CN105440177B - Catalyst component for olefin polymerization and preparation method thereof and olefin polymerization catalysis and its application - Google Patents
Catalyst component for olefin polymerization and preparation method thereof and olefin polymerization catalysis and its application Download PDFInfo
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- CN105440177B CN105440177B CN201410404254.XA CN201410404254A CN105440177B CN 105440177 B CN105440177 B CN 105440177B CN 201410404254 A CN201410404254 A CN 201410404254A CN 105440177 B CN105440177 B CN 105440177B
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- electron donor
- internal electron
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- donor compound
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 103
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 182
- -1 glycol ester compounds Chemical class 0.000 claims abstract description 72
- 230000003197 catalytic effect Effects 0.000 claims abstract description 57
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 32
- 239000011777 magnesium Substances 0.000 claims abstract description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 235000013849 propane Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 4
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical class CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 3
- QGUNIPCNTNBTOZ-UHFFFAOYSA-N 9,9-dimethoxy-1-methylfluorene Chemical class C1=CC(C)=C2C(OC)(OC)C3=CC=CC=C3C2=C1 QGUNIPCNTNBTOZ-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- CFTPMYRYBGHONP-UHFFFAOYSA-N 1,3-dimethoxyoctane Chemical class CCCCCC(OC)CCOC CFTPMYRYBGHONP-UHFFFAOYSA-N 0.000 claims description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 2
- ASFLIXVTLOHGHE-UHFFFAOYSA-N 5-benzoyloxyheptan-3-yl benzoate Chemical class C=1C=CC=CC=1C(=O)OC(CC)CC(CC)OC(=O)C1=CC=CC=C1 ASFLIXVTLOHGHE-UHFFFAOYSA-N 0.000 claims 1
- 230000037048 polymerization activity Effects 0.000 abstract description 22
- 229920000098 polyolefin Polymers 0.000 abstract description 9
- 238000000034 method Methods 0.000 description 64
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 25
- 239000002956 ash Substances 0.000 description 25
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 19
- 239000004743 Polypropylene Substances 0.000 description 17
- 229920001155 polypropylene Polymers 0.000 description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- 235000011147 magnesium chloride Nutrition 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 10
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical class COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000010210 aluminium Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 7
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 3
- 229910001623 magnesium bromide Inorganic materials 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 229910001641 magnesium iodide Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NOWCPSTWMDNKTI-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylcyclohexane Chemical class COCC(COC)C1CCCCC1 NOWCPSTWMDNKTI-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LXDLZEOLVBFSIH-UHFFFAOYSA-N 2,4-dimethylheptane-3,5-diol Chemical class CCC(O)C(C)C(O)C(C)C LXDLZEOLVBFSIH-UHFFFAOYSA-N 0.000 description 2
- AUGLSFONVIKZLA-UHFFFAOYSA-N 2-methylheptane-3,5-diol Chemical class CCC(O)CC(O)C(C)C AUGLSFONVIKZLA-UHFFFAOYSA-N 0.000 description 2
- FCJQIBTXXFQMRP-UHFFFAOYSA-N 3,4-dimethylheptane-3,5-diol Chemical class CCC(O)C(C)C(C)(O)CC FCJQIBTXXFQMRP-UHFFFAOYSA-N 0.000 description 2
- WGWYVCDLCIIIEK-UHFFFAOYSA-N 3-ethyl-4-methylheptane-3,5-diol Chemical class CCC(O)C(C)C(O)(CC)CC WGWYVCDLCIIIEK-UHFFFAOYSA-N 0.000 description 2
- AREOBENUACTGHH-UHFFFAOYSA-N 3-methylheptane-3,5-diol Chemical class CCC(O)CC(C)(O)CC AREOBENUACTGHH-UHFFFAOYSA-N 0.000 description 2
- SPYJMVVDPTYGPQ-UHFFFAOYSA-N 4,4-dimethylheptane-3,5-diol Chemical class CCC(O)C(C)(C)C(O)CC SPYJMVVDPTYGPQ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 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
- 239000002826 coolant Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- BQWORYKVVNTRAW-UHFFFAOYSA-N heptane-3,5-diol Chemical class CCC(O)CC(O)CC BQWORYKVVNTRAW-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002680 magnesium Chemical class 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000003136 n-heptyl 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])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 150000003961 organosilicon 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
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- NOAIBMQZUGBONL-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)benzene Chemical class COCC(C)(COC)C1=CC=CC=C1 NOAIBMQZUGBONL-UHFFFAOYSA-N 0.000 description 1
- HBMODDNTUPGVFW-UHFFFAOYSA-N (1,3-dimethoxy-2-phenylpropan-2-yl)benzene Chemical class C=1C=CC=CC=1C(COC)(COC)C1=CC=CC=C1 HBMODDNTUPGVFW-UHFFFAOYSA-N 0.000 description 1
- UQPREOUZEIKSCT-UHFFFAOYSA-N (2-cyclohexyl-1,3-dimethoxybutan-2-yl)cyclohexane Chemical class C1CCCCC1C(C(C)OC)(COC)C1CCCCC1 UQPREOUZEIKSCT-UHFFFAOYSA-N 0.000 description 1
- MEPSBRTXOHFWCF-UHFFFAOYSA-N (2-cyclohexyl-1,3-dimethoxypropan-2-yl)cyclohexane Chemical class C1CCCCC1C(COC)(COC)C1CCCCC1 MEPSBRTXOHFWCF-UHFFFAOYSA-N 0.000 description 1
- DYJIIMFHSZKBDY-UHFFFAOYSA-N (3-benzoyloxy-2,2-dimethylpropyl) benzoate Chemical class C=1C=CC=CC=1C(=O)OCC(C)(C)COC(=O)C1=CC=CC=C1 DYJIIMFHSZKBDY-UHFFFAOYSA-N 0.000 description 1
- CFMYNHGXOMKGNH-UHFFFAOYSA-N (5-benzoyloxy-3,5-dimethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)(CC)CC(C)(CC)OC(=O)C1=CC=CC=C1 CFMYNHGXOMKGNH-UHFFFAOYSA-N 0.000 description 1
- FUAJDGBYYQBUPU-UHFFFAOYSA-N (5-benzoyloxy-5-ethyl-4-methyloctan-3-yl) benzoate Chemical class C=1C=CC=CC=1C(=O)OC(CC)C(C)C(CC)(CCC)OC(=O)C1=CC=CC=C1 FUAJDGBYYQBUPU-UHFFFAOYSA-N 0.000 description 1
- CELOJHLXFPSJPH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylbenzene Chemical class COCC(COC)C1=CC=CC=C1 CELOJHLXFPSJPH-UHFFFAOYSA-N 0.000 description 1
- HPFWUWXYBFOJAD-UHFFFAOYSA-N 1-chloro-4-(1,3-dimethoxypropan-2-yl)benzene Chemical compound COCC(COC)C1=CC=C(Cl)C=C1 HPFWUWXYBFOJAD-UHFFFAOYSA-N 0.000 description 1
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical class COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 description 1
- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical class COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 description 1
- PPHMKLXXVBJEHR-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)hexane Chemical class CCCCC(COC)COC PPHMKLXXVBJEHR-UHFFFAOYSA-N 0.000 description 1
- YELMYILCQYAKNF-UHFFFAOYSA-N 2,2-dimethylheptane-3,5-diol Chemical class CCC(O)CC(O)C(C)(C)C YELMYILCQYAKNF-UHFFFAOYSA-N 0.000 description 1
- QHDADHHODABHLK-UHFFFAOYSA-N 2,2-dimethylpentane-1,3-diol Chemical class CCC(O)C(C)(C)CO QHDADHHODABHLK-UHFFFAOYSA-N 0.000 description 1
- BGPXIJMCQMCQDU-UHFFFAOYSA-N 2,3-dimethylheptane-3,5-diol Chemical class CCC(O)CC(C)(O)C(C)C BGPXIJMCQMCQDU-UHFFFAOYSA-N 0.000 description 1
- ZEZQEANYDTVVNB-UHFFFAOYSA-N 2,5-dimethylheptane-3,5-diol Chemical class CCC(C)(O)CC(O)C(C)C ZEZQEANYDTVVNB-UHFFFAOYSA-N 0.000 description 1
- CPHZAYIWNZNICS-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-diol Chemical class CC(C)C(O)CC(O)C(C)C CPHZAYIWNZNICS-UHFFFAOYSA-N 0.000 description 1
- QCCJUUZWWCHCPY-UHFFFAOYSA-N 2-(benzoyloxymethyl)butyl benzoate Chemical class C=1C=CC=CC=1C(=O)OCC(CC)COC(=O)C1=CC=CC=C1 QCCJUUZWWCHCPY-UHFFFAOYSA-N 0.000 description 1
- AYHZIFGWOPQPID-UHFFFAOYSA-N 2-(benzoyloxymethyl)hexyl benzoate Chemical class C=1C=CC=CC=1C(=O)OCC(CCCC)COC(=O)C1=CC=CC=C1 AYHZIFGWOPQPID-UHFFFAOYSA-N 0.000 description 1
- CMFPYSAYYUSFQC-UHFFFAOYSA-N 2-ethylpentane-1,3-diol Chemical class CCC(O)C(CC)CO CMFPYSAYYUSFQC-UHFFFAOYSA-N 0.000 description 1
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical group CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 1
- HSWPDAWSEQBNHF-UHFFFAOYSA-N 2-methyl-4-propylheptane-3,5-diol Chemical class CCCC(C(O)CC)C(O)C(C)C HSWPDAWSEQBNHF-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical class OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 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
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 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
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a kind of catalyst component for olefin polymerization and preparation method thereof and olefin polymerization catalysis and its application.The catalytic component contains the reaction product of following components：(i) magnesium-containing compound；(ii) titanium-containing compound；And (iii) internal electron donor；Wherein, the internal electron donor is the combination of internal electron donor compound a, internal electron donor compound b and internal electron donor compound c, the internal electron donor compound a is glycol ester compounds shown in formula I, the internal electron donor compound b is diether compound shown in formula II, and the internal electron donor compound c is alkylene oxides compound shown in formula III.When the catalyst component for olefin polymerization of the present invention is used for olefinic polymerization, with the vertical structure directionality of height, polymerization activity is higher simultaneously, and can obtain the olefin polymer of high isotactic index and low ash content in the case where not using or using minimal amount of external electron donor.
Description
Technical field
The present invention relates to a kind of catalyst component for olefin polymerization and preparation method thereof and olefin polymerization catalysis and its application.
Background technology
It is well known that using magnesium, titanium, halogen and electron donor compound as the solid Titanium series catalyst component of basis,
For olefinic polyreaction, especially there is higher polymerization activity and vertical structure directionality in propylene polymerization.Wherein, electron
Body compound is one of essential ingredient in catalytic component, isotactic index, molecular weight to polymerization activity, polymer
Conclusive effect is played with important indicators such as molecular weight distributions.With the development of internal electron donor compound, catalyzed polyolefin
Agent is continuously updated the replacement.
There is different characteristics using the catalyst containing different internal electron donors, for example, some catalyst are with higher
Polymerization activity, there is some catalyst preferable hydrogen response, the vistanexes of some catalyst preparations to have wider
Molecular weight distribution etc..And in the industrial production of polyolefin, the highly desirable catalyst with excellent comprehensive performance, especially
It is the also catalyst with high directionality while with high activity, high hydrogen response.
The vertical structure directionality of catalyst decides the isotactic index of polymer, and isotactic index is one of polymer important
Performance indicator, polyacrylic isotactic index is higher, and alignment degree, crystallinity are also higher, the hardness of product, rigidity, modulus,
The mechanical performances such as fracture and yield strength all increased, and fusing point, thermal stability, resistance to ag(e)ing and resistance to width are penetrated performance and also accordingly carried
It is high.Therefore, in order to improve the vertical structure directionality of catalyst, researchers are carrying out always a large amount of research work.Some grind
The middle catalyst using two kinds of (or two or more) internal electron donors containing compounding is studied carefully to make up containing single interior electron
The deficiency of the performance of the catalyst of body, to improve the performance of catalyst.But the effect of compounding is not several electron donors
The simple superposition of performance.For example, it is generally low using monocarboxylic esters as the polypropylene isotacticity obtained by the catalyst of internal electron donor,
Product need to take off random object.And WO03002617 is disclosed and a kind of being used cooperatively obtained use with monocarboxylic esters and dicarboxylic esters
It is good in the hydrogen response of the catalytic component and catalyst of olefinic polymerization, the catalyst, but stereoselectivity and polymerization activity
Still it is not very high.
Diol-lipid compound and two ethers are used in catalytic component and catalyst disclosed in CN101724102A
Closing object compounding is used as internal electron donor, the catalyst containing the internal electron donor to be used for the polymerization work with superelevation when olefinic polymerization
Property and higher vertical structure directionality.Compared with similar catalyst, the active and vertical structure directionality of the catalyst is in higher
It is horizontal.Therefore, if further increasing the vertical structure directionality of olefin polymerization catalysis on this basis, be it is particularly valuable, this
It is very favorable for producing some polypropylene with high isotactic.
Therefore, a kind of catalyst of high comprehensive performance is developed, i.e., is had while keeping high activity higher vertical
Structure directionality so that olefin polymer have the catalyst of higher isotactic index and lower content of ashes be still one there is an urgent need for
It solves the problems, such as.
Invention content
The purpose of the present invention overcomes the drawbacks described above of olefin polymerization catalysis in the prior art and provides a kind of olefinic polymerization
Catalytic component and preparation method thereof and olefin polymerization catalysis and its application.
The present inventor has been surprisingly found that in the course of the research, makees using diol-lipid compound and diether compound compounding
For the alkylene oxides compound for being added a small amount of on the basis of internal electron donor, olefin polymerization catalysis can be made to keep high polymerization
Under the premise of active, vertical structure directionality is further improved.Thus, prepare olefin polymer using the catalytic component
When, the alkene of high isotactic index and low ash content can be obtained in the case where not using or using minimal amount of external electron donor
Hydrocarbon polymer.
The present invention provides a kind of catalyst component for olefin polymerization, which contains the reaction product of following components：
(i) magnesium-containing compound；
(ii) titanium-containing compound；And
(iii) internal electron donor；
Wherein, the internal electron donor is internal electron donor compound a, internal electron donor compound b and internal electron donor
The combination of compound c, the internal electron donor compound a are glycol ester compounds shown in formula I, the internal electron donor chemical combination
Object b is diether compound shown in formula II, and the internal electron donor compound c is alkylene oxides compound shown in formula III,
In formula I, R1And R2It is identical or different, it is each independently C1-C10Linear or branched alkyl group, C3-C20Substitution or
Unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20's
One kind in substituted or unsubstituted alkaryl, aromatic ring in the aryl, aralkyl or alkaryl optionally by selected from halogen,
C1-C6Linear or branched alkyl group and C1-C6Alkoxy in one or more substitutions；
R3、R4、R5、R6And R1-R2nIt is identical or different, it is each independently hydrogen, halogen, C1-C20Linear chain or branched chain alkane
Base, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substitution or unsubstituted
Alkaryl, C7-C20Substituted or unsubstituted aralkyl, C2-C10Linear chain or branched chain alkylene and C10-C20Condensed ring virtue
One kind in base, R3、R4、R5、R6And R1-R2nOptionally contain hetero atom, the hetero atom is nitrogen, oxygen, sulphur, silicon, halogen and phosphorus
In it is one or more；
Alternatively, R3、R4、R5、R6And R1-R2nIn two or more be mutually bonded, to form ring；
N is the integer of 0-10；
In formula II, R '1、R’2、R’3、R’4、R’5And R '6It is identical or different, it is each independently hydrogen, halogen, C1-C20It is straight
Chain or branched alkyl, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Take
Generation or unsubstituted aralkyl and C7-C20Substituted or unsubstituted alkaryl in one kind；
R’7And R '8It is identical or different, it is each independently C1-C20Linear or branched alkyl group, C3-C20Substitution or do not take
The naphthenic base in generation, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20Substitution
Or one kind in unsubstituted alkaryl；
Alternatively, R '1、R’2、R’3、R’4、R’5And R '6In two or more be mutually bonded, to form ring；
In formula III, R "1And R "2It is identical or different, it is each independently hydrogen, C1-C5Linear or branched alkyl group or halogenated
Alkyl.
The present invention also provides a kind of preparation method of above-mentioned catalyst component for olefin polymerization, this method includes containing above-mentioned
Magnesium carrier is reacted with the titanium compound, and before and after, during the magnesium-containing carrier is reacted with the titanium compound
The internal electron donor is added in one or more periods.
In addition, the present invention also provides a kind of olefin polymerization catalysis, which contains：
(1) above-mentioned catalyst component for olefin polymerization；
(2) as the alkyl aluminum compound of co-catalyst；And
(3) optionally, external donor compound.
The present invention also provides application of the above-mentioned olefin polymerization catalysis in olefinic polyreaction.
The catalyst component for olefin polymerization of the present invention is by using glycol ester compounds, diether compound and alkylene oxides
Compound compounding is used as internal electron donor component, when it being made to be used for olefinic polymerization, has high vertical structure directionality, while polymerizeing work
Property is higher, and can obtain high isotactic index and low ash content in the case where not using or using minimal amount of external electron donor
The olefin polymer of content.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of catalyst component for olefin polymerization, which contains the reaction product of following components：
(i) magnesium-containing compound；
(ii) titanium-containing compound；And
(iii) internal electron donor；
Wherein, the internal electron donor is internal electron donor compound a, internal electron donor compound b and internal electron donor
The combination of compound c.
According to the present invention, the internal electron donor compound a is glycol ester compounds shown in formula I,
In formula I, R1And R2It is identical or different, it is each independently C1-C10Linear or branched alkyl group, C3-C20Substitution or
Unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20's
One kind in substituted or unsubstituted alkaryl, aromatic ring in the aryl, aralkyl or alkaryl optionally by selected from halogen,
C1-C6Linear or branched alkyl group and C1-C6Alkoxy in one or more substitutions；In formula I, the content of bracket " [] "
Indicate that key connects n carbon atom successively, and each carbon atom also connects with 2 substituent group keys, i.e., n carbon atom is shared in bracket
And R1、R2、R3…R2nEqual 2n substituent group.
R3、R4、R5、R6And R1-R2nIt is identical or different, it is each independently hydrogen, halogen, C1-C20Linear chain or branched chain alkane
Base, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substitution or unsubstituted
Alkaryl, C7-C20Substituted or unsubstituted aralkyl, C2-C10Linear chain or branched chain alkylene and C10-C20Condensed ring virtue
One kind in base, R3、R4、R5、R6And R1-R2nOptionally contain hetero atom, the hetero atom is nitrogen, oxygen, sulphur, silicon, halogen and phosphorus
In it is one or more；
Alternatively, R3、R4、R5、R6And R1-R2nIn two or more be mutually bonded, with formed saturation or it is unsaturated
Ring；
N is the integer of 0-10, as n=0, in glycol ester compounds shown in formula I, and substituent group R3、R4Carbon atom it is straight
It is R to connect with substituent group5、R6Carbon atom bonding connect；
In the present invention, C1-C20The example of linear or branched alkyl group can include but is not limited to：Methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, 1- ethyl propyls, 2- methyl butyls, 3- methyl fourths
Base, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls, n-heptyl, 2- methylhexyls,
3- methylhexyls, 4- methylhexyls, 5- methylhexyls, n-heptyl, n-octyl, n-nonyl, positive decyl, tetrahydrochysene geranyl, positive ten
Dialkyl group, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-octadecane base, NSC 77136 base and just
Eicosyl.
In the present invention, C3-C20The example of substituted or unsubstituted naphthenic base can include but is not limited to：Cyclopropyl, ring
Butyl, cyclopenta, cyclohexyl, 4- methylcyclohexyls, 4- ethylcyclohexyls, 4- n-propyls cyclohexyl, 4- normal-butyls cyclohexyl, ring
Undecyl and cyclo-dodecyl.
In the present invention, C6-C20The example of substituted or unsubstituted aryl can include but is not limited to：Phenyl, methylbenzene
Base, ethylphenyl, 4- tert-butyl-phenyls etc..
In the present invention, C7-C20Substituted or unsubstituted aralkyl refer to carbon atom number be that 7-20 taking with aryl
The alkyl group of Dai Ji.C7-C20The example of substituted or unsubstituted aralkyl can include but is not limited to：3- phenyl propyls,
Benzyl etc..
In the present invention, C7-C20Substituted or unsubstituted alkaryl refer to carbon atom number be that 7-20 taking with alkyl
The aryl group of Dai Ji.C7-C20The example of substituted or unsubstituted alkaryl can include but is not limited to：Aminomethyl phenyl, second
Base phenyl etc..
In the present invention, C1-C6The example of alkoxy can include but is not limited to：Methoxyl group, ethyoxyl, positive propoxy,
Isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy and own oxygen
Base.
In the present invention, C2-C10The example of linear chain or branched chain alkylene can include but is not limited to：Vinyl, propylene
Base, cyclobutenyl, pentenyl, octenyl etc..
In the present invention, C10-C20The example of fused ring aryl can include but is not limited to：Naphthalene, anthryl, phenanthryl, pyrenyl
Deng.
According to the present invention, the example of the internal electron donor compound a can include but is not limited to：1,3- propylene glycol hexichol
Formic acid esters, 2- methyl-1,3-propanediols dibenzoate, 2- ethyl -1,3- propylene glycol dibenzoates, 2- propyl -1,3- third
Bisbenzoate, 2- butyl -1,3- propylene glycol dibenzoates, 2,2- dimethyl -1,3- propylene glycol dibenzoates, 2-
Ethyl -2- butyl -1,3- propylene glycol dibenzoates, 2,2- diethyl -1,3- propylene glycol dibenzoates, 2- methyl -2- third
Base -1,3- propylene glycol dibenzoates, 2- isopropyl -2- isopentyl -1,3- propylene glycol dibenzoates, 2,4-PD hexichol
Formic acid esters, 3- methyl -2,4-PD dibenzoate, 3- ethyls -2,4-PD dibenzoate, 3- propyl -2,4- penta
Bisbenzoate, 3- butyl -2,4-PD dibenzoate, 3,3- dimethyl -2,4-PD dibenzoate, 2-
Methyl-1,3- glycol dibenzoates, 2,2- dimethyl -1,3- glycol dibenzoates, 2- ethyl -1,3- pentanediols two
Benzoic ether, 2- butyl -1,3- glycol dibenzoates, 2- methyl-1s, 3- glycol dibenzoates, 2- ethyls -1,3-
Glycol dibenzoate, 2- propyl -1,3- glycol dibenzoates, 2- butyl -1,3- glycol dibenzoates, 2,2-
Dimethyl -1,3- glycol dibenzoates, 2- methyl-1s, 3- glycol dibenzoates, 2,2- dimethyl -1,3- pentanediols
Dibenzoate, 2- ethyl -1,3- glycol dibenzoates, 2- butyl -1,3- glycol dibenzoates, 2,2,4- front threes
Base -1,3- glycol dibenzoates, 3- methyl -3- butyl -2,4-PD dibenzoate, 2,2- dimethyl -1,5- penta
Bisbenzoate, 1,6-HD dibenzoate, 6- heptene -2,4- heptandiols dibenzoate, 2- methyl -6- heptan
Alkene -2,4- heptandiols dibenzoate, 3- methyl -6- heptene -2,4- heptandiols dibenzoate, 4- methyl -6- heptene -2,4-
Heptandiol dibenzoate, 5- methyl -6- heptene -2,4- heptandiols dibenzoate, 6- methyl -6- heptene -2,4- heptandiols
Dibenzoate, 3- ethyl -6- heptene -2,4- heptandiols dibenzoate, 4- ethyl -6- heptene -2,4- heptandiol hexichol first
Acid esters, 5- ethyl -6- heptene -2,4- heptandiols dibenzoate, 6- ethyl -6- heptene -2,4- heptandiols dibenzoate, 3-
Propyl -6- heptene -2,4- heptandiols dibenzoate, 4- propyl -6- heptene -2,4- heptandiols dibenzoate, 5- propyl -6-
Heptene -2,4- heptandiols dibenzoate, 6- propyl -6- heptene -2,4- heptandiols dibenzoate, heptene -2 3- butyl -6-,
4- heptandiols dibenzoate, 4- butyl -6- heptene -2,4- heptandiols dibenzoate, 5- butyl -6- heptene -2,4- heptan two
Alcohol dibenzoate, 6- butyl -6- heptene -2,4- heptandiols dibenzoate, 3,5- dimethyl -6- heptene -2,4- heptandiols
Dibenzoate, 3,5- diethyl -6- heptene -2,4- heptandiols dibenzoate, 3,5- dipropyl -6- heptene -2,4- heptan two
Alcohol dibenzoate, 3,5- dibutyl -6- heptene -2,4- heptandiols dibenzoate, 3,3- dimethyl -6- heptene -2,4- heptan
Bisbenzoate, 3,3- diethyl -6- heptene -2,4- heptandiols dibenzoate, 3,3- dipropyl -6- heptene -2,4-
Heptandiol dibenzoate, 3,3- dibutyl -6- heptene -2,4- heptandiols dibenzoate, 3,5- heptandiols dibenzoate,
2- methyl -3,5- heptandiols dibenzoate, 3- methyl -3,5- heptandiols dibenzoate, 4- methyl -3,5- heptandiol hexichol
Formic acid esters, 5- methyl -3,5- heptandiols dibenzoate, 6- methyl -3,5- heptandiols dibenzoate, 3- ethyls -3,5- heptan
Bisbenzoate, 4- ethyl -3,5- heptandiols dibenzoate, 5- ethyl -3,5- heptandiols dibenzoate, 3- third
Base -3,5- heptandiols dibenzoate, 4- propyl -3,5- heptandiols dibenzoate, 3- butyl -3,5- heptandiol dibenzoic acids
Ester, 2,3- dimethyl -3,5- heptandiols dibenzoate, 2,4- dimethyl -3,5- heptandiols dibenzoate, 2,5- diformazans
Base -3,5- heptandiols dibenzoate, 2,6- dimethyl -3,5- heptandiols dibenzoate, 3,3- dimethyl -3,5- heptandiols
Dibenzoate, 4,4- dimethyl -3,5- heptandiols dibenzoate, 6,6- dimethyl -3,5- heptandiols dibenzoate, 2,
6- dimethyl -3,5- heptandiols dibenzoate, 3,4- dimethyl -3,5- heptandiols dibenzoate, 3,5- dimethyl -3,5-
Heptandiol dibenzoate, 3,6- dimethyl -3,5- heptandiols dibenzoate, 4,5- dimethyl -3,5- heptandiol hexichol first
Acid esters, 4,6- dimethyl -3,5- heptandiols dibenzoate, 4,4- dimethyl -3,5- heptandiols dibenzoate, 6,6- diformazans
Base -3,5- heptandiols dibenzoate, 2- methyl -3- ethyl -3,5- heptandiols dibenzoate, 2- methyl -4- ethyls -3,5-
Heptandiol dibenzoate, 2- methyl -5- ethyl -3,5- heptandiols dibenzoate, 3- methyl -3- ethyl -3,5- heptandiols
Dibenzoate, 3- methyl -4- ethyl -3,5- heptandiols dibenzoate, 3- methyl -5- ethyl -3,5- heptandiol hexichol first
Acid esters, 4- methyl -3- ethyl -3,5- heptandiols dibenzoate, 4- methyl -4- ethyl -3,5- heptandiols dibenzoate, 4-
Methyl -5- ethyl -3,5- heptandiols dibenzoate, 2- methyl -3- propyl -3,5- heptandiols dibenzoate, 2- methyl -4-
Propyl -3,5- heptandiols dibenzoate, 2- methyl -5- propyl -3,5- heptandiols dibenzoate, propyl -3 3- methyl -3-,
5- heptandiols dibenzoate, 3- methyl -4- propyl -3,5- heptandiols dibenzoate, 3- methyl -5- propyl -3,5- heptan two
Alcohol dibenzoate, 4- methyl -3- propyl -3,5- heptandiols dibenzoate, 4- methyl -4- propyl -3,5- heptandiol hexichol
Formic acid esters, 4- methyl -5- propyl -3,5- heptandiol dibenzoates etc..
Under preferable case, the internal electron donor compound a is glycol ester compounds shown in formula IV,
In formula IV, R7、R8、R9、R10、R11And R12It is identical or different, it is each independently hydrogen or C1-C20Linear chain or branched chain
Alkyl.
Under most preferred case, the internal electron donor compound a is 2,4- glycol dibenzoates and/or 3,5- heptan two
Alcohol dibenzoate.
According to the present invention, the internal electron donor compound b is diether compound shown in formula II,
In formula II, R '1、R’2、R’3、R’4、R’5And R '6It is identical or different, it is each independently hydrogen, halogen, C1-C20It is straight
Chain or branched alkyl, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Take
Generation or unsubstituted aralkyl and C7-C20Substituted or unsubstituted alkaryl in one kind；
R’7And R '8Can be identical or different, and it is each independently C1-C20Linear or branched alkyl group, C3-C20Substitution
Or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20
Substituted or unsubstituted alkaryl in one kind；
Alternatively, R '1、R’2、R’3、R’4、R’5And R '6In two or more be mutually bonded, with formed saturation or not
The ring of saturation.
In the case of preferred, the internal electron donor compound b is 1,3- diether compounds shown in formula V,
In formula V, R '9And R '10Can be identical or different, it is each independently hydrogen, halogen, C1-C18Linear chain or branched chain alkane
Base, C3-C18Substituted or unsubstituted naphthenic base, C6-C18Substituted or unsubstituted aryl and C7-C18Substitution or unsubstituted
Aralkyl in one kind, alternatively, R '9And R '10It is mutually bonded, to form ring；R’11And R '12Can be identical or different, respectively
It independently is C1-C10Linear or branched alkyl group.
According to the present invention, the example of the internal electron donor compound b can include but is not limited to：2- (2- ethyl hexyls
Base) -1,3- dimethoxy propanes, 2- isopropyl -1,3- dimethoxy propanes, 2- butyl -1,3- dimethoxy propanes, 2- Zhong Ding
Base -1,3- dimethoxy propanes, 2- cyclohexyl -1,3- dimethoxy propanes, 2- phenyl -1,3- dimethoxy propanes, 2- (2- benzene
Base ethyl) -1,3- dimethoxy propanes, 2- (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes, 2- (p- chlorphenyl) -1,3-
Dimethoxy propane, 2- (diphenyl methyl) -1,3- dimethoxy propanes, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2,
2- bicyclopentyl -1,3- dimethoxy propanes, 2,2- diethyl -1,3- dimethoxy propanes, 2,2- dipropyl -1,3- dimethoxies
Base propane, 2,2- diisopropyl -1,3- dimethoxy propanes, 2,2- dibutyl -1,3- dimethoxy propanes, 2- methyl -2- third
Base -1,3- dimethoxy propanes, 2- methyl -2- benzyl -1,3- dimethoxy propanes, 2- methyl -2- ethyl -1,3- dimethoxys
Propane, 2- methyl -2- isopropyl -1,3- dimethoxy propanes, 2- methyl -2- phenyl -1,3- dimethoxy propanes, 2- methyl -
Bis- (2- the cyclohexyl-ethyls) -1,3- dimethoxy propanes of 2- cyclohexyl -1,3- dimethoxy propanes, 2,2-, 2- methyl -2- isobutyls
Base -1,3- dimethoxy propanes, 2- methyl -2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2,2- diisobutyls -1,3-
Dimethoxy propane, 2,2- diphenyl -1,3- dimethoxy propanes, 2,2- dibenzyl -1,3- dimethoxy propanes, 2,2- are bis-
(cyclohexyl methyl) -1,3- dimethoxy propanes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, 2- (1- methyl fourths
Base) -2- isopropyl -1,3- dimethoxy propanes, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes, 2- phenyl -2- be different
Propyl -1,3- dimethoxy propanes, 2- phenyl -2- sec-butyl -1,3- dimethoxy propanes, 2- benzyl -2- isopropyls -1,3- two
Methoxy propane, 2- cyclopenta -2- isopropyl -1,3- dimethoxy propanes, 2- cyclopenta -2- sec-butyl 1,3- dimethoxys third
Alkane, 2- cyclohexyl -2- isopropyl -1,3- dimethoxy propanes, 2- cyclohexyl -2- sec-butyl -1,3- dimethoxy propanes, 2- are different
Propyl -2- sec-butyls -1,3- dimethoxy propane, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propanes, 9,9- bis-
Methoxy fluorenes.
Under most preferred case, the internal electron donor compound b is 2- isopropyl -2- isopentyl -1,3- dimethoxy third
Alkane and/or 9,9- dimethoxy-methyl fluorenes.
In the present invention, 1, the 3- diether compounds be referred to CN1020448C, CN100348624C and
Method disclosed in CN1141285A synthesizes.Repeats no more herein.
According to the present invention, the internal electron donor compound c is alkylene oxides compound shown in III,
In formula III, R "1And R "2It is identical or different, it is each independently hydrogen, C1-C5Linear or branched alkyl group or halogenated
Alkyl, it is preferable that R "1And R "2It is identical or different, it is each independently hydrogen, C1-C3Linear or branched alkyl group or alkyl halide
Base, in the case of further preferred, R "1And R "2Can be hydrogen, methyl, ethyl, propyl, chloromethyl, Chloroethyl, chloro third
Base, bromomethyl, bromoethyl or Bromopropyl.
Under most preferred case, the internal electron donor compound c is ethylene oxide, propylene oxide, epoxy butane, epoxy chlorine
It is one or more in propane, epoxy chlorobutane, epoxy bromopropane and epoxy bromobutane.
The present inventor has found in the course of the research, using 2,4- glycol dibenzoates and/or 3,5- heptan two
Alcohol dibenzoate as internal electron donor compound a, using 2- isopropyls -2- isopentyl -1,3- dimethoxy propane and/or
9,9- dimethoxy-methyl fluorenes use ethylene oxide, propylene oxide, epoxy butane, epoxy as internal electron donor compound b
One or more conduct internal electron donor compound c in chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy bromobutane,
By internal electron donor compound a, interior electron compound b and internal electron donor compound c with the use of the olefinic polymerization prepared
When catalytic component is used for olefinic polymerization, there is high vertical structure directionality, while polymerization activity is higher, and can without using
Or the olefin polymer of high isotactic index and low ash content is obtained in the case of using minimal amount of external electron donor.
Catalyst component for olefin polymerization according to the present invention, the present invention be by using internal electron donor compound a, it is interior to
Electron compound b and internal electron donor compound c is applied in combination to be referred to obtain with high isotactic as internal electron donor component
The olefin polymer of number and low ash content, in the case of preferred, in the catalytic component, the internal electron donor compound
A, the molar ratio of the internal electron donor compound b and the internal electron donor compound c dosages is 0.5-10：1-12：1；Into
In the case of one step is preferred, the internal electron donor compound a, the internal electron donor compound b and the internal electron donor
The molar ratio of compound c dosages is 1-7：1.5-10：1.
The present invention's major improvement is that improvement to the internal electron donor in catalyst component for olefin polymerization, in this hair
In bright, using glycol ester compounds shown in formula I as diether compound shown in internal electron donor compound a and formula II as
Internal electron donor compound b and using alkylene oxides compound shown in formula III as internal electron donor compound c, and by three
It is used in combination as internal electron donor so that when the catalytic component is used for olefinic polymerization, there is high vertical structure directionality, simultaneously
Polymerization activity is higher, and can be obtained in the case where not using or using minimal amount of external electron donor high isotactic index and
Low-ash olefin polymer.In the present invention, when preparing the catalytic component, to the magnesium-containing compound, described contain
There is no particular limitation for the molar ratio of titanium compound and the internal electron donor amounts of components, can become in a wider scope
Dynamic, under preferable case, the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor dosage is 1：
10-200：0.04-0.8, in the case of further preferred, the magnesium-containing compound, the titanium-containing compound and the interior electron
The molar ratio of body dosage is 1：20-180：0.05-0.5, further preferably in the case of, the magnesium-containing compound, it is described contain titanizing
The molar ratio for closing object and the internal electron donor dosage is 1：50-120：0.2-0.4.
According to the present invention, the catalytic component is preferably prepared by the following method：By above-mentioned magnesium-containing compound with it is above-mentioned
Titanium-containing compound reacts, and one before and after, during the magnesium-containing compound is reacted with the titanium-containing compound or
The internal electron donor is added in multiple periods.
In the case of, according to the invention it is preferred to, the magnesium-containing compound can be formula VI shown in magnesium-containing compound and/or
The adduct of magnesium-containing compound shown in formula VI,
MgR13R14Formula VI,
In formula VI, R13And R14Can be identical or different, it is each independently halogen, C1-C5Straight or branched alkoxyl
And C1-C5Linear or branched alkyl group in one kind.
In the catalyst component for olefin polymerization of the present invention, the adduct of magnesium-containing compound shown in the formula VI refers to
MgR13R14·fR0OH·gE·hH2O, wherein R0For C1-C18Alkyl, preferably C1-C5Alkyl, more preferably methyl, second
Base, n-propyl and isopropyl；F is the preferably 2-3.5 within the scope of 0.1-6；E is a kind of electron donor compound, should
Electron donor can be well known in the art various Donor compounds, g is within the scope of 0-2；H is in 0-0.7's
Within the scope of.Preferably, in formula VI, R13And R14It is each independently halogen, such as can be one kind in chlorine, bromine and iodine.
In the case of, according to the invention it is preferred to, the magnesium-containing compound can be dimethoxy magnesium, diethoxy magnesium, two
Propoxyl group magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, methoxy magnesium chloride, methoxyl group
Magnesium bromide, methoxyl group magnesium iodide, ethyoxyl magnesium chloride, ethyoxyl magnesium bromide, ethyoxyl magnesium iodide, propoxyl group magnesium chloride, the third oxygen
Base magnesium bromide, propoxyl group magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, magnesium dichloride, dibrominated
Magnesium, magnesium diiodide, the alcohol adducts of magnesium dichloride, the alcohol adducts of dibrominated magnesium and magnesium diiodide alcohol adducts at least
It is a kind of.In the case of further preferably, the magnesium compound is the alcohol adducts of magnesium dichloride, the alcohol adducts of the magnesium dichloride
For spheric granules.
In the present invention, the magnesium-containing compound is prepared for method known in the art, such as is referred to
CN1091748A, CN101050245A, CN101486722A, CN102796132A, CN102796129A and CN102796128A
Disclosed in the preparation method of adduct of magnesium halides carrier prepare.
Usually, the preparation method of the alcohol adducts of the magnesium dichloride of the spherical shape may include：By by magnesium dichloride
With R0OH carries out high shear at a temperature of 90-140 DEG C in a dispersion medium, and obtained reaction product is then placed in temperature
For in -20 DEG C to 0 DEG C of cooling medium, to form spheric granules, washed and drying can be obtained spherical magnesium dichloride
Alcohol adducts, wherein R0For C1-C18Alkyl, preferably C1-C5Alkyl, more preferably methyl, ethyl, n-propyl and different
Propyl.Magnesium dichloride and R0The molar ratio of OH can be 1：1-6, preferably 1：2-4.
The method of the high shear for example can be side disclosed in method, US6020279 disclosed in CN1330086
Method disclosed in method and CN1463990A disclosed in method, CN1580136A.The decentralized medium can be hydrocarbon system solvent,
Such as：Kerosene, white oil, silicone oil, paraffin oil and vaseline oil.The cooling medium can be pentane, hexane, heptane, petroleum ether
With raffinating oil in petroleum refining process.
When the alcohol adducts of the magnesium dichloride are spheric granules, by the way that the alcohol adducts of magnesium dichloride are contained with described
It is urged obtained from titanium compound, internal electron donor compound a, internal electron donor compound b and internal electron donor compound c reactions
Agent component is also spheric granules.
In the present invention, the titanium-containing compound can be titanium-containing compound commonly used in the art.Preferably, the titanizing is closed
Object is VIII compound represented of Formula VII and/or formula：
TiXp(OR15)4-pFormula VII,
TiXq(OR15)3-qFormula VIII,
In Formula VII and formula VIII, X is halogen, R15For C1-C20Alkyl, p be 1-4 integer, q be 1-3 integer.
In the case of further preferably, the titanium-containing compound is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy
Titanium chloride, dibutoxy titanium chloride, butoxy titanium trichloride, triethoxy titanium chloride, diethoxy titanium chloride, ethyoxyl
It is one or more in titanium trichloride and titanium trichloride.Under most preferred case, the titanium-containing compound is titanium tetrachloride.
Preferably, the method for preparing catalytic component further includes that liquid is filtered to and recycled solid, reusable liquid
Titanium compound (such as titanium tetrachloride) washs the solid of recycling, relative to every gram of magnesium-containing compound, the titanium compound of the liquid
Dosage be preferably 8mL-40mL, the ingredient of solid catalyst then repeatedly washed with atent solvent again.The inertia is molten
Agent can be selected from aliphatic and aromatic hydrocarbons, for example, hexane, heptane, octane, decane, toluene etc..
In the preparation method of the catalytic component for olefinic polymerization, the internal electron donor component contains described
It is added in the period one or more of before and after, during the reacting of magnesium compound and the titanium-containing compound.It is described
Period before the reacting of magnesium-containing compound and the titanium-containing compound refers to that it in reactor is added in the magnesium compound
Period afterwards and before being warming up to reaction temperature.
In the present invention, when preparing the catalytic component, the internal electron donor compound a, internal electron donor chemical combination
Object b and internal electron donor compound c can be added to by several times or simultaneously the mixed of the magnesium-containing compound and the titanium-containing compound
It closes in object.It is described the internal electron donor compound a, internal electron donor compound b and internal electron donor c to be added to by several times
When in the mixture of magnesium-containing compound and the titanium-containing compound, the internal electron donor compound a and interior both can first be added
Electron donor compound b adds the internal electron donor compound c；The internal electron donor compound can also first be added
C adds the internal electron donor compound a and internal electron donor compound b.Preferably, by electron donor compound a, b, c
It is added to together after mixing in the mixture of the magnesium-containing compound and the titanium-containing compound.
According to the present invention, the magnesium-containing compound can be according to method disclosed in the prior art with reacting for titanium-containing compound
Implement, for example, titanium-containing compound can be cooled to 0 DEG C or less (preferably -5 to -35 DEG C), chemical combination containing magnesium is then added
Object, and be stirred at such a temperature 10-60 minutes, it is warming up to reaction temperature (preferably 60-130 DEG C) later, and anti-at this
It is maintained 0.5-10 hours at a temperature of answering.Be added in temperature-rise period internal electron donor compound a, internal electron donor compound b and
Internal electron donor compound c.Then liquid is filtered to and recycled solid, the titanium compound of liquid is used in combination to handle the solid one of recycling
It is secondary or multiple, finally, repeatedly washed with atent solvent, to obtain catalytic component.
The present invention also provides a kind of olefin polymerization catalysis, which contains：
(1) above-mentioned catalyst component for olefin polymerization；
(2) as the alkyl aluminum compound of co-catalyst；And
(3) optionally, external donor compound.
According to the present invention, in above-mentioned olefin polymerization catalysis, the alkyl aluminum compound can be field of olefin polymerisation
The alkyl aluminum compound of the common various co-catalysts that can be used as olefin polymerization catalysis.Under preferable case, the alkyl
Aluminium compound is Ⅸ compound represented of formula,
AlR’n'X’3-n'Formula Ⅸ,
In formula Ⅸ, R ' is C1-C8Alkyl or halogenated alkyl, X ' be halogen, n ' be 1-3 integer.In formula Ⅸ, X ' is preferred
To be one or more in chlorine, bromine and iodine, more preferably chlorine.
In the case of further preferably, the alkyl aluminum compound is triethyl aluminum, tri-propyl aluminum, three n-butylaluminums, three different
Butyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, a chlorine diethyl
Base aluminium, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride, Al (n-C6H13)3With Al (n-C8H17)3In it is one or more.
Most preferably, the alkyl aluminum compound is triethyl aluminum and/or triisobutyl aluminium.
According to the present invention, the dosage of the alkyl aluminum compound can be the conventional amount used of this field.Preferable case, it is described
The molar ratio of aluminium in alkyl aluminum compound and the titanium in the catalytic component is 1-500：1.In the case of further preferably, institute
The molar ratio for stating the aluminium in alkyl aluminum compound and the titanium in the catalytic component is 10-300：1, in the case of most preferred,
The molar ratio of aluminium in the alkyl aluminum compound and the titanium in the catalytic component is 20-200：1.
Due to the present invention olefin polymerization catalysis in only to the internal electron donor group in catalyst component for olefin polymerization
Divide and improved, therefore, the type and content of the external electron donor in olefin polymerization catalysis of the invention are not special
It limits.In the case of preferred, the molar ratio of aluminium and the external donor compound dosage in the alkyl aluminum compound is
2-500：1, more preferably 5-200：1；Or external electron donor is not used.
According to the present invention, the external donor compound can be that commonly used in the art various can realize above-mentioned purpose
External donor compound, such as：Carboxylic acid, carboxylic acid anhydride, carboxylate, ketone, ether, alcohol, lactone, organic phosphorus compound and organic
It is one or more in silicon compound.Preferably, the external donor compound is organo-silicon compound shown in formula Ⅹ,
(R16)m’(R17)p’Si(OR18)q’Formula Ⅹ,
In formula Ⅹ, R16、R17And R18It is each independently C1-C18Alkyl, optionally contain hetero atom, the hetero atom
It is one or more in F, Cl, Br, N and I；M ' and p ' is each independently the integer of 0-2, and q ' is the integer of 1-3, and m ',
P ' and q's ' and be 4.
Under preferable case, R16And R17It is each independently C3-C10Linear or branched alkyl group, C3-C10Alkylene, C3-
C10Alkylidene, C3-C10Substituted or unsubstituted naphthenic base and C6-C10Substituted or unsubstituted aryl in it is a kind of, optionally
Ground contains hetero atom, and the hetero atom is one or more in F, Cl, Br, N and I；R18For C1-C10Linear chain or branched chain alkane
Base, more preferably methyl.
According to the present invention, the specific example of the organo-silicon compound can be but be not limited to：Cyclohexyl methyl dimethoxy
Base silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, diphenyl
Dimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclohexyl trimethoxy silane,
In tert-butyl trimethoxy silane, tertiary hexyl trimethoxysilane and 2- ethyl piperidine base -2- t-butyldimethoxysilanes
It is one or more.
In the case of further preferably, the external donor compound is Cyclohexyl Methyl Dimethoxysilane and/or two
Cyclopenta dimethoxysilane.
The present invention also provides application of the above-mentioned olefin polymerization catalysis in olefinic polyreaction.
Theing improvement is that for the present invention uses a kind of new catalyst for olefinic polymerization, and specific kind of alkene
Class, the polymerisation process of alkene and condition can be same as the prior art.
According to the present invention, the method for olefinic polymerization is included under olefin polymerization conditions, make one or more alkene with it is above-mentioned
Olefin polymerization catalysis contacts, and at least one of described alkene is by formula CH2The alkene that=CHR is indicated, wherein R is hydrogen or C1-
C6Linear or branched alkyl group.
The olefin polymerization catalysis of the present invention can be used for the homopolymerization of alkene, can be used for a variety of alkene being total to
Polymerization.At least one of described alkene is by formula CH2The alkene that=CHR is indicated, wherein R is hydrogen or C1-C6Linear chain or branched chain
Alkyl.It is described by formula CH2The specific example of alkene that=CHR is indicated may include：Ethylene, propylene, 1- n-butenes, 1- positive penta
Alkene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene.It is described by formula CH under preferable case2The alkene that=CHR is indicated is second
It is one or more in alkene, propylene, 1- n-butenes, 1- n-hexylenes and 4-methyl-1-pentene.It is highly preferred that described by formula CH2=
The alkene that CHR is indicated is propylene.
The olefin polymerization conditions can be the normal condition of this field.Usually, the olefin polymerization conditions can wrap
It includes：Temperature is 0-150 DEG C, and the time is 0.1-5 hours, pressure 0.01-10MPa.Preferably, the olefin polymerization conditions packet
It includes：Temperature is 60-100 DEG C, and the time is 0.5-3 hours, pressure 0.5-5MPa.The pressure of the present invention refers both to gauge pressure.The alkene
The dosage of polymerized hydrocarbon catalyst can be the various conventional amount useds of prior art alkene catalyst.In the course of the polymerization process, hydrogen can
The molecular weight and melt index that polymer is adjusted in polymerization container are added to as polymer molecular weight conditioning agent.
The present invention will be described in detail by way of examples below.
Performance test involved in following embodiment is as follows：
1, polymer isotactic index：It is measured (heptane boiling extracting 6 hours) using heptane extraction process：It is dry poly- by 2 grams
Object sample is closed, is placed in extractor after being extracted 6 hours with boiling heptane, residue is dried to the polymer weight obtained by constant weight
(g) it is isotactic index with the ratio of 2 (g).
2, the measurement of polymer content of ashes：It is measured according to GB/T 9345-1988.
3, the Ti content in catalyst component for olefin polymerization uses spectrophotometry, with 722 type light of Shanghai analytical instrument factory
The mass fraction of Ti in grid spectrophotometric determination catalytic component.
Embodiment 1
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
In the 300mL being sufficiently displaced from by high pure nitrogen in the glass reaction bottle of stirring, the tetrachloro of 0.912mol is added
The hexane for changing titanium and 10mL is cooled to -20 DEG C, and the spherical chlorination magnesium alcoholate (MgCl of 8g (0.0372mol) are added2·
2.6C2H5OH is synthesized according to method magnesium dichloride disclosed in CN1330086A with ethyl alcohol), under stiring, stage by stage slowly
It heats up, 2,4- glycol dibenzoates are added in temperature-rise period, and (internal electron donor compound a) 5mmol, 2- isopropyls -2- is different
Amyl -1,3- dimethoxy propanes (internal electron donor compound b) 5mmol and epoxychloropropane (internal electron donor compound c)
1.5mmol is continuously heating to 110 DEG C, reaches after temperature after constant temperature 0.5h, filters and remove liquid, into the solid phase being obtained by filtration
Titanium tetrachloride processing is added.Then it is washed five times with hexane, spherical catalyst components A1 is obtained after vacuum drying.
Elemental analysis is the results show that the Ti content in spherical catalyst components A1 is 2.8%.
Propylene polymerization：It in the autoclave of a 5L, is purged using stream of nitrogen gas, then in stream of nitrogen gas
Introduce 0.25mmol triethyl aluminums, 0.01mmol Cyclohexyl Methyl Dimethoxysilanes (CHMMS), 10mL anhydrous hexane and
The spherical catalyst components A1 of 4mg.Autoclave is closed, the liquid propene of hydrogen 2NL and 2.3L is added.70 DEG C are warming up to, polymerization 1.0 is small
When.The test result of the isotactic index and content of ashes of polymer and the polymerization activity of catalyst is shown in Table 1.
Embodiment 2
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, and poly- third is prepared according to the method for embodiment 1
Alkene, unlike, in propylene polymerization processes, do not introduce Cyclohexyl Methyl Dimethoxysilane.Obtained polyacrylic isotactic
The test result of the polymerization activity of index and content of ashes and catalyst is shown in Table 1.
Embodiment 3
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, the difference is that 2,4- pentanediol hexichol first is added
Acid esters (internal electron donor compound a) 4.5mmol, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane (internal electron donors
(internal electron donor compound c) 4mmol, obtain catalytic component A3 for compound b) 6mmol and epoxychloropropane.
And polypropylene is prepared according to the method for embodiment 1, except that replacing catalyst group using catalytic component A3
Divide A1.The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1.
Embodiment 4
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization A4 is prepared according to the method for embodiment 3.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, and poly- third is prepared according to the method for embodiment 1
Alkene, unlike, in propylene polymerization processes, catalytic component A1 is replaced using catalytic component A4, and do not introduce it is outer to
Electron Cyclohexyl Methyl Dimethoxysilane.The polymerization of obtained polyacrylic isotactic index and content of ashes and catalyst
Active test result is shown in Table 1.
Embodiment 5
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, it is different to be added without 2- isopropyls -2-
Amyl -1,3- dimethoxy propane, 9,9- dimethoxy-methyls fluorenes is added, and (internal electron donor compound b) 5mmol, are catalyzed
Agent component A5.
And polypropylene is prepared according to the method for embodiment 1, the difference is that replacing catalyst group using catalytic component A5
Divide A1.The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1.
Embodiment 6
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization A6 is prepared according to the method for embodiment 5.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, and poly- third is prepared according to the method for embodiment 1
Alkene, unlike, in propylene polymerization processes, catalytic component A1 is replaced using catalytic component A6, and do not introduce it is outer to
Electron Cyclohexyl Methyl Dimethoxysilane.The polymerization of obtained polyacrylic isotactic index and content of ashes and catalyst
Active test result is shown in Table 1.
Embodiment 7
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, it is added without 2,4- pentanediol hexichol
Formic acid esters, 3,5- heptandiols dibenzoate is added, and (internal electron donor compound a) 5mmol obtain catalytic component A7.
And polypropylene is prepared according to the method for embodiment 1, the difference is that replacing catalyst group using catalytic component A7
Divide A1.The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1.
Embodiment 8
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization A8 is prepared according to the method for embodiment 7.
And polypropylene is prepared according to the method for embodiment 1, unlike, in propylene polymerization processes, using catalyst group
Divide A8 to replace catalytic component A1, and does not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.Obtained polypropylene
Isotactic index and the test result of the polymerization activity of content of ashes and catalyst be shown in Table 1.
Embodiment 9
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, 2,4- pentanediol hexichol first is added
Acid esters (internal electron donor compound a) 3mmol, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane (internal electron donors
(internal electron donor compound c) 1mmol, obtain catalytic component A9 for conjunction object b) 7mmol and epoxychloropropane.
And polypropylene is prepared according to the method for embodiment 1, the difference is that replacing catalyst group using catalytic component A9
Divide A1.The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1.
Embodiment 10
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization A10 is prepared according to the method for embodiment 9.
And polypropylene is prepared according to the method for embodiment 1, unlike, in propylene polymerization processes, using catalyst group
Divide A10 to replace catalytic component A1, and does not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.Obtained polypropylene
Isotactic index and the test result of the polymerization activity of content of ashes and catalyst be shown in Table 1.
Embodiment 11
The present embodiment is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the olefinic polymerization of the present invention
Method.
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, 2,4- pentanediol hexichol first is added
Acid esters (internal electron donor compound a) 3.5mmol, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane (internal electron donors
(internal electron donor compound c) 0.5mmol, obtain catalytic component A11 for compound b) 5mmol and epoxychloropropane.
And polypropylene is prepared according to the method for embodiment 1, the difference is that replacing catalyst using catalytic component A11
Component A1.The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1.
Comparative example 1
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, preparing catalytic component process
In, being added without 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, (internal electron donor compound b) and epoxychloropropane are (interior
Electron donor compound c), 2,4- glycol dibenzoates are only added, and (internal electron donor compound a) 5mmol, are catalyzed
Agent component B1.
And polypropylene is prepared according to the method for embodiment 1, unlike, in propylene polymerization processes, using catalyst group
Divide B1 to replace catalytic component A1,2.5mmol triethyl aluminums, 0.1mmol Cyclohexyl Methyl Dimethoxysilanes is added
(CHMMS).The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1
Comparative example 2
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, preparing catalytic component process
In, it is added without 2,4- glycol dibenzoates (interior Donor compound a) and epoxychloropropane (internal electron donor compound
C), only (internal electron donor compound b) 6.0mmol, are urged addition 2- isopropyl -2- isopentyl -1,3- dimethoxy propane
Agent component B2.
And polypropylene is prepared according to the method for embodiment 1, except that replacing catalyst group using catalytic component B2
Divide A1.The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1.
Comparative example 3
Catalyst component for olefin polymerization is prepared according to the method for embodiment 1, unlike, preparing catalytic component process
In, being added without epoxychloropropane, (internal electron donor compound c) only adds 2,4- glycol dibenzoate (internal electron donors
Closing object a) 5mmol and 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, (internal electron donor compound b) 5mmol, obtain
Catalytic component B3.
And polypropylene is prepared according to the method for embodiment 1, unlike, in propylene polymerization processes, using catalyst group
B3 is divided to replace catalytic component A1.The survey of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst
Test result is shown in Table 1.
Comparative example 4
Catalyst component for olefin polymerization B4 is prepared according to the method for comparative example 3.
And polypropylene is prepared according to the method for embodiment 1, unlike, in propylene polymerization processes, except that adopting
Catalytic component A1 is replaced with catalytic component B4, and does not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.
To polyacrylic isotactic index and the test result of the polymerization activity of content of ashes and catalyst be shown in Table 1.
Comparative example 5
Catalyst component for olefin polymerization is prepared according to the method for embodiment 9, unlike, preparing catalytic component process
In, being added without epoxychloropropane, (2,4- glycol dibenzoate (internal electron donors are only added in internal electron donor compound c)
Compound a) (internal electron donor compound b) 7mmol, obtain 3mmol and 2- isopropyl -2- isopentyl -1,3- dimethoxy propane
To catalytic component B5.
And polypropylene is prepared according to the method for embodiment 1, except that replacing catalyst group using catalytic component B5
Divide A1.The test result of the polymerization activity of obtained polyacrylic isotactic index and content of ashes and catalyst is shown in Table 1.
Comparative example 6
Catalyst component for olefin polymerization B6 is prepared according to the method for comparative example 5.
And polypropylene is prepared according to the method for embodiment 1, except that in propylene polymerization processes, using catalyst group
Divide B6 to replace catalytic component A1, and does not introduce external electron donor Cyclohexyl Methyl Dimethoxysilane.
Table 1
From table 1 embodiment 1-11 compared with the data of comparative example 1-2 as can be seen that it is provided by the invention containing it is interior to electricity
The catalyst for the catalytic component that donor compound a, internal electron donor compound b and internal electron donor compound c are compounded
Polymerization activity and vertical structure directionality obviously higher than containing only diol-lipid internal electron donor or containing only two ethers internal electron donors
Catalyst.And the polymer obtained using polymerization catalyst provided by the invention, content of ashes will be far below containing only two
The polymer that alkoxide internal electron donor or polymerization catalyst containing only two ethers internal electron donors obtain.The embodiment from table 1
1-11 is compared with the data of comparative example 3-6 as can be seen that three kinds of internal electron donor compounds of use of the present invention compounded
Catalyst is urged with what 2,4-PD dibenzoate and 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes compounded
Agent is compared, and while keeping the high activity and low ash content of phase same level, vertical structure directionality has further raising,
The equal higher of isotactic index of resulting polymers.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of catalyst component for olefin polymerization, which contains the reaction product of following components：
(i) magnesium-containing compound；
(ii) titanium-containing compound；And
(iii) internal electron donor；
It is characterized in that, the internal electron donor is internal electron donor compound a, internal electron donor compound b and interior electron
The combination of body compound c, the internal electron donor compound a are glycol ester compounds shown in formula I, the internal electron donor
It is diether compound shown in formula II to close object b, and the internal electron donor compound c is alkylene oxides chemical combination shown in formula III
Object,
In formula I, R1And R2It is identical or different, it is each independently C1-C10Linear or branched alkyl group, C3-C20Substitution or do not take
The naphthenic base in generation, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20Substitution
Or one kind in unsubstituted alkaryl, the aromatic ring in the aryl, aralkyl or alkaryl is optionally by selected from halogen, C1-C6
Linear or branched alkyl group and C1-C6Alkoxy in one or more substitutions；
R3、R4、R5、R6And R1-R2nIt is identical or different, it is each independently hydrogen, halogen, C1-C20Linear or branched alkyl group, C3-
C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted alkane virtue
Base, C7-C20Substituted or unsubstituted aralkyl, C2-C10Linear chain or branched chain alkylene and C10-C20Fused ring aryl in
One kind, R3、R4、R5、R6And R1-R2nOptionally contain hetero atom, the hetero atom is one in nitrogen, oxygen, sulphur, silicon, halogen and phosphorus
Kind is a variety of；
Alternatively, R3、R4、R5、R6And R1-R2nIn two or more be mutually bonded, to form ring；
N is the integer of 0-10；
In formula II, R '1、R’2、R’3、R’4、R’5And R '6It is identical or different, it is each independently hydrogen, halogen, C1-C20Straight chain or
Branched alkyl, C3-C20Substituted or unsubstituted naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substitution or
Unsubstituted aralkyl and C7-C20Substituted or unsubstituted alkaryl in one kind；
R’7And R '8It is identical or different, it is each independently C1-C20Linear or branched alkyl group, C3-C20It is substituted or unsubstituted
Naphthenic base, C6-C20Substituted or unsubstituted aryl, C7-C20Substituted or unsubstituted aralkyl and C7-C20Substitution or not
One kind in substituted alkaryl；
Alternatively, R '1、R’2、R’3、R’4、R’5And R '6In two or more be mutually bonded, to form ring；
In formula III, R "1And R "2It is identical or different, it is each independently hydrogen, C1-C5Linear or branched alkyl group or halogenated alkyl,
The internal electron donor compound a, the internal electron donor compound b and the internal electron donor compound c dosages
Molar ratio is 0.5-10：1-12：1,
Titanium-containing compound is cooled to 0 DEG C hereinafter, magnesium-containing compound is then added, and be stirred 10-60 points at such a temperature
Clock is warming up to reaction temperature, and is maintained 0.5-10 hours under the reaction temperature later, and interior electron is added in temperature-rise period
Body compound a, internal electron donor compound b and internal electron donor compound c.
2. catalytic component according to claim 1, wherein the internal electron donor compound a, the internal electron donor
The molar ratio of compound b and the internal electron donor compound c dosages is 1-7：1.5-10：1.
3. catalytic component according to claim 1, wherein the internal electron donor compound a is two shown in formula IV
Alcohol ester compounds,
In formula IV, R7、R8、R9、R10、R11And R12It is identical or different, it is each independently hydrogen or C1-C20Linear chain or branched chain alkane
Base.
4. catalytic component according to claim 3, wherein the internal electron donor compound a is 2,4- pentanediols two
Benzoic ether and/or 3,5- heptandiol dibenzoates.
5. catalytic component according to claim 1, wherein the internal electron donor compound b be formula V shown in 1,
3- diether compounds,
In formula V, R '9And R '10It is identical or different, it is each independently hydrogen, halogen, C1-C18Linear or branched alkyl group, C3-C18
Substituted or unsubstituted naphthenic base, C6-C18Substituted or unsubstituted aryl and C7-C18Substituted or unsubstituted aralkyl
In one kind, alternatively, R '9And R '10It is mutually bonded, to form ring；R’11And R '12It is identical or different, it is each independently C1-C10
Linear or branched alkyl group.
6. catalytic component according to claim 5, wherein the internal electron donor compound b is that 2- isopropyls -2- is different
Amyl -1,3- dimethoxy propanes and/or 9,9- dimethoxy-methyl fluorenes.
7. catalytic component according to claim 1, wherein in formula III, R "1And R "2It is identical or different, each independently
For hydrogen, C1-C3Linear or branched alkyl group or halogenated alkyl.
8. catalytic component according to claim 7, wherein the internal electron donor compound c is ethylene oxide, epoxy
It is one or more in propane, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy bromobutane.
9. catalytic component according to claim 1, wherein the magnesium-containing compound, the titanium-containing compound with it is described
The molar ratio of internal electron donor dosage is 1：10-200：0.04-0.8.
10. catalytic component according to claim 1, wherein the magnesium-containing compound, the titanium-containing compound with it is described
The molar ratio of internal electron donor dosage is 1：20-180：0.05-0.5.
11. a kind of olefin polymerization catalysis, which contains：
(1) catalyst component for olefin polymerization described in any one of claim 1-10；
(2) as the alkyl aluminum compound of co-catalyst；And
(3) optionally, external donor compound.
12. application of the olefin polymerization catalysis described in claim 11 in olefinic polyreaction.
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| CN111072810B (en) * | 2018-10-19 | 2022-05-24 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN115975084B (en) * | 2021-10-15 | 2025-02-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application |
| CN115975079B (en) * | 2021-10-15 | 2025-02-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application |
| CN116375911A (en) * | 2023-05-25 | 2023-07-04 | 山东京博石油化工有限公司 | Catalyst for olefin polymerization, preparation method thereof, and method for olefin polymerization |
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