6mL concentration.It is poly-
Compound（Terpolymer before and after the hydrogenation of part）Structure is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 6
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, it is 0.5mol/L n-BuLis that step (2) adds 0.67mL concentration.It is poly-
Compound（Terpolymer before and after the hydrogenation of part）Structure is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 7
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, it is 0.5mol/L n-BuLis that step (3) adds 5.0mL concentration.It is poly-
Compound（Terpolymer before and after the hydrogenation of part）It is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 8
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, step (3) adds isoprene 160g, 0.5mL tetrahydrofurfuryl alcohol ether
And 2.5mL concentration is 0.5mol/L n-BuLis.Polymer（Terpolymer before and after the hydrogenation of part）Structure is shown in Table 1.Sulfuration
Rubber performance is shown in Table 2.
Embodiment 9
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, step (4) adds 2.0mol/L n-BuLis.Polymer（Part hydrogen
Terpolymer before and after change）Structure is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 10
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, the double tetrahydrochysene bran propane of step (4) addition 0.4mL and 1.0mL concentration are
0.5mol/L n-BuLis, step（5）Middle addition 0.6mmol silicon tetrachlorides, step（6）In hydrogenation reaction temperature be 40
DEG C, hydrogenation reaction pressure is 0.5MPa, and the response time is 5 minutes.Post-consumer polymer structure is shown in Table 1.Vulcanite performance is shown in Table 2.
Embodiment 11
The present embodiment is used for illustrating terpolymer of the invention and preparation method thereof.
It is basic to repeat embodiment 1, except that, formula when partially hydrogenated terpolymer is kneaded is as follows：
Rubber is 100 parts of terpolymer of part hydrogenation;40 parts of white carbon;5 parts of aromatic naphtha；5 parts of Zinc Oxide;2 parts of stearic acid;Sulfur
1.70 part;2.5 parts of accelerator;Age resistor 1.0.Vulcanite performance is shown in Table 2.
Comparative example 1
It is basic to repeat embodiment 1, except that, hydrogenation reaction is not gone on after the completion of polyreaction.Vulcanite
Performance is shown in Table 2.
Comparative example 2
It is basic to repeat embodiment 1, except that, during hydrogenation reaction, catalyst amount is 0.06gNi/100g polymer,
Hydrogenation reaction temperature is 70 DEG C, and hydrogenation reaction pressure is 3.0MPa, and the response time is 180 minutes.After hydrogenation reaction is completed, Jing is surveyed
Fixed, in polymer, the degree of hydrogenation of polybutadiene section and polyisoprene section is all higher than 98%.Due in polybutadiene section in polymer
Isosorbide-5-Nitrae-construction unit complete hydrogenation post-consumer polymer in have longer polyethylene segment, cause have part in hydrogenation process
Polymer is separated out from solution, affects being normally carried out for hydrogenation reaction, in addition the elasticity of alkadienes section complete hydrogenation post-consumer polymer
Reduce, it is impossible to which routinely rubber is processed, also cannot use in enterprising enforcement of tire.
1. polymer architecture data of table
Table 1（It is continuous）
Note：Degradation takes LP-61 type ageing oven hot-air accelerated ageings, and aging condition is 100 DEG C × 24h, aging
Then storage period 16h carries out quantitative measurement, and carry out Performance comparision with unaged sample to aging rear sample afterwards.Below
In table 1,1,2-PB refer to 1,3-butadiene with 1,2- polymerization methodses formed construction unit, Isosorbide-5-Nitrae-PB refer to 1,3-butadiene with
The construction unit that 1,4- polymerization methodses are formed；Isosorbide-5-Nitrae-PI refer to isoprene with 1,2- polymerization methodses formed construction unit, 3,
4-PI refers to isoprene with the construction unit of 3,4- polymerization methodses formation, and in table, the data of the content of construction unit are with ternary
On the basis of the gross weight of copolymer.
Table 2
Note：Degradation takes LP-61 type ageing oven hot-air accelerated ageings, and aging condition is 100 DEG C × 24h, aging
Then storage period 16h carries out quantitative measurement, and carry out Performance comparision with unaged sample to aging rear sample afterwards.
The partial hydrogenation terpolymer that present invention offer be can be seen that by 2 data of table has preferably Physical Mechanical
Can, the Dynamic Viscoelastic spectrogram with wide distribution, partial hydrogenation terpolymer cured properties and existing skill that the present invention is provided
The vulcanizate of the terpolymer not being hydrogenated with that art is provided is compared, and following performance is improved：（1）Ageing-resistant performance is improved；
（2）Tan δ-value when -20 DEG C is improved, and illustrates that the wet-sliding resistant performance of ice and snow road is improved；（3）Tan δ-value when 0 DEG C is improved, explanation
Wet-sliding resistant performance under low temperature is improved；（4）Tan δ-value when 60 DEG C is substantially reduced, and illustrates that rolling resistance is substantially reduced.
The part hydrogenation terpolymer that the present invention is provided is used to can improving when preparing tire ice and snow road and low temperature
Anti-slippery, is conducive to improving the safety of tire running process, and especially rolling resistance during high temperature is greatly lowered, favorably
It is energy-saving in tire, while the life-span of tire can be improved, reach.
Make reinforcing agent using white carbon alternative carbon black additionally, can also be seen that by 2 data of table, protected in anti-slippery substantially
Hold it is constant under conditions of, can further reduce tan δ-value during 60 DEG C of vulcanizate, rolling resistance during high temperature is further dropped
It is low, can be used for the production of energy-saving tire.
Claims (37)
1. a kind of partially hydrogenated terpolymer, shown in the structure such as formula (I) of the partially hydrogenated terpolymer：
In formula (I), A is partially hydrogenated 1,3-butadiene homopolymerization section, B is isoprene homopolymerization section；C is partially hydrogenated benzene second
Alkene and 1,3- butadiene binary copolymerization sections or partially hydrogenated styrene and isoprene binary copolymerization section；D is part hydrogenation
Styrene, 1,3- butadiene and isoprene ternary polymerization section；X is the residue of multifunctional coupling agent, and,
Wherein, e, f, g, j are respectively the arm number of A, B, C, D, and respectively more than or equal to zero, and one of them when being zero, other three
Person is respectively more than or equal to the quantity of the residue that 1, m-e-f-g-j is multifunctional coupling agent, and m-e-f-g-j >=0,3≤e+f+g
+ j≤25,
Characterized in that, the degree of hydrogenation of the construction unit derived from 1,3-butadiene be 5-90%, wherein, 1,3-butadiene with 1,
The degree of hydrogenation of the construction unit that 2- polymerization methodses are formed is 60-95%, and 1,3-butadiene is with the structure of Isosorbide-5-Nitrae-polymerization methodses formation
The degree of hydrogenation of unit is 2-20%；
The degree of hydrogenation of the construction unit derived from isoprene be 5-90%, the structure that isoprene is formed with 3,4- polymerization methodses
The degree of hydrogenation of unit is 10-40%, and the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-30%；
The degree of hydrogenation of the construction unit derived from monovinylarene is less than 5%；
The number-average molecular weight of the A is 5000-500000, and the number-average molecular weight of the B is 5000-500000, and the number of the C is equal
Molecular weight is 20000-500000, and the C is 5-50 weight % derived from cinnamic structural unit content, derived from 1,3- fourths
The content of the construction unit of diene or isoprene is 50-95 weight %, and the number-average molecular weight of the D is 20000-500000,
Contents of the D derived from cinnamic construction unit is 5-50 weight %, and the construction unit derived from 1,3-butadiene contains
Measure as 5-85 weight %, the content of the construction unit derived from isoprene is 5-85 weight %.
2. partially hydrogenated terpolymer according to claim 1, wherein, m-e-f-g-j>0,3≤e+f+g+j≤
22；X is many vinyl-arenes, polyfunctional epoxide, group with imine moiety, aldehyde, ketone, acid anhydride, ester, polyisocyanates and many halogen
The residue of one or more in compound.
3. partially hydrogenated terpolymer according to claim 1, wherein, the construction unit derived from 1,3-butadiene
Degree of hydrogenation be 10-60%, wherein, the degree of hydrogenation of the construction unit that 1,3-butadiene is formed with 1,2- polymerization methodses is 70-
90%, the degree of hydrogenation of the construction unit that 1,3-butadiene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-18%；
The degree of hydrogenation of the construction unit derived from isoprene be 10-60%, the knot that isoprene is formed with 3,4- polymerization methodses
The degree of hydrogenation of structure unit is 15-35%, and the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-20%；
The degree of hydrogenation of the construction unit derived from monovinylarene is less than 2%.
4. partially hydrogenated terpolymer according to claim 1, wherein, the A is partially hydrogenated 1,3- fourths two
Polyamino alkenyl section, the number-average molecular weight of the A is 30000-180000；And 1,3- butadiene is formed with 1,2- polymerization methodses in A
Structural unit content is 8-80 weight %.
5. partially hydrogenated terpolymer according to claim 4, wherein, the number-average molecular weight of the A is 50000-
120000；And the structural unit content that 1,3- butadiene is formed with 1,2- polymerization methodses in A is as 8-50 weight %.
6. partially hydrogenated terpolymer according to claim 4, wherein, in A, 1,3-butadiene is with 1,2- polymerization sides
The structural unit content that formula is formed is 10-30 weight %.
7. partially hydrogenated terpolymer according to claim 1, wherein, the B is partially hydrogenated isoprene
Homopolymerization section, the number-average molecular weight of the B is 30000-180000；And the structure that isoprene is formed with 3,4- polymerization methodses in B
Unit content is 7-80 weight %.
8. partially hydrogenated terpolymer according to claim 7, wherein, the number-average molecular weight of the B is 50000-
120000；And the structural unit content that isoprene is formed with 3,4- polymerization methodses in B is as 8-70 weight %.
9. partially hydrogenated terpolymer according to claim 7, wherein, in B, isoprene is with 3,4- polymerization methodses
The structural unit content of formation is 8-60 weight %.
10. partially hydrogenated terpolymer according to claim 1, wherein, the C be partially hydrogenated styrene and
1,3-butadiene or styrene and isoprene copolymer section, wherein, it is 15-40 weights derived from cinnamic structural unit content
Amount %, the content derived from 1,3-butadiene or the construction unit of isoprene are 60-85 weight %；Number-average molecular weight is
50000-250000；Wherein, on the basis of the weight of the construction unit derived from 1,3-butadiene, 1,3-butadiene is poly- with 1,2-
The structural unit content that conjunction mode is formed is 8-95 weight %；On the basis of the weight of the construction unit derived from isoprene,
The structural unit content that isoprene is formed with 3,4- polymerization methodses is as 8-95 weight %.
11. partially hydrogenated terpolymers according to claim 10, wherein, the number-average molecular weight of the C is
80000-180000, wherein, on the basis of the weight of the construction unit derived from 1,3-butadiene, 1,3-butadiene is poly- with 1,2-
The structural unit content that conjunction mode is formed is 20-75 weight %；On the basis of the weight of the construction unit derived from isoprene,
The structural unit content that isoprene is formed with 3,4- polymerization methodses is as 20-75 weight %.
12. partially hydrogenated terpolymers according to claim 10, wherein, the C is with derived from 1,3-butadiene
Construction unit weight on the basis of, the structural unit content that 1,3-butadiene is formed with 1,2- polymerization methodses is 25-55 weights
Amount %；On the basis of the weight of the construction unit derived from isoprene, the structure that isoprene is formed with 3,4- polymerization methodses
Unit content is 25-55 weight %.
13. partially hydrogenated terpolymers according to claim 1, wherein, the D be partially hydrogenated styrene,
1,3-butadiene and isoprene ternary polymerization section, and the content derived from cinnamic construction unit is 15-40 weight %, is spread out
The content for being conigenous the construction unit of 1,3-butadiene is 10-75 weight %, and the content of the construction unit derived from isoprene is
10-75 weight %；The number-average molecular weight of the D is 50000-250000；Wherein, with the construction unit derived from 1,3-butadiene
On the basis of the gross weight of the construction unit derived from isoprene, formed with 1,2- polymerization methodses derived from 1,3-butadiene
The structural unit content sum that construction unit and isoprene are formed with 3,4- polymerization methodses is as 8-95 weight %.
14. partially hydrogenated terpolymers according to claim 13, wherein, the number-average molecular weight of the D is
80000-180000；Wherein, with the total of the construction unit derived from 1,3-butadiene and the construction unit derived from isoprene
On the basis of weight, the construction unit formed with 1,2- polymerization methodses derived from 1,3-butadiene and isoprene are with 3,4- polymerization sides
The structural unit content sum that formula is formed is 20-75 weight %.
15. partially hydrogenated terpolymers according to claim 13, wherein, the D is with derived from 1,3-butadiene
Construction unit and the construction unit derived from isoprene gross weight on the basis of, derived from 1,3-butadiene with 1,2- be polymerized
The construction unit and isoprene that mode is formed is heavy as 30-55 with the structural unit content sum that 3,4- polymerization methodses are formed
Amount %.
16. partially hydrogenated terpolymers according to claim 1, wherein, the partially hydrogenated terpolymer
Coupling efficiency be 20-100 weight %.
17. partially hydrogenated terpolymers according to claim 16, wherein, the partially hydrogenated terpolymer
Coupling efficiency be 30-80 weight %.
18. partially hydrogenated terpolymers according to claim 16, wherein, the partially hydrogenated terpolymer
Coupling efficiency be 40-70 weight %.
A kind of 19. preparation methoies of partially hydrogenated terpolymer, the method are comprised the following steps：
(1) in the presence of the first noble gases, under the first alkene anionic polymerization conditions, in the first reactor, by 1,3-
Butadiene is contacted in the first solvent with the first initiator, so that 1,3-butadiene is polymerized, obtains the living chain of A；
In the presence of the second noble gases, under the second alkene anionic polymerization conditions, in the second reactor, by isoprene
Contact in the second solvent with the second initiator, so that isoprene is polymerized, obtain the living chain of B；
In the presence of the 3rd noble gases, under alkatrienes anionic polymerization conditions, in the 3rd reactor, by styrene with
1,3-butadiene or isoprene are contacted in the 3rd solvent with the 3rd initiator, so that styrene and 1,3-butadiene or isoamyl
Diene is polymerized, and obtains the living chain of C；
In the presence of the 4th noble gases, under alkatetraenes anionic polymerization conditions, in the 4th reactor, by styrene,
1,3-butadiene and isoprene are contacted in the 4th solvent with the 4th initiator, so that styrene, 1,3-butadiene and isoamyl
Diene is polymerized, and obtains the living chain of D；
(2) multiple functionalized coupling agent will be added to carry out idol after the tetra- kinds of living chain mix homogeneously of A, B, C and D obtained in step (1)
Connection, coupling reaction add terminator terminating reaction after terminating, and obtain copolymer solution to be hydrogenated with；
(3) under hydrogenation conditions, in the presence of a hydrogenation catalyst, make the copolymerization to be hydrogenated with after terminating reaction in step (2)
Thing solution and hydrogen contact, to obtain meeting the partially hydrogenated terpolymer of following condition：
The degree of hydrogenation of the construction unit derived from 1,3-butadiene is 5-90%, wherein, 1,3-butadiene is with 1,2- polymerization methodses
The degree of hydrogenation of the construction unit of formation is 60-95%, and 1,3-butadiene is with the hydrogenation of the construction unit of Isosorbide-5-Nitrae-polymerization methodses formation
Spend for 2-20%；
The degree of hydrogenation of the construction unit derived from isoprene be 5-90%, the structure that isoprene is formed with 3,4- polymerization methodses
The degree of hydrogenation of unit is 10-40%, and the degree of hydrogenation of the construction unit that isoprene is formed with Isosorbide-5-Nitrae-polymerization methodses is as 2-30%；
The degree of hydrogenation of the construction unit derived from monovinylarene is less than 5%；
The number-average molecular weight of the A is 5000-500000, and the number-average molecular weight of the B is 5000-500000, and the number of the C is equal
Molecular weight is 20000-500000, and the C is 5-50 weight % derived from cinnamic structural unit content, derived from 1,3- fourths
The content of the construction unit of diene or isoprene is 50-95 weight %, and the number-average molecular weight of the D is 20000-500000,
Contents of the D derived from cinnamic construction unit is 5-50 weight %, and the construction unit derived from 1,3-butadiene contains
Measure as 5-85 weight %, the content of the construction unit derived from isoprene is 5-85 weight %.
20. methods according to claim 19, wherein, the hydrogenation catalyst is the mixing of major catalyst and promoter
Thing, major catalyst are periodic table of elements group VIII metal compound, and promoter is alkyl metal cpd.
21. methods according to claim 20, wherein, major catalyst is periodic table of elements group VIII metal coordination compound.
22. methods according to claim 20, wherein, the major catalyst is nickel naphthenate and/or nickel octoate, described to help
Catalyst is triisobutyl aluminium and/or triethyl aluminum, and the mol ratio of the promoter in terms of aluminum and the major catalyst in terms of nickel
For 1-7:1.
23. methods according to claim 22, wherein, the promoter in terms of aluminum and major catalyst in terms of nickel mole
Than for 3-6:1.
24. methods according to claim 20, wherein, the consumption of the hydrogenation catalyst is 0.01-0.08gNi/100g
Treat hydrogenated copolymer.
25. methods according to claim 24, wherein, the consumption of the hydrogenation catalyst is 0.02-0.06gNi/100g
Treat hydrogenated copolymer.
26. methods according to any one in claim 19-25, wherein, the hydrogenation conditions include：Reaction temperature
Spend for 30-120 DEG C；Reaction pressure 0.1-4.0MPa；Response time is 2-180 minutes.
27. methods according to claim 26, wherein, the hydrogenation conditions include：Reaction temperature is 40-70 DEG C；
Reaction pressure 0.2-3.0MPa；Response time is 5-60 minutes.
28. methods according to claim 19, wherein, the first alkene anionic polymerization conditions include：Temperature is 20-
100 DEG C, the time is 10-120 minutes；The second alkene anionic polymerization conditions include：Temperature is 20-100 DEG C, and the time is
10-120 minutes；The alkatrienes anionic polymerization conditions include：Temperature is 30-100 DEG C, and the time is 30-120 minutes；Institute
Stating alkatetraenes anionic polymerization conditions includes：Temperature is 30-100 DEG C, and the time is 30-120 minutes.
29. methods according to claim 28, wherein, the first alkene anionic polymerization conditions include：Temperature is 40-
70 DEG C, the time is 30-60 minutes；The second alkene anionic polymerization conditions include：Temperature is 40-70 DEG C, and the time is 30-60
Minute；The alkatrienes anionic polymerization conditions include：Temperature is 40-80 DEG C, and the time is 30-90 minutes；The tetraene
Hydrocarbon anionic polymerization conditions include：Temperature is 40-80 DEG C, and the time is 30-90 minutes.
30. methods according to claim 19, wherein, the weight ratio of tetra- kinds of living chains of A, B, C and D is 1：0.1-10：
0.2-10：0.2-10.
31. methods according to claim 19, wherein, the multiple functionalized coupling agent is many vinyl-arenes, multifunctional
Epoxide, group with imine moiety, aldehyde, ketone, acid anhydride, one or more in ester and polyhalide；The multiple functionalized coupling
The consumption of agent is so that tetra- kinds of living chain 20-100% of A, B, C and D are coupled.
32. methods according to claim 31, wherein, the ester includes polyisocyanates.
33. methods according to claim 31, wherein, the multiple functionalized coupling agent be divinylbenzene, tetrachloromethane,
One or more in Silicon chloride., butter of tin and dimethyl terephthalate (DMT)；The consumption of the multiple functionalized coupling agent with
Make tetra- kinds of living chain 30-80% of A, B, C and D coupled.
34. methods according to claim 19, wherein, the multiple functionalized coupling agent is tetravinyl silane.
35. methods according to claim 31, wherein, the multiple functionalized coupling agent is Silicon chloride. and/or four chlorinations
Stannum.
The partially hydrogenated terpolymer that method in 36. claim 19-35 described in any one is prepared.
Partially hydrogenated terpolymer in 37. claim 1-18 and 36 described in any one answering in tire tread glue
With.
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| US4116917A (en) * | 1976-02-10 | 1978-09-26 | Shell Oil Company | Hydrogenated star-shaped polymer |
| CN1138055A (en) * | 1995-05-30 | 1996-12-18 | 国际壳牌研究有限公司 | Process for preparing asymmetric radial polymers |
| CN1291223A (en) * | 1998-02-19 | 2001-04-11 | 国际壳牌研究有限公司 | Star polymer viscosity index improver for oil compositions |
| CN101460598A (en) * | 2006-03-10 | 2009-06-17 | 科腾聚合物美国有限责任公司 | Viscosity index improver for lubricating oils |
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|---|---|---|---|---|
| US4116917A (en) * | 1976-02-10 | 1978-09-26 | Shell Oil Company | Hydrogenated star-shaped polymer |
| CN1138055A (en) * | 1995-05-30 | 1996-12-18 | 国际壳牌研究有限公司 | Process for preparing asymmetric radial polymers |
| CN1291223A (en) * | 1998-02-19 | 2001-04-11 | 国际壳牌研究有限公司 | Star polymer viscosity index improver for oil compositions |
| CN101460598A (en) * | 2006-03-10 | 2009-06-17 | 科腾聚合物美国有限责任公司 | Viscosity index improver for lubricating oils |
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