CN102875704A - Olefin polymerization catalyst, preparation method and application thereof - Google Patents
Olefin polymerization catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN102875704A CN102875704A CN2012103265999A CN201210326599A CN102875704A CN 102875704 A CN102875704 A CN 102875704A CN 2012103265999 A CN2012103265999 A CN 2012103265999A CN 201210326599 A CN201210326599 A CN 201210326599A CN 102875704 A CN102875704 A CN 102875704A
- Authority
- CN
- China
- Prior art keywords
- silane
- compound
- magnesium
- olefin polymerization
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 81
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002685 polymerization catalyst Substances 0.000 title abstract 4
- -1 magnesium halide Chemical class 0.000 claims abstract description 116
- 239000003054 catalyst Substances 0.000 claims abstract description 94
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 239000004593 Epoxy Substances 0.000 claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 30
- 239000011777 magnesium Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 94
- 238000006116 polymerization reaction Methods 0.000 claims description 82
- 238000006555 catalytic reaction Methods 0.000 claims description 73
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 73
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 57
- 238000010792 warming Methods 0.000 claims description 45
- 235000011147 magnesium chloride Nutrition 0.000 claims description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 23
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 23
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 20
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 18
- 238000005660 chlorination reaction Methods 0.000 claims description 12
- 150000003254 radicals Chemical class 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 150000001399 aluminium compounds Chemical class 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 claims description 4
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 claims description 4
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 4
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- YPOAFLZSPBOWFM-UHFFFAOYSA-N 2-(5-phenylpentoxy)ethanol Chemical compound C1(=CC=CC=C1)CCCCCOCCO YPOAFLZSPBOWFM-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 3
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- SXNLMXPRYYYOSO-UHFFFAOYSA-N (2,3-dimethylcyclopentyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1CCC(C)C1C SXNLMXPRYYYOSO-UHFFFAOYSA-N 0.000 claims description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- 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 claims description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- IPBRZLMGGXHHMS-UHFFFAOYSA-N 1-chloro-2-phenoxybenzene Chemical compound ClC1=CC=CC=C1OC1=CC=CC=C1 IPBRZLMGGXHHMS-UHFFFAOYSA-N 0.000 claims description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 2
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 claims description 2
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 claims description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 2
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 claims description 2
- FTJVOUKRKPQVRL-UHFFFAOYSA-N 2-ethylhexoxysilane Chemical compound CCCCC(CC)CO[SiH3] FTJVOUKRKPQVRL-UHFFFAOYSA-N 0.000 claims description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 claims description 2
- IUADYGVMSDKSMB-UHFFFAOYSA-N 4-methyl-1-phenylpentan-2-ol Chemical compound CC(C)CC(O)CC1=CC=CC=C1 IUADYGVMSDKSMB-UHFFFAOYSA-N 0.000 claims description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 claims description 2
- CADAOKXOWMHTKV-UHFFFAOYSA-N C(C)O[Ti](OCC)OCC.[Cl] Chemical compound C(C)O[Ti](OCC)OCC.[Cl] CADAOKXOWMHTKV-UHFFFAOYSA-N 0.000 claims description 2
- ZFIVOWBNAYBZJR-UHFFFAOYSA-N CCCO[Mg] Chemical compound CCCO[Mg] ZFIVOWBNAYBZJR-UHFFFAOYSA-N 0.000 claims description 2
- QWXOIPFZTLXVQB-UHFFFAOYSA-N CCO[SiH](OCC)C1CCCC1 Chemical class CCO[SiH](OCC)C1CCCC1 QWXOIPFZTLXVQB-UHFFFAOYSA-N 0.000 claims description 2
- ABHDMIUXUBITMX-UHFFFAOYSA-N CCO[SiH](OCC)c1ccccc1C Chemical class CCO[SiH](OCC)c1ccccc1C ABHDMIUXUBITMX-UHFFFAOYSA-N 0.000 claims description 2
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 claims description 2
- BCZTVWYUIJTQOY-UHFFFAOYSA-N CO[SiH](OC)c1ccccc1C Chemical compound CO[SiH](OC)c1ccccc1C BCZTVWYUIJTQOY-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- BCSZALSGPTYQQW-UHFFFAOYSA-N O(C)[SiH](OC)OC.[Cl] Chemical compound O(C)[SiH](OC)OC.[Cl] BCSZALSGPTYQQW-UHFFFAOYSA-N 0.000 claims description 2
- IJUZIFGEBYXQJT-UHFFFAOYSA-N O(CC)[SiH](OCC)OCC.[Cl] Chemical compound O(CC)[SiH](OCC)OCC.[Cl] IJUZIFGEBYXQJT-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- ABXDUVOCXLVBNG-UHFFFAOYSA-M [Ti]OC1=CC=CC=C1 Chemical compound [Ti]OC1=CC=CC=C1 ABXDUVOCXLVBNG-UHFFFAOYSA-M 0.000 claims description 2
- RBIILJCATVGHHI-UHFFFAOYSA-N [diethoxy(phenyl)silyl]methanamine Chemical compound NC[Si](OCC)(OCC)C1=CC=CC=C1 RBIILJCATVGHHI-UHFFFAOYSA-N 0.000 claims description 2
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- FWCTZJNNLCYVMA-UHFFFAOYSA-L butan-1-ol;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCCO.CCCCO FWCTZJNNLCYVMA-UHFFFAOYSA-L 0.000 claims description 2
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical class [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 claims description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical group CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 claims description 2
- AFNPFLDWLMEASV-UHFFFAOYSA-N butyl-diethoxy-methylsilane Chemical group CCCC[Si](C)(OCC)OCC AFNPFLDWLMEASV-UHFFFAOYSA-N 0.000 claims description 2
- OOSZILWKTQCRSZ-UHFFFAOYSA-N butyl-dimethoxy-methylsilane Chemical group CCCC[Si](C)(OC)OC OOSZILWKTQCRSZ-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 2
- HJZDEHICJSNDGK-UHFFFAOYSA-N cyclopentyl(ethoxy)silane Chemical class C1(CCCC1)[SiH2]OCC HJZDEHICJSNDGK-UHFFFAOYSA-N 0.000 claims description 2
- MGGAITMRMJXXMT-UHFFFAOYSA-N cyclopentyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCC1 MGGAITMRMJXXMT-UHFFFAOYSA-N 0.000 claims description 2
- YRMPTIHEUZLTDO-UHFFFAOYSA-N cyclopentyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCC1 YRMPTIHEUZLTDO-UHFFFAOYSA-N 0.000 claims description 2
- RJAXOUUONIIIER-UHFFFAOYSA-N cyclopentyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)C1CCCC1 RJAXOUUONIIIER-UHFFFAOYSA-N 0.000 claims description 2
- JXZQBPNJNQYXGF-UHFFFAOYSA-N cyclopentyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCC1 JXZQBPNJNQYXGF-UHFFFAOYSA-N 0.000 claims description 2
- HLQNMKCXJLHAGZ-UHFFFAOYSA-N cyclopentyl-methoxy-methylsilane Chemical compound CO[SiH](C)C1CCCC1 HLQNMKCXJLHAGZ-UHFFFAOYSA-N 0.000 claims description 2
- ARIUTOVBISGHSG-UHFFFAOYSA-N cyclopentylmethoxysilane Chemical compound C1(CCCC1)CO[SiH3] ARIUTOVBISGHSG-UHFFFAOYSA-N 0.000 claims description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 claims description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 claims description 2
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 claims description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002680 magnesium Chemical class 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical class [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 claims description 2
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000005574 norbornylene group Chemical group 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- IOPAQHDEQBHWEB-UHFFFAOYSA-N trimethoxy-(2-methylcyclopentyl)silane Chemical compound CO[Si](OC)(OC)C1CCCC1C IOPAQHDEQBHWEB-UHFFFAOYSA-N 0.000 claims description 2
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 claims description 2
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 claims description 2
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000005023 xylyl group Chemical group 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 150000001350 alkyl halides Chemical class 0.000 abstract 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 238000009826 distribution Methods 0.000 description 30
- 238000005406 washing Methods 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 229940091250 magnesium supplement Drugs 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000843 powder Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229960002337 magnesium chloride Drugs 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000008139 complexing agent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 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
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940073589 magnesium chloride anhydrous Drugs 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
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-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
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000967 suction filtration Methods 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
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to an olefin polymerization catalyst, a preparation method and application thereof. The olefin polymerization catalyst comprises a main catalyst and a cocatalyst; wherein the main catalyst consists of magnesium halide, transition metal halide, organic alcohol compound, phosphate compound, epoxy alkyl halide, organic siloxane compound and organic alcohol ether compound; the cocatalyst comprises one or more of organic aluminum compounds. The preparation method of the olefin polymerization catalyst comprises the following steps: dispersing magnesium halide in an organic solvent, sequentially adding an organic alcohol compound, a phosphate compound and an epoxy alkyl halide compound, and heating, stirring and dissolving; then sequentially adding an organic siloxane compound and an organic alcohol ether compound; then, dropwise adding a transition metal halide compound to obtain a main catalyst; the main catalyst and the auxiliary catalyst are stored separately and combined when in use. The spherical main catalyst provided by the invention is combined with the cocatalyst, so that the catalytic activity is high.
Description
Technical field
The present invention relates to a kind of olefin polymerization catalysis and preparation method thereof and application, belong to olefin polymerization catalysis and field of olefin polymerisation.
Background technology
The existing nearly 60 years history of Ziegler-Natta catalyst development, during the polyolefin catalysts such as metallocene and Nonmetallocene have appearred, but its industrial problems is more, difficult etc. such as promotor costliness, load.Therefore at present, with regard to industrial production and share of market, traditional Z-N catalyzer will be the absolute leader of field of olefin polymerisation in following for some time.In recent years, Z-N catalyst prod both domestic and external emerges in an endless stream, and catalyst stability and catalytic activity also improve constantly.But catalyzer is still having deficiency aspect granule regularizing and the size distribution, and gained polyolefin products tap density is low, fine powder content is high, the problems such as sticking still, extension still, obstruction pipeline in causing producing, and this greatly affects productivity effect.At present, be badly in need of in the production developing that a kind of preparation technology is simple, the uniform spherical catalyst of size distribution.
The technology of at present disclosed relevant preparation spherical catalyst mainly concentrates on and adopts the spherical carrier of catalyst aspect, and the preparation method of ball type carrier is many, such as reprecipitation method, recrystallization method and chemical reaction method etc.
Mostly the conventional polyolefins spherical catalyst is to prepare first spherical magnesium chloride and add and the thing carrier by the method for physics shaping.Patent CN1718595A discloses a kind of spherical catalyst for olefinic polymerization, this spherical catalyst component comprises and is carried on the magnesium halide active carrier at least a titanium compound and at least a electron donor compound randomly, and wherein said magnesium halide active carrier is to rotate under super gravity field by magnesium halide/alcohol adducts melt to disperse the solid particulate that obtains.
Patent CN1404416A discloses a kind of preparation method of magnesium dihalide ball type carrier, the method be by with the molten adduct emulsion dispersion of magnesium dihalide and Lewis base in liquid phase medium, then this emulsion is cooled off fast, obtained form of spherical particles carrier adducts under certain condition.
Patent CN1397568A also discloses a kind of spherical polyolefin catalyst preparation method, that Magnesium Chloride Anhydrous and alcohol are obtained magnesium chloride alcohol adduct melt according to a certain ratio, add again after certain organic complexing agent, stirring at low speed is disperseed in methyl-silicone oil and whiteruss blending agent, and cooling forms the spherical particle of MgCl2-alcohol-organic complexing agent mixture rapidly again.
Patent CN101712732A discloses a kind of preparation method of spherical catalyst for propylene polymerization.This patent prepares first ball type carrier: in the reactor, add white oil and silicone oil, drop into magnesium chloride and the ethanol of certain proportioning, melting; Move to after the melting and add in advance hexane and be chilled in-30 ℃ the reactor, outlet temperature is no more than 0 ℃; Suction filtration, washing makes ball type carrier.
But the preparation of magnesium halide spherical adduct in these class methods often needs high melt temperature and low Formation temperature, and sometimes also needs dealcoholation treatment, complicated process of preparation, and energy consumption is large.
Along with going deep into of research, it is found that, by adding suitable precipitation agent, can prepare spherical carrier of catalyst with the mode of crystallization of the dissolution and precipitation.Such as, patent CN101857650A, disclose a kind of preparation method of easy spherical polyolefin catalyst carrier, be specially and anhydrous magnesium halide is dissolved in tetrahydrofuran (THF) forms solution, take glycol ether as precipitation agent, slowly splash into glycol ether in the magnesium halide solution, keep high-speed stirring, gained system standing demix is isolated bottom precipitation and washing, after isolate again precipitation after gained precipitation soaked with muriate or alkyl aluminum solutions, and with alkane its washing is obtained spherical carrier of catalyst.
People also find, just can not prepare spherical catalyst with physical method, the purpose that equally also can reach with chemical reaction method.Than the physical method of preparation magnesium halide ball type carrier, the advantage of chemical process is that the preparation method is simple, and energy consumption is low.Such as, patent CN87102324A discloses the manufacture method of the spherical carrier of catalyst of used in alpha-olefines polymerization, the chlorine-containing organic compounds that specifically associates with certain electron donor, in alkyl magnesium, aikyiaiurnirsoxan beta and/or the aluminium mixture prefabricated for siloxanes and necessary electron donor, react, then obtain ball type carrier.
Patent CN102040683A discloses a kind of ball type carrier preparation method for olefin polymerization catalysis, this ball type carrier preparation method is, magnesium chloride, white oil and the ethanol of certain proportioning reacts first and forms the pure and mild thing of magnesium chloride, reacts with the oxyethane compounds again.Gained carrier granule form is good, and size is adjustable, narrow diameter distribution.
These chemical reaction methods are lower than physical method energy consumption, obtained progress, but they all are to prepare first ball type carrier, prepare spherical olefin polymerization catalysis by resulting ball type carrier again, comprise two steps.Obtain spherical catalyst if can need not to prepare ball type carrier, just can simplify technique, and further reduce energy consumption.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of olefin polymerization catalysis, its Primary Catalysts has that particle form is spherical in shape, the uniform advantage of size distribution, makes the polymer bulk density for preparing high in conjunction with promotor, and fine powder is few.
The present invention also aims to provide the preparation method of above-mentioned olefin polymerization catalysis.This preparation technology is simple, and is low for equipment requirements, and energy consumption is little, and environmental pollution is little.
For reaching above-mentioned purpose, the invention provides a kind of olefin polymerization catalysis, it comprises Primary Catalysts and promotor;
Wherein, the raw material of described Primary Catalysts is comprised of magnesium halide, transition metal halide, organic alcohol compound, phosphate compound, epoxy haloalkane compound, organosilicone compounds and Organic Alcohol ether compound;
The mol ratio of described magnesium halide, described transition metal halide, described organic alcohol compound, described phosphate compounds, described epoxy halo alkanes compound, described organosilicone compounds is 1: (1-30): (1-5): (0.1-10): (1-20): (0.001-0.4);
The mass ratio of described magnesium halide and described Organic Alcohol ether compound is 1: (0.001-0.2);
Described promotor includes one or more the combination in the machine aluminium compound;
The mol ratio of the transition metal halide in described promotor and the described Primary Catalysts is (30-500): 1;
Described magnesium halide comprises formula M g (R
1)
aX
1 bShown in one or more combination in the compound, in the formula, R
1Be C
1-C
20Aliphatic group, C
1-C
20Fatty alkoxyl group, C
3-C
20Alicyclic radical or C
6-C
20Aryl radical, X
1Be halogen, a be 0 or 1, b be 1 or 2, a+b=2;
Described transition metal halide comprises formula M (R
2)
4-mX
2 mShown in one or more combination in the compound, in the formula, M is Ti, Zr, Hf, Fe, Co or Ni, X
2Be Cl, Br or F, m is 1 to 4 integer, R
2Be C
1-C
20Aliphatic group, C
1-C
20Fatty alkoxyl group, C
5-C
20Cyclopentadienyl and derivative, C
6-C
20Aryl radical, COR ' or COOR ', wherein, R ' is C
1-C
10Aliphatic group or C
6-C
10Aryl radical;
Described phosphate compounds comprises general formula (R
3O)
3The combination of one or more shown in the PO in the compound, in the formula, R
3Be C
1-C
20Aliphatic group, C
3-C
20Alicyclic radical or C
6-C
20Aryl radical;
Described epoxy halogen alkyl compound comprises general formula C
nH
(2n-1)OX
3Shown in one or more combination in the compound, this compounds is straight-chain molecule, an end group is epoxide group, another end group is replaced by a halogen atom, in the formula, n is the integer of 3-20, X
3Be halogen;
Described organosilicone compounds comprises general formula R
c 4X
d 4Si (OR
5)
eShown in one or more combination in the compound, in the formula, R
4Be alkyl, X
4Be halogen, R
5Be alkyl, c, d and e are integer, and 0≤c＜2,0≤d＜2, and 0＜e≤4, c+d+e=4;
Described Organic Alcohol ether compound comprises general formula HO (CH
2)
fO (CH
2)
gR
6Shown in one or more combination in the compound, in the formula, f is 1 to 20 integer, g is 1 to 10 integer, R
6Be aliphatic group, cycloalkyl or aryl radical, wherein, described aliphatic group is general formula C
hH
2h+1, C
hH
2h-1Or C
hH
2h-3Shown in a kind of in the group, 1≤h＜30 and h are integer, described cycloalkyl and described aryl radical are respectively general formula C
iH
2i-1, C
iH
2i-3, C
iH
2i-5Or
CIH
2i-7Shown in a kind of in the group, 3≤i＜30 and i are integer.
In above-mentioned olefin polymerization catalysis, preferably, described magnesium halide comprises one or more the combination 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 and the butyl magnesium chloride etc.More preferably, described magnesium halide is magnesium dichloride.
In above-mentioned olefin polymerization catalysis, preferably, the formula M (R of described transition metal halide
2)
4-mX
2 mIn R
2Can be 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.
In above-mentioned olefin polymerization catalysis, preferably, described transition metal halide comprises one or more the combination 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 and trichlorine one phenoxide titanium etc.More preferably, described transition metal halide is titanium tetrachloride.
In above-mentioned olefin polymerization catalysis, described organic alcohol compound comprises C
1-C
15Straight-chain alkyl alcohol, C
1-C
15Branched alkyl alcohol, C
1-C
15Cycloalkyl alcohol, C
1-C
15The pure and mild C of isomery
6-C
20Aromatic alcohol in one or more combination.Preferably, described organic alcohol compound comprises ethanol, ethylene glycol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 1,3-PD, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, sorbyl alcohol, hexalin, methyl-cyclohexanol, benzylalcohol, xylyl alcohol and Isobutyl Benzyl Carbinol etc.More preferably, described organic alcohol compound is one or more the combination in ethanol, butanols, 2-Ethylhexyl Alcohol and the glycerol.
In above-mentioned olefin polymerization catalysis, preferably, described phosphate compound comprises one or more the combination in tributyl phosphate, tri hexyl phosphate, trioctyl phosphate and the TNPP tri n pentyl phosphate etc.More preferably, described phosphate compound is tributyl phosphate.
In above-mentioned olefin polymerization catalysis, preferably, described epoxy haloalkane compound comprises one or more the combination in epoxy chloropropane, epoxy chlorobutane, epoxy chloropentane, epoxy iodopropane, epoxy butyl iodide, epoxy iodopentane, epoxy bromopropane and the epoxy n-butyl bromide etc.More preferably, described epoxy haloalkane compound is epoxy chloropropane.
In above-mentioned olefin polymerization catalysis, preferably, described organosilicone compounds comprises 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, 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, the combination of one or more in two cyclopentyl-methyl methoxy silane and the cyclopentyl dimethyl methyl TMOS etc.More preferably, described organosilicone compounds is tetramethoxy-silicane and/or tetraethoxysilane.
In above-mentioned olefin polymerization catalysis, preferably, described Organic Alcohol ether compound comprises ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol propyl ether, dihydroxypropane single-ether, butyleneglycol list propyl ether, 2-(2-cyclopentyl oxyethyl group) ethanol, 3-(2-cyclohexyl oxyethyl group) propyl alcohol, 2-(5-phenyl pentyloxy) ethanol, 4-(3-(naphthyl) propoxy-) butanols, 2-(3-epoxy ethyl propoxy-) ethanol, the combination of one or more in 2-(2-furyl oxyethyl group) ethanol and 3-(the 3-pyridyl propoxy-) propyl alcohol etc.Contain renovation agent Organic Alcohol ether compound in the Primary Catalysts of the present invention, it can improve Primary Catalysts particle form and the size distribution situation of separating out.
In above-mentioned olefin polymerization catalysis, described promotor is for common are machine aluminium compound, preferably, described promotor comprises one or more the combination in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride and the methylaluminoxane (MAO) etc.
The present invention also provides the preparation method of above-mentioned olefin polymerization catalysis, and it may further comprise the steps:
Magnesium halide is scattered in the organic solvent, adds successively organic alcohol compound, phosphate compounds and epoxy halogen alkyl compound, then 30-100 ℃ of lower stirring and dissolving, preferably, at 70-90 ℃ of lower stirring and dissolving, afterwards isothermal reaction 1-5h;
Under 10-70 ℃ of agitation condition, add successively organosilicone compounds and Organic Alcohol ether compound, then isothermal reaction 0.5-3h;
Under-30 ℃ to 30 ℃ agitation conditions, the speed dropping metal halide compound with 15mL/h-40mlL/h drips and finishes rear isothermal reaction 0.5-5h;
Be warming up to 20-100 ℃, preferably, be warming up to 60-90 ℃, isothermal reaction 0.5-5h then, in this process, solid particulate is separated out gradually;
With normal hexane washed product 4-6 time, remove by filter unreacted reactant, then vacuum-drying obtains Primary Catalysts;
Described promotor includes one or more the combination in the machine aluminium compound, and it can obtain by ordinary method;
Described Primary Catalysts separates with described promotor to be deposited, and merges in use.
In above-mentioned preparation method, described organic solvent comprises C
5-C
15Stable hydrocarbon, C
5-C
10Alicyclic hydrocarbon, C
6-C
15Aromatic hydrocarbon and C
2-C
10The saturated heterocyclic hydrocarbon in one or more combination.Preferably, described organic solvent comprises one or more the combination in toluene, dimethylbenzene, normal hexane, normal heptane, octane and the n-decane etc.More preferably, described organic solvent is one or more the combination in toluene, normal hexane, normal heptane and the n-decane.
The present invention also provides the application as the catalyzer of the equal polymerization of alkene or ethene and copolymerization monomer copolymerizable of above-mentioned olefin polymerization catalysis.Preferably, described comonomer can be C
3-C
20Alpha-olefin; More preferably, described comonomer comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 1,3-dibutene, isoprene, vinylbenzene, vinyl toluene and norbornylene etc.
In the present invention, in the preparation process of Primary Catalysts, in phosphate compound, epoxy alkyl halide compound, organic alcohol compound, magnesium halide, organosilicone compounds and organic solvent system, by adding the Organic Alcohol ether compound, improve magnesium halide and separate out situation, thereby obtain that particle form is spherical in shape, the uniform Primary Catalysts of size distribution.By adding in use promotor, the activity of Primary Catalysts, stability are increased.Catalyst loadings provided by the invention is high, and catalytic activity is high; Resulting polymer bulk density is high, and fine powder is few; Be applicable to slurry polymerization processes, gas-phase polymerization process or polymerization mix technique; And preparation technology is simple, and is low for equipment requirements, and energy consumption is little, and environmental pollution is little.
Description of drawings
Fig. 1 is the size distribution figure of the Primary Catalysts of embodiment 1;
Fig. 2 is the size distribution figure of the Primary Catalysts of Comparative Examples 1;
Fig. 3 is the scanning electron microscope diagram of the Primary Catalysts of embodiment 1;
Fig. 4 is the scanning electron microscope diagram of the Primary Catalysts of Comparative Examples 1.
Embodiment
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.
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 50 ℃, add successively tetraethoxysilane 0.05mL, ethylene glycol monomethyl ether 0.02mL, isothermal reaction 2h.Be cooled to-5 ℃, drip the 15mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 40 ℃, add successively tetraethoxysilane 0.02mL, ethylene glycol monoethyl ether 0.02mL, isothermal reaction 2h.Be cooled to-5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 3
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 1mL, tributyl phosphate 2.5mL, epoxy chloropropane 1.5mL is warming up to 80 ℃ and stirs simultaneously, afterwards isothermal reaction 2h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.01mL, ethylene glycol monobutyl ether 0.01mL, isothermal reaction 2h.Be cooled to-5 ℃, drip the 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 4
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 1.5mL, tributyl phosphate 1.5mL, epoxy chloropropane 1mL is warming up to 85 ℃ and stirs simultaneously, afterwards isothermal reaction 2h.Be cooled to 50 ℃, add successively tetraethoxysilane 0.02mL, ethylene glycol propyl ether 0.04mL, isothermal reaction 2h.Be cooled to 0 ℃, drip the 30mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 85 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 3mL, tributyl phosphate 1.8mL, epoxy chloropropane 1.3mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 ℃, add successively tetraethoxysilane 0.05mL, dihydroxypropane single-ether 0.02mL, isothermal reaction 2h.Be cooled to 0 ℃, drip the 30mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.7mL, tributyl phosphate 1mL, epoxy chloropropane 2mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 2h.Be cooled to 70 ℃, add successively tetraethoxysilane 0.01mL, butyleneglycol list propyl ether 0.02mL, isothermal reaction 2h.Be cooled to 0 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.1mL, tributyl phosphate 2mL, epoxy chloropropane 1mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 45 ℃, add successively tetraethoxysilane 0.03mL, 2-(2-cyclopentyl oxyethyl group) ethanol 0.05mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 8
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2mL, tributyl phosphate 2.5mL, epoxy chloropropane 1.6mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 65 ℃, add successively tetraethoxysilane 0.05mL, 3-(2-cyclohexyl oxyethyl group) propyl alcohol 0.05mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 9
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 1.9mL, tributyl phosphate 3mL, epoxy chloropropane 2mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.02mL, 2-(5-phenyl pentyloxy) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 1.5mL, tributyl phosphate 1mL, epoxy chloropropane 3mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 ℃, add successively tetraethoxysilane 0.01mL, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 11
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.05mL, 2-(3-epoxy ethyl propoxy-) ethanol 0.02mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 12
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy iodopropane 4mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.01mL, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 13
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy bromopropane 1.7mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.03mL, 3-(3-pyridyl propoxy-) propyl alcohol 0.02mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 14
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, propyl alcohol 1.5mL, tributyl phosphate 2mL, epoxy iodopropane 4mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.01mL, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 15
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, butanols 1mL, tributyl phosphate 2mL, epoxy iodopropane 4mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.01mL, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 16
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, propylene glycol 1mL, tributyl phosphate 2mL, epoxy iodopropane 4mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add successively tetraethoxysilane 0.01mL, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 17
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, propyl alcohol 1mL, tributyl phosphate 1mL, epoxy chloropropane 3mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 ℃, add successively tetraethoxysilane 0.01mL, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains mobile wicked, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 18
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, propylene glycol 1mL, tributyl phosphate 1mL, epoxy chloropropane 3mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 ℃, add successively tetraethoxysilane 0.01mL, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Embodiment 19
Present embodiment provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride, toluene 40mL, butanols 1mL, tributyl phosphate 1mL, epoxy chloropropane 3mL is warming up to 90 ℃ and stirs simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 ℃, add successively tetraethoxysilane 0.01mL, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of present embodiment, the two merges in use.
Comparative Examples 1
This Comparative Examples provides a kind of olefin polymerization catalysis, and it prepares by following steps:
In the reactor that process nitrogen was fully replaced, add the 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL.Be warming up to 85 ℃ and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 ℃, add tetraethoxysilane 0.05mL, isothermal reaction 2h.Be cooled to 5 ℃, drip the 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 ℃, isothermal reaction 2h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of normal hexane washing, and drying obtains good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape.Promotor is the AlEt of 2mmol/mL
3Hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of this Comparative Examples, the two merges in use.
Application examples 1
Method and result that the prepared olefin polymerization catalysis catalyzed ethylene polymerization reaction of above-described embodiment 1-19 and Comparative Examples 1 should use-case be provided.This ethylene polymerization may further comprise the steps: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added the Primary Catalysts 20mg of embodiment 1-19 and Comparative Examples 1 in the still successively, dehydration normal hexane 1000mL, promotor AlEt
3Hexane solution 1.2mL (2mmol/mL), be warming up to 80 ℃ after, be filled with hydrogen 0.28MPa, be filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.React complete after, the polymkeric substance for preparing is weighed, calculate catalytic efficiency, catalytic efficiency represents divided by Primary Catalysts consumption (g) with polymer weight (kg); Adopt ICP to detect Primary Catalysts titanium content a; The tap density of polymkeric substance is according to ASTM D 1,895 2003 standard testings; The detection method of polyethylene fine powder content is method of sieving, and as detected object, experimental result is as shown in table 1 less than 200 purpose polyethylene fine powders.
Application examples 2
The method and the result that should use-case provide the prepared olefin polymerization catalysis catalyzed ethylene of above-described embodiment 1-19 and Comparative Examples 1 and 1-hervene copolymer to close reaction.This copolymerization may further comprise the steps: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added the Primary Catalysts 20mg of embodiment 1-19 and Comparative Examples 1 in the still successively, dehydration normal hexane 1000mL, promotor AlEt
3Hexane solution 1.2mL (2mmol/mL), add 30mL 1-hexene.After being warming up to 80 ℃, be filled with hydrogen 0.28MPa, be filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.The method of calculation of catalytic efficiency are with application examples 1, and experimental result is as shown in table 1.
As shown in table 1, the charge capacity of the catalyzer that embodiment provides and catalytic activity are higher than the catalyzer that Comparative Examples 1 provides; The prepared polyethylene tap density of the catalyzer that embodiment provides is high, and fine powder is few, and the prepared polymer bulk density of the catalyzer that Comparative Examples 1 provides is low, and fine powder is more.As depicted in figs. 1 and 2, the size distribution of the Primary Catalysts that provides of embodiment 1 is more even compared to the Primary Catalysts of Comparative Examples 1; As shown in Figure 3 and Figure 4, the particle form of the Primary Catalysts that embodiment 1 provides is spherical in shape, and the particle form of the Primary Catalysts of Comparative Examples 1 is irregular.Hence one can see that, and embodiment can improve magnesium halide and separate out situation by adding the Organic Alcohol ether compound, thereby obtain that particle form is spherical in shape, the uniform Primary Catalysts of size distribution; Add in use promotor, the activity of Primary Catalysts, stability are increased.
Table 1
Claims (15)
1. olefin polymerization catalysis, it comprises Primary Catalysts and promotor;
Wherein, the raw material of described Primary Catalysts is comprised of magnesium halide, transition metal halide, organic alcohol compound, phosphate compound, epoxy haloalkane compound, organosilicone compounds and Organic Alcohol ether compound;
The mol ratio of described magnesium halide, described transition metal halide, described organic alcohol compound, described phosphate compounds, described epoxy halo alkanes compound, described organosilicone compounds is 1: (1-30): (1-5): (0.1-10): (1-20): (0.001-0.4);
The mass ratio of described magnesium halide and described Organic Alcohol ether compound is 1: (0.001-0.2);
Described promotor includes one or more the combination in the machine aluminium compound;
The mol ratio of the transition metal halide in described promotor and the described Primary Catalysts is (30-500): 1;
Described magnesium halide comprises formula M g (R
1)
aX
1 bShown in one or more combination in the compound, in the formula, R
1Be C
1-C
20Aliphatic group, C
1-C
20Fatty alkoxyl group, C
3-C
20Alicyclic radical or C
6-C
20Aryl radical, X
1Be halogen, a be 0 or 1, b be 1 or 2, and a+b=2;
Described transition metal halide comprises formula M (R
2)
4-mX
2 mShown in one or more combination in the compound, in the formula, M is Ti, Zr, Hf, Fe, Co or Ni, X
2Be Cl, Br or F, m is 1 to 4 integer, and R is C
1-C
20Aliphatic group, C
1-C
20Fatty alkoxyl group, C
5-C
20Cyclopentadienyl and derivative, C
6-C
20Aryl radical, COR ' or COOR ', wherein, R ' is C
1-C
10Aliphatic group or C
6-C
10Aryl radical;
Described phosphate compounds comprises general formula (R
3O)
3The combination of one or more shown in the PO in the compound, in the formula, R
3Be C
1-C
20Aliphatic group, C
3-C
20Alicyclic radical or C
6-C
20Aryl radical;
Described epoxy halogen alkyl compound comprises general formula C
nH
(2n-1)OX
3Shown in one or more combination in the compound, in the formula, n is the integer of 3-20, X
3Be halogen;
Described organosilicone compounds comprises general formula R
c 4X
d 4Si (OR
5)
eShown in one or more combination in the compound, in the formula, R
4Be alkyl, X
4Be halogen, R
5Be alkyl, c, d and e are integer, and 0≤c＜2,0≤d＜2,0＜e≤4, and c+d+e=4;
Described Organic Alcohol ether compound comprises general formula HO (CH
2)
fO (CH
2)
gR
6Shown in one or more combination in the compound, in the formula, f is 1 to 20 integer, g is 1 to 10 integer, R
6Be aliphatic group, cycloalkyl or aryl radical, wherein, described aliphatic group is general formula C
hH
2h+1, C
hH
2h-1Or C
hH
2h-3Shown in a kind of in the group, 1≤h＜30 and h are integer, described cycloalkyl and described aryl radical are respectively general formula C
iH
2i-1, C
iH
2i-3, C
iH
2i-5Or C
iH
2i-7Shown in a kind of in the group, 3≤i＜30 and i are integer.
2. olefin polymerization catalysis according to claim 1, wherein, described magnesium halide comprises one or more the combination 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 and the butyl magnesium chloride.
3. olefin polymerization catalysis according to claim 1, wherein, described transition metal halide comprises one or more the combination 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 and trichlorine one phenoxide titanium.
4. olefin polymerization catalysis according to claim 1, wherein, described organic alcohol compound comprises C
1-C
15Straight-chain alkyl alcohol, C
1-C
15Branched alkyl alcohol, C
1-C
15Cycloalkyl alcohol, C
1-C
15The pure and mild C of isomery
6-C
20Aromatic alcohol in one or more combination.
5. olefin polymerization catalysis according to claim 4, wherein, described organic alcohol compound comprises one or more the combination in ethanol, ethylene glycol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 1,3-PD, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, sorbyl alcohol, hexalin, methyl-cyclohexanol, benzylalcohol, xylyl alcohol and the Isobutyl Benzyl Carbinol.
6. olefin polymerization catalysis according to claim 1, wherein, described phosphate compound comprises one or more the combination in tributyl phosphate, tri hexyl phosphate, trioctyl phosphate and the TNPP tri n pentyl phosphate.
7. olefin polymerization catalysis according to claim 1, wherein, described epoxy haloalkane compound comprises one or more the combination in epoxy chloropropane, epoxy chlorobutane, epoxy chloropentane, epoxy iodopropane, epoxy butyl iodide, epoxy iodopentane, epoxy bromopropane and the epoxy n-butyl bromide.
8. olefin polymerization catalysis according to claim 1, wherein, described organosilicone compounds comprises 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, 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, the combination of one or more in two cyclopentyl-methyl methoxy silane and the cyclopentyl dimethyl methyl TMOS.
9. olefin polymerization catalysis according to claim 1, wherein, described Organic Alcohol ether compound comprises ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol propyl ether, dihydroxypropane single-ether, butyleneglycol list propyl ether, 2-(2-cyclopentyl oxyethyl group) ethanol, 3-(2-cyclohexyl oxyethyl group) propyl alcohol, 2-(5-phenyl pentyloxy) ethanol, 4-(3-(naphthyl) propoxy-) butanols, 2-(3-epoxy ethyl propoxy-) ethanol, the combination of one or more in 2-(2-furyl oxyethyl group) ethanol and 3-(the 3-pyridyl propoxy-) propyl alcohol.
10. olefin polymerization catalysis according to claim 1, wherein, described promotor comprises one or more the combination in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride and the methylaluminoxane.
11. the preparation method of each described olefin polymerization catalysis of claim 1-10, it may further comprise the steps:
Magnesium halide is scattered in the organic solvent, adds successively organic alcohol compound, phosphate compounds and epoxy halogen alkyl compound, then at 30-100 ℃ of lower stirring and dissolving, afterwards isothermal reaction 1-5h;
Under 10-70 ℃ of agitation condition, add successively organosilicone compounds and Organic Alcohol ether compound, then isothermal reaction 0.5-3h;
Under-30 ℃ to 30 ℃ agitation conditions, drip the metal halide compound, drip and finish rear isothermal reaction 0.5-5h;
Be warming up to 20-100 ℃, isothermal reaction 0.5-5h then, in this process, solid particulate is separated out gradually;
With normal hexane washed product 4-6 time, remove by filter unreacted reactant, then vacuum-drying obtains Primary Catalysts;
Described promotor includes one or more the combination in the machine aluminium compound;
Described Primary Catalysts separates with described promotor to be deposited, and merges in use.
12. preparation method according to claim 11, wherein, described organic solvent comprises C
5-C
15Stable hydrocarbon, C
5-C
10Alicyclic hydrocarbon, C
6-C
15Aromatic hydrocarbon and C
2-C
10The saturated heterocyclic hydrocarbon in one or more combination.
13. each described olefin polymerization catalysis of claim 1-10 is as the application of the catalyzer of the equal polymerization of alkene or ethene and copolymerization monomer copolymerizable.
14. application according to claim 13, wherein, described comonomer is C
3-C
20Alpha-olefin.
15. application according to claim 14, wherein, described comonomer comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 1,3-dibutene, isoprene, vinylbenzene, vinyl toluene and norbornylene.
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