CN112029020A - Long-chain alpha-olefin polymerization catalyst composition and polymerization method - Google Patents
Long-chain alpha-olefin polymerization catalyst composition and polymerization method Download PDFInfo
- Publication number
- CN112029020A CN112029020A CN201910479602.2A CN201910479602A CN112029020A CN 112029020 A CN112029020 A CN 112029020A CN 201910479602 A CN201910479602 A CN 201910479602A CN 112029020 A CN112029020 A CN 112029020A
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- China
- Prior art keywords
- aluminum
- olefin
- alkyl
- aluminum hydride
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004711 α-olefin Substances 0.000 title claims abstract description 77
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000002685 polymerization catalyst Substances 0.000 title claims description 21
- 238000000034 method Methods 0.000 title abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 19
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- 150000002909 rare earth metal compounds Chemical class 0.000 claims abstract description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- -1 aluminum compound Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 claims description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 6
- YLJFTSZNOGBPOG-UHFFFAOYSA-N benzyl(ethyl)alumane Chemical compound C(C1=CC=CC=C1)[AlH]CC YLJFTSZNOGBPOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 5
- XLFSJFNMOZJHDV-UHFFFAOYSA-N ethyl-(4-methylphenyl)alumane Chemical compound C1(=CC=C(C=C1)[AlH]CC)C XLFSJFNMOZJHDV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Chemical group 0.000 claims description 4
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052773 Promethium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012036 alkyl zinc reagent Substances 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- LBKYCOGBBDATCR-UHFFFAOYSA-N benzyl(diethyl)alumane Chemical compound CC[Al](CC)CC1=CC=CC=C1 LBKYCOGBBDATCR-UHFFFAOYSA-N 0.000 claims description 3
- QVYYDVDCJHTESX-UHFFFAOYSA-M benzyl(ethyl)alumanylium;chloride Chemical compound [Cl-].CC[Al+]CC1=CC=CC=C1 QVYYDVDCJHTESX-UHFFFAOYSA-M 0.000 claims description 3
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 3
- LLHTVHHWJJDSSP-UHFFFAOYSA-N bis(4-methylphenyl)alumane Chemical compound C1(=CC=C(C=C1)[AlH]C1=CC=C(C=C1)C)C LLHTVHHWJJDSSP-UHFFFAOYSA-N 0.000 claims description 3
- GTDUJCSUIQCLOZ-UHFFFAOYSA-M bis(4-methylphenyl)alumanylium;chloride Chemical compound [Cl-].C1=CC(C)=CC=C1[Al+]C1=CC=C(C)C=C1 GTDUJCSUIQCLOZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- GJDATTLXPMXFQF-UHFFFAOYSA-M chloro(dicyclohexyl)alumane Chemical compound [Cl-].C1CCCCC1[Al+]C1CCCCC1 GJDATTLXPMXFQF-UHFFFAOYSA-M 0.000 claims description 3
- DFGSACBYSGUJDZ-UHFFFAOYSA-M chloro(dihexyl)alumane Chemical compound [Cl-].CCCCCC[Al+]CCCCCC DFGSACBYSGUJDZ-UHFFFAOYSA-M 0.000 claims description 3
- ISFMCQATCMRFPY-UHFFFAOYSA-M chloro(diphenyl)alumane Chemical compound [Cl-].C=1C=CC=CC=1[Al+]C1=CC=CC=C1 ISFMCQATCMRFPY-UHFFFAOYSA-M 0.000 claims description 3
- LKRBKNPREDAJJQ-UHFFFAOYSA-M chloro-di(propan-2-yl)alumane Chemical compound [Cl-].CC(C)[Al+]C(C)C LKRBKNPREDAJJQ-UHFFFAOYSA-M 0.000 claims description 3
- CDHICTNQMQYRSM-UHFFFAOYSA-N di(propan-2-yl)alumane Chemical compound CC(C)[AlH]C(C)C CDHICTNQMQYRSM-UHFFFAOYSA-N 0.000 claims description 3
- RQXXJDTUITUSMU-UHFFFAOYSA-M dibenzyl(chloro)alumane Chemical compound [Cl-].C=1C=CC=CC=1C[Al+]CC1=CC=CC=C1 RQXXJDTUITUSMU-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- DODCHQVKECHKRP-UHFFFAOYSA-N dibenzylalumane Chemical compound C(C1=CC=CC=C1)[AlH]CC1=CC=CC=C1 DODCHQVKECHKRP-UHFFFAOYSA-N 0.000 claims description 3
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 claims description 3
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 claims description 3
- VKTXATHVMNFXEF-UHFFFAOYSA-N dicyclohexylalumane Chemical compound C1(CCCCC1)[AlH]C1CCCCC1 VKTXATHVMNFXEF-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- CPDVHGLWIFENDJ-UHFFFAOYSA-N dihexylalumane Chemical compound C(CCCCC)[AlH]CCCCCC CPDVHGLWIFENDJ-UHFFFAOYSA-N 0.000 claims description 3
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 claims description 3
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 3
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 3
- GNPSMYTXIPVJDU-UHFFFAOYSA-N dioctylalumane Chemical compound C(CCCCCCC)[AlH]CCCCCCCC GNPSMYTXIPVJDU-UHFFFAOYSA-N 0.000 claims description 3
- QRQUTSPLBBZERR-UHFFFAOYSA-M dioctylalumanylium;chloride Chemical compound CCCCCCCC[Al](Cl)CCCCCCCC QRQUTSPLBBZERR-UHFFFAOYSA-M 0.000 claims description 3
- HIVRDDZUKVNKAO-UHFFFAOYSA-N diphenylalumane Chemical compound C1(=CC=CC=C1)[AlH]C1=CC=CC=C1 HIVRDDZUKVNKAO-UHFFFAOYSA-N 0.000 claims description 3
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 claims description 3
- ZMXPNWBFRPIZFV-UHFFFAOYSA-M dipropylalumanylium;chloride Chemical compound [Cl-].CCC[Al+]CCC ZMXPNWBFRPIZFV-UHFFFAOYSA-M 0.000 claims description 3
- 229940069096 dodecene Drugs 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- CWTIARSERPPKIK-UHFFFAOYSA-M ethyl-(4-methylphenyl)alumanylium;chloride Chemical compound [Cl-].CC[Al+]C1=CC=C(C)C=C1 CWTIARSERPPKIK-UHFFFAOYSA-M 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Chemical group 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 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 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 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 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- SPWITGQNMOBZGJ-UHFFFAOYSA-M chloro(dipentyl)alumane Chemical compound [Cl-].CCCCC[Al+]CCCCC SPWITGQNMOBZGJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims 1
- 229920013639 polyalphaolefin Polymers 0.000 abstract description 39
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000000379 polymerizing effect Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000006228 supernatant Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 229940125782 compound 2 Drugs 0.000 description 10
- 239000012968 metallocene catalyst Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229940125904 compound 1 Drugs 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229940125898 compound 5 Drugs 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000012985 polymerization agent Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KDUNMLRPPVCIGP-UHFFFAOYSA-N CC(C)[Zn]C(C)C Chemical group CC(C)[Zn]C(C)C KDUNMLRPPVCIGP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- KFGIWFDCFBPRNI-UHFFFAOYSA-N dipentylaluminum Chemical compound CCCCC[Al]CCCCC KFGIWFDCFBPRNI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NEPIVOURWZEXGS-UHFFFAOYSA-N ethyl-bis(4-methylphenyl)alumane Chemical compound C=1C=C(C)C=CC=1[Al](CC)C1=CC=C(C)C=C1 NEPIVOURWZEXGS-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 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 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical group 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 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 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
Classifications
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
- C07C2/34—Metal-hydrocarbon complexes
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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Abstract
The invention discloses a method for polymerizing poly alpha-olefin (PAO) by using alpha-olefin as a polymerization raw material and using a ternary metallocene rare earth metal catalyst composition system. The invention takes single or mixed long-chain alpha-olefin as a polymerization raw material, uses a bridged metallocene rare earth metal compound as a main catalyst, and synthesizes mPAO with excellent viscosity-temperature performance under the condition of matching with a cocatalyst and a chain transfer agent. The mPAO obtained by the method has relatively high viscosity index, and the kinematic viscosity of the mPAO can be greatly adjusted by changing the temperature or using different chain transfer agents.
Description
Technical Field
The invention relates to a composition prepared by polymerizing long-chain alpha-olefin and a polymerization method, belongs to the technical field of poly-alpha-olefin synthetic oil, and particularly relates to a polymerization method for synthesizing poly-alpha-olefin by using single or mixed long-chain alpha-olefin as a raw material.
Background
Poly Alpha Olefin (PAO) is one kind of synthetic base oil, is a synthetic hydrocarbon lubricating oil prepared by a chemical synthesis method, has relatively regular long-chain alkane as a composition, is a synthetic lubricating oil base oil with excellent performance, and is one of the most widely applied base oil stocks in the current synthetic engine oil, gear oil and other industrial oil and grease. The synthetic oil prepared by the method greatly expands the application range of the lubricating grease under low temperature, high load and other harsh conditions, and provides excellent viscosity-temperature performance, thermal oxidation stability, lubricating and wear-resisting properties and detergency, thereby greatly prolonging the oil change period, slowing down the corrosion and wear of equipment, reducing the maintenance period of the equipment, and improving the utilization rate and service life of the equipment.
Polyalphaolefins are typically produced by olefin catalytic polymerization techniques using monomeric or mixed olefins in the alpha-olefin range from C8 to C12 and the polymerization catalyst is a Lewis acid type catalyst or a Ziegler-Natta catalyst. The use performance of the base oil is improved by improving the polymerization process and the polymerization catalyst. Over the years, there has been a great improvement and advancement in the technology of poly-alpha-olefin production.
To distinguish from conventional PAOs, the polyalphaolefins synthesized using metallocene catalysts are referred to as metallocene polyalphaolefins, i.e., mpao (metallocene PAO). In general, PAO molecules possess an overhanging backbone from which side chains of varying lengths extend in a disordered manner. The mPAO adopts a metallocene catalyst synthesis process, metallocene is a single-active-center catalyst, and a very uniform chemical product can be obtained by the unique geometric structure of the catalyst, so that the mPAO has a comb-shaped structure and does not have an upright side chain. This shape possesses improved rheological and flow characteristics compared to conventional PAOs, and thus may better provide shear stability, lower pour point and higher viscosity index, particularly with much higher shear stability than conventional PAOs due to fewer side chains. These characteristics dictate that mpaos are targeted for high severity applications, including powertrain and gear oils, compressor lubricants, transmission fluids, and industrial lubricants.
The metallocene catalytic synthesis process has the following characteristics: firstly, metallocene catalyzed alpha-olefin polymerization has very high catalytic activity which can be as high as dozens or even hundreds of kilograms of PAO per gram of catalyst, so the amount of the catalyst and cocatalyst consumed in the synthesis process is very small; secondly, because the metallocene catalyst is a single-active-center catalyst, the single-active-center polyolefin catalyst can well control the microstructure of the synthesized polyolefin molecules, namely the catalytic polymerization degree can be effectively adjusted along with the change of the process, and the catalyst has great elasticity, so that the chemical structure, the molecular weight and the molecular weight distribution of the polyolefin molecules can be accurately controlled, the PAO product with the required viscosity grade can be directly produced according to the actual requirement by utilizing the characteristic, and the production process flow is simplified; moreover, the catalytic system has high catalytic activity, so the reaction period is only about 2 hours, the production period is greatly shortened, and the production efficiency is improved; finally, because the used catalyst and cocatalyst are small in amount, the post-treatment process is simple, and the emission of three wastes can be effectively reduced.
Chinese patent publication No. CN1549852 discloses a process for the preparation of one or more olefin oligomers in the presence of a single site catalyst. Preferably, the olefin is an alpha-olefin and the oligomer is a Polyalphaolefin (PAO). The PAO so produced is completely or substantially free of tertiary hydrogen due to isomerization. Thus, the PAO has improved biodegradability, improved oxidation resistance, and/or a relatively higher viscosity index. The PAO has many useful applications such as being a lubricant component.
The lubricating oil composition of the invention of Chinese patent with publication number CN101617033 contains 1-5 mm kinematic viscosity at 100 DEG C2A lubricating base oil and a kinematic viscosity at 100 ℃ of 20 to 2000mm2At least 1/s selected from the group consisting of Olefin Copolymers (OCP) and Polyalphaolefins (PAO), having a kinematic viscosity at 100 ℃ of 8.0mm2(ii) less than s and a viscosity index of 155 or more.
U.S. patent 6548723 discloses a method for preparing lube base oil PAO by oligomerization of 1-decene and ethylene under catalysis of metallocene or organic metal amine salt, wherein the catalyst is mainly non-bridged cyclopentadienyl metallocene, and the obtained PAO is low-viscosity base oil when Al/Zr is 1000.
U.S. Pat. No. 4,6706828 uses meso-silicon bridged bis-indenyl substituted bridged metallocene catalyst to synthesize PAO in the presence of hydrogen and uses 1-decene as raw material, the catalytic performance of different meso and rac structures is different, and the viscosity-temperature performance of the catalyst system and the obtained PAO product is greatly influenced by changing the configuration ratio and hydrogen pressure of the catalyst.
The Chinese patent publication No. CN105062555 discloses that mPAO with excellent viscosity-temperature performance is synthesized by taking coal-made alpha-olefin produced by a Fischer-Tropsch synthesis process as a polymerization raw material under the action of a metallocene catalyst; the method replaces the expensive pure alpha-olefin polymerization raw material, reduces the production cost of PAO on one hand, and improves the economy of the Fischer-Tropsch synthesis process on the other hand.
Most of the above patents mention the polymerization of 1-decene or 1-octene obtained by oligomerization of ethylene as raw material to obtain mPAO, and also mention the synthesis of mPAO from coal-derived α -olefins as raw material. The catalytic system disclosed by the invention can be used for polymerizing single long-chain alpha-olefin and can also be used for catalyzing and polymerizing mixed long-chain alpha-olefin, such as coal-made alpha-olefin produced by a Fischer-Tropsch synthesis process. In addition, the PAO with excellent viscosity-temperature performance can be obtained by polymerization by using the ternary metallocene rare earth metal catalyst composition disclosed by the invention, and compared with the prior art, the obtained PAO has relatively higher viscosity index, and the kinematic viscosity can be adjusted in a large range. Particularly, the fluorenyl substituent and the electron-withdrawing effect of the substituent on the cyclopentadiene in the main catalyst can regulate and control the molecular weight of the polymer, which has important guiding significance for developing and preparing the metallocene rare earth metal catalyst with low viscosity mPAO in the future, and in addition, the viscosity of the polymer can be further regulated and controlled by matching with different cocatalysts, which has important significance for developing new PAO products with different brands and from low to high viscosity.
Disclosure of Invention
The present invention aims to provide a metallocene rare earth catalyst composition for alpha-olefin polymerization and a polymerization method thereof. The rare earth metallocene catalyst composition comprises a ternary catalytic system of a main catalyst, a cocatalyst and a chain transfer agent, and is suitable for the polymerization of single or mixed long-chain alpha-olefin.
In order to achieve the above object, the present invention provides a long-chain α -olefin polymerization catalyst composition, which comprises a main catalyst, a cocatalyst and a chain transfer agent, wherein the main catalyst is a bridged rare earth metallocene compound having a structure represented by formula (I):
wherein Ln is a rare earth metal; y is carbon, silicon or germanium; r1And R2Is cyclopentadienyl, indenyl or fluorenyl containing substituents, equal to or different from each other, wherein the substituents are independently selected from methyl, ethyl, propyl, n-butyl, tert-butyl or hexyl; r3To initiate the agglomeration; r4And R5Independently selected from hydrogen, alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 1 to 6 carbon atoms, and halogenoalkyl groups having 1 to 6 carbon atoms.
Preferably, in the long-chain α -olefin polymerization catalyst composition provided by the present invention, Ln is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
Preferably, in the catalyst composition for polymerization of long-chain alpha-olefin provided by the present invention, R is1And R2The substituents on (a) are independently selected from substituted or unsubstituted aliphatic, aromatic or cyclic groups, or combinations thereof.
Preferably, in the catalyst composition for polymerization of long-chain alpha-olefin provided by the present invention, R is3Is one of alkyl, alkynyl, trimethylsilyl, alkoxy, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen F, Cl, Br and I.
Preferably, in the long-chain α -olefin polymerization catalyst composition provided by the present invention, the bridged metallocene rare earth metal compound is one of compounds represented by the following structural formula:
preferably, in the long-chain alpha-olefin polymerization catalyst composition provided by the invention, the cocatalyst is alkylaluminoxane and/or organoboron.
Preferably, in the long-chain alpha-olefin polymerization catalyst composition provided by the invention, the alkylaluminoxane is one or more selected from methylaluminoxane, ethylaluminoxane, n-propylaluminoxane and n-butylaluminoxane; the organoboron reagent is selected from [ Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]And B (C)6F5)3One or more of them.
Preferably, in the long-chain alpha-olefin polymerization catalyst composition provided by the invention, the chain transfer agent is an aluminum compound and/or zinc alkyl; wherein the aluminum compound is of the formula AlX3Alkyl aluminum of formula HAlX2And an alkyl aluminum hydride of the formula AlX2One or more of Cl and alkyl aluminum chloride, wherein X is alkyl; the alkyl zinc reagent is selected from one or more of dimethyl zinc, diethyl zinc and diisopropyl zinc.
Preferably, in the long-chain α -olefin polymerization catalyst composition provided by the present invention, the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, trihexyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl-p-tolyl aluminum, and diethyl benzyl aluminum.
Preferably, in the long chain α -olefin polymerization catalyst composition provided by the present invention, the alkyl aluminum hydride is selected from one or more of dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, ethylbenzyl aluminum hydride, ethyl-p-tolyl aluminum hydride and ethylbenzyl aluminum hydride.
Preferably, in the long chain α -olefin polymerization catalyst composition provided by the present invention, the alkyl aluminum chloride is selected from one or more of dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, dipentylaluminum chloride, dihexylaluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, ethylbenzylaluminum chloride, and ethyl-p-tolylaluminum chloride.
Preferably, in the long-chain alpha-olefin polymerization catalyst composition provided by the invention, the molar ratio of aluminum in the cocatalyst to metal in the main catalyst is 10-5000: 1; the molar ratio of boron in the cocatalyst to metal in the main catalyst is 1-200: 1.
Preferably, in the long-chain alpha-olefin polymerization catalyst composition provided by the invention, the molar ratio of aluminum in the chain transfer agent to metal in the main catalyst is 1-500: 1; the molar ratio of zinc in the chain transfer agent to metal in the main catalyst is 1-500: 1.
The invention also provides the application of the long-chain alpha-olefin polymerization agent composition in single or mixed long-chain alpha-olefin polymerization, wherein the single or mixed long-chain alpha-olefin is selected from one or more of 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene and 1-hexadecene.
The invention provides an application of a long-chain alpha-olefin polymerization agent composition in single or mixed long-chain alpha-olefin polymerization, wherein the polymerization conditions are as follows: in the presence of inert gas, adding single or mixed long-chain alpha-olefin, a main catalyst, a chain transfer agent and a cocatalyst in sequence to carry out polymerization reaction; the temperature of the polymerization reaction is 0-180 ℃.
The invention can also be described in more detail as follows:
the invention provides a long-chain alpha-olefin polymerization catalyst composition, which comprises a main catalyst, a cocatalyst and a chain transfer agent,
first, the present invention provides a procatalyst of the above catalyst composition, which is a bridged metallocene rare earth metal compound having the structural formula (I):
wherein Ln is a rare earth metal; y is carbon, silicon or germanium; r3Is an initiating group linked to a rare earth metal; r4And R5Are identical or different from each other, can be hydrogen, have a value of 1 to 6An alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and a halogenoalkyl group having 1 to 6 carbon atoms.
Wherein Ln is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R3is one of alkyl, alkynyl, trimethylsilyl, alkoxy, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen F, Cl, Br and I;
R1and R2May be represented by any one of chemical formula 1, chemical formula 2, and chemical formula 3, the same as or different from each other;
[ chemical formula 1 ]
[ chemical formula 2 ]
[ chemical formula 3 ]
In chemical formulas 1, 2 and 3, R1To R18Identical to or different from each other, independently hydrogen, halogen, C1～C20Alkyl radical, C2～C20Alkenyl radical, C1～C20Alkylsilyl group, C1～C20Silylalkyl group, C1～C20Alkoxysilyl group, C1～C20Alkoxy radical, C6～C20Aryl radical, C7～C20Alkylaryl or C7～C20An arylalkyl group.
In the metallocene rare earth metal compound of the present invention, the substituents of chemical formulae 1, 2 and 3 are more specifically described as follows.
C1～C20The alkyl group may include a linear or branched alkyl group, and specifically, it may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc., however, it is not limited thereto.
C2～C20The alkenyl group may include a linear or branched alkenyl group, and specifically, it may be a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, etc., however, it is not limited thereto.
C1～C20The alkoxy group may be methoxy, ethoxy, phenoxy, cyclohexyloxy, etc., however, it is not limited thereto.
According to an embodiment of the present invention, a specific example of the compound represented by structural formula (I) may be one of the compounds represented by the following structural formula, however, is not limited thereto:
secondly, the present invention also provides a cocatalyst for the above metallocene catalyst composition, which can be an alkylaluminoxane reagent and/or an organoboron reagent.
Wherein, the alkylaluminoxane is selected from one or more of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane and n-butylaluminoxane; the organoboron reagent is selected from [ Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]、B(C6F5)3One or more of them.
Third, the present invention also provides a chain transfer agent for the above metallocene catalyst composition, the chain transfer agent comprising an aluminum reagent and/or a zinc alkyl reagent. Wherein the aluminum reagent is of the formula AlX3Alkyl aluminum of formula HAlX2Of the formula AlX2Alkylaluminum chloride of Cl and X is an alkyl group. The alkyl zinc reagent is selected from one or more of dimethyl zinc, diethyl zinc and diisopropyl zinc.
Wherein the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, trihexyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl di-p-tolyl aluminum and diethyl benzyl aluminum.
The alkyl aluminum hydride is selected from one or more of dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, ethyl benzyl aluminum hydride, ethyl p-tolyl aluminum hydride and ethyl benzyl aluminum hydride.
The alkyl aluminum chloride is selected from one or more of dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, ethyl benzyl aluminum chloride and ethyl p-tolyl aluminum chloride.
The rare earth metallocene catalyst composition provided by the invention can be used for producing alpha-olefin polymers, is particularly suitable for single or mixed long-chain alpha-olefin polymerization, can regulate and control the kinematic viscosity in a large range, and obtains a PAO viscosity index which is relatively higher than that obtained by the prior art.
The polymerization process provided by the present invention is described in detail below: in the presence of inert gas, adding single or mixed long-chain alpha-olefin, a main catalyst, a cocatalyst and a chain transfer agent in sequence to carry out polymerization reaction; the polymerization temperature is 20 ℃ to 150 ℃, preferably 80 ℃ to 120 ℃. The single or mixed long-chain alpha-olefin used in the invention is selected from one or a mixture of more of 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene and 1-hexadecene.
Further, the molar ratio of the aluminum in the cocatalyst to the metal in the main catalyst is 10-5000: 1; or the molar ratio of the boron in the cocatalyst to the metal in the main catalyst is 1-200: 1. Wherein the molar ratio of aluminum in the chain transfer agent to metal in the main catalyst is 1-500: 1; or the molar ratio of the zinc in the chain transfer agent to the metal in the main catalyst is 1-500: 1.
The polymerization time is generally 2 hours, the stirring is stopped, the reaction is stopped by water, the supernatant is poured out by centrifugation, and unreacted monomers are removed by rotary evaporation of the supernatant, so that the mPAO with excellent viscosity-temperature performance can be obtained.
The beneficial effects of the invention are as follows:
the catalytic system disclosed by the invention can be used for polymerizing single long-chain alpha-olefin and can also be used for catalyzing and polymerizing mixed long-chain alpha-olefin, such as coal-made alpha-olefin produced by a Fischer-Tropsch synthesis process. In addition, the PAO with excellent viscosity-temperature performance can be obtained by polymerization by using the ternary metallocene rare earth metal catalyst composition disclosed by the invention, and compared with the prior art, the obtained PAO has relatively higher viscosity index and adjustable kinematic viscosity in a large range, thereby having important significance for developing new PAO products with different brands and from low to high viscosity.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the following examples are only for the understanding of the present invention, and the scope of the present invention is not limited thereto or thereby. The method for testing the viscosity-temperature performance of mPAO in the invention comprises the following steps:
petroleum product kinematic viscometry and dynamic viscometer algorithms: GB/T265
Calculation of viscosity index of petroleum products: GB/T1995.
Homogeneously catalyzed olefin copolymerization
Comparative example 1
Compound 1 and catalyst composition thereof for catalyzing alpha-olefin polymerization
The bridged metallocene rare earth compound used in this comparative example is compound 1, shown by the following structural formula:
[ Compound 1 ]
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, added into the reaction flask under the protection of 1ml of triethylaluminum (1.0mol/l in toluene) nitrogen and stirred for half an hour. 20mg of Compound 1 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the reaction at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out the supernatant, and performing rotary evaporation on the supernatant to remove unreacted monomers to obtain mPAO with excellent viscosity-temperature performance.
Comparative example 2
Compound 1 and catalyst composition thereof for catalyzing alpha-olefin polymerization
The polymerization conditions and the operation were the same as in comparative example 1, except that the polymerization temperature was maintained at 100 ℃.
Example 1
Compound 2 and catalyst composition thereof for catalyzing alpha-olefin polymerization
The bridged metallocene rare earth compound used in this example is compound 2, shown by the following structural formula:
[ Compound 2 ]
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, added into the reaction flask under the protection of 1ml of triethylaluminum (1.0mol/l in toluene) nitrogen and stirred for half an hour. 20mg of Compound 2 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the temperature at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out the supernatant, and performing rotary evaporation on the supernatant to remove unreacted monomers to obtain mPAO with excellent viscosity-temperature performance.
Example 2
Compound 2 and catalyst composition thereof for catalyzing alpha-olefin polymerization
The polymerization conditions and procedure were the same as in example 1, except that the polymerization temperature was maintained at 100 ℃.
The kinematic viscosity at 100 ℃ and the composition data of the polyalphaolefins obtained in comparative examples 1 and 2, and examples 1 and 2 were measured, and the results are shown in Table 1.
Table 1 analysis of the composition and viscosity of the resulting polymer product
As can be seen from the data in table 1: as the polymerization temperature increases, the dimer content in the product increases, the trimer content does not change significantly, while the tetramer and above components decrease resulting in a decrease in viscosity of the resulting mPAO with increasing polymerization temperature. Comparing compound 1 and compound 2, we have readily found that the polymerization of compound 2 results in a polyalphaolefin product having a significantly lower viscosity than the polymerization of compound 1, i.e., examples 1 and 2 are significantly more suitable for preparing a low viscosity mPAO than comparative examples 1 and 2. That is to say, the electron-withdrawing effect of the fluorenyl substituent and the cyclopentadienyl substituent in the main catalyst can regulate and control the molecular weight of the polymer, which has important guiding significance for developing and preparing the low-viscosity mPAO metallocene rare earth metal catalyst in the future.
Example 3
Compound 3 and catalyst composition thereof for catalyzing alpha-olefin polymerization
The bridged metallocene rare earth compound used in this example is compound 3, shown by the following structural formula:
[ Compound 3 ]
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, added into the reaction flask under the protection of 1ml of triethylaluminum (1.0mol/l in toluene) nitrogen and stirred for half an hour. 20mg of Compound 3 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the temperature at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out the supernatant, and performing rotary evaporation on the supernatant to remove unreacted monomers to obtain mPAO with excellent viscosity-temperature performance.
Example 4
Compound 4 and catalyst composition thereof for catalyzing alpha-olefin polymerization
The bridged metallocene rare earth compound used in this example is compound 3, shown by the following structural formula:
[ Compound 4 ]
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, added into the reaction flask under the protection of 1ml of triethylaluminum (1.0mol/l in toluene) nitrogen and stirred for half an hour. 20mg of Compound 4 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the reaction at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out the supernatant, and performing rotary evaporation on the supernatant to remove unreacted monomers to obtain mPAO with excellent viscosity-temperature performance.
Example 5
Compound 5 and catalyst composition thereof for catalyzing alpha-olefin polymerization
The bridged metallocene rare earth compound used in this example is compound 5, shown by the following structural formula:
[ Compound 5 ]
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, added into the reaction flask under the protection of 1ml of triethylaluminum (1.0mol/l in toluene) nitrogen and stirred for half an hour. 20mg of Compound 5 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the temperature at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out supernatant liquid, and performing rotary evaporation on the supernatant liquid to remove unreacted monomers to obtain the mPAO with excellent viscosity-temperature performance.
The mPAO viscosity data synthesized from the different procatalysts in the above examples and comparative examples are shown in table 2.
TABLE 2 viscosity temperature data of mPAO synthesized with different main catalysts
As can be seen from the data in Table 2, the viscosity index of mPAO obtained in the above examples and comparative examples is larger than 200, which indicates that mPAO with excellent viscosity-temperature performance can be obtained when the bridged rare earth metallocene catalyst is used as a main catalyst.
Example 6
Application of triisobutylaluminum chain transfer agent in catalyzing alpha-olefin polymerization
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, and added into the reaction flask under the protection of 1ml of triisobutylaluminum (1.0mol/l in toluene) nitrogen, and stirred for half an hour. 20mg of Compound 2 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the temperature at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out the supernatant, and performing rotary evaporation on the supernatant to remove unreacted monomers to obtain mPAO with excellent viscosity-temperature performance.
Example 7
Application of diethyl aluminum hydride chain transfer agent in catalyzing alpha-olefin polymerization
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, and 1ml of diethyl aluminum hydride (1.0mol/l in toluene) is added into the reaction flask under the protection of nitrogen and stirred for half an hour. 20mg of Compound 2 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the temperature at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out the supernatant, and performing rotary evaporation on the supernatant to remove unreacted monomers to obtain mPAO with excellent viscosity-temperature performance.
Example 8
Application of diisopropyl zinc chain transfer agent in catalyzing alpha-olefin polymerization
200ml of alpha-olefin mixture are metered into a 500ml reaction flask equipped with magnetic stirring under the protection of high-purity nitrogen, heated to 90 ℃, added into the reaction flask under the protection of 1ml of diisopropylzinc (1.0mol/l in toluene) nitrogen and stirred for half an hour. 20mg of Compound 2 was weighed, dissolved in 2ml of Methylaluminoxane (MAO) (1.0mol/l in tolumen), and the prepared catalyst solution was added to a reaction flask, and polymerization was started while maintaining the temperature at 90 ℃. After 2 hours, adding water to terminate the reaction, centrifuging, pouring out the supernatant, and performing rotary evaporation on the supernatant to remove unreacted monomers to obtain mPAO with excellent viscosity-temperature performance.
The kinematic viscosity at 100 ℃ of the polyalphaolefins obtained in examples 1, 6, 7 and 8 above was measured, and the results are shown in Table 3.
TABLE 3 comparison of kinematic viscosities at 100 ℃ of the polymers obtained in examples 1, 6, 7, 8
As can be seen from the data in table 3: under the same other conditions, the kinematic viscosity of mPAO can be obviously adjusted by only changing the type of the chain transfer agent. That is, the introduction of different chain transfer agents can greatly adjust the molecular weight of the polymer, which is of great significance for producing mPAO with different viscosities.
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 (11)
1. A long chain alpha-olefin polymerization catalyst composition comprises a main catalyst, a cocatalyst and a chain transfer agent, and is characterized in that the main catalyst is a bridged metallocene rare earth metal compound and has a structure shown in a formula (I):
wherein Ln isA rare earth metal; y is carbon, silicon or germanium; r1And R2Is cyclopentadienyl, indenyl or fluorenyl containing substituents, equal to or different from each other, wherein the substituents are independently selected from methyl, ethyl, propyl, n-butyl, tert-butyl or hexyl; r3To initiate the agglomeration; r4And R5Independently selected from hydrogen, alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 1 to 6 carbon atoms, and halogenoalkyl groups having 1 to 6 carbon atoms.
2. The long chain alpha olefin polymerization catalyst composition of claim 1, characterized in that: the Ln is one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
the R is1And R2The substituents on (a) are independently selected from substituted or unsubstituted aliphatic, aromatic or cyclic groups, or combinations thereof;
R3is one of alkyl, alkynyl, trimethylsilyl, alkoxy, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen F, Cl, Br and I.
3. The long chain alpha olefin polymerization catalyst composition of claim 1 wherein the bridged metallocene rare earth metal compound is one of the compounds represented by the following structural formula:
4. the long chain alpha olefin polymerization catalyst composition of claim 1, wherein the cocatalyst is an alkylaluminoxane and/or an organoboron.
5. The long chain α -olefin polymerizer composition according to claim 4, wherein the alkylaluminoxane is one or more selected from methylaluminoxane, ethylaluminoxane, n-propylaluminoxane and n-butylaluminoxane; the organoboron reagent is selected from [ Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]And B (C)6F5)3One or more of them.
6. The long chain alpha olefin polymerizer composition according to claim 1, wherein the chain transfer agent is an aluminum compound and/or a zinc alkyl; wherein the aluminum compound is of the formula AlX3Alkyl aluminum of formula HAlX2And an alkyl aluminum hydride of the formula AlX2One or more of Cl and alkyl aluminum chloride, wherein X is alkyl; the alkyl zinc reagent is selected from one or more of dimethyl zinc, diethyl zinc and diisopropyl zinc.
7. A long-chain α -olefin polymerizer composition according to claim 6, wherein:
the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, trihexyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl-p-tolyl aluminum and diethyl benzyl aluminum;
the alkyl aluminum hydride is selected from one or more of dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, ethyl benzyl aluminum hydride, ethyl p-tolyl aluminum hydride and ethyl benzyl aluminum hydride;
the alkyl aluminum chloride is selected from one or more of dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, ethyl benzyl aluminum chloride and ethyl p-tolyl aluminum chloride.
8. The long chain alpha olefin polymerization catalyst composition of claim 4 or 5, wherein the molar ratio of aluminum in the co-catalyst to the metal in the procatalyst is 10-5000: 1; the molar ratio of boron in the cocatalyst to metal in the main catalyst is 1-200: 1.
9. The long chain alpha olefin polymerizer composition according to claim 6 or 7, wherein the molar ratio of aluminum in the chain transfer agent to the metal in the procatalyst is from 1 to 500: 1; the molar ratio of zinc in the chain transfer agent to metal in the main catalyst is 1-500: 1.
10. Use of a long chain α -olefin polymerizer composition according to any one of claims 1-9 in the polymerization of single or mixed long chain α -olefins, wherein the single or mixed long chain α -olefin is selected from one or more of 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, and 1-hexadecene.
11. Use of a long chain alpha olefin polymerizer composition, as claimed in claim 10, in single or mixed long chain alpha olefin polymerization, under polymerization conditions: in the presence of inert gas, adding single or mixed long-chain alpha-olefin, a main catalyst, a chain transfer agent and a cocatalyst in sequence to carry out polymerization reaction; the temperature of the polymerization reaction is 0-180 ℃.
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