CN111620975A - Binuclear rare earth olefin polymerization catalyst and application thereof - Google Patents
Binuclear rare earth olefin polymerization catalyst and application thereof Download PDFInfo
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- CN111620975A CN111620975A CN202010310196.XA CN202010310196A CN111620975A CN 111620975 A CN111620975 A CN 111620975A CN 202010310196 A CN202010310196 A CN 202010310196A CN 111620975 A CN111620975 A CN 111620975A
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- rare earth
- olefin polymerization
- dinuclear
- polymerization catalyst
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 108
- -1 rare earth olefin Chemical class 0.000 title claims abstract description 79
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 44
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000002879 Lewis base Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 238000012546 transfer Methods 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012986 chain transfer agent Substances 0.000 claims description 3
- 229920003244 diene elastomer Polymers 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- UIMPAOAAAYDUKQ-UHFFFAOYSA-N 1-methoxy-4-(4-methoxyphenyl)benzene Chemical group C1=CC(OC)=CC=C1C1=CC=C(OC)C=C1 UIMPAOAAAYDUKQ-UHFFFAOYSA-N 0.000 claims description 2
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 claims description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- YBYJTJHBRZHMAA-UHFFFAOYSA-N FC=1C(=C(C(=C(C1)F)F)F)F.FC=1C(=C(C(=C(C1)F)F)F)F.FC=1C(=C(C(=C(C1)F)F)F)F.[B] Chemical compound FC=1C(=C(C(=C(C1)F)F)F)F.FC=1C(=C(C(=C(C1)F)F)F)F.FC=1C(=C(C(=C(C1)F)F)F)F.[B] YBYJTJHBRZHMAA-UHFFFAOYSA-N 0.000 claims description 2
- GIPRODQYBYOZGL-UHFFFAOYSA-N FC=1C(=C(C(=C(C1)F)F)F)F.[B] Chemical compound FC=1C(=C(C(=C(C1)F)F)F)F.[B] GIPRODQYBYOZGL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000005418 aryl aryl group Chemical group 0.000 claims description 2
- LBKYCOGBBDATCR-UHFFFAOYSA-N benzyl(diethyl)alumane Chemical compound CC[Al](CC)CC1=CC=CC=C1 LBKYCOGBBDATCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- OTACYDLCOLOKPA-UHFFFAOYSA-N dibenzyl(ethyl)alumane Chemical compound C=1C=CC=CC=1C[Al](CC)CC1=CC=CC=C1 OTACYDLCOLOKPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XLFSJFNMOZJHDV-UHFFFAOYSA-N ethyl-(4-methylphenyl)alumane Chemical compound C1(=CC=C(C=C1)[AlH]CC)C XLFSJFNMOZJHDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003106 haloaryl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Natural products C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- MCWWHQMTJNSXPX-UHFFFAOYSA-N tribenzylalumane Chemical compound C=1C=CC=CC=1C[Al](CC=1C=CC=CC=1)CC1=CC=CC=C1 MCWWHQMTJNSXPX-UHFFFAOYSA-N 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical class C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 229920002857 polybutadiene Polymers 0.000 abstract description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000005298 paramagnetic effect Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 description 2
- 229910003317 GdCl3 Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012485 toluene extract Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a binuclear rare earth olefin polymerization catalyst and application thereof, the binuclear rare earth olefin polymerization catalyst consists of a main catalyst, a cocatalyst and a chain transfer reagent, wherein the main catalyst is a binuclear rare earth complex with stable Lewis base and is represented by the chemical formula [ I]And chemical formula [ II]Represents:
Description
Technical Field
The invention relates to a catalyst for binuclear rare earth olefin polymerization, in particular to a catalyst for binuclear metallocene rare earth olefin polymerization with stable Lewis base and application thereof.
Background
The catalyst system for olefin rubber is a key to the production technology of olefin rubber, and currently used catalyst systems mainly include nickel (Ni) based, titanium (Ti) based, cobalt (Co) based, rare earth neodymium (Nd) based, and lithium (Li) based (zingiber officinale, et al, rare earth butadiene rubber, published by metallurgical industry, 2016, 39). Among them, the rare earth catalyst is the most distinctive and excellent in comprehensive performance, and the olefin rubber produced by using the rare earth catalyst has high cis-structure content, high linear structure regularity, high molecular weight and narrow distribution.
The Changchun acclimatization institute of Chinese academy of sciences in 1970 successfully developed a ternary catalytic system of rare earth carboxylate, alkylaluminum and alkylaluminum chloride for preparing high cis-polybutadiene rubber (rare earth catalytic synthetic rubber article [ C ]. scientific Press, 1980, 25). In the 80 s of the 20 th century, Bayer AG, Germany (At133rd meeting of the Rubber Division of ACS,1988,4, 19; At133rd meeting of the Rubber Division of ACS,1988,10,18) and Enichem AG, Italy (Kautschuk Gummi Kunststiffe,1993,6,458) successively realized the industrialization of rare earth polybutadiene Rubber. The rare earth catalysts currently used in industry are mainly ternary neodymium catalysts, and the core technology thereof is mainly mastered by Lanxess company in Germany (EP2311889, EP2363303, EP2676968, EP3057998, CN102574955, CN102762613, CN104395351 and CN107254008) and by the research groups of Changchun nationality institute (CN01128284, CN01128287, US7288611, CN01128289, CN03127180 and CN 200610016949).
Currently, the research on single-site rare earth metal catalysts with specific structures for the directional polymerization of conjugated dienes has been well developed, which have the characteristics of high activity and narrow molecular weight distribution in the catalytic diene polymerization reaction (J.Organomet.chem.,2001,621,327; Macromol.chem.Phys.,2003,204,1747; Macromol.chem.Phys.,2004,205,737; Angew.chem.,2005,117,2649; Angew.chem.Int.Ed.,2005,44, 2593; Macromolecules 1999,32, 9078; Macromolecules2001,34,1539; Macromolecules 2003,36, 7923; Macromolecules 2004,37, 5860; Macromolecules 2006,39, 1359-Bufonic 1363; Dalton, 2008,2531; Angel.chem.Int.Ed.2007, 46,1909; Soc.4984, 130, 2008, 130).
Since rare earth elements are usually +3 valent, the cationic single-active-center rare earth catalyst for olefin polymerization is usually in a single-metallocene or non-metallocene structure, and the double-metallocene rare earth catalyst has no catalytic activity theoretically because no reaction site is inserted after cationization. The double Lewis base bridges 2 molecules of mononuclear double metallocene rare earth complex, hopefully, the aim of improving the catalytic activity is achieved by the synergistic action between double metals or the change of the coordination mode between metal and ligand. Some dinuclear or polynuclear rare earth metal complexes previously reported are usually bridged by sigma bond coordination of H or alkyl (Macromolecules 2004,37, 5860; Macromolecules 2006,39, 1359-.
Disclosure of Invention
The invention aims to provide a binuclear rare earth olefin polymerization catalyst, in particular to a binuclear metallocene rare earth catalyst composition with stable Lewis base, which is particularly suitable for preparing high cis-conjugated diene rubber.
In order to achieve the purpose, the binuclear rare earth olefin polymerization catalyst provided by the invention consists of a main catalyst, a cocatalyst and a chain transfer reagent; the main catalyst is a binuclear rare earth complex with stable Lewis base, and is represented by chemical formula [ I ] and chemical formula [ II ]:
wherein Ln is a transition metal element of group IIIB;
x is selected from one of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, N-bis (trimethylsilyl) amino;
R1to R18The same or different, each independently selected from hydrogen and C1-C10At least one of saturated alkyl groups of (a);
the cocatalyst is selected from the group consisting of formula [ III]A compound shown as the formula (I); chemical formula [ III]Expressed as: [ EH]+[BA4]-、[E]+[BA4]-or BA3Wherein E is a nitrogen or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, and A is selected from C6-C30Aryl or haloaryl, C1-C10At least one of an alkyl group or a haloalkyl group.
The chain transfer agent is selected from the group consisting of formula [ IV]A compound shown as the formula (I); chemical formula [ IV]Expressed as: al (R)19)(R20)(R21) Wherein Al is aluminum element, R19To R21The same or different, each independently selected from hydrogen, halogen, C1-C10At least one of alkyl or haloalkyl.
In the dinuclear rare earth olefin polymerization catalyst of the present invention, Ln is at least one selected from scandium, yttrium, and lanthanoid rare earth metal elements, and Y and Gd are more preferable.
The binuclear rare earth olefin polymerization catalyst of the present invention comprises, in the presence of,
are bis-Lewis bases linked by aliphatic or aromatic structural unitsThe compound, which does not contain acidic hydrogen, is at least one selected from the group consisting of pyridine, 2, 6-lutidine, 4 '-bipyridine, 4-dimethylaminopyridine, N, N, N', N '-tetramethylp-phenylenediamine, N, N, N', N '-tetramethylethylenediamine, p-dimethoxybenzene, and 4,4' -dimethoxybiphenyl, but is not limited thereto; further preferred is 4,4' -bipyridine.
The dinuclear rare earth olefin polymerization catalyst of the present invention, wherein X is selected from one of, but not limited to, trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, N-bis (trimethylsilyl) amine; more preferably, o- (N, N-dimethylamino) benzyl is used.
The dinuclear rare earth olefin polymerization catalyst of the present invention is characterized in that R1To R18The same or different, each independently selected from hydrogen and C1-C10Saturated alkyl groups of (a); wherein, C1-C10The saturated alkyl group of (b) is preferably at least one selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl, but is not limited thereto; more preferably methyl.
The binuclear rare earth olefin polymerization catalyst of the present invention is synthesized by coordination reaction between a mononuclear rare earth complex and a bis-Lewis base compound, in which the binuclear rare earth complex represented by the chemical formula [ I ] and the chemical formula [ II ] is generated in situ, and is directly used in polymerization reaction.
In the dinuclear rare earth olefin polymerization catalyst, when the dinuclear rare earth complex is generated, the molar ratio of the double Lewis base to the mononuclear rare earth complex is 0.5/1.
In the dinuclear rare earth olefin polymerization catalyst of the present invention, the compound represented by the formula [ III ] is preferably at least one selected from the group consisting of a triphenyl (methyl) -tetrakis (pentafluorobenzene) boron salt, a phenyl-dimethylamino-tetraphenylboron salt, a tris (pentafluorobenzene) boron salt, and a triphenyl boron salt, and is more preferably a phenyl-dimethylamino-tetraphenylboron salt.
In the dinuclear rare earth olefin polymerization catalyst of the present invention, the compound represented by the formula [ IV ] is preferably at least one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, and ethyl-p-tolylaluminum, but is not limited thereto; further preferred is triisobutylaluminum.
The binuclear rare earth complexes of the present invention can be prepared according to scheme C:
(a)
(b)
as shown in the figure, the route (a) is the synthesis of the non-bridged binuclear rare earth complex, and the route (b) is the synthesis of the silicon-bridged binuclear rare earth complex. The mononuclear rare earth complex reacts with 0.5 equivalent of double Lewis base, the reaction solvent is toluene, the reaction temperature is 25 ℃, separation is not carried out after the reaction is finished, and the mononuclear rare earth complex is directly used for olefin polymerization after the reaction is reacted with a cocatalyst.
The dinuclear rare earth olefin polymerization catalyst of the present invention is characterized in that the molar ratio of the compound represented by the formula [ III ] to the main catalyst is preferably 0.1/1 to 10/1, more preferably 1.0/1 to 2.0/1; the molar ratio of the compound represented by the formula [ IV ] to the main catalyst is preferably 1/1 to 10000/1, and more preferably 10/1 to 1000/1.
The invention also provides an application of the binuclear rare earth olefin polymerization catalyst in preparation of high cis-conjugated diene rubber.
In the binuclear rare earth olefin polymerization catalyst of the present invention, an alkylaluminum reagent represented by the chemical formula [ IV ] may be added in advance to a reaction system to be mixed with a polymerization monomer. The compound represented by the formula [ IV ] is mainly used as a polymer chain transfer agent, and the amount thereof has a large influence on the molecular weight of the polymer. In addition, the catalyst also serves as a main impurity removal reagent to react with impurities in the polymerized monomers for impurity removal. Therefore, when the molar ratio of the compound represented by the formula [ IV ] to the co-catalyst is in the above range, the problem of partial deactivation of the catalyst due to incomplete removal of impurities from the polymerized monomers can be avoided; further, the molecular weight distribution of the polymer can be controlled within a suitable range.
The binuclear rare earth olefin polymerization catalyst is used for preparing a conjugated diene polymer, the preparation process is homogeneous solution polymerization, a polymerization solvent is usually n-hexane, the binuclear rare earth olefin polymerization catalyst provided by the invention can catalyze the polymerization of 1, 3-butadiene with high activity, and polybutadiene rubber prepared by polymerization reaction has high cis-1, 4-content and narrow molecular weight distribution; compared with the corresponding mononuclear rare earth catalyst, the binuclear rare earth olefin polymerization catalyst has higher catalytic activity, and an olefin polymer generated by polymerization reaction has higher stereoregularity.
Drawings
FIG. 1 is a 1H-NMR spectrum of the compound shown in example 1;
FIG. 2 is a 1H-NMR spectrum of the compound shown in example 2;
FIG. 3 is a 1H-NMR spectrum of the compound shown in example 5.
Detailed Description
The present invention is described in detail by referring to the preferred examples below, and although the following examples are carried out on the premise of the technical scheme provided by the present invention, detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Wherein, part of the mononuclear rare earth complex can be synthesized by the reference (Journal of organometallic chemistry,322(1987) 321-.
In the following examples, the synthesis of the binuclear rare earth olefin polymerization catalyst and the catalytic olefin polymerization reaction are carried out under anhydrous and anaerobic conditions unless otherwise specified, and are realized by inert gas glove box or Schlenk technology, and the solvents used in the experiments are all subjected to anhydrous and anaerobic treatment; the invention is not so limited.
Furthermore, nuclear magnetic resonance of rare earth metal complexes1The H-NMR spectrum was tested by Bruker Ascend 600MHz, and part of the compounds could not be characterized by 1H-NMR due to paramagnetic properties. Cis-1, 4 selective passage of polymers13C-NMR spectrogram determination is carried out in an inverse gating decoupling mode; the molecular weight and molecular weight distribution of the polymer were measured by PL-GPC50 gel permeation chromatography.
Example 1
Preparation of mononuclear rare earth complex 1
At 0 ℃, n-butyllithium was slowly added dropwise to a Cp × hexane solution, followed by natural warming to room temperature and stirring overnight, yielding a large amount of pale yellow precipitate. And then, carrying out suction filtration in an inert gas glove box, washing the obtained solid with hexane for 2 times, and drying under vacuum to obtain light yellow powder solid, namely the CpLi compound. Slowly adding Cp Li in THF solution to YCl at room temperature3nTHF, followed by heating to reflux overnight. After the reaction, the THF solution was drained and extracted with toluene. Concentrating the toluene extract, and recrystallizing at-30 deg.C to obtain white solid, i.e. rare earth chloride Cp2YCl2Li(THF)2。
Slowly dropwise adding a toluene solution of ortho-dimethylaminobenzyllithium (AbzLi) to Cp at-30 DEG C2YCl2Li(THF)2Then the temperature of the solution was naturally raised to room temperature, and the reaction was continued for 4 hours. Filtering with sand core funnel after reaction, vacuum drying filtrate to obtain yellow oily matter, washing with small amount of n-hexane to obtain light yellow powder, i.e. Cp2The YAbz product (compound 1).
Nuclear magnetic data:1H-NMR(600MHz,C6D6):1.86(s,30H,Cp-Me),2.14(s,6H,N-Me),2.28(br,2H,Y-CH2),6.71(d,J＝6Hz,1H),6.81(t,J＝6Hz,2H),7.05(t,J＝6Hz,2H),7.29(d,J＝6Hz,1H)。
example 2
Preparation of mononuclear rare earth complex 2
Alkyl lithium (TMSCH) was added at-30 deg.C2Li) was slowly added dropwise to Cp2YCl2Li(THF)2Then the temperature of the solution was naturally raised to room temperature, and the reaction was continued for 4 hours. Filtering with sand core funnel after reaction, vacuum drying filtrate to obtain yellow oily matter, washing with small amount of n-hexane to obtain light yellow powder, i.e. Cp2YACH2TMS product (compound 2).
Nuclear magnetic data:1H-NMR(600MHz,C6D6):0.00(s,2H,CH2TMS),0.44(s,9H,SiMe3),1.98(s,30H,Cp-Me)。
example 3
Preparation of mononuclear rare earth complex 3
Synthesis of Compound 3 referring to the synthesis of Compound 1, YCl in the starting Material3Replacement of nTHF to GdCl3nTHF, the experimental procedure was consistent and the product was obtained as a pale yellow powder solid. Due to the paramagnetic character of the + 3-valent Gd compound, NMR characterization was not possible, only on Cp-2GdCl2Li(THF)2X-ray single crystal diffraction characterization was performed.
Example 4
Preparation of mononuclear rare earth complex 4
Synthesis of Compound 4 referring to the synthesis of Compound 2, YCl in the starting Material3.nTHF is changed into GdCl3nTHF, the experimental procedure was consistent and the product was obtained as a pale yellow powder solid. Due to the paramagnetic character of the + 3-valent Gd compound, NMR characterization was not possible, only on Cp-2GdCl2Li(THF)2X-ray single crystal diffraction characterization was performed.
Example 5
Preparation of mononuclear rare earth complex 5
N-butyllithium (2.4M in n-Hexane) was slowly added dropwise to dimethylsilyl Me at-30 deg.C2And (3) adding the Si-bridged bis (tetramethylcyclopentadiene) ligand into an ether solution, then heating to room temperature, continuously stirring for 2 hours, and after the reaction is finished, pumping out the solvent in vacuum to obtain a light yellow solid, namely the dilithium salt of the ligand. Then the dilithium salt in THF was slowly added dropwise to YCl at-30 deg.C3(THF) n in THF suspension, after completion of the dropwise addition, the reaction solution was heated to reflux and the reaction was continued overnight. After the reaction is finished, pumping out THF under vacuum, adding toluene for extraction, filtering, pumping out the filtrate, and washing with a small amount of anhydrous hexane to obtain white solid powder, namely Si (CpMe)4)2YCl2Li(THF)2。
Slowly adding toluene suspension of benzyl lithium into toluene suspension of metallocene rare earth halide at-30 ℃, continuing to react overnight after the toluene suspension is heated to room temperature, filtering to remove generated LiCl after the reaction is finished, taking out the solvent from the filtrate in vacuum, and washing twice with a small amount of anhydrous n-hexane to obtain rare earth benzyl compound Si (CpMe)4)2YAbz (Compound 5).
Nuclear magnetic data:1H-NMR(600MHz,C6D6):0.94(s,3H,Si-Me),1.03(s,3H,Si-Me),1.39(s,2H,Y-CH2),1.45(s,6H,Cp-Me),1.76(s,6H,Cp-Me),2.00(s,6H,N-Me),2.07(d,12H,J＝6Hz,Cp-Me),6.56(m,1H,Ar-H),6.75(m,1H,Ar-H),7.02(m,1H,Ar-H),7.19(m,1H,Ar-H)。
example 6
Preparation of mononuclear rare earth complex 6
N-butyllithium (2.4M in n-Hexane) was slowly added dropwise to dimethylsilyl Me at-30 deg.C2And (3) adding the Si-bridged bis (tetramethylcyclopentadiene) ligand into an ether solution, then heating to room temperature, continuously stirring for 2 hours, and after the reaction is finished, pumping out the solvent in vacuum to obtain a light yellow solid, namely the dilithium salt of the ligand. Then the dilithium salt in THF was slowly added dropwise to YCl at-30 deg.C3(THF) n in THF suspension, after completion of the dropwise addition, the reaction solution was heated to reflux and the reaction was continued overnight. After the reaction is finished, pumping out THF under vacuum, adding toluene for extraction, filtering, pumping out the filtrate, and washing with a small amount of anhydrous hexane to obtain white solid powder, namely Si (CpMe)4)2YCl2Li(THF)2。
Reacting LiCH at-30 ℃2Si (CpMe) was added slowly to TMS in toluene4)2YCl2Li(THF)2Heating to room temperature, reacting overnight, filtering to remove generated LiCl, vacuum-removing solvent from filtrate, washing with small amount of anhydrous n-hexane twice to obtain rare earth benzyl compound Si (CpMe)4)2YCH2TMS (Compound 6). NMR characterization was not possible due to the paramagnetic nature of the +3 valent Gd compound.
Examples 7 to 10
Introducing a toluene solution of 4,4' -bipyridyl into a toluene solution of a mononuclear rare earth complex 1-4 at room temperature, immediately changing the solution from light yellow to dark yellow, and then continuously stirring for 15min at room temperature to obtain a dark brown solution, namely the in-situ prepared binuclear rare earth complex 7-10 (compound 7-10) which is directly used for a polymerization experiment.
Examples 11 to 12
Methods for the synthesis of binuclear rare earth complexes corresponding to examples 11-12 reference compounds 7-10, prepared in situ and used directly in polymerization experiments.
Example 13
Evaluation of catalyst polymerization:
in an inert gas glove box, 14.4g (2.16g,40mmol) of a hexane solution (mass fraction 15%) of 1, 3-butadiene was weighed in a 100mL round-bottomed flask, 0.2mL (1M,0.2mmol) of a hexane solution of triisobutylaluminum was added, and stirred at room temperature for 30min, and a toluene solution of the binuclear rare earth complex (0.02mmol) of example 7 and [ PhNHMe were added to the polymerization solution2][B(C6F5)4]A toluene suspension of (2). After polymerization for 30min at room temperature, the polymerization system became viscous and the polymerization monomers were completely consumed. After the polymerization was completed, the reaction flask was taken out of the inert gas glove box, anhydrous methanol was slowly added with stirring until the polymer was completely precipitated, 0.02g of BHT antioxidant (1% of the polymer mass) was added, the polymer was washed with anhydrous methanol 3 times, placed in a vacuum oven to dry at 70 ℃ for 5 hours, and weighed.
The polymerization results are shown in Table 1.
Examples 14 to 16
Evaluation of catalyst polymerization:
butadiene polymerization was performed according to the same method as in example 13, except that the dinuclear rare earth complexes of examples 8 to 10 were sequentially used.
The polymerization results are shown in Table 1.
Examples 17 to 18
Evaluation of catalyst polymerization:
butadiene polymerization was performed according to the same method as in example 13, using the binuclear rare earth complex of example 6, except that the molar ratios of butadiene to rare earth were 10000 and 20000, respectively.
The polymerization results are shown in Table 1.
TABLE 1 examples 13-18
Description of the drawings: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4],[B]N/[Ln]＝1.2
As can be seen from the data in the table, the catalytic activity is higher when the central metal is Y, but the cis-1, 4 selectivity is lower than 90%; and when the central metal is Gd, the catalytic activity is lower, but the cis-1, 4 selectivity can reach 99 percent.
Comparative examples 1 to 4
Butadiene polymerization was performed according to the same method as in example 13, except that the mononuclear rare earth complexes of examples 1 to 4 were sequentially used.
The polymerization results are shown in Table 2.
TABLE 2 COMPARATIVE EXAMPLES 1 to 4
Description of the drawings: (1) [ B ]]N＝[PhNHMe2][B(C6F5)4],[B]N/[Ln]＝1.2
By comparison (example 13, comparative example 1, example 15 and comparative example 3), it can be seen that the use of the mononuclear rare earth metal complex as the cocatalyst results in a much lower degree of both the catalyst activity and the stereoregularity of the polymerization product than the binuclear rare earth metal complex under the same polymerization experimental conditions.
As described above, the dinuclear rare earth olefin polymerization catalyst containing the dinuclear double-metallocene rare earth metal complex connected by the Lewis base has the advantages of high activity, high stereoselectivity and the like compared with the corresponding mononuclear rare earth complex in the olefin polymerization reaction.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (21)
1. A binuclear rare earth olefin polymerization catalyst is characterized by comprising a main catalyst, a cocatalyst and a chain transfer reagent; the main catalyst is a binuclear rare earth complex with stable Lewis base and is represented by a chemical formula [ I ] and a chemical formula [ II ]:
2. the dinuclear rare earth olefin polymerization catalyst of claim 1 wherein Ln is a group IIIB transition metal element;
the above-mentioned
Is a double Lewis base compound connected by an aliphatic chain or an aromatic hydrocarbon structural unit and does not contain acidic hydrogen;
x is selected from one of trimethylsilylmethyl, bis (trimethylsilyl) methyl, tris (trimethylsilyl) methyl, o- (N, N-dimethylamino) benzyl, and N, N-bis (trimethylsilyl) amine;
the R is1To R18Same or different and are selected from hydrogen and C1-C10At least one of saturated alkyl groups of (a);
the cocatalyst is selected from the chemical formula [ III]A compound shown as the formula (I); the chemical formula [ III]Is [ EH ]]+[BA4]-、[E]+[BA4]-or BA3Wherein E is a nitrogen or carbon-containing neutral or cationic Lewis acid, B is boron, H is hydrogen, and A is selected from C6-C30Aryl or haloaryl of and C1-C10At least one of alkyl or haloalkyl;
the chain transfer agent is selected from the group consisting of formula [ IV]A compound shown as the formula (I); the chemical formula [ IV]Is Al (R)19)(R20)(R21) Wherein Al is aluminum element, R19To R21Same or different and are selected from hydrogen, halogen and C1-C10At least one of alkyl or haloalkyl.
3. The dinuclear rare earth olefin polymerization catalyst of claim 2, wherein Ln is at least one selected from scandium, yttrium, and lanthanoid rare earth elements.
4. The dinuclear rare earth olefin polymerization catalyst of claim 3, wherein Ln is Y and Gd.
5. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein said catalyst is characterized in that
Is at least one selected from 2, 6-lutidine, 4 '-bipyridine, 4-dimethylaminopyridine, N, N, N', N '-tetramethylp-phenylenediamine, N, N, N', N '-tetramethylethylenediamine, p-dimethoxybenzene and 4,4' -dimethoxybiphenyl.
6. The dinuclear rare earth olefin polymerization catalyst of claim 5, wherein said catalyst is characterized in that
Is 4,4' -bipyridine.
7. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein X is o- (N, N-dimethylamino) benzyl.
8. The dinuclear rare earth olefin polymerization catalyst of claim 2, wherein R is1To R18Is selected from C1-C10Saturated alkyl of (a), said C1-C10Saturated alkyl of (2)Is at least one selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl.
9. The dinuclear rare earth olefin polymerization catalyst of claim 8, wherein said C is1-C10The saturated alkyl group of (2) is a methyl group.
10. The dinuclear rare earth olefin polymerization catalyst according to claim 1, wherein the dinuclear rare earth complex represented by the chemical formula [ I ] and the chemical formula [ II ] is generated in situ, synthesized by a coordination reaction between a mononuclear rare earth complex and a bis-lewis base compound, and directly used for polymerization.
11. The dinuclear rare earth olefin polymerization catalyst according to claim 10, wherein said dinuclear rare earth complex is formed according to the following route:
(a)
(b)
wherein, the route (a) is the synthesis of non-bridging binuclear rare earth complex, the route (b) is the synthesis of silicon bridging binuclear rare earth complex, the mononuclear rare earth complex reacts with the double Lewis base, the reaction solvent is toluene, the separation is not carried out after the reaction, and the catalyst is directly used for olefin polymerization after the reaction with a cocatalyst.
12. The dinuclear rare earth olefin polymerization catalyst of claim 11, wherein the molar ratio of the bis-lewis base to the mononuclear rare earth complex is 0.5/1.
13. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the compound represented by the formula [ III ] is at least one selected from the group consisting of triphenyl (methyl) -tetrakis (pentafluorobenzene) boron salt, phenyl-dimethylamino-tetraphenylboron salt, tris (pentafluorobenzene) boron salt, and triphenylboron salt.
14. The dinuclear rare earth olefin polymerization catalyst according to claim 13, wherein said compound represented by the formula [ III ] is a phenyl-dimethylamino-tetraphenylboron salt.
15. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the molar ratio of the compound represented by the formula [ III ] to the procatalyst is 0.1/1 to 10/1.
16. The dinuclear rare earth olefin polymerization catalyst according to claim 15, wherein the molar ratio of the compound represented by the formula [ III ] to the procatalyst is 1.0/1 to 2.0/1.
17. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the compound represented by the formula [ IV ] is at least one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, diethylbenzylaluminum, and ethyl-p-tolylaluminum.
18. The dinuclear rare earth olefin polymerization catalyst according to claim 17, wherein said compound represented by the formula [ IV ] is triisobutylaluminum.
19. The dinuclear rare earth olefin polymerization catalyst according to claim 2, wherein the molar ratio of the compound represented by the formula [ IV ] to the main catalyst is 1/1 to 10000/1.
20. The dinuclear rare earth olefin polymerization catalyst of claim 19, wherein the molar ratio of the compound of formula [ IV ] to the procatalyst is from 10/1 to 1000/1.
21. Use of the dinuclear rare earth olefin polymerization catalyst according to any one of claims 1 to 20 in the preparation of a high cis-conjugated diene rubber.
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