CN103113500A - Alkene coordination polymerization catalyst as well as preparation method and application thereof - Google Patents
Alkene coordination polymerization catalyst as well as preparation method and application thereof Download PDFInfo
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- CN103113500A CN103113500A CN2013100342521A CN201310034252A CN103113500A CN 103113500 A CN103113500 A CN 103113500A CN 2013100342521 A CN2013100342521 A CN 2013100342521A CN 201310034252 A CN201310034252 A CN 201310034252A CN 103113500 A CN103113500 A CN 103113500A
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- catalysts
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000012718 coordination polymerization Methods 0.000 title abstract 4
- 239000002685 polymerization catalyst Substances 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 118
- 239000007787 solid Substances 0.000 claims abstract description 97
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 85
- -1 magnesium halide Chemical class 0.000 claims abstract description 78
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 62
- 239000011777 magnesium Substances 0.000 claims abstract description 37
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 33
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 19
- 150000003624 transition metals Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 256
- 238000006243 chemical reaction Methods 0.000 claims description 183
- 238000010792 warming Methods 0.000 claims description 116
- 238000003756 stirring Methods 0.000 claims description 100
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 36
- 238000001291 vacuum drying Methods 0.000 claims description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- 229960004424 carbon dioxide Drugs 0.000 claims description 9
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920002101 Chitin Polymers 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 150000002899 organoaluminium compounds Chemical group 0.000 claims description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 27
- 239000001257 hydrogen Substances 0.000 abstract description 26
- 239000004698 Polyethylene Substances 0.000 abstract description 17
- 229920000573 polyethylene Polymers 0.000 abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 150000003961 organosilicon compounds Chemical class 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000007613 slurry method Methods 0.000 abstract 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 94
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 90
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 70
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 70
- 229910052757 nitrogen Inorganic materials 0.000 description 45
- 235000011147 magnesium chloride Nutrition 0.000 description 35
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 33
- 238000009826 distribution Methods 0.000 description 31
- 238000005406 washing Methods 0.000 description 31
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 27
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 238000006555 catalytic reaction Methods 0.000 description 15
- 230000018044 dehydration Effects 0.000 description 15
- 238000006297 dehydration reaction Methods 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VBZVMYHKYPZDEB-UHFFFAOYSA-N C(C)O[Si](OC1CCCC1)(OCC)OCC Chemical compound C(C)O[Si](OC1CCCC1)(OCC)OCC VBZVMYHKYPZDEB-UHFFFAOYSA-N 0.000 description 2
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 description 2
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 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 description 2
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 description 2
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 150000002680 magnesium Chemical class 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- RSQXQPJKEFZBGI-UHFFFAOYSA-N triethyl hexyl silicate Chemical compound CCCCCCO[Si](OCC)(OCC)OCC RSQXQPJKEFZBGI-UHFFFAOYSA-N 0.000 description 2
- KVHHJVNRKAZGMT-UHFFFAOYSA-N triethyl pentyl silicate Chemical compound CCCCCO[Si](OCC)(OCC)OCC KVHHJVNRKAZGMT-UHFFFAOYSA-N 0.000 description 2
- 229940057402 undecyl alcohol Drugs 0.000 description 2
- SXNLMXPRYYYOSO-UHFFFAOYSA-N (2,3-dimethylcyclopentyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1CCC(C)C1C SXNLMXPRYYYOSO-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 description 1
- IPBRZLMGGXHHMS-UHFFFAOYSA-N 1-chloro-2-phenoxybenzene Chemical compound ClC1=CC=CC=C1OC1=CC=CC=C1 IPBRZLMGGXHHMS-UHFFFAOYSA-N 0.000 description 1
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- CADAOKXOWMHTKV-UHFFFAOYSA-N C(C)O[Ti](OCC)OCC.[Cl] Chemical compound C(C)O[Ti](OCC)OCC.[Cl] CADAOKXOWMHTKV-UHFFFAOYSA-N 0.000 description 1
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- ABHDMIUXUBITMX-UHFFFAOYSA-N CCO[SiH](OCC)c1ccccc1C Chemical class CCO[SiH](OCC)c1ccccc1C ABHDMIUXUBITMX-UHFFFAOYSA-N 0.000 description 1
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 description 1
- BCZTVWYUIJTQOY-UHFFFAOYSA-N CO[SiH](OC)c1ccccc1C Chemical compound CO[SiH](OC)c1ccccc1C BCZTVWYUIJTQOY-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
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- BCSZALSGPTYQQW-UHFFFAOYSA-N O(C)[SiH](OC)OC.[Cl] Chemical compound O(C)[SiH](OC)OC.[Cl] BCSZALSGPTYQQW-UHFFFAOYSA-N 0.000 description 1
- IJUZIFGEBYXQJT-UHFFFAOYSA-N O(CC)[SiH](OCC)OCC.[Cl] Chemical compound O(CC)[SiH](OCC)OCC.[Cl] IJUZIFGEBYXQJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- ABXDUVOCXLVBNG-UHFFFAOYSA-M [Ti]OC1=CC=CC=C1 Chemical compound [Ti]OC1=CC=CC=C1 ABXDUVOCXLVBNG-UHFFFAOYSA-M 0.000 description 1
- RBIILJCATVGHHI-UHFFFAOYSA-N [diethoxy(phenyl)silyl]methanamine Chemical compound NC[Si](OCC)(OCC)C1=CC=CC=C1 RBIILJCATVGHHI-UHFFFAOYSA-N 0.000 description 1
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- FWCTZJNNLCYVMA-UHFFFAOYSA-L butan-1-ol;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCCO.CCCCO FWCTZJNNLCYVMA-UHFFFAOYSA-L 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical class [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical group CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- AFNPFLDWLMEASV-UHFFFAOYSA-N butyl-diethoxy-methylsilane Chemical group CCCC[Si](C)(OCC)OCC AFNPFLDWLMEASV-UHFFFAOYSA-N 0.000 description 1
- OOSZILWKTQCRSZ-UHFFFAOYSA-N butyl-dimethoxy-methylsilane Chemical group CCCC[Si](C)(OC)OC OOSZILWKTQCRSZ-UHFFFAOYSA-N 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- HJZDEHICJSNDGK-UHFFFAOYSA-N cyclopentyl(ethoxy)silane Chemical class C1(CCCC1)[SiH2]OCC HJZDEHICJSNDGK-UHFFFAOYSA-N 0.000 description 1
- MGGAITMRMJXXMT-UHFFFAOYSA-N cyclopentyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCC1 MGGAITMRMJXXMT-UHFFFAOYSA-N 0.000 description 1
- YRMPTIHEUZLTDO-UHFFFAOYSA-N cyclopentyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCC1 YRMPTIHEUZLTDO-UHFFFAOYSA-N 0.000 description 1
- RJAXOUUONIIIER-UHFFFAOYSA-N cyclopentyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)C1CCCC1 RJAXOUUONIIIER-UHFFFAOYSA-N 0.000 description 1
- JXZQBPNJNQYXGF-UHFFFAOYSA-N cyclopentyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCC1 JXZQBPNJNQYXGF-UHFFFAOYSA-N 0.000 description 1
- HLQNMKCXJLHAGZ-UHFFFAOYSA-N cyclopentyl-methoxy-methylsilane Chemical compound CO[SiH](C)C1CCCC1 HLQNMKCXJLHAGZ-UHFFFAOYSA-N 0.000 description 1
- ARIUTOVBISGHSG-UHFFFAOYSA-N cyclopentylmethoxysilane Chemical compound C1(CCCC1)CO[SiH3] ARIUTOVBISGHSG-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- VVKJJEAEVBNODX-UHFFFAOYSA-N diethoxy-di(propan-2-yl)silane Chemical compound CCO[Si](C(C)C)(C(C)C)OCC VVKJJEAEVBNODX-UHFFFAOYSA-N 0.000 description 1
- OXSKWPFZITXGFK-UHFFFAOYSA-N diethoxy-methyl-(2-methylbutan-2-yl)silane Chemical compound CCO[Si](C)(OCC)C(C)(C)CC OXSKWPFZITXGFK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 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
- 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 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical class [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 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
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- QYBKVVRRGQSGDC-UHFFFAOYSA-N triethyl methyl silicate Chemical compound CCO[Si](OC)(OCC)OCC QYBKVVRRGQSGDC-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- IOPAQHDEQBHWEB-UHFFFAOYSA-N trimethoxy-(2-methylcyclopentyl)silane Chemical compound CO[Si](OC)(OC)C1CCCC1C IOPAQHDEQBHWEB-UHFFFAOYSA-N 0.000 description 1
- RZIDDAABTIZZOW-UHFFFAOYSA-N trimethyl pentyl silicate Chemical compound CCCCCO[Si](OC)(OC)OC RZIDDAABTIZZOW-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides an alkene coordination polymerization catalyst as well as a preparation method and an application thereof. The alkene coordination polymerization catalyst consists of a primary catalyst and an auxiliary catalyst, and is characterized in that the primary catalyst consists of a magnesium halide carrier, a transition metal halide, an ethanol with the carbon number of less than 5, an ethanol with the carbon number of greater than 5, an organosilicon compound and a polyhydroxy solid, wherein the mass ratio of the polyhydroxy solid to the magnesium halide carrier is (0.05-20):100. The catalyst solid particle is in a good shape of sphere, the catalyst is high in activity, the hydrogen regulation performance is favorable, and the melt index MFR of polyethylene can be regulated within 0.1g/10min-600g/10min. The alkene coordination polymerization catalyst is suitable for slurry-method polymerization process, gas-phase-method polymerization process or combination polymerization process.
Description
Technical field
The invention belongs to olefin polymerization catalysis and field of olefin polymerisation, be specifically related to for the catalyzer of the equal polymerization of alkene or copolymerization and the preparation method of catalyzer.
Background technology
Olefin polymerization catalysis is the core of polyolefin polymerization technology, development from olefin polymerization catalysis, sum up and mainly contain two aspects: (1) exploitation can prepare property or the more excellent polyolefin resin catalyzer of performance, as metallocene catalyst and non-luxuriant late transition metal catalyst etc.; (2) for the production of general purpose polyolefin resin, on the basis of further improving catalyst performance, simplify catalyst preparation process, reduce the catalyzer cost, develop environment amenable technology, to increase the benefit, enhance the competitiveness.Before the eighties in 20th century, the emphasis of polyethylene catalysts research is to pursue catalyst efficiency, and through the effort of nearly 30 years, the catalytic efficiency of polyethylene catalysts was the order of magnitude and improves, thereby has simplified polyolefinic production technique, has reduced energy consumption and material consumption.
The Ziegler-Natta catalyst existing nearly 60 years history so far of coming out, although during occurred as polyolefin catalysts such as metallocene and Nonmetallocenes, its industrial problems is more, as the promotor costliness, the Primary Catalysts load also has difficulties etc.Therefore, just present industrial production and share of market, traditional Z-N catalyzer will be the leader of following for some time internal olefin polymerization field.In recent years, Z-N catalyst prod both domestic and external emerges in an endless stream, and catalyst stability and polymerization catalyzed activity also improve constantly.But still having deficiency aspect hydrogen response, control granules of catalyst regularity and size distribution.Need develop in producing at present that preparation technology is simple, hydrogen response good, size distribution spherical or class spherical catalyst uniformly.
Patent 96106647.4X discloses a kind of olefin polymerization catalysis and preparation method thereof, with carrier MgCl
2Be dissolved in a kind of mixture of pure and mild alkane, form liquid MgCl
2Alcohol adducts, this liquid MgCl
2Alcohol adducts and TiCl
4Contact obtain olefin polymerization catalysis, but the hydrogen regulation performance of catalyzer is poor, and poly melting index MFR can only regulate in 0.1g/10min – 220g/10min.
patent 93102795.0 discloses a kind of spherical catalyst of α-for olefines polymerization, it is stated from magnesium chloride alcohol adduct carrier by the halogen titanium compound and forms, it is characterized in that carrier by alcohol with magnesium chloride at silicone oil, direct synthesizing chlorinated magnesium alcoholate ball type carrier in the white oil medium, begin reaction with the halogen titanium compound at-20 ℃ of temperature, under the polynary ester of organic acid exists, rising temperature of reaction to 110～130 ℃, obtain catalyzer, this catalyzer is applicable to alpha-olefin, as ethene, propylene, the equal polymerization reaction of butene-1 etc. and the copolymerization of their mixture.
Patent 200480008242.X discloses a kind of olefin polymerization catalysis and preparation method thereof, with carrier MgCl
2Directly be dissolved in ethanol and prepared solid MgCl
2Alcohol adducts, then with TiCl
4Load on solid MgCl
2Obtained olefin polymerization catalysis on alcohol adducts.
Patent 200810223088.8 discloses catalyzer and has comprised main catalyst component and at least a organo-aluminium compound; Main catalyst component comprises the magnesium mixture, at least a titanium compound, at least a organic alcohol compound.The magnesium mixture is that magnesium halide is dissolved in resulting product in the mixed solvent that contains organic epoxide and organo phosphorous compounds.In the preparation process of this catalyzer, do precipitation additive with alkane compound.This catalyzer has high catalytic activity and hydrogen response preferably.
Patent 200910083230.8 at 10-150 ℃, is dissolved in magnesium halide in the mixed solvent of organic epoxy compounds, organo phosphorous compounds, aromatic solvent and alkane, then adds organic alcohol compound, drip again titanium compound, add silicoorganic compound after dropwising, be warming up to 60-110 ℃, reacted 0.5-24 hour, in temperature-rise period, particle is separated out and formed to solids gradually, and reaction is removed unreacted reactant and solvent after finishing, and adopt the inert solvent washing, obtain main catalyst component.
This patent finds, in catalyst preparation process, adds organic solvent, adds carbonatoms to be less than or equal to 5 alcohol, adds carbonatoms greater than 5 alcohol, MgCl
2After grain dissolution, then add silicoorganic compound, preparation liquid MgCl
2Alcohol adducts, then with TiCl
4With this liquid MgCl
2The alcohol adducts contact adds the poly-hydroxy solids afterwards again, obtains olefin polymerization catalysis, can improve the particle form of solid main catalyst and the hydrogen regulation performance of catalyst olefinic polymerization.The particle form of olefin polymerization catalysis provided by the present invention is good, and size distribution is even, non-stick container wall, easily processing; The catalyzer hydrogen regulation performance is excellent, and poly melting index MFR can regulate in 0.1g/10min – 600g/10min; Catalyst loadings is high, and catalyst activity is high; Morphology is good, and tap density is high, and fine powder is few; Be applicable to slurry polymerization processes, gas-phase polymerization process or polymerization mix technique; The preparation technology of Primary Catalysts is simple, and is low for equipment requirements, and energy consumption is little, and environmental pollution is little.
Summary of the invention
The object of the present invention is to provide a kind of olefinic polymerization or the Catalysts for Olefin Polymerization of ethene and copolymerization monomer copolymerizable and preparation method of described catalyzer of can be used for.
The Catalysts for Olefin Polymerization that can be used for olefinic polymerization or ethene and copolymerization monomer copolymerizable provided by the present invention is comprised of Primary Catalysts and promotor; Described Primary Catalysts is by magnesium halide, transition metal halide, C
1-5Alcohol, greater than C
5Alcohol, silicoorganic compound and poly-hydroxy solids form.In one aspect of the invention, magnesium halide, transition metal halide, C
1-5Alcohol, greater than C
5The mol ratio of pure and mild silicoorganic compound be: 1:(1-40): (0.015): (0.01-10): (0.01-10).Aspect one of them, the mass ratio of described poly-hydroxy solids and magnesium halide carrier is (0.0520): 100 of the present invention.The mol ratio of Primary Catalysts and promotor is (1:10)-500.Described Primary Catalysts and promotor with magnitude relation be: the transition metal halide in Primary Catalysts and the mol ratio of promotor are 1:(10-500).
Wherein promotor can adopt the promotor for olefin polymerization catalysis well known in the art.For example, described promotor is organo-aluminium compound, preferred triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, second chlorodiethyl aluminium, methylaluminoxane MAO etc.
Wherein, described magnesium halide is as carrier, and it is selected from general formula (1) is Mg (R)
aX
bCompound at least a, wherein R is selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
3～C
20Alicyclic radical or C
6～C
20Aryl radical; X is selected from halogen, Cl for example, Br and F; A=0,1 or 2, b=1 or 2, a+b=2.Described magnesium halide specifically can be selected from least a in magnesium dichloride, dibrominated magnesium, two magnesium iodides, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination propoxy-magnesium, chlorination butoxy magnesium, chlorination phenoxy group magnesium, magnesium ethylate, isopropoxy magnesium, butoxy magnesium, chlorination isopropoxy magnesium, butyl magnesium chloride etc., wherein, described magnesium halide is preferably magnesium dichloride.
Wherein, to be selected from general formula (2) be M (R to described transition metal halide
1)
4-mX
mCompound at least a, in formula, M is Ti, Zr, Hf, Fe, Co or Ni; X is halogen atom, is selected from Cl, Br, F; M is 1 to 4 integer; R
1Be selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
1～C
20Cyclopentadienyl and derivative, C
1～C
20Aryl radical, COR` or COOR`, R` has C
1～C
10Aliphatic group or have C
6～C
10Aryl radical.R
1Can be selected from: at least a in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, ortho-, meta-or p-aminomethyl phenyl, meta-aminomethyl phenyl, p-aminomethyl phenyl, ortho-, meta-or p-sulfonic group phenyl, formyl radical, acetyl or benzoyl base etc.Described Ti, Zr, Hf, Fe, Co, the transition metal halides such as Ni can be selected from one or more the mixing in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, tetrabutyl titanate, isopropyl titanate, methoxyl group titanous chloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, four phenoxide titaniums, a chlorine triple phenoxyl titanium, two chlorodiphenyl oxygen base titaniums, trichlorine one phenoxide titanium.Wherein, described transition metal halide is preferably titanium tetrachloride.In one aspect of the invention, in described Catalysts for Olefin Polymerization, the mol ratio of transition metal halide and magnesium halide is preferably (1-40): 1.
Wherein, described C
1-5Alcohol (in the present invention sometimes also referred to as " less than C
5Alcohol ") be that carbonatoms is less than or equal to 5 Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol, be preferably Fatty Alcohol(C12-C14 and C12-C18), be for example ethanol, methyl alcohol, propyl alcohol, butanols or amylalcohol, be preferably ethanol.In one aspect of the invention, C in described Catalysts for Olefin Polymerization
1-5Alcohol and the mol ratio of magnesium halide preferred (0.01 – 5): 1.Add C
1-5Alcohol especially ethanol can obviously improve the hydrogen regulation performance of catalyzer.
Wherein, described greater than C
5Alcohol be that carbonatoms is C
6– C
20Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol or aromatic alcohol, preferred fat alcohol, optional enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol, pentadecanol or hexadecanol in Fatty Alcohol(C12-C14 and C12-C18), preferred isooctyl alcohol.In one aspect of the invention, in described Catalysts for Olefin Polymerization greater than C
5Alcohol and the mol ratio of magnesium halide preferred (0.01 – 10): 1.
Wherein, described silicoorganic compound meet general formula R
x 3R
y 4Si (OR
5)
zOr general formula (R
6O) (R
7O) (R
8O) (R
9O) Si, wherein R
3And R
4Be respectively alkyl or halogen, R
5, R
6, R
7, R
8And R
9C
1To C
20Alkyl or cyclic hydrocarbon radical, 0≤x≤2,0≤y≤2, and 0＜z≤4, x+y+z=4.silicoorganic compound can be selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, the n-propyl triethoxyl silane, the n-propyl Trimethoxy silane, the decyl Trimethoxy silane, the decyl triethoxyl silane, cyclopentyl-trimethoxy-silane, the cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, isobutyl triethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dibutyl dimethoxy silane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, the tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, Cyclohexylmethyldimethoxysilane, the methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, the aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, two cyclopentyl-methyl methoxy silane, cyclopentyl dimethyl methyl TMOS, diethoxy isopropoxy tert.-butoxy silane, three isopropoxy tert.-butoxy silane, diisopropoxy two tert.-butoxy silane, diethoxy cyclohexyloxy tert.-butoxy silane, diethoxy phenoxy group tert.-butoxy silane, one oxyethyl group diisopropoxy tert.-butoxy silane, oxyethyl group isopropoxy tert.-butoxy cyclohexyloxy silane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon, triethoxy hexyloxy silicon, one or more in trimethoxy pentyloxy silicon or triethoxy phenoxy group silicon etc.A kind of in preferred tetramethoxy-silicane, tetraethoxysilane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon or triethoxy hexyloxy silicon.In one aspect of the invention, in described Catalysts for Olefin Polymerization, the mol ratio of silicoorganic compound and magnesium halide is (0.01-10): 1.
Wherein, described poly-hydroxy solids refers to have polyhydric solid compounds or with the solid-state material of polyol or itself have polyhydric solid-state material.For example, the poly-hydroxy solids can be carbonoxide pipe, carbonoxide ball, graphite oxide, silica gel, polymer alumina, poly-hydroxy POSS(polyhedraloligomeric silsesquioxanes), Mierocrystalline cellulose, polysaccharide, chitin etc.In one aspect of the invention, the mass ratio of poly-hydroxy solids and magnesium halide carrier described in described Catalysts for Olefin Polymerization is (0.05 – 20): 100.Wherein, described poly-hydroxy POSS can be dihydroxyl POSS, trihydroxy-POSS, tetrahydroxy POSS, hexahydroxy-POSS or eight hydroxyl POSS etc.
One of advantage of the present invention is to add simultaneously C in the preparation process of solid main catalyst
1-5Pure and mild greater than C
5Alcohol, described C
1-5Alcohol be that carbonatoms is less than or equal to 5 Fatty Alcohol(C12-C14 and C12-C18), be selected from ethanol, methyl alcohol, propyl alcohol, butanols or amylalcohol, preferred alcohol.C
1-5Alcohol and the mol ratio of magnesium halide preferred (0.015): 1.Described greater than C
5Alcohol be that carbonatoms is C
6C
20Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol or aromatic alcohol, preferred fat alcohol, select enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol, pentadecanol or hexadecanol in Fatty Alcohol(C12-C14 and C12-C18), preferred isooctyl alcohol, described isooctyl alcohol is 2-ethyl-1-hexanol.Greater than C
5Alcohol and the mol ratio of magnesium halide preferred (0.01 – 10): 1.Add C
1-5Alcohol especially ethanol can obviously improve the hydrogen regulation performance of catalyzer.
Another advantage of the present invention is to add the poly-hydroxy solids in the preparation process of solid main catalyst.The present invention is not produced any restriction, the contriver thinks, add the poly-hydroxy solids can improve the particle form of solid main catalyst.The present invention is not produced any restriction, the contriver thinks, adds the poly-hydroxy solids can eliminate the static of solid main catalyst particle, and the particle non-stick container wall of solid main catalyst is easy to process.Described poly-hydroxy solids is carbonoxide pipe, carbonoxide ball, graphite oxide, silica gel, polymer alumina, poly-hydroxy POSS, Mierocrystalline cellulose, polysaccharide, chitin etc.
The invention provides the method for the above-mentioned olefin polymerization catalysis of preparation, it comprises the following steps:
1) magnesium halide carrier is scattered in organic solvent, adds C
1-5Pure and mild greater than C
5Alcohol, in 30 to 150 ℃ of lower stirring and dissolving 1 are to 5h, preferred 60 ℃ to 130 ℃;
2) with 1) solution that obtains is cooled to 10 to 80 ℃, adds silicoorganic compound, and reaction 0.5 is to 3h;
3) under-25 to 30 ℃, with step 2) mixture that obtains contacts with transition metal halide, then adds the poly-hydroxy solids, and react 0.5-5h under-25 to 30 ℃, be warming up to again 20-150 ℃, preferred 50-120 ℃, reaction 0.5-5h, in temperature-rise period, solid particulate is separated out gradually, after reaction finishes, with toluene or normal hexane washed product 4-6 time, remove by filter unreacted reactant, vacuum-drying obtains the pulverulent solids Primary Catalysts.Wherein vacuum-drying temperature is 40 ℃ to 130 ℃, preferred 50 ℃ to 100 ℃.The vacuum-drying time is 0.5 hour to 5 hours, preferred 1 hour to 4 hours.
Preferably, the mol ratio of wherein said transition metal halide and described magnesium halide can be: (1-40): 1; The mass ratio of described poly-hydroxy solids and magnesium halide carrier is (0.1-10): 100.Preferred, described magnesium halide carrier, transition metal halide, C
1-5Alcohol, greater than C
5The mol ratio of pure and mild silicoorganic compound be: 1:(1-40): (0.01-5): (0.01-10): (0.01-10).
The solid main catalyst that obtains is mainly by Mg, Ti, and Cl, C, Si, O, H etc. are elementary composition.
Described organic solvent is selected from C
5～C
15Stable hydrocarbon, C
5～C
10Alicyclic hydrocarbon, C
6～C
15Aromatic hydrocarbon or C
3～C
10The saturated heterocyclic hydrocarbon, preferred toluene, dimethylbenzene, hexane, heptane, octane, decane hexanaphthene or tetrahydrofuran (THF), or their mixed solvent.
The preparation method of olefin polymerization catalysis provided by the present invention also comprises the step of promotor with the solid main catalyst combination that obtains.Can adopt the promotor for olefin polymerization catalysis well known in the art.For example, described promotor is organo-aluminium compound, preferred triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, second chlorodiethyl aluminium, methylaluminoxane MAO etc.The mol ratio of Primary Catalysts and promotor is (1:10)-500.
The present invention also provides the application of aforementioned Catalysts for Olefin Polymerization.The purposes of olefin polymerization catalysis provided by the present invention is: the copolymerization catalyst that can be used as vinyl polymerization or propylene polymerization or ethene (or propylene) and alpha-olefin.Wherein, described alpha-olefin is selected from C
3～C
20Alkene, preferred propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentenes, 4-methyl-1-pentene, 1,3-butadiene, isoprene, vinylbenzene, vinyl toluene etc.
Olefin polymerization catalysis provided by the present invention has following beneficial effect:
The Primary Catalysts particle form of the alpha-olefinic copolymerization catalyzer that provides of the present invention is good, spherical in shape, the non-stick container wall, easily process; The hydrogen regulation performance of catalyzer is excellent, and poly melting index MFR can regulate in 0.1g/10min-600g/10min; Catalyst activity is high; Be applicable to slurry polymerization processes, endless tube polymerization technique, gas-phase polymerization process or polymerization mix technique; The preparation method is simple, and is low for equipment requirements, and environmental pollution is little.
Adopt GC to measure ethanol and other pure quality percentage composition in Primary Catalysts, the results are shown in Table 1.
Adopt ICP to measure Mg in Primary Catalysts, the quality percentage composition of Ti and Si.
The condition determination of the melting index of polyethylene and polyethylene and ethylene copolymers is that testing load is that 5kg, temperature are 190 ℃.
The condition determination of the melting index of isotatic polypropylene is that testing load is that 2.16kg, temperature are 230 ℃.
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited only to following embodiment.
Embodiment
Embodiment 1
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, isooctyl alcohol 6.5ml stirs and is warming up to 120 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 5ml, reaction 2h.System is down under-15 ℃, drips the 30ml titanium tetrachloride, then add fructose 0.01 gram, reaction 1h is warming up to 110 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 2
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 30ml, ethanol 0.25ml, isooctyl alcohol 7ml stirs and is warming up to 120 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tetraethoxysilane 0.5ml, reaction 2h.System is down under-10 ℃, drips the 20ml titanium tetrachloride, then add tetrahydroxy eight siloxanes 0.2 grams, reaction 1h is warming up to 100 ℃ and reacts 3h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 10 ℃ in reactor, be added dropwise to the 40ml titanium tetrachloride, reaction 1h is warming up to 65 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 60 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 3
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, isooctyl alcohol 8ml stirs and is warming up to 100 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 2ml, reaction 2h.System is down under-15 ℃, drips the 15ml titanium tetrachloride, then add tetrahydroxy POSS0.2 gram, reaction 1h is warming up to 65 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and hexane washed twice (each 30 milliliters) after 2 hours, adds n-decane 20ml at 0 ℃ in 70 ℃ of vacuum-dryings in reactor, be added dropwise to the 25ml titanium tetrachloride, and reaction 1h is warming up to 65 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 4
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 2ml, isooctyl alcohol 7ml stirs and is warming up to 90 ℃, reaction 4h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add triethoxy methoxy silane 0.5ml, reaction 2h.System is down under-15 ℃, drips the 15ml titanium tetrachloride, then add eight hydroxyl POSS0.1 grams, reaction 1h is warming up to 120 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered.Add n-decane 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 80 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 5
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.1ml, isooctyl alcohol 4ml stirs and is warming up to 80 ℃, reaction 5h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 4ml, reaction 2h.System is down under-15 ℃, drips the 15ml titanium tetrachloride, then add carbonoxide pipe 0.05 gram, reaction 3h is warming up to 90 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 90 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 6
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 2.5ml, isooctyl alcohol 3ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 8ml, reaction 2h.System is down under-15 ℃, drips the 40ml titanium tetrachloride, then add carbonoxide ball 0.05 gram, reaction 1h is warming up to 70 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 100 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 7
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, isooctyl alcohol 6.5ml stirs and is warming up to 60 ℃, reaction 4h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively triethoxy cyclopentyloxy silane 3ml and ethanol 0.2ml, reaction 3h.System is down under-15 ℃, drips the 15ml titanium tetrachloride, then add graphite oxide 0.05 gram, reaction 1h is warming up to 65 ℃ and reacts 4h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 20 ℃ in reactor, be added dropwise to the 40ml titanium tetrachloride, reaction 1h is warming up to 65 ℃ and reacts 3h again.Stop stirring, standing, layering is filtered, twice of toluene wash (each 30 milliliters), and four times (each 30 milliliters) of hexane washing in 60 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 8
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.3ml, decyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively diethoxy isopropoxy tert.-butoxy silane 5ml, reaction 3h.System is down under-10 ℃, drips the 30ml titanium tetrachloride, then add silica gel 0.1 gram, reaction 1h is warming up to 80 ℃ and reacts 3h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 15 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 15 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 60 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 9
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, propyl alcohol 3ml, isooctyl alcohol 6.5ml stirs and is warming up to 50 ℃, reaction 5h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add aluminum oxide 0.05 gram, reaction 1h is warming up to 90 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 110 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 10
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 30ml, butanols 4ml, isooctyl alcohol 6.5ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under-5 ℃, drips the 15ml titanium tetrachloride, then add chitin 0.03 gram, reaction 1h is warming up to 90 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 10 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 10 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 120 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 11
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, methyl alcohol 2ml, lauryl alcohol 5ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is cooled to 25 ℃, then is added dropwise in the 25ml titanium tetrachloride that is in-10 ℃, then add modified-cellulose 0.07 gram, at 0 ℃ of reaction 1h, be warming up to 110 ℃ and react again 2h in 4 hours.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 12
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.5ml, isooctyl alcohol 6.5ml stirs and is warming up to 120 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tetraethoxysilane 6ml, reaction 2h.System is cooled to 25 ℃, then is added dropwise in the 25ml titanium tetrachloride that is in-15 ℃, then add magnesium chloride 0.2 gram, at-5 ℃ of reaction 1h, be warming up to 100 ℃ and react again 2h in 4 hours.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 13
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.1ml, isooctyl alcohol 6.5ml stirs and is warming up to 110 ℃, reaction 3h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 2ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add silica gel 0.05 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 3h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 2h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 14
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6.5ml stirs and is warming up to 100 ℃, reaction 4h, solid dissolves the solution that forms homogeneous fully.System is down under-15 ℃, drips the 15ml titanium tetrachloride, then add dihydroxyl POSS0.1 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 15
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.4ml, isooctyl alcohol 6.5ml stirs and is warming up to 120 ℃, reaction 0.5h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add succinate 6ml, reaction 2h.System is down under-15 ℃, drips the 15ml titanium tetrachloride, then add trihydroxy-six siloxanes 0.05 grams, reaction 1h is warming up to 90 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and hexane washed twice (each 30 milliliters) adds n-decane 20ml at 0 ℃ in 60 ℃ of vacuum-dryings after 2 hours in reactor, be added dropwise to the 25ml titanium tetrachloride, and reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add n-decane 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 16
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.5ml, methyl alcohol 1ml, isooctyl alcohol 7ml stirs and is warming up to 100 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add silica gel 0.15 gram, reaction 1h is warming up to 100 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 110 ℃ and reacts 2h again.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 110 ℃ and reacts 2h again.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 17
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, propyl alcohol 2ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add carbonoxide ball 0.03 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 18
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add season pentanediol 0.08 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 19
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add tetramethylolmethane 0.1 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 20
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add pyrocatechol 0.08 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 21
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add fructose 0.1 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 22
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add starch 0.08 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 23
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add Mierocrystalline cellulose 0.08 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 24
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1ml, isooctyl alcohol 6ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 6ml, reaction 2h.System is down under 0 ℃, drips the 15ml titanium tetrachloride, then add chitosan 0.1 gram, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Comparative Examples 1
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, decane 20ml, isooctyl alcohol 6.5ml stirs and is warming up to 110 ℃, reaction 2h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 5ml, reaction 2h.System is down under-15 ℃, drips the 15ml titanium tetrachloride, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 80 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.The hydrogen regulation performance of catalyzer is poor.
Comparative Examples 2
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, decane 20ml, ethanol 2ml, isooctyl alcohol 6.5ml stirs and is warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 5ml, reaction 2h.System is down under-15 ℃, drips the 15ml titanium tetrachloride, reaction 1h is warming up to 90 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, hexane washed twice (each 30 milliliters) is filtered in layering.Add toluene 20ml at 0 ℃ in reactor again, be added dropwise to the 25ml titanium tetrachloride, reaction 1h is warming up to 80 ℃ of reaction 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 60 ℃ of vacuum-dryings 2 hours, obtain the pulverulent solids Primary Catalysts.MgCl
2Alcohol adducts is separated out solid when lesser temps.The particle form of Primary Catalysts is poor.
Application mode one
Vinyl polymerization: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 20mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 1.17ml (2mmol/ml) is filled with hydrogen 0.73MPa after being warming up to 70 ℃, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 2h.
Application mode two
Ethylene copolymerization: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component 20mg successively in still, dehydration hexane 1000ml, AlEt
3Solution 1.17ml (2mmol/ml) adds the 30ml1-hexene.After being warming up to 70 ℃, be filled with hydrogen 0.28MPa, then be filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Application mode three
Propylene polymerization: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component 10mg successively in still, dehydration hexane 1000ml, AlEt
3Solution 1.17ml (2mmol/ml) adds external electron donor triethoxy cyclopentyloxy silicon 4ml (0.18M hexane solution), after being warming up to 80 ℃, is filled with hydrogen 0.1MPa, then is filled with propylene to 3MPa, constant voltage isothermal reaction 2h.Polyacrylic melting index MFR=111g/10min.
Polymerization result sees Table 2.
Melt index sees Table 3.
Embodiment 25
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1.5ml, isooctyl alcohol 6.5ml stirs and is warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tetraethoxysilane 2ml, reaction 2h.System is down under-5 ℃, drips the 25ml titanium tetrachloride, then add graphene oxide 0.03 gram, reaction 1h; Be warming up to 110 ℃ in 4 hours, then react 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Vinyl polymerization
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.1MPa after being warming up to 70 ℃, then is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 253.2 grams, tap density BD=0.35, melting index MFR=0.3g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.28MPa after being warming up to 70 ℃, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain polyethylene 220.5 grams, tap density BD=0.33, melting index MFR=4.1g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 50mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 3.0ml (2mmol/ml) is filled with hydrogen 0.73MPa after being warming up to 70 ℃, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 183.6 grams, tap density BD=0.29, melting index MFR=580g/10min.
Embodiment 26
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 1.5ml, isooctyl alcohol 6.5ml stirs and is warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tetraethoxysilane 2ml, reaction 2h.System is cooled to 25 ℃, then is added dropwise in the 25ml titanium tetrachloride that is in-15 ℃, then add silica gel 0.15 gram, at 0 ℃ of reaction 1h; Be warming up to 110 ℃ in 4 hours, then react 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Vinyl polymerization
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.1MPa after being warming up to 70 ℃, then is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 265.3 grams, tap density BD=0.35, melting index MFR=0.28g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.28MPa after being warming up to 70 ℃, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain polyethylene 228.3 grams, tap density BD=0.33, melting index MFR=3.4g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 50mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 3.0ml (2mmol/ml) is filled with hydrogen 0.73MPa after being warming up to 70 ℃, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 199.1 grams, tap density BD=0.30, melting index MFR=540g/10min.Comparative Examples 3
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, ethanol 0.3ml, isooctyl alcohol 6.5ml stirs and is warming up to 120 ℃, reaction 3h, solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tetraethoxysilane 2ml, reaction 2h.System is cooled to 25 ℃, then is added dropwise in the 25ml titanium tetrachloride that is in-15 ℃, at 0 ℃ of reaction 1h; Be warming up to 110 ℃ in 4 hours, then react 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Vinyl polymerization
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 7mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.1MPa after being warming up to 70 ℃, then is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 215.3 grams, tap density BD=0.33, melting index MFR=0.1g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.28MPa after being warming up to 70 ℃, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain polyethylene 218.3 grams, tap density BD=0.31, melting index MFR=1.5g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 50mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 3.0ml (2mmol/ml) is filled with hydrogen 0.73MPa after being warming up to 70 ℃, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 222.1 grams, tap density BD=0.29, melting index MFR=486g/10min.
Comparative Examples 4
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, n-decane 20ml, isooctyl alcohol 6ml stirs and is warming up to 90 ℃, reaction 3h, solid not exclusively dissolves.Be cooled under 60 ℃, add tetraethoxysilane 2ml, reaction 2h.System is cooled to 25 ℃, then is added dropwise in the 25ml titanium tetrachloride that is in-15 ℃, at 0 ℃ of reaction 1h; Be warming up to 110 ℃ in 4 hours, then react 2h.Stop stirring, standing, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 4 hours, obtain the pulverulent solids Primary Catalysts.
Vinyl polymerization
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.1MPa after being warming up to 70 ℃, then is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 115.3 grams, tap density BD=0.30, melting index MFR=0.15g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 0.6ml (2mmol/ml) is filled with hydrogen 0.28MPa after being warming up to 70 ℃, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain polyethylene 88.3 grams, tap density BD=0.29, melting index MFR=1.6g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 50mg successively in still, dehydration hexane 1000ml, promotor AlEt
3Solution 3.0ml (2mmol/ml) is filled with hydrogen 0.73MPa after being warming up to 70 ℃, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 52.1 grams, tap density BD=0.27, melting index MFR=187g/10min.
Mg in table 1 Primary Catalysts, Si, C
1-5Alkoxyl group and greater than C
5The quality percentage composition of alkoxyl group
Table 2
Table 3
Claims (10)
1. Catalysts for Olefin Polymerization, it is comprised of Primary Catalysts and promotor, it is characterized in that: described Primary Catalysts is by magnesium halide, transition metal halide, C
1-5Alcohol, greater than C
5Alcohol, silicoorganic compound and poly-hydroxy solids form; Wherein said magnesium halide, transition metal halide, C
1-5Alcohol, greater than C
5The mol ratio of pure and mild silicoorganic compound be: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10); The mass ratio of wherein said poly-hydroxy solids and magnesium halide is (0.05 – 20): 100, be preferably (0.5 – 15): 100; Transition metal halide in wherein said Primary Catalysts and the mol ratio of promotor are 1:(10-500).
2. Catalysts for Olefin Polymerization according to claim 1, it is characterized in that: it is Mg (R) that described magnesium halide is selected from general formula (1)
aX
bCompound at least a, wherein R is selected from C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
3～C
20Alicyclic radical and C
6～C
20Aryl radical; X is halogen; A=0,1 or 2, b=1 or 2, and a+b=2.
3. Catalysts for Olefin Polymerization according to claim 1, it is characterized in that: it is M (R that transition metal halide is selected from general formula (2)
1)
4-mX
mCompound at least a, in formula, M is Ti, Zr, Hf, Fe, Co or Ni; X is halogen atom, is selected from Cl, Br and F; M is 1 to 4 integer; R
1Be C
1～C
20Aliphatic group, C
1～C
20Fatty alkoxyl group, C
1～C
20Cyclopentadienyl or derivatives thereof, C
1～C
20Aryl radical, COR` or COOR`, wherein R` is C
1～C
10Fatty group or C
1The aromatic base of～C10.
4. Catalysts for Olefin Polymerization according to claim 1, is characterized in that: described C
1-5Alcohol be that carbonatoms is less than or equal to 5 Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol.
5. Catalysts for Olefin Polymerization according to claim 1, is characterized in that: described greater than C
5Alcohol be that carbonatoms is C
6-C
20Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol or aromatic alcohol.
6. Catalysts for Olefin Polymerization according to claim 1, it is characterized in that: described silicoorganic compound meet general formula R
x 3R
y 4Si (OR
5)
zOr general formula (R
6O) (R
7O) (R
8O) (R
9O) Si, wherein R
3And R
4Be respectively alkyl or halogen, R
5, R
6, R
7, R
8And R
9Respectively C
1To C
20Alkyl or cyclic hydrocarbon radical, 0≤x≤2,0≤y≤2, and 0＜z≤4, x+y+z=4.
7. Catalysts for Olefin Polymerization according to claim 1, it is characterized in that: described poly-hydroxy solids is selected from carbonoxide pipe, carbonoxide ball, graphite oxide, silica gel, polymer alumina, poly-hydroxy POSS, Mierocrystalline cellulose, polysaccharide and chitin, preferably, wherein said poly-hydroxy POSS is dihydroxyl POSS, trihydroxy-POSS, tetrahydroxy POSS, hexahydroxy-POSS or eight hydroxyl POSS.
8. prepare the method for the described Catalysts for Olefin Polymerization of any one in claim 1-7, it comprises the following steps:
1) described magnesium halide is scattered in organic solvent, adds described C
1-5Pure and mild described greater than C
5Alcohol, in 50 to 150 ℃ of lower stirring and dissolving 1 are to 5h;
2) with 1) solution that obtains is cooled to 10 ℃ to 80 ℃, adds described silicoorganic compound, and reaction 0.5 is to 3h;
3) under-25 to 30 ℃, with step 2) mixture that obtains contacts with described transition metal halide, then add described poly-hydroxy solids, and react 0.5-5h under-25 to 30 ℃, then be warming up to 20-150 ℃, reaction 0.5-5h; Adopt toluene or hexane washed product, remove by filter unreacted reactant, vacuum-drying obtains the pulverulent solids Primary Catalysts,
Preferably, wherein said organic solvent is selected from C
5～C
15Stable hydrocarbon, C
5～C
10Alicyclic hydrocarbon, C
6～C
15Aromatic hydrocarbon or C
3～C
10Saturated heterocyclic hydrocarbon and their mixed solvent;
Preferably, the mol ratio of wherein said transition metal halide and described magnesium halide is: (1-40): 1; The mass ratio of described poly-hydroxy solids and magnesium halide is (0.1-10): 100;
Preferred, wherein said magnesium halide, transition metal halide, C
1-5Alcohol, greater than C
5The mol ratio of pure and mild silicoorganic compound be: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10).
9. method according to claim 8, also comprise the step of promotor with the solid main catalyst combination that obtains, and is preferred, wherein said promotor is organo-aluminium compound, is for example triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, second chlorodiethyl aluminium or methylaluminoxane MAO
Preferred, wherein the mol ratio of Primary Catalysts and promotor is (1:10)-500.
10. the application of the described Catalysts for Olefin Polymerization of any one in claim 1-7, it is characterized in that: described Catalysts for Olefin Polymerization is used for vinyl polymerization, propylene polymerization, ethene and the copolymerization of alpha-olefin or the copolymerization of propylene and alpha-olefin, and described alpha-olefin is selected from C
3～C
20Alkene.
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| CN106543301A (en) * | 2016-12-06 | 2017-03-29 | 宁波大学 | A kind of preparation method and application of the Ziegler Natta catalyst for efficiently preparing low entanglement polyethylene |
| CN109201117A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of support type ethylene oligomerisation catalyst and its preparation method and application |
| CN112430282A (en) * | 2020-11-18 | 2021-03-02 | 浙江大学 | Polyolefin with low melting index and application thereof |
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| CN106543301A (en) * | 2016-12-06 | 2017-03-29 | 宁波大学 | A kind of preparation method and application of the Ziegler Natta catalyst for efficiently preparing low entanglement polyethylene |
| CN106543301B (en) * | 2016-12-06 | 2018-10-12 | 宁波大学 | A kind of preparation method and application for the Ziegler-Natta catalyst efficiently preparing low entanglement polyethylene |
| CN109201117A (en) * | 2017-07-06 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of support type ethylene oligomerisation catalyst and its preparation method and application |
| CN109201117B (en) * | 2017-07-06 | 2021-11-16 | 中国石油化工股份有限公司 | Supported ethylene oligomerization catalyst, and preparation method and application thereof |
| CN112430282A (en) * | 2020-11-18 | 2021-03-02 | 浙江大学 | Polyolefin with low melting index and application thereof |
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