CN117430738A - Catalyst component for olefin polymerization, catalyst and application thereof - Google Patents
Catalyst component for olefin polymerization, catalyst and application thereof Download PDFInfo
- Publication number
- CN117430738A CN117430738A CN202210827412.7A CN202210827412A CN117430738A CN 117430738 A CN117430738 A CN 117430738A CN 202210827412 A CN202210827412 A CN 202210827412A CN 117430738 A CN117430738 A CN 117430738A
- Authority
- CN
- China
- Prior art keywords
- benzimidazole
- carboxylic acid
- methyl ester
- acid methyl
- bis
- 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.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 239000011777 magnesium Substances 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 150000002367 halogens Chemical class 0.000 claims abstract description 29
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims abstract description 5
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- -1 nitro, amino Chemical group 0.000 claims description 260
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 13
- OJHVSVKKRBFAEY-UHFFFAOYSA-N methyl benzimidazole-1-carboxylate Chemical compound C1=CC=C2N(C(=O)OC)C=NC2=C1 OJHVSVKKRBFAEY-UHFFFAOYSA-N 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 9
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- MJABXZWILYUAEB-UHFFFAOYSA-N benzimidazole-1-carboxylic acid Chemical compound C1=CC=C2N(C(=O)O)C=NC2=C1 MJABXZWILYUAEB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 4
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 claims description 3
- IOQPCIJYSRTMEJ-UHFFFAOYSA-N C(C)(C)N(C(=O)N1C=NC2=C1C=CC=C2)C(C)C Chemical compound C(C)(C)N(C(=O)N1C=NC2=C1C=CC=C2)C(C)C IOQPCIJYSRTMEJ-UHFFFAOYSA-N 0.000 claims description 3
- NOYFALUWIWPYGH-UHFFFAOYSA-N COC(=O)N1C(=NC2=C1C=CC=C2)C1=CC=CC=C1 Chemical compound COC(=O)N1C(=NC2=C1C=CC=C2)C1=CC=CC=C1 NOYFALUWIWPYGH-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- KSXNZGIGSBSYLU-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]benzimidazole Chemical compound C1=CC(C(F)(F)F)=CC=C1N1C2=CC=CC=C2N=C1 KSXNZGIGSBSYLU-UHFFFAOYSA-N 0.000 claims description 2
- RHXSYTACTOMVLJ-UHFFFAOYSA-N 1H-benzimidazole-2-carboxylic acid Chemical compound C1=CC=C2NC(C(=O)O)=NC2=C1 RHXSYTACTOMVLJ-UHFFFAOYSA-N 0.000 claims description 2
- DTCYSRAEJHGSNY-UHFFFAOYSA-N 2-methoxy-2-(2-methoxypropan-2-yloxy)propane Chemical compound COC(C)(C)OC(C)(C)OC DTCYSRAEJHGSNY-UHFFFAOYSA-N 0.000 claims description 2
- BPYHGTCRXDWOIQ-UHFFFAOYSA-N 3-nitropyridin-2-amine Chemical compound NC1=NC=CC=C1[N+]([O-])=O BPYHGTCRXDWOIQ-UHFFFAOYSA-N 0.000 claims description 2
- LKXXWIRKYZPMMS-UHFFFAOYSA-N 6-ethyl-1h-benzimidazole Chemical compound CCC1=CC=C2N=CNC2=C1 LKXXWIRKYZPMMS-UHFFFAOYSA-N 0.000 claims description 2
- RFPOYGARIHBHDV-UHFFFAOYSA-N 6-propan-2-yl-1h-benzimidazole Chemical compound CC(C)C1=CC=C2N=CNC2=C1 RFPOYGARIHBHDV-UHFFFAOYSA-N 0.000 claims description 2
- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- JZRIIAYLOPWOHN-UHFFFAOYSA-N benzimidazole-1-carboxamide Chemical compound C1=CC=C2N(C(=O)N)C=NC2=C1 JZRIIAYLOPWOHN-UHFFFAOYSA-N 0.000 claims description 2
- KEAQRENIDURQFY-UHFFFAOYSA-N benzyl benzimidazole-1-carboxylate Chemical compound C1=NC2=CC=CC=C2N1C(=O)OCC1=CC=CC=C1 KEAQRENIDURQFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- PDFVBOBULUSKAW-UHFFFAOYSA-N cyclohexyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C1CCCCC1 PDFVBOBULUSKAW-UHFFFAOYSA-N 0.000 claims description 2
- RTYZQVDVGVAXSW-UHFFFAOYSA-N cyclohexylmethyl(diethoxy)silane Chemical compound CCO[SiH](OCC)CC1CCCCC1 RTYZQVDVGVAXSW-UHFFFAOYSA-N 0.000 claims description 2
- LITADYQPNQQQCR-UHFFFAOYSA-N cyclopentyl-diethyl-methoxysilane Chemical compound CC[Si](CC)(OC)C1CCCC1 LITADYQPNQQQCR-UHFFFAOYSA-N 0.000 claims description 2
- MUQCQZPQDMXYAA-UHFFFAOYSA-N cyclopentyl-dimethoxy-(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(OC)C1CCCC1 MUQCQZPQDMXYAA-UHFFFAOYSA-N 0.000 claims description 2
- BGNDGZWNHDJSEE-UHFFFAOYSA-N cyclopentyl-dimethoxy-(4-methylcyclohexyl)silane Chemical compound C1CC(C)CCC1[Si](OC)(OC)C1CCCC1 BGNDGZWNHDJSEE-UHFFFAOYSA-N 0.000 claims description 2
- JOUWRCGZMOSOCD-UHFFFAOYSA-N cyclopentyl-dimethoxy-propan-2-ylsilane Chemical compound CO[Si](OC)(C(C)C)C1CCCC1 JOUWRCGZMOSOCD-UHFFFAOYSA-N 0.000 claims description 2
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 claims description 2
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 2
- AQKIYZKRFDDSDJ-UHFFFAOYSA-N diethyl-hexyl-methoxysilane Chemical compound CCCCCC[Si](CC)(CC)OC AQKIYZKRFDDSDJ-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- KEFHHBBQDBFTFZ-UHFFFAOYSA-N dimethoxy-[(4-methylcyclohexyl)methyl]silane Chemical compound CC1CCC(CC1)C[SiH](OC)OC KEFHHBBQDBFTFZ-UHFFFAOYSA-N 0.000 claims description 2
- OHYUZCOXLZERPH-UHFFFAOYSA-N dimethoxy-[2-(4-methylcyclohexyl)ethyl]silane Chemical compound CC1CCC(CC1)CC[SiH](OC)OC OHYUZCOXLZERPH-UHFFFAOYSA-N 0.000 claims description 2
- ZAUVNAJLSYVDBY-UHFFFAOYSA-N dimethoxy-[3-(4-methylcyclohexyl)propyl]silane Chemical compound CC1CCC(CC1)CCC[SiH](OC)OC ZAUVNAJLSYVDBY-UHFFFAOYSA-N 0.000 claims description 2
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 claims description 2
- CMFVMOIFTUDPNL-UHFFFAOYSA-N dimethoxy-bis(4-methylcyclohexyl)silane Chemical compound C1CC(C)CCC1[Si](OC)(OC)C1CCC(C)CC1 CMFVMOIFTUDPNL-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 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
- 125000002883 imidazolyl group Chemical group 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
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- FUMSHFZKHQOOIX-UHFFFAOYSA-N methoxy(tripropyl)silane Chemical compound CCC[Si](CCC)(CCC)OC FUMSHFZKHQOOIX-UHFFFAOYSA-N 0.000 claims description 2
- LKUBWDNDGBVKFK-UHFFFAOYSA-N methyl 1h-benzimidazole-2-carboxylate Chemical compound C1=CC=C2NC(C(=O)OC)=NC2=C1 LKUBWDNDGBVKFK-UHFFFAOYSA-N 0.000 claims description 2
- WJHHIVYNOVTVGY-UHFFFAOYSA-N methyl 3h-benzimidazole-5-carboxylate Chemical compound COC(=O)C1=CC=C2N=CNC2=C1 WJHHIVYNOVTVGY-UHFFFAOYSA-N 0.000 claims description 2
- GDHBUYPYSHHFAU-UHFFFAOYSA-N n,n-diphenylbenzimidazole-1-carboxamide Chemical compound C1=NC2=CC=CC=C2N1C(=O)N(C=1C=CC=CC=1)C1=CC=CC=C1 GDHBUYPYSHHFAU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-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
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 claims 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000007787 solid Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- 235000011147 magnesium chloride Nutrition 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- GSURLQOINUQIIH-UHFFFAOYSA-N triheptyl phosphate Chemical compound CCCCCCCOP(=O)(OCCCCCCC)OCCCCCCC GSURLQOINUQIIH-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- WVPGXJOLGGFBCR-UHFFFAOYSA-N trioctyl phosphate Chemical compound CCCCCCCCOP(=O)(OCCCCCCCC)OCCCCCCCC WVPGXJOLGGFBCR-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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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)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides a catalyst component for olefin polymerization, a catalyst and application thereof, wherein the catalyst component contains magnesium, titanium, halogen and an internal electron donor, the internal electron donor is a compound shown in a general formula I, the structure of the compound shown in the general formula I is as follows,in the general formula I, R 2 ～R 5 The same or different is hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C6-C30 aryl, C4-C30 heterocyclic group, halogen atom, alkoxy or substituent containing nitrogen atom; r is R 1 、R 6 The same or different are hydrogen, C1-C15 aliphatic chains or substituent groups containing hetero atoms; the hetero atoms being selected from nitrogen, sulfur, oxygen, phosphorusAnd at least one of silicon. The polymer prepared by the catalyst containing the catalyst component has higher melt index and wide molecular weight distribution, and can effectively improve the processability of products.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a catalyst component for olefin polymerization, a catalyst and application thereof.
Background
The internal electron donor is an important component of Ziegler-Natta polyolefin catalysts, and plays a decisive role in the catalytic activity of the catalysts, the hydrogen regulation sensitivity and the molecular weight distribution of the polyolefin products. In the current common industrial catalysts, the internal electron donor is mostly phthalate compounds. With the increasing interest in health, as one of the common industrial plasticizers, the application of plastic products containing phthalate compounds is greatly limited, and in particular, the european union REACH regulations have adopted stricter limitation measures for plasticizers in 2019, and this act requires all plastic products exported to the european union, wherein the content of the plasticizer is increased from the original content of each plasticizer to 0.1% or less, and the total content of several plasticizers is increased to 0.1% or less. The related national standard GB/T29498-2020 is also implemented in China to standardize the use of phthalate compounds in consumer products for limitation. Therefore, in the development of new polyolefin Ziegler-Natta catalyst technology, catalysts containing no phthalate compounds have become fundamental requirements for many aspects such as green, health, and environmental protection. At present, various novel internal electron donor compounds have been developed for replacing phthalate compounds, and mainly diether compounds (such as 1, 3-diether, see patent CN 1463274A), dicarboxylic acid ester compounds (such as succinate, see patent CN1313869 a) and glycol ester compounds (such as 1, 3-glycol ester, see patent CN1436766 a) are common.
In recent years, a number of electron donor compounds of novel structures have been developed for olefin polymerization catalysts, and among them, a class of compounds other than plasticizers has a nitrogen atom structure in its molecular structure, and has been attracting attention as an internal electron donor preparation catalyst. The nitrogen atoms exist in a mode of forming fatty amine, and exist in the structure of fatty chain or N-alkyl heterocycle according to the chemical bond of the unequal SP3 hybridization structure, for example, a substituted fatty amine group/amide ester compound, such as the compound shown in patent CN101104589A and patent US2012322962, and the compound is used as a catalyst for preparing an internal electron donor, so that the defects of low orientation capability or high xylene soluble content of the prepared polymer exist; functional groups such as aromatic amine and imine can also be formed, and chemical bonds with an equal or unequal SP2 hybridization structure exist in five-membered or six-membered nitrogen aromatic heterocycle or substituent groups at alpha position, such as compounds disclosed in patent CN112759531A and patent CN105085746B, but the prepared catalyst has the problem of low orientation capability or lower melt index of the product; cyano (-CN) can also be formed and exists in the compound in an unequal SP hybridization mode, for example, a cyano ketone compound disclosed in patent CN1715301A and a cyano ester compound disclosed in patent CN1242780A are adopted as polyolefin catalysts, the catalysts remain in plastic products in the olefin polymerization process, and if the products have trace decomposition in the use process, the generated toxic free cyanide is extremely easy to cause harm to human health. Therefore, for the application of nitrogen-containing internal electron donors of non-plasticizers in the field, there is still a need to improve the catalyst and its components so as to make them have better directing ability and catalytic activity and make the prepared product more suitable for downstream product processing.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst component for olefin polymerization, a catalyst containing the catalyst component and application thereof, wherein an organic compound containing benzimidazole structures is introduced into the catalyst component as an internal electron donor, the internal electron donor does not contain plasticizers, nitrogen atoms in the internal electron donor simultaneously contain SP2 and SP3 for hybridization, and the obtained catalyst containing the catalyst component has high activity and good stereospecificity, and particularly the prepared polymer has wide molecular weight distribution and can effectively improve the processability of products.
In a first aspect, the invention provides a catalyst component for olefin polymerization, wherein the catalyst component contains magnesium, titanium, halogen and an internal electron donor, the internal electron donor is a compound shown in a general formula I, the structure of the compound shown in the general formula I is as follows,
in the general formula I, R 2 ～R 5 The same or different is hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C6-C30 halogen substituted or unsubstituted aryl, C4-C30 heterocyclic group, halogen atom, alkoxy or substituent containing nitrogen atom; r is R 1 、R 6 The same or different is hydrogen, C1-C15 alkyl or substituent containing hetero atom; the heteroatom is selected from at least one of nitrogen, sulfur, oxygen, phosphorus, and silicon.
As a specific embodiment of the present invention, preferably, in formula I, R 2 ～R 5 The same or different, each independently is a C1-C10 alkyl group, a C2-C15 alkenyl group, a C6-C15 halogen substituted or unsubstituted aromatic group, a C4-C15 heterocyclic group, a halogen atom, an alkoxy group or a substituent containing a nitrogen atom; preferably, each is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, methoxy, isopropyl ether, tert-butyl ether, phenyl, halophenyl, naphthyl, biphenyl, nitro, amino, pyridine, thiophene, or quinoline.
As a specific embodiment of the present invention, preferably, in formula I, R 6 is-O-R 7 or-N-R 8 (-R 9 ) Wherein R is 7 、R 8 And R is 9 Each independently is hydrogen, a C1-C30 alkyl group, a C2-C30 alkenyl group, a C6-C30 halogen substituted or unsubstituted aryl group, a C4-C30 heterocyclic group, a halogen atom, an alkoxy group, or a substituent containing a nitrogen atom; preferably, R 7 、R 8 And R is 9 Each independently is hydrogen, C1-C10 alkyl, C2-C15 alkenyl, C6-C15 halogen substituted or unsubstituted aryl, C4-C15 heterocyclic, halogen atom, nitro, amino or alkoxy.
As a specific embodiment of the present invention, preferably, the catalyst component has a magnesium element content of 1wt% to 89.7wt%, a titanium element content of 0.2wt% to 20wt%, a halogen content of 10wt% to 80wt%, and an internal electron donor content of 0.1wt% to 30wt%, based on the mass of the catalyst component; more preferably, the content of magnesium element is 10-45 wt%, the content of titanium element is 1.5-10 wt%, the content of halogen is 20-45 wt%, and the content of internal electron donor is 1-15 wt%; still more preferably, the content of magnesium element is 15wt% to 25wt%, the content of titanium element is 2wt% to 5wt%, the content of halogen is 30wt% to 41wt%, and the content of internal electron donor is 5wt% to 13wt%.
As a specific embodiment of the present invention, the compound represented by the general formula I is preferably selected from the group consisting of 1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-diphenyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-ethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-ethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-ethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (2-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (3-ethylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (2-n-propylphenyl) -1-carboxylic acid methyl ester, 1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (2-isopropylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-n-butylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-n-butylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-n-butylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2, 4-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2, 4, 6-trimethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5-phenyl-6- (4-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5-phenyl-6- (4-isopropylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5-phenyl-6- (2, 4-dimethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5-phenyl-6- (2, 4, 6-trimethylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5-phenyl-6- (2-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5-phenyl-1-benzimidazole-carboxylic acid methyl ester, 5-phenyl-6- (2-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-nitrophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2, 4, 6-trinitrophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-dimethyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-diethyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-di-n-propyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-di-isopropyl-1H-benzimidazole-carboxylic acid methyl ester, 5, 6-di-n-butyl-1H-benzimidazole-carboxylic acid methyl ester, 5, 6-di-isobutyl-1H-benzimidazole-carboxylic acid methyl ester, 5, 6-trinitrophenyl-1-carboxylic acid methyl ester, 5, 6-dimethyl-1-benzimidazole-carboxylic acid methyl ester, 5, 6-dimethyl-1-carboxylic acid methyl ester, 5, 1-dimethyl-1-benzimidazole-carboxylic acid methyl ester, 5, 1-dimethyl-1-carboxylic acid methyl ester, 5, 6-bis (1-methylpentyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-di-n-pentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-dipentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-n-propyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-n-butyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-dimethyl-6-isobutyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-n-pentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-isopentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-ethyl-6-n-propyl-1H-benzimidazole-1-carboxylic acid methyl ester, 6-methyl-1H-benzimidazole-carboxylic acid methyl ester, 6-methyl-1-isopropyl-1-benzimidazole-carboxylic acid methyl ester, 6-nitro-1-benzimidazole-1-carboxylic acid methyl ester, 6-n-butyl-1H-benzimidazole-carboxylic acid methyl ester, 5-dimethyl-1-isobutyl 1-carboxylic acid methyl ester, 5-dimethyl-1H-benzimidazole-carboxylic acid methyl ester, 5-methyl-isopentyl-1-benzimidazole-carboxylic acid methyl ester, 5-methyl-1-isopropyl-1-carboxylic acid, 1,1' -carbonylbis (5-methyl-1H-benzimidazole), 1' -carbonylbis (5-ethyl-1H-benzimidazole), 1' -carbonylbis (5-isopropyl-1H-benzimidazole), 1-phenyl-1 ' - (1H-benzimidazolyl) -methanone, 1- (1H-imidazolyl) -1' - (1H-benzimidazolyl) -methanone, 1- (5-methyl-1H-imidazolyl) -1' - (5-methyl-1H-benzimidazolyl) -methanone, 1- (2-ethyl-3-methyl-1H-imidazolyl) -1' - (1H-benzimidazolyl) -methanone, 1H-benzimidazole-1-carboxamide, N, N-diphenyl-1H-benzimidazole-1-carboxamide, N-bis (4-methylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-methylphenyl) -1H-benzimidazole-1-carboxamide, 4, 5-bis (3-methylphenyl) -1H-benzimidazole-1-carboxamide, N, N-bis (4-ethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-ethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-ethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (4-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N, N-bis (4-isopropylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-isopropylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (4-N-butylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-N-butylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-N-butylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2, 4-methylphenyl) -1H-benzimidazole-1-carboxamide, N-phenyl-N- (4-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N-phenyl-N- (4-isopropylphenyl) -1H-benzimidazole-1-carboxamide, N-phenyl-N- (2, 4-dimethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (4-chlorophenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-chlorophenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-chlorophenyl) -1H-benzimidazole-1-carboxamide, N, N-bis (4-nitrophenyl) -1H-benzimidazole-1-carboxamide, N-dimethyl-1H-benzimidazole-1-carboxamide, N-diethyl-1H-benzimidazole-1-carboxamide, N-di-N-propyl-1H-benzimidazole-1-carboxamide, N, N-diisopropyl-1H-benzimidazole-1-carboxamide, N-di-N-butyl-1H-benzimidazole-1-carboxamide, N-diisobutyl-1H-benzimidazole-1-carboxamide, N, n-bis (1-methylpropyl) -1H-benzimidazole-1-carboxamide, N-bis (1-methylbutyl) -1H-benzimidazole-1-carboxamide, N-bis (1-methylpentyl) -1H-benzimidazole-1-carboxamide, N-di-N-pentyl-1H-benzimidazole-1-carboxamide, N, N-dipentyl-1H-benzimidazole-1-carboxamide, N-methyl-N-N-propyl-1H-benzimidazole-1-carboxamide, N-methyl-N-isopropyl-1H-benzimidazole-1-carboxamide, N-methyl-N-N-butyl-1H-benzimidazole-1-carboxamide, ethyl 1H-benzimidazole-1-carboxylate, trifluoroethyl 1H-benzimidazole-1-carboxylate, propyl 1H-benzimidazole-1-carboxylate, N-butyl 1H-benzimidazole-1-carboxylate, isobutyl 1H-benzimidazole-1-carboxylate, N-pentyl 1H-benzimidazole-1-carboxylate, isopentyl 1H-benzimidazole-1-carboxylate, 2-methylbutyl 1H-benzimidazole-1-carboxylate, 2-dimethylpropyl 1H-benzimidazole-1-carboxylate, N-hexyl 1H-benzimidazole-1-carboxylate, 1H-benzimidazole-1-carboxylic acid (2-propen) methyl ester, 1H-benzimidazole-1-carboxylic acid benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-methyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-methoxy) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-ethyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-n-propyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-isopropyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-n-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-isobutyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-tert-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid-1-naphtalene methyl ester, 1H-benzimidazole-1-carboxylic acid cinnamyl ester, 1H-benzimidazole-1-carboxylic acid (9-fluorenylmethyl) ester, 1H-benzimidazole-1-carboxylic acid phenol ester, 1H-benzimidazole-1-carboxylic acid (4-isopropyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-n-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-tert-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (1-tert-butyl) benzyl ester, 1H-benzimidazole-carboxylic acid (1-benzyl ester, 1-benzimidazole-2-carboxylic acid (4-tert-butyl) benzyl ester, 1-benzimidazole-1-carboxylic acid (1-naphtyl) ester, 1-benzimidazole-carboxylic acid (1-naphtyl ester), 1H-benzimidazole-1-carboxylic acid (4-n-propyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (4-n-butyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (4-methylisopropyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (2, 6-dimethyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (2, 6-di-tert-butyl) phenol ester, 1- (4-trifluoromethylphenyl) -1H-benzimidazole, 1- (2, 4, 6-triisopropylsulfonyl) -1H-benzimidazole, 2-methyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-ethyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-butyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-bromo-1H-benzimidazole-1-carboxylic acid methyl ester, 2-phenyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-mercapto-1H-benzimidazole-1-carboxylic acid methyl ester, 2-isopropyl-1H-benzimidazole-carboxylic acid methyl ester, 2-tert-butyl-1-carboxylic acid methyl ester, 2-ethoxy-1-benzimidazole-carboxylic acid ethyl ester, benzimidazole-1-carboxylic acid methyl ester, one or more of methyl 6-nitro-1H-benzimidazole-2-ethyl acetate-1-carboxylate, methyl 5, 6-dimethyl-1H-benzimidazole-2-ethyl acetate-1-carboxylate, methyl 1H-benzimidazole-2-thioacetate-1-carboxylate, methyl 1H-benzimidazole-6-carboxylate, methyl 2-methyl-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide, 2-methoxy-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide, 2-tert-butyl-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide, 2-diisopropylphosphine-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide.
As a specific embodiment of the present invention, preferably, the magnesium in the catalyst component is derived from a magnesium compound, the magnesium compound is a magnesium halide and/or a magnesium alkoxide compound, further preferably, the magnesium halide is magnesium chloride or hydrated magnesium chloride, the magnesium alkoxide compound is a carrier or solution prepared by mixing magnesium chloride with a C1 to C12 alcohol, still further preferably, a carrier or solution prepared by mixing magnesium chloride with a C1 to C4 alcohol, and still further preferably, ethoxymagnesium.
As a specific embodiment of the present invention, preferably, the titanium in the catalyst component is derived from a titanium compound having the general formula TiX n (OR) 4-n Wherein X is a halogen atom, more preferably a chlorine atom; n is 1-4; r is a C1-C20 alkane, more preferably a C1-C10 alkane, still more preferably n-butyl, isobutyl or 2-ethylhexyl.
As a specific embodiment of the present invention, the titanium compound is preferably at least one selected from the group consisting of titanium tetrahalide and titanium alkoxide, and more preferably at least one selected from the group consisting of titanium tetrachloride and tetrabutyl titanate.
In a second aspect, the present invention provides a catalyst comprising component (a) and component (B), and optionally component (C), the component (a) being a catalyst component according to any one of claims 1 to 5, the component (B) being an organoaluminum compound, and the component (C) being an organosilicon compound.
As a specific embodiment of the present invention, the organoaluminum compound is preferably one or more selected from the group consisting of trialkylaluminum, dialkylaluminum chloride, alkylaluminum chloride and alkylaluminoxane, more preferably one or more selected from the group consisting of trialkylaluminum, dialkylaluminum chloride, alkylaluminum chloride and alkylaluminoxane wherein the alkyl group is a C1 to C20 alkyl group, and still more preferably one or more selected from the group consisting of trialkylaluminum and dialkylaluminum chloride.
As a specific embodiment of the present invention, preferably, the organoaluminum compound is at least one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride; further preferred are triethylaluminum and/or triisobutylaluminum.
As a specific embodiment of the present invention, preferably, the organosilicon compound is a compound represented by the general formula II, the structure of the compound represented by the general formula II is as follows,
R A m Si(OR B ) 4-m
general formula II
Wherein m is more than or equal to 0 and less than or equal to 3, R A And R is B Identical or different, R A Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom, R B Is alkyl, cycloalkyl, aryl, haloalkyl or amine; further preferably, R A Is C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl, amino, halogen or hydrogen atom, R B Is C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl or amino; still more preferably, the organosilicon compound is selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, tri-n-propylmethoxysilane, dimethyldimethoxysilane, di-At least one of propyldimethoxy silane, dibutyldimethoxy silane, dipentyl dimethoxy silane, diisopropyldimethoxy silane, diisobutyldimethoxy silane, dimethyldiethoxy silane, cyclohexylmethyl diethoxy silane, cyclohexylmethyl dimethoxy silane, cyclohexyldimethylmethoxy silane, hexyldiethylmethoxy silane, dicyclopentyldimethoxy silane, cyclopentyldiethylmethoxy silane, cyclopentylisopropyldimethoxy silane, cyclopentylisobutyldimethoxy silane, 4-methylcyclohexylmethyl dimethoxy silane, 4-methylcyclohexylethyldimethoxy silane, 4-methylcyclohexylpropyl dimethoxy silane, bis (4-methylcyclohexyl) dimethoxy silane, 4-methylcyclohexylpentyl dimethoxy silane, 4-methylcyclohexylcyclopentyl dimethoxy silane, diphenyldimethoxy silane, diphenyldiethoxy silane, phenyltriethoxy silane, phenyltrimethoxy silane, vinyltrimethoxy silane, tetramethoxy silane, tetraethoxy silane, tetrapropoxy silane, tetrabutoxy silane; still more preferably, the organosilicon compound is selected from at least one of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and diisopropyldimethoxysilane.
As a specific embodiment of the present invention, the molar ratio of the components (A), (B) and (C) is preferably 1 (5-2000): 0-500, more preferably 1 (10-800): 0-300, still more preferably 1 (50-200): 0-30.
The catalyst component for olefin polymerization using the above-mentioned compound as an internal electron donor can be prepared by the following optional method:
method 1: an inert diluent may be added to a homogeneous solution of magnesium halide in the organic epoxy compound and the organic phosphorus compound. The homogeneous solution is mixed with titanium tetrahalide or its derivative, and when a precipitation-assisting agent is present in the reaction system, a solid is precipitated. And (3) carrying the compound shown in the general formula I on a solid object, and treating the solid object by using titanium tetrahalide or an inert diluent to obtain the solid catalyst component comprising titanium, magnesium, halogen, an electron donor and the like.
The organic epoxy compound preferably includes at least one of C2-C15 aliphatic alkane, alkene, diene, halogenated aliphatic alkene, oxide of diene, glycidyl ether and internal ether. Specific compounds are butylene oxide, propylene oxide, ethylene oxide, butadiene double oxide, epichlorohydrin, butylene oxide, chloropentane oxide, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, tetrahydropyran, etc. More preferably, it comprises ethylene oxide, propylene oxide, epichlorohydrin, tetrahydrofuran, tetrahydropyran.
The organic phosphorus compound preferably includes hydrocarbyl or halogenated hydrocarbyl esters of orthophosphoric acid or phosphorous acid, and specific examples of the organic phosphorus compound are trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphoric acid, tripentyl orthophosphoric acid, trihexyl orthophosphoric acid, triheptyl orthophosphoric acid, trioctyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite or benzyl phosphite, etc., more preferably tributyl orthophosphoric acid, triethyl orthophosphoric acid, etc.
The inert diluent is preferably at least one of C5-C20 alkane, cycloalkane and arene, such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene or derivatives thereof, etc., more preferably hexane, toluene.
The titanium tetrahalide or its derivative may be represented by the general formula TiX n (OR) 4-n Wherein R is a C1-C20 hydrocarbon radical, X is halogen, n=1-4, preferably TiCl 4 。
The precipitation aid preferably includes an organic acid anhydride, an organic acid, an ether, a ketone or an ester, specifically such as acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, methyl ethyl ketone, acetone, benzophenone, diethyl ether, propyl ether, butyl ether, malonate, succinic acid ester, maleic acid ester, glutaric acid ester, 2, 4-pentanediol ester, 3, 5-heptanediol ester, 9-dibenzoyl fluorene, etc., more preferably includes phthalic anhydride, malonic acid ester, (R, R) -2, 4-pentanediol ester, (S, S) -2, 4-pentanediol ester, 3, 5-heptanediol ester.
Method 2: suspending alkoxy magnesium or alkoxy magnesium chloride in inert solvent to form suspension, mixing the suspension solution with tetrahalogenated titanium or its derivative to obtain solid. And then contacting the compound shown in the general formula I with a solid substance to obtain the solid catalyst comprising titanium, magnesium, halogen, electron donor and other components.
The inert diluent is preferably at least one of C5-C20 alkane, cycloalkane and arene, such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene or derivatives thereof, etc., more preferably hexane, toluene.
The titanium tetrahalide or its derivative may be represented by the general formula TiX n (OR) 4-n Wherein R is a C1-C20 hydrocarbon radical, X is halogen, n=1-4, preferably TiCl 4 。
Method 3: fully mixing and stirring magnesium halide or an organic magnesium compound, an alcohol compound and titanate or a titanium halide compound in an inert solvent, heating and cooling to obtain a spherical carrier or adding the inert solvent to obtain a uniform alkoxide solution. Mixing the carrier or the uniform solution with titanium tetrahalide or a derivative thereof, maintaining at a low temperature for a period of time, heating, adding the compound shown in the general formula I, treating with titanium tetrahalide or an inert diluent, treating with the compound, and finally filtering, washing and drying to obtain the solid catalyst comprising components such as titanium, magnesium, halogen, electron donor and the like.
The magnesium halide preferably includes at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium methoxychloride, magnesium ethoxychloride, magnesium propoxychloride, magnesium butoxychloride, and the like, and more preferably magnesium dichloride and/or magnesium ethoxychloride.
The organomagnesium compound preferably includes at least one of dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, methylethyl magnesium, methylpropyl magnesium, methylbutyl magnesium, ethylpropyl magnesium, ethylbutyl magnesium, dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, ethoxyethyl magnesium, dibutoxy magnesium, diisobutoxy magnesium, and the like, more preferably dibutyl magnesium, diethyl magnesium, or diethoxy magnesium.
Method 4: the magnesium halide is dissolved in the organic epoxy compound and the organic phosphorus compound to form a uniform solution, and an inert diluent and an internal electron donor, such as the compound shown in the general formula I, can be added. Mixing the solution with titanium tetrahalide or its derivative, maintaining at low temperature for a period of time, heating, treating with titanium tetrahalide or inert diluent, treating with the compound shown in the general formula I, filtering, washing, and drying to obtain solid catalyst containing titanium, magnesium, halogen, electron donor, etc.
Method 5: the polyolefin catalyst solid components prepared according to the methods 1-4 are dispersed in a medium, and are subjected to a prepolymerization reaction with a small amount of propylene or ethylene gas or ethylene-propylene mixture gas with different proportions to prepare a prepolymerization catalyst, wherein the prepolymerization catalyst can be stored and dispersed in the medium, and can also be used after filtration, washing and pumping.
The dispersion medium may be at least one of C5-C31 alkane, cycloalkane and arene such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene or derivatives thereof, white oil, etc., or at least one of lubricating oil products such as simethicone, cyclomethicone, aminosilicone, polymethylphenylsiloxane, polyether polysiloxane copolymer, etc., wherein the dispersion medium more preferably includes hexane, white oil.
The prepolymerization temperature may range from-30℃to 100℃and more preferably from 0 to 40 ℃. The ratio of the ethylene-propylene mixture is from 1:100 to 100:1 (v/v), more preferably from 1:20 to 20:1.
A small amount of AlR with the general formula can be added in the preparation process of the prepolymerized catalyst K X 3-K Wherein R is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms, X is halogen, and K is an integer of 1 to 3; specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride and sesquiethylaluminum chloride are selected, and triethylaluminum and triisobutylaluminum are preferable. And optionally organosilicon compounds such as cyclohexylmethyldimethoxysilane. The prepolymerized catalyst can be stored for a long period of time in an inert environment.
In a third aspect, the present invention provides a process for the polymerisation of olefins selected from one or more of ethylene, propylene, butene-1, 4-methyl-1-pentene, 1-hexene, in the presence of the above catalyst component or catalyst. The olefin polymerization method is carried out according to a known polymerization method, is suitable for gas phase, liquid phase or gas-liquid combination reaction, and is particularly suitable for a prepolymerized catalyst component prepared by the method 5 for a process device without prepolymerization.
As a specific embodiment of the present invention, preferably, the polymerization is propylene homo-polymerization or copolymerization of ethylene and an α -olefin, further preferably, the polymerization temperature is 0 to 150 ℃, still further preferably 60 to 90 ℃.
In summary, the catalyst component or the catalyst provided by the invention is suitable for the field of olefin polymerization, in particular for the field of propylene polymerization. When the catalyst is used for olefin polymerization reaction, satisfactory catalyst activity and stereospecificity of the catalyst can be obtained, wherein the polymer has wide molecular weight distribution, and the processability of the polymer can be effectively improved.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The testing method comprises the following steps:
1. polymer Melt Index (MI): according to GB/T3682-2000;
2. propylene polymer isotacticity index (i.i.): determination by n-heptane extraction: 2g of dried polymer sample is put in an extractor and is extracted by boiling heptane for 6 hours, and the ratio of the weight (g) of the polymer obtained by drying the residue to constant weight to 2 (g) is isotacticity;
3. polymer molecular weight distribution MWD (mwd=mw/Mn): PL-GPC220 was used, with trichlorobenzene as solvent, at 150℃C (standard: polystyrene, flow rate: 1.0mL/min, column: 3xPlgel 10 μm MlxED-B300 x7.5 nm).
4. Activity calculation: catalyst activity= (mass of polyolefin produced)/(mass of catalyst solid component) g/g.
Examples
(1) Preparation of the compound:
the preparation of the compounds is mainly described in the literature Organometallics 2021,40,14,2265-2271, chem. Commun.,2014,50,4751-4754 and International patent WO 2015039606A 1, some of which are modified and adapted.
EXAMPLE 1 Synthesis of Compound 1H-benzimidazole-1-carboxylic acid methyl ester
1.86g of sodium hydride (60% dispersed in mineral oil) was rapidly weighed and placed in a 250mL three-necked flask, connected with nitrogen and a balance addition funnel, and the reaction apparatus was placed in an ice bath at 0deg.C, and repeatedly evacuated and purged with nitrogen to exhaust air. 50mL of anhydrous tetrahydrofuran was added to the three-necked flask, and stirring was started. 5g of benzimidazole was weighed and dispersed in another 30mL of anhydrous tetrahydrofuran and transferred to an equilibrated addition funnel under nitrogen. Dropwise adding benzimidazole solution into sodium hydride dispersion liquid at 0 ℃ for 30 minutes; after which the temperature was slowly raised to room temperature and stirring was continued for 1 hour. Methyl chloroformate 4.4g was dispersed in 10mL anhydrous tetrahydrofuran and added dropwise to the reaction flask at room temperature using a syringe. Stirring was continued for 15 minutes and then the reaction was refluxed at a temperature of 4 hours. The reaction was then quenched with a small amount of dilute hydrochloric acid (1N, 50 mL), and the reaction solution was extracted with ethyl acetate and water at least three times. The organic phase was dried over sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to give a yellow oily liquid, which was dried by suction to give 4.8 g of the product in 64% yield. 1 H-NMR(500MHz,d 6 -DMSO):δ8.15(s,1H),7.82～7.78(m,1H),7.46～7.34(m,3H),3.45(s,3H)。
EXAMPLE 2 Synthesis of the Compound N, N-diisopropyl-1H-benzimidazole-1-carboxamide
The preparation method is similar to that of example 1, only methyl chloroformate is replaced by N, N-diisopropylamine acyl chloride, the reaction time of heating reflux is prolonged to 8 hours, and the yield is 78%. 1 H-NMR(500MHz,d 6 -DMSO):δ8.11(s,1H),7.89～7.82(m,1H),7.52～7.44(m,3H),3.54～3.34(m,2H),1.53～1.34(m,12H)。
EXAMPLE 3 Synthesis of Compound 1H-benzimidazole-1-carboxylic acid (9-fluorenylmethyl) ester
The preparation method is similar to that of example 1, the compound methyl chloroformate is replaced by (9-fluorenylmethyl) chloroformate, the reaction time of heating reflux is prolonged to 16 hours, and the product is purified by ethanol recrystallization, and the yield is 32%. 1 H-NMR(500MHz,d 6 -DMSO):δ8.13(s,1H),7.89(s,1H),7.71～7.63(m,3H),7.55～7.11(m,9H),4.25(d,2H)。
EXAMPLE 4 Compound 1-phenyl-1' - (1H-benzimidazolyl) -methanone
2g of benzimidazole, 2.7g of benzaldehyde and 0.6g of potassium iodide are sequentially added into a 100mL double-mouth bottle, and a magneton is placed into the bottle, wherein the adding volume ratio is 3:1 and 50mL of a mixed solvent of ethylene glycol dimethyl ether and water, and stirring was started. After stirring for 30 minutes, 6.5g of a 70% strength aqueous solution of t-butyl hydroperoxide was slowly added by means of a syringe, and a condenser was connected to the upper outlet of the double-necked flask. The temperature of the reaction flask was gradually raised by using an oil bath, and the reaction was continued for 16 hours at 95 ℃. After the reaction is finished, the reaction is carried out The flask was cooled to room temperature, quenched with a small amount of dilute hydrochloric acid (1 n,10mL, n being the equivalent concentration, representing the number of mL equivalents of solute in 1L of solution), and repeatedly extracted and washed with ethyl acetate and brine at least three times. The organic phase is dried by anhydrous sodium sulfate, decompressed and concentrated, and then separated and purified by a silica gel chromatographic column to obtain a pure product with the yield of 58 percent. 1 H-NMR(500MHz,d 6 -DMSO):δ8.18(s,1H),8.15～8.12(m,1H),7.79～7.75(m,1H),7.71(d,2H),7.67～7.61(m,1H),7.58～7.52(m,2H),7.48～7.42(m,2H)。
EXAMPLE 5 Compound 5-methyl-1H-benzimidazole-1-carboxylic acid methyl ester
The preparation was carried out in analogy to example 1, in which the compound benzimidazole was replaced by 5-methylbenzimidazole in 62% yield. 1 H-NMR(500MHz,d 6 -DMSO):δ8.12(s,1H),7.79～7.71(m,1H),7.42～7.35(m,2H),3.42(s,3H),2.37(s,3H)。
EXAMPLE 6 Compound 2-phenyl-1H-benzimidazole-1-carboxylic acid methyl ester
The preparation was carried out in analogy to example 1, in which the compound benzimidazole was replaced by 2-phenylbenzimidazole in 62% yield. 1 H-NMR(500MHz,d 6 -DMSO):7.81～7.79(m,1H),7.63～7.58(m,2H),7.53～7.48(m,3H),7.21～7.15(m,3H),3.37(s,3H)。
EXAMPLE 7 Compound 2-benzimidazole ethyl acetate-1-carboxylic acid methyl ester
The preparation was carried out in analogy to example 1, in which the compound benzimidazole was replaced by ethyl 2-benzimidazole acetate in 22% yield. 1 H-NMR(500MHz,d 6 -DMSO):7.87～7.85(m,1H),7.70～7.63(m,3H),4.21～4.15(q,2H),3.47(s,3H),2.32(s,2H),1.22(t,3H)。
EXAMPLE 8 Synthesis of the Compound 2-diisopropylphosphine-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide
2.8g of the compound synthesized in example 2 was added to a 250mL double-necked flask which had been sufficiently replaced with nitrogen, anhydrous tetrahydrofuran was added, the temperature was controlled to-78℃with a bath of liquid nitrogen and acetone, 5mL of n-butyllithium (2.5 mol/L in n-hexane) was slowly dropped into the reaction system, and after stirring for 15 minutes, the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1 hour, and the reaction solution was cooled to-78℃and 2mL of chlorodiisopropylphosphine was slowly dropped, and the temperature was raised and stirred overnight. After the completion of the reaction, the reaction was quenched with a small amount of diluted hydrochloric acid (1N, 100 mL), and the reaction mixture was extracted with ethyl acetate and water for at least three times. The organic phase is dried over sodium sulphate, concentrated under reduced pressure and purified by recrystallisation from diethyl ether/n-hexane to give 1.8g of the product in 43% yield. 1 H-NMR(500MHz,d 6 -DMSO):δ7.85～7.83(m,1H),7.71～7.66(m,3H),3.55～3.48(m,2H),1.57～1.38(m,12H),1.29～1.18(m,14H)。
(2) Preparation of the catalyst
Example 9
To a reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of Epichlorohydrin (ECH), 12.5mL of tributyl phosphate (TBP) were added in this order, and the temperature was raised to 50℃with stirring and maintained for 2.5 hours. After the solid is completely dissolved, 1.4g of phthalic anhydride is added, the solution is continuously maintained for 1 hour, cooled to below-25 ℃, tiCl is added dropwise within 1 hour 4 60mL, slowly warmed to 80 ℃, gradually precipitating a solid, adding 6mmol of the compound prepared in example 1, and maintaining the temperature for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to give a solid. 100mL of toluene was added, the temperature was raised to 110℃and three washes were performed for 10 minutes each. Then 60mL of hexane is added for three times of washing,after drying in vacuo, 6.7g of a catalyst solid was obtained, which contained 2.78wt% of Ti, 18.55wt% of Mg, 35.81wt% of Cl and 9.8wt% of an internal electron donor.
Example 10
As in example 9, only the methyl 1H-benzimidazole-1-carboxylate was replaced with the compound of example 2.
Example 11
As in example 9, only the methyl 1H-benzimidazole-1-carboxylate was replaced with the compound of example 3.
Example 12
As in example 9, only the methyl 1H-benzimidazole-1-carboxylate was replaced with the compound of example 4.
Example 13
As in example 9, only the methyl 1H-benzimidazole-1-carboxylate was replaced with the compound of example 5.
Example 14
As in example 9, only the methyl 1H-benzimidazole-1-carboxylate was replaced with the compound of example 6.
Example 15
As in example 9, only the methyl 1H-benzimidazole-1-carboxylate was replaced with the compound of example 7.
Example 16
As in example 9, only the methyl 1H-benzimidazole-1-carboxylate was replaced with the compound of example 8.
Example 17
4.8g of anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent were charged in a 500ml reactor equipped with a stirrer under nitrogen protection, heated to 130℃and reacted for 1.5 hours until the magnesium chloride was completely dissolved. 1.4g of phthalic anhydride was added thereto, and the reaction was continued at 130℃for 1 hour to obtain an alcohol compound, which was cooled to room temperature. The above alcohol was added dropwise to 120ml of titanium tetrachloride solution pre-chilled to-22℃under nitrogen protection, the temperature was slowly raised to 100℃and 6mmol of the compound of the structure described in example 8 was added thereto, and the temperature was raised to 110℃for 2 hours. The mixture was filtered while it was still hot, 120ml of titanium tetrachloride was added thereto, and the mixture was reacted at 110℃for 2 hours, followed by filtration. The solid particles were washed 4 times with anhydrous hexane and dried under vacuum to give 6.6g of a catalyst solid composition comprising 2.55wt% of Ti, 20.31wt% of Mg, 38.8wt% of Cl and 11.3wt% of an internal electron donor.
Example 18
Into a reactor fully replaced by high-purity nitrogen, 300mL of TiCl was introduced 4 Cooling to-20deg.C, adding magnesium chloride alkoxide carrier 7.0g (see patent CN 1330086A), stirring, heating to 40deg.C in stages, adding 6mmol of the structural compound described in example 8, maintaining the temperature for 2 hr, and filtering. TiCl is added again 4 100mL was warmed to 110℃and treated three times. 60mL of hexane is added for three times, and 5.6g of catalyst solid component which comprises 1.73wt% of Ti, 23.87wt% of Mg, 40.33wt% of Cl and 12.5wt% of internal electron donor is obtained after vacuum drying.
Example 19
In a reactor fully replaced by high purity nitrogen, 300mL TiCl was added 4 Cooling to-20 ℃, adding 7.0g of magnesium ethoxide, heating to 40 ℃ in stages under stirring, adding 6mmol of the compound with the structure described in example 8, maintaining the temperature for 3 hours, and filtering. TiCl is added 4 100mL was warmed to 110℃and treated three times. 60mL of hexane is added for three times, and 5.8g of catalyst solid component which comprises 2.43wt% of Ti, 21.13wt% of Mg, 33.71wt% of Cl and 10.2wt% of internal electron donor is obtained after drying.
Example 20
500mL of glass reaction vessel was purged overnight with high-purity nitrogen, about 300mL of n-hexane was added under slight positive pressure, stirring was started at 850rpm, and the temperature of the reaction system was controlled at 10℃with an oil bath. After the reaction system was stabilized, the catalyst sample in example 10 was dissolved in a small amount of hexane and added to the reaction vessel, and a small amount of triethylaluminum was added, al/Ti (mol/mol) =3 was controlled, a certain amount of propylene was introduced, and the prepolymerization was performed until the propylene was completely consumed, and a prepolymerization catalyst having a prepolymerization multiple of about 2 was obtained based on the propylene gas consumption. After the reaction is finished, the pressure is released, and the hexane solution in which the prepolymerized catalyst is dispersed is collected under the protection of inert gas.
Example 21
As in example 20, only the reaction solvent n-hexane was replaced with white oil.
Example 22
As in example 20, the solvent was drained only after the completion of the reaction.
Comparative example 1
To a reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of Epichlorohydrin (ECH), 12.5mL of tributyl phosphate (TBP) were added in this order, and the temperature was raised to 50℃with stirring and maintained for 2.5 hours. After the solid was completely dissolved, 1.4g of phthalic anhydride was added and the reaction was continued for 1 hour. Cooling the solution to below-25 ℃, and dripping TiCl in 1 hour 4 Slowly heating to 80 ℃, gradually precipitating a solid, adding 6mmol of di-n-butyl phthalate (DNBP), and maintaining the temperature for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to give a solid. 100mL of toluene was added, the temperature was raised to 110℃and three washes were performed for 10 minutes each. And adding 60mL of hexane, washing for three times, and drying to obtain the catalyst solid component.
Polymerization reaction
The method adopts an atmospheric slurry polymerization method: the 500mL glass reaction kettle is firstly purged with high-purity nitrogen overnight, propylene gas is used for full replacement in advance before reaction feeding, about 200mL of n-decane is added under the condition of micro positive pressure of the propylene gas, stirring is started, the rotating speed is 2000rpm, and the temperature of a reaction system is controlled at 70 ℃ by using an oil bath. After the polymerization reaction system is stabilized, the weighed dry powder of the catalyst sample in the example or the comparative example is dissolved by a small amount of hexane, or a certain volume of prepolymerized catalyst white oil or hexane slurry with known concentration is extracted, and is added into a reaction kettle, triethylaluminum and tetraethoxysilane are simultaneously added, al/Ti (mol/mol) =100, al/Si (mol/mol) =25 are controlled, propylene pressure is kept between 0.04 and 0.05MPa, and polymerization is carried out for 2 hours. After the reaction is finished, the pressure is released, the polypropylene product is collected by filtration, and the catalyst activity is calculated after drying and weighing.
The resulting polymerization data are shown in Table 1.
TABLE 1
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As can be seen from examples 9 to 19 and comparative example 1 above, when the catalyst of the present invention is used for propylene polymerization, the obtained polymer has a higher melt index and a broad molecular weight distribution, and the processability of the polymer is effectively improved.
Any numerical value recited in this disclosure includes all values incremented by one unit from the lowest value to the highest value if there is only a two unit interval between any lowest value and any highest value. For example, if the amount of one component, or the value of a process variable such as temperature, pressure, time, etc., is stated to be 50-90, it is meant in this specification that values such as 51-89, 52-88 … …, and 69-71, and 70-71 are specifically recited. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 units may be considered as appropriate. This is only a few examples of the specific designations. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (15)
1. A catalyst component for olefin polymerization is characterized in that the catalyst component contains magnesium, titanium, halogen and an internal electron donor, the internal electron donor is a compound shown in a general formula I,
in the general formula I, R 2 ～R 5 The same or different, each independently is hydrogen, C1-C30 alkyl, C2-C30 alkenyl, C6-C30 halogen substituted or unsubstituted aryl, C4-C30 heterocyclic group, halogen atom, alkoxy or substituent containing nitrogen atom; r is R 1 、R 6 The same or different are each independently hydrogen, a C1-C15 hydrocarbon group or a heteroatom-containing substituent; the heteroatom is selected from at least one of nitrogen, sulfur, oxygen, phosphorus, and silicon.
2. The catalyst component according to claim 1, characterized in that in formula I, R 2 ～R 5 The same or different, each independently is a C1-C10 alkyl group, a C2-C15 alkenyl group, a C6-C15 halogen substituted or unsubstituted aromatic group, a C4-C15 heterocyclic group, a halogen atom, an alkoxy group or a substituent containing a nitrogen atom; preferably, each is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, methoxy, isopropyl ether, tert-butyl ether, phenyl, halophenyl, naphthyl, biphenyl, nitro, amino, pyridine, thiophene, or quinoline.
3. The catalyst component according to claim 1 or 2, characterized in that in formula I, R 6 is-O-R 7 or-N-R 8 (-R 9 ) Wherein R is 7 、R 8 And R is 9 Each independently is hydrogen, a C1-C30 alkyl group, a C2-C30 alkenyl group, a C6-C30 halogen substituted or unsubstituted aryl group, a C4-C30 heterocyclic group, a halogen atom, an alkoxy group, or a substituent containing a nitrogen atom; preferably, R 7 、R 8 And R is 9 Each independently ofThe standing is hydrogen, C1-C10 alkyl, C2-C15 alkenyl, C6-C15 halogen substituted or unsubstituted aryl, C4-C15 heterocyclic group, halogen atom, nitro, amino or alkoxy.
4. A catalyst component according to any one of claims 1 to 3, characterized in that the magnesium element content in the catalyst component is 1 to 89.7wt%, the titanium element content is 0.2 to 20wt%, the halogen content is 10 to 80wt%, and the internal electron donor content is 0.1 to 30wt%, based on the mass of the catalyst component; preferably, the content of magnesium element is 10-45 wt%, the content of titanium element is 1.5-10 wt%, the content of halogen is 20-45 wt%, and the content of internal electron donor is 1-15 wt%; more preferably, the content of magnesium element is 15wt% to 25wt%, the content of titanium element is 2wt% to 5wt%, the content of halogen is 30wt% to 41wt%, and the content of internal electron donor is 5wt% to 13wt%. .
5. The catalyst component according to any of claims 1 to 4, characterized in that the compound of formula I is selected from the group consisting of 1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-diphenyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-ethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-ethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-ethylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (4-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (2-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (4-ethylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5, 6-bis (3-ethylphenyl) -1-carboxylic acid methyl ester, 1H-benzimidazole-carboxylic acid methyl ester, 1-bis (3-ethylphenyl) -1-carboxylic acid methyl ester, 5, 6-bis (2-isopropylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-n-butylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-n-butylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-n-butylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2, 4-methylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2, 4, 6-trimethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5-phenyl-6- (4-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5-phenyl-6- (4-isopropylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5-phenyl-6- (2, 4-dimethylphenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5-phenyl-6- (2, 4, 6-trimethylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5-phenyl-6- (2-n-propylphenyl) -1H-benzimidazole-carboxylic acid methyl ester, 5-phenyl-1-benzimidazole-carboxylic acid methyl ester, 5-phenyl-6- (2-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (3-chlorophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (4-nitrophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-bis (2, 4, 6-trinitrophenyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-dimethyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-diethyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-di-n-propyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-di-isopropyl-1H-benzimidazole-carboxylic acid methyl ester, 5, 6-di-n-butyl-1H-benzimidazole-carboxylic acid methyl ester, 5, 6-di-isobutyl-1H-benzimidazole-carboxylic acid methyl ester, 5, 6-trinitrophenyl-1-carboxylic acid methyl ester, 5, 6-dimethyl-1-benzimidazole-carboxylic acid methyl ester, 5, 6-dimethyl-1-carboxylic acid methyl ester, 5, 1-dimethyl-1-benzimidazole-carboxylic acid methyl ester, 5, 1-dimethyl-1-carboxylic acid methyl ester, 5, 6-bis (1-methylpentyl) -1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-di-n-pentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-dipentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-n-propyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-isopropyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-n-butyl-1H-benzimidazole-1-carboxylic acid methyl ester 5-methyl-6-isobutyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-n-pentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-methyl-6-isopentyl-1H-benzimidazole-1-carboxylic acid methyl ester, 5-ethyl-6-n-propyl-1H-benzimidazole-1-carboxylic acid methyl ester, 6-methyl-1H-benzimidazole-1-carboxylic acid methyl ester, 6-nitro-1H-benzimidazole-1-carboxylic acid methyl ester, 5, 6-dinitro-1H-benzimidazole-1-carboxylic acid methyl ester, 1' -carbonylbis (1H-benzimidazole), 1,1' -carbonylbis (5-methyl-1H-benzimidazole), 1' -carbonylbis (5-ethyl-1H-benzimidazole), 1' -carbonylbis (5-isopropyl-1H-benzimidazole), 1-phenyl-1 ' - (1H-benzimidazolyl) -methanone, 1- (1H-imidazolyl) -1' - (1H-benzimidazolyl) -methanone, 1- (5-methyl-1H-imidazolyl) -1' - (5-methyl-1H-benzimidazolyl) -methanone, 1- (2-ethyl-3-methyl-1H-imidazolyl) -1' - (1H-benzimidazolyl) -methanone, 1H-benzimidazole-1-carboxamide, N, N-diphenyl-1H-benzimidazole-1-carboxamide, N-bis (4-methylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-methylphenyl) -1H-benzimidazole-1-carboxamide, 4, 5-bis (3-methylphenyl) -1H-benzimidazole-1-carboxamide, N, N-bis (4-ethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-ethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-ethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (4-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N, N-bis (4-isopropylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-isopropylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (4-N-butylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-N-butylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-N-butylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (2, 4-methylphenyl) -1H-benzimidazole-1-carboxamide, N-phenyl-N- (4-N-propylphenyl) -1H-benzimidazole-1-carboxamide, N-phenyl-N- (4-isopropylphenyl) -1H-benzimidazole-1-carboxamide, N-phenyl-N- (2, 4-dimethylphenyl) -1H-benzimidazole-1-carboxamide, N-bis (4-chlorophenyl) -1H-benzimidazole-1-carboxamide, N-bis (2-chlorophenyl) -1H-benzimidazole-1-carboxamide, N-bis (3-chlorophenyl) -1H-benzimidazole-1-carboxamide, N, N-bis (4-nitrophenyl) -1H-benzimidazole-1-carboxamide, N-dimethyl-1H-benzimidazole-1-carboxamide, N-diethyl-1H-benzimidazole-1-carboxamide, N-di-N-propyl-1H-benzimidazole-1-carboxamide, N, N-diisopropyl-1H-benzimidazole-1-carboxamide, N-di-N-butyl-1H-benzimidazole-1-carboxamide, N-diisobutyl-1H-benzimidazole-1-carboxamide, N, n-bis (1-methylpropyl) -1H-benzimidazole-1-carboxamide, N-bis (1-methylbutyl) -1H-benzimidazole-1-carboxamide, N-bis (1-methylpentyl) -1H-benzimidazole-1-carboxamide, N-di-N-pentyl-1H-benzimidazole-1-carboxamide, N, N-dipentyl-1H-benzimidazole-1-carboxamide, N-methyl-N-N-propyl-1H-benzimidazole-1-carboxamide, N-methyl-N-isopropyl-1H-benzimidazole-1-carboxamide, N-methyl-N-N-butyl-1H-benzimidazole-1-carboxamide, ethyl 1H-benzimidazole-1-carboxylate, trifluoroethyl 1H-benzimidazole-1-carboxylate, propyl 1H-benzimidazole-1-carboxylate, N-butyl 1H-benzimidazole-1-carboxylate, isobutyl 1H-benzimidazole-1-carboxylate, N-pentyl 1H-benzimidazole-1-carboxylate, isopentyl 1H-benzimidazole-1-carboxylate, 2-methylbutyl 1H-benzimidazole-1-carboxylate, 2-dimethylpropyl 1H-benzimidazole-1-carboxylate, N-hexyl 1H-benzimidazole-1-carboxylate, 1H-benzimidazole-1-carboxylic acid (2-propen) methyl ester, 1H-benzimidazole-1-carboxylic acid benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-methyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-methoxy) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-ethyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-n-propyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-isopropyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-n-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-isobutyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-tert-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid-1-naphtalene methyl ester, 1H-benzimidazole-1-carboxylic acid cinnamyl ester, 1H-benzimidazole-1-carboxylic acid (9-fluorenylmethyl) ester, 1H-benzimidazole-1-carboxylic acid phenol ester, 1H-benzimidazole-1-carboxylic acid (4-isopropyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-n-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (4-tert-butyl) benzyl ester, 1H-benzimidazole-1-carboxylic acid (1-tert-butyl) benzyl ester, 1H-benzimidazole-carboxylic acid (1-benzyl ester, 1-benzimidazole-2-carboxylic acid (4-tert-butyl) benzyl ester, 1-benzimidazole-1-carboxylic acid (1-naphtyl) ester, 1-benzimidazole-carboxylic acid (1-naphtyl ester), 1H-benzimidazole-1-carboxylic acid (4-n-propyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (4-n-butyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (4-methylisopropyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (2, 6-dimethyl) phenol ester, 1H-benzimidazole-1-carboxylic acid (2, 6-di-tert-butyl) phenol ester, 1- (4-trifluoromethylphenyl) -1H-benzimidazole, 1- (2, 4, 6-triisopropylsulfonyl) -1H-benzimidazole, 2-methyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-ethyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-butyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-bromo-1H-benzimidazole-1-carboxylic acid methyl ester, 2-phenyl-1H-benzimidazole-1-carboxylic acid methyl ester, 2-mercapto-1H-benzimidazole-1-carboxylic acid methyl ester, 2-isopropyl-1H-benzimidazole-carboxylic acid methyl ester, 2-tert-butyl-1-carboxylic acid methyl ester, 2-ethoxy-1-benzimidazole-carboxylic acid ethyl ester, benzimidazole-1-carboxylic acid methyl ester, one or more of methyl 6-nitro-1H-benzimidazole-2-ethyl acetate-1-carboxylate, methyl 5, 6-dimethyl-1H-benzimidazole-2-ethyl acetate-1-carboxylate, methyl 1H-benzimidazole-2-thioacetate-1-carboxylate, methyl 1H-benzimidazole-6-carboxylate, methyl 2-methyl-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide, 2-methoxy-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide, 2-tert-butyl-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide, 2-diisopropylphosphine-1H-benzimidazole-1- (N, N-diisopropyl) carboxamide.
6. The catalyst component according to any one of claims 1 to 5, characterized in that the magnesium in the catalyst component is derived from a magnesium compound, which is a magnesium halide and/or a magnesium alkoxide compound, preferably the magnesium halide is magnesium chloride or hydrated magnesium chloride, and the magnesium alkoxide compound is a carrier or solution prepared by mixing magnesium chloride with a C1-C12 alcohol, more preferably a carrier or solution prepared by mixing magnesium chloride with a C1-C4 alcohol, even more preferably ethoxymagnesium.
7. The catalyst component according to any of claims 1 to 6, wherein the titanium in the catalyst component is derived from a titanium compound of the general formula TiX n (OR) 4-n Wherein X is a halogen, preferably a chlorine atom; n is 1-4; r is a C1-C20 alkane, preferably a C1-C10 alkane, more preferably n-butyl, isobutyl or 2-ethylhexyl.
8. The catalyst component according to any of claims 1 to 7, characterized in that the titanium compound is selected from at least one of titanium tetrahalides, alkoxy titanium, preferably from at least one of titanium tetrachloride, tetrabutyl titanate.
9. A catalyst comprising component (a) and component (B), and optionally component (C), wherein component (a) is a catalyst component according to any one of claims 1 to 8, component (B) is an organoaluminum compound, and component (C) is an organosilicon compound.
10. The catalyst according to claim 9, wherein the organoaluminum compound is selected from one or more of trialkylaluminum, dialkylaluminum chloride, alkylaluminum oxyalkyl, preferably one or more of trialkylaluminum, dialkylaluminum chloride, alkylaluminum oxyalkyl is a C1-C20 alkyl group, more preferably one or more of trialkylaluminum and dialkylaluminum chloride.
11. The catalyst according to claim 9 or 10, wherein the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monohydride, ethylaluminum sesquichloride and ethylaluminum dichloride; preferably triethylaluminium and/or triisobutylaluminium.
12. The catalyst according to any one of claims 9 to 11, wherein the organosilicon compound is a compound of the general formula II, the structure of the compound of the general formula II is as follows,
R A m Si(OR B ) 4-m
general formula II
Wherein m is more than or equal to 0 and less than or equal to 3, R A Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom, R B Is alkyl, cycloalkyl, aryl, haloalkyl or amine; preferably, R A Is C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl, amino, halogen or hydrogen atom, R B Is C1-C10 alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C1-C10 haloalkyl or amino; more preferably, the organosilicon compound is selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, tri-n-propylmethoxysilane, and dimethylAt least one of dimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, dipentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dimethyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethylmethoxysilane, hexyldiethylmethoxysilane, dicyclopentyldimethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, 4-methylcyclohexylmethyldimethoxysilane, 4-methylcyclohexylethyldimethoxysilane, 4-methylcyclohexylpropyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylpentylmethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane; more preferably, the organosilicon compound is at least one selected from the group consisting of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and diisopropyldimethoxysilane.
13. Catalyst according to any one of claims 9 to 12, characterized in that the molar ratio of components (a), (B) and (C) is 1 (5-2000): (0-500), preferably 1 (10-800): (0-300), more preferably 1 (50-200): (0-30).
14. A process for the polymerization of olefins, characterized in that said olefins are polymerized in the presence of the catalyst component according to any of claims 1 to 8 or the catalyst according to any of claims 9 to 13, said olefins being selected from one or more of ethylene, propylene, butene-1, 4-methyl-1-pentene, 1-hexene.
15. The process according to claim 14, characterized in that the polymerization is a propylene homo-polymerization or a copolymerization of ethylene with an α -olefin, preferably the polymerization temperature is 0 to 150 ℃, more preferably 60 to 90 ℃.
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