CN114106223A - Catalyst system for olefin polymerization and olefin polymerization method - Google Patents
Catalyst system for olefin polymerization and olefin polymerization method Download PDFInfo
- Publication number
- CN114106223A CN114106223A CN202010901448.6A CN202010901448A CN114106223A CN 114106223 A CN114106223 A CN 114106223A CN 202010901448 A CN202010901448 A CN 202010901448A CN 114106223 A CN114106223 A CN 114106223A
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- China
- Prior art keywords
- dimethoxypropane
- tetra
- phosphate
- compound
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 53
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 22
- -1 alkyl aluminum compound Chemical class 0.000 claims abstract description 100
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 44
- 239000011949 solid catalyst Substances 0.000 claims abstract description 39
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 19
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- 150000003609 titanium compounds Chemical class 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 claims description 7
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- XHTYQFMRBQUCPX-UHFFFAOYSA-N 1,1,3,3-tetramethoxypropane Chemical compound COC(OC)CC(OC)OC XHTYQFMRBQUCPX-UHFFFAOYSA-N 0.000 claims description 6
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- HPOWOWTVWZELDK-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)cyclohexane Chemical compound COCC(C)(COC)C1CCCCC1 HPOWOWTVWZELDK-UHFFFAOYSA-N 0.000 claims description 4
- QSVIFMIHOCWOPL-UHFFFAOYSA-N 1,1,1,2-tetraethoxyethane Chemical compound CCOCC(OCC)(OCC)OCC QSVIFMIHOCWOPL-UHFFFAOYSA-N 0.000 claims description 4
- VPZFYLQMPOIPKH-UHFFFAOYSA-N 1,1,1,2-tetramethoxyethane Chemical compound COCC(OC)(OC)OC VPZFYLQMPOIPKH-UHFFFAOYSA-N 0.000 claims description 4
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 claims description 4
- HSZRAYCXTBWDMX-UHFFFAOYSA-N CCC(C)OC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 Chemical compound CCC(C)OC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 HSZRAYCXTBWDMX-UHFFFAOYSA-N 0.000 claims description 4
- REYVDGWJUHQGNC-UHFFFAOYSA-N CCC(C)OCC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 Chemical compound CCC(C)OCC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 REYVDGWJUHQGNC-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- OUPPKRIDJAMCCA-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,3-dimethylbutane Chemical compound COCC(C)(C(C)C)COC OUPPKRIDJAMCCA-UHFFFAOYSA-N 0.000 claims description 3
- NGMVWDKVVMVTTM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylbutane Chemical compound COCC(C(C)C)COC NGMVWDKVVMVTTM-UHFFFAOYSA-N 0.000 claims description 3
- CWVKCYDPJZCDMC-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)-2-methyloctane Chemical compound CCCCC(CC)CC(C)(COC)COC CWVKCYDPJZCDMC-UHFFFAOYSA-N 0.000 claims description 3
- ASFLIXVTLOHGHE-UHFFFAOYSA-N 5-benzoyloxyheptan-3-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(CC)OC(=O)C1=CC=CC=C1 ASFLIXVTLOHGHE-UHFFFAOYSA-N 0.000 claims description 3
- SLNUADCUVQWUJA-UHFFFAOYSA-N CCC(C)OC(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound CCC(C)OC(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 SLNUADCUVQWUJA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- BSALDGPEFGOAJZ-UHFFFAOYSA-N dibutyl naphthalene-1,2-dicarboxylate Chemical compound C1=CC=CC2=C(C(=O)OCCCC)C(C(=O)OCCCC)=CC=C21 BSALDGPEFGOAJZ-UHFFFAOYSA-N 0.000 claims description 3
- XTBBZRRBOAVBRA-UHFFFAOYSA-N dimethyl phenyl phosphate Chemical compound COP(=O)(OC)OC1=CC=CC=C1 XTBBZRRBOAVBRA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 125000005591 trimellitate group Chemical group 0.000 claims description 3
- NOAIBMQZUGBONL-UHFFFAOYSA-N (1,3-dimethoxy-2-methylpropan-2-yl)benzene Chemical compound COCC(C)(COC)C1=CC=CC=C1 NOAIBMQZUGBONL-UHFFFAOYSA-N 0.000 claims description 2
- PWTBCKHYGJDQDC-UHFFFAOYSA-N (4-tert-butylphenyl) dimethyl phosphate Chemical compound COP(=O)(OC)OC1=CC=C(C(C)(C)C)C=C1 PWTBCKHYGJDQDC-UHFFFAOYSA-N 0.000 claims description 2
- MISPJWXLQJXWHM-UHFFFAOYSA-N (5-benzoyloxy-4-ethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CC)C(CC)OC(=O)C1=CC=CC=C1 MISPJWXLQJXWHM-UHFFFAOYSA-N 0.000 claims description 2
- KVJHGPAAOUGYJX-UHFFFAOYSA-N 1,1,3,3-tetraethoxypropane Chemical compound CCOC(OCC)CC(OCC)OCC KVJHGPAAOUGYJX-UHFFFAOYSA-N 0.000 claims description 2
- FHBAGVNIWPLUOK-UHFFFAOYSA-N 1,1,5,5-tetramethoxypentane Chemical compound COC(OC)CCCC(OC)OC FHBAGVNIWPLUOK-UHFFFAOYSA-N 0.000 claims description 2
- CELOJHLXFPSJPH-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylbenzene Chemical compound COCC(COC)C1=CC=CC=C1 CELOJHLXFPSJPH-UHFFFAOYSA-N 0.000 claims description 2
- NOWCPSTWMDNKTI-UHFFFAOYSA-N 1,3-dimethoxypropan-2-ylcyclohexane Chemical compound COCC(COC)C1CCCCC1 NOWCPSTWMDNKTI-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- ROSQVPGTZCDBOC-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C)(COC)CC(C)C ROSQVPGTZCDBOC-UHFFFAOYSA-N 0.000 claims description 2
- XAGXJWYEHBCLPN-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylbutane Chemical compound COCC(C)(CC)COC XAGXJWYEHBCLPN-UHFFFAOYSA-N 0.000 claims description 2
- SVJCEDKUVMVBKM-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-2-methylpentane Chemical compound CCCC(C)(COC)COC SVJCEDKUVMVBKM-UHFFFAOYSA-N 0.000 claims description 2
- FDLMLTYTOFIPCK-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-3-methylpentane Chemical compound CCC(C)C(COC)COC FDLMLTYTOFIPCK-UHFFFAOYSA-N 0.000 claims description 2
- PPHMKLXXVBJEHR-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)hexane Chemical compound CCCCC(COC)COC PPHMKLXXVBJEHR-UHFFFAOYSA-N 0.000 claims description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 2
- JUJMPCLNRKYKRA-UHFFFAOYSA-N 2,4-dimethoxybutylcyclohexane Chemical compound COCCC(OC)CC1CCCCC1 JUJMPCLNRKYKRA-UHFFFAOYSA-N 0.000 claims description 2
- FXPIHWVISVNIIK-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylheptane Chemical compound CCCC(C)C(COC)(COC)C(C)C FXPIHWVISVNIIK-UHFFFAOYSA-N 0.000 claims description 2
- HYNSSLXYPGIRFR-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylhexane Chemical compound CCC(C)C(COC)(COC)C(C)C HYNSSLXYPGIRFR-UHFFFAOYSA-N 0.000 claims description 2
- RGHIYOCUMCUWAQ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,5-dimethylhexane Chemical compound COCC(COC)(CC(C)C)C(C)C RGHIYOCUMCUWAQ-UHFFFAOYSA-N 0.000 claims description 2
- WAHDOBRAAIQNTA-UHFFFAOYSA-N 3,5-dimethoxypentylcyclohexane Chemical compound COCCC(OC)CCC1CCCCC1 WAHDOBRAAIQNTA-UHFFFAOYSA-N 0.000 claims description 2
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims description 2
- VIJVFTUOJNTXCA-UHFFFAOYSA-N 4-ethyl-1-methoxy-2-(methoxymethyl)octane Chemical compound CCCCC(CC)CC(COC)COC VIJVFTUOJNTXCA-UHFFFAOYSA-N 0.000 claims description 2
- IQOGYODSZCRBFT-UHFFFAOYSA-N C(C(OC1CCCCC1)(OC1CCCCC1)OC1CCCCC1)OC1CCCCC1 Chemical compound C(C(OC1CCCCC1)(OC1CCCCC1)OC1CCCCC1)OC1CCCCC1 IQOGYODSZCRBFT-UHFFFAOYSA-N 0.000 claims description 2
- ZWKWEGQRVLVKLE-UHFFFAOYSA-N CCCCC(C(OCCCC)OCCCC)C(OCCCC)OCCCC Chemical compound CCCCC(C(OCCCC)OCCCC)C(OCCCC)OCCCC ZWKWEGQRVLVKLE-UHFFFAOYSA-N 0.000 claims description 2
- CNGTVTZBYUHCAH-UHFFFAOYSA-N CCCCCOC(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound CCCCCOC(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 CNGTVTZBYUHCAH-UHFFFAOYSA-N 0.000 claims description 2
- QGRULHQLMUPRNF-UHFFFAOYSA-N CCCCCOC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 Chemical compound CCCCCOC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 QGRULHQLMUPRNF-UHFFFAOYSA-N 0.000 claims description 2
- BRIBUBVNYWCALI-UHFFFAOYSA-N CCCOC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 Chemical compound CCCOC1=CC=CC2=CC=C(C=C(C=CC=C3)C3=C3)C3=C12 BRIBUBVNYWCALI-UHFFFAOYSA-N 0.000 claims description 2
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 claims description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 2
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 claims description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- XSEJRZMALXVCGH-UHFFFAOYSA-N P(=O)(OC)(OC)OC1=CC=C(C=C1)C(C)C Chemical compound P(=O)(OC)(OC)OC1=CC=C(C=C1)C(C)C XSEJRZMALXVCGH-UHFFFAOYSA-N 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- VDZDYDLIDXQASZ-UHFFFAOYSA-N [1-cyclohexyl-3-methoxy-2-(methoxymethyl)propan-2-yl]cyclohexane Chemical compound C1CCCCC1C(COC)(COC)CC1CCCCC1 VDZDYDLIDXQASZ-UHFFFAOYSA-N 0.000 claims description 2
- AMDVEEKNUQSFMN-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]benzene Chemical compound COCC(COC)(C(C)C)C1=CC=CC=C1 AMDVEEKNUQSFMN-UHFFFAOYSA-N 0.000 claims description 2
- PQIDFVXMOZQINS-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylbutan-2-yl]cyclohexane Chemical compound COCC(COC)(C(C)C)C1CCCCC1 PQIDFVXMOZQINS-UHFFFAOYSA-N 0.000 claims description 2
- FQRCETUIJFMCNV-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]benzene Chemical compound CCC(C)C(COC)(COC)C1=CC=CC=C1 FQRCETUIJFMCNV-UHFFFAOYSA-N 0.000 claims description 2
- IHLHFXVNTFWZRQ-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]cyclohexane Chemical compound CCC(C)C(COC)(COC)C1CCCCC1 IHLHFXVNTFWZRQ-UHFFFAOYSA-N 0.000 claims description 2
- NELZYGXHSKMGPM-UHFFFAOYSA-N [1-methoxy-2-(methoxymethyl)-3-methylpentan-2-yl]cyclopentane Chemical compound CCC(C)C(COC)(COC)C1CCCC1 NELZYGXHSKMGPM-UHFFFAOYSA-N 0.000 claims description 2
- XHGYQNSJWDRDBT-UHFFFAOYSA-N [2,2-bis(methoxymethyl)-3-methylbutyl]benzene Chemical compound COCC(COC)(C(C)C)CC1=CC=CC=C1 XHGYQNSJWDRDBT-UHFFFAOYSA-N 0.000 claims description 2
- GMIJLGFPOXCNBC-UHFFFAOYSA-N [2-(benzoyloxymethyl)-5-methyl-2-propan-2-ylhexyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C(C)C)(CCC(C)C)COC(=O)C1=CC=CC=C1 GMIJLGFPOXCNBC-UHFFFAOYSA-N 0.000 claims description 2
- UKEUPAFEWAEVGQ-UHFFFAOYSA-N [3-methoxy-2-(methoxymethyl)-2-methylpropyl]benzene Chemical compound COCC(C)(COC)CC1=CC=CC=C1 UKEUPAFEWAEVGQ-UHFFFAOYSA-N 0.000 claims description 2
- JXQCBJLNEGKSCN-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]benzene Chemical compound COCC(COC)CCC1=CC=CC=C1 JXQCBJLNEGKSCN-UHFFFAOYSA-N 0.000 claims description 2
- AWLBWJXVYGYRNY-UHFFFAOYSA-N [4-methoxy-3-(methoxymethyl)butyl]cyclohexane Chemical compound COCC(COC)CCC1CCCCC1 AWLBWJXVYGYRNY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- FPGRDBPTRVSBLF-UHFFFAOYSA-N bis(2-methylpropyl) 2,2-dimethylbutanedioate Chemical compound CC(C)COC(=O)CC(C)(C)C(=O)OCC(C)C FPGRDBPTRVSBLF-UHFFFAOYSA-N 0.000 claims description 2
- WNVMVIYFKFGESM-UHFFFAOYSA-N bis(2-methylpropyl) 2,3-di(propan-2-yl)butanedioate Chemical compound CC(C)COC(=O)C(C(C)C)C(C(C)C)C(=O)OCC(C)C WNVMVIYFKFGESM-UHFFFAOYSA-N 0.000 claims description 2
- RQRAFBDBIOAJDS-UHFFFAOYSA-N bis(2-methylpropyl) 2-ethyl-2-methylbutanedioate Chemical compound CC(C)COC(=O)C(C)(CC)CC(=O)OCC(C)C RQRAFBDBIOAJDS-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- YNNMAKHCPBRNEI-UHFFFAOYSA-N dibutyl (2-propan-2-ylphenyl) phosphate Chemical compound CCCCOP(=O)(OCCCC)OC1=CC=CC=C1C(C)C YNNMAKHCPBRNEI-UHFFFAOYSA-N 0.000 claims description 2
- KRHJRRGRZABDAR-UHFFFAOYSA-N dibutyl (3-methylphenyl) phosphate Chemical compound CCCCOP(=O)(OCCCC)OC1=CC=CC(C)=C1 KRHJRRGRZABDAR-UHFFFAOYSA-N 0.000 claims description 2
- AXVQGNPTHCNQLJ-UHFFFAOYSA-N dibutyl (4-methylphenyl) phosphate Chemical compound CCCCOP(=O)(OCCCC)OC1=CC=C(C)C=C1 AXVQGNPTHCNQLJ-UHFFFAOYSA-N 0.000 claims description 2
- VTCHFSNTCCVHRC-UHFFFAOYSA-N dibutyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCCCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCCCC VTCHFSNTCCVHRC-UHFFFAOYSA-N 0.000 claims description 2
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 claims description 2
- XGERSOIQMWHXGW-UHFFFAOYSA-N diethyl (2-propan-2-ylphenyl) phosphate Chemical compound CCOP(=O)(OCC)OC1=CC=CC=C1C(C)C XGERSOIQMWHXGW-UHFFFAOYSA-N 0.000 claims description 2
- SSZYPXOZRNWJER-UHFFFAOYSA-N diethyl (4-propan-2-ylphenyl) phosphate Chemical compound CCOP(=O)(OCC)OC1=CC=C(C(C)C)C=C1 SSZYPXOZRNWJER-UHFFFAOYSA-N 0.000 claims description 2
- WGFNXLQURMLAGC-UHFFFAOYSA-N diethyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCC WGFNXLQURMLAGC-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 239000003350 kerosene Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 125000003944 tolyl group Chemical group 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the technical field of olefin polymerization catalysts, and discloses a catalyst system for olefin polymerization and an olefin polymerization method. The catalyst system comprises the reaction product of: 1) a solid catalyst component comprising titanium, magnesium, a halogen and an internal electron donor compound; 2) an alkyl aluminum compound; 3) an external electron donor compound, wherein the external electron donor compound is at least one selected from tetraoxyl compounds shown in a formula (I) or a formula (II): r1、R2、R3、R4、R1、R2、R3The same or different, each is selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched double bond-containing alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl or arylalkyl group having 7 to 20 carbon atoms.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a catalyst system for olefin polymerization and an olefin polymerization method.
Background
It is known that the catalyst systems used in the homopolymerization or copolymerization of alpha-olefins generally consist of three parts, including in particular: (1) a main catalyst (solid catalyst component), (2) a cocatalyst (usually an alkylaluminium compound), and (3) an external electron donor compound added during polymerization.
The use of one or several external electron donor compounds to control the stereoregularity and morphology of the polymer during the polymerization reaction is well known to the person skilled in the art. In addition to affecting the stereoregularity of the polymer, the external electron donor often affects other properties of the catalyst to varying degrees. Although a variety of compounds are known as external electron donors, the use of different external electron donor compounds for a particular catalyst may result in different polymer properties. The choice of a suitable external electron donor may be particularly compatible with a particular catalyst system, i.e. finding a suitable external electron donor may significantly improve some aspects of the performance of the polymer product, and it would therefore be highly advantageous to find a set of external electron donors which, for a particular catalyst, give polymers with outstanding properties in some respects.
Patent documents with application numbers CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN200410073623.8 and CN200410073621.9 respectively describe catalyst components using polyol ester compounds and phthalic acid ester compounds to compound an internal electron donor, when the catalyst components are used for propylene polymerization, the external electron donor hydrocarbyl dialkoxysilane used is an external electron donor commonly used in industry at present, such as methylcyclohexyldimethoxysilane (CHMMS) and the like.
Patent documents CN101724102B, CN102234339B, CN1121368C, CN100348624C, CN101560273A, CN1743348A, US9133286, etc. describe catalyst components using diether compounds alone or in combination with polyol ester compounds as internal electron donors, when the catalyst components are used for propylene polymerization, the external electron donor used is hydrocarbyl dialkoxysilane which is a commonly used external electron donor in industry at present, such as methylcyclohexyldimethoxysilane (CHMMS), etc.
Patent documents CN107629153, CN107629154, CN107629155 and CN107629156 describe that the catalyst composition using diether compound and phosphate compound as internal electron donor also uses different external electron donors commonly used in industry, such as diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane and the like besides methylcyclohexyldimethoxysilane, and the catalyst system shows high hydrogen response, high orientation ability and narrow molecular weight distribution of the prepared polymer.
In addition, patent document CN1453298A also uses different external electron donors as comparison, such as diisobutyldimethoxysilane, Dicyclopentyldimethoxysilane (DCPMS), bis (cyclobutylmethyl) dimethoxysilane, etc., in addition to methylcyclohexyldimethoxysilane, and the catalyst system shows high activity, high orientation ability and wide molecular weight distribution of the prepared polymer.
The research on the existing olefin polymerization catalysts has been mainly focused on improving properties such as olefin polymerization activity and polymer tacticity, and the aforementioned objects have been achieved. However, in the case that the kind of the external electron donor is not changed, it is difficult to control the properties (e.g., isotactic index and melt index) of the polymer to some extent by adjusting the amount of the external electron donor, so that the application of the olefin polymerization catalyst is limited. For this reason, it is necessary to develop a new catalyst to solve the problem.
Disclosure of Invention
The inventors of the present invention have unexpectedly found in research work that a polymer having excellent overall properties can be obtained by combining a specific solid catalyst component with a tetraoxyl compound as an external electron donor during olefin polymerization in the presence of a catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound under the same polymerization conditions. By adjusting the polymerization conditions and the external electron donor component structure, the obtained catalyst has the characteristics of improved hydrogen regulation sensitivity, slow polymerization activity attenuation and the like. Based on this finding, the present invention provides a catalyst system for olefin polymerization and an olefin polymerization process.
In a first aspect the present invention provides a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
1) a solid catalyst component comprising titanium, magnesium, a halogen and an internal electron donor compound;
2) an alkyl aluminum compound;
3) an external electron donor compound selected from at least one of the tetrahydrocarbyloxy compounds represented by formula (I) or formula (II):
in the formula (I) and the formula (II), R1、R2、R3、R4、R1、R2、R3The same or different, each is selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched double bond-containing alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl or arylalkyl group having 7 to 20 carbon atoms.
A second aspect of the present invention provides an olefin polymerization process comprising: contacting one or more olefins with the catalyst system described above under olefin polymerization conditions.
Compared with conventional external electron donors such as C-donor and D-donor, the external electron donor compound in the catalyst system is combined with the solid catalyst component, so that the catalyst system has the characteristics of improved hydrogen regulation sensitivity, slow polymerization activity attenuation and the like under the condition of keeping good comprehensive performance of the catalyst system, and is beneficial to long-period industrial production of the catalyst system.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
1) a solid catalyst component comprising titanium, magnesium, a halogen and an internal electron donor compound;
2) an alkyl aluminum compound;
3) an external electron donor compound selected from at least one of the tetrahydrocarbyloxy compounds represented by formula (I) or formula (II):
in the formula (I) and the formula (II), R1、R2、R3、R4、R1、R2、R3The same or different, each is selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched double bond-containing alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl or arylalkyl group having 7 to 20 carbon atoms.
In the present invention, the straight-chain or branched alkyl group having 1 to 20 carbon atoms means a straight-chain alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms.
The linear or branched double bond-containing alkylene group having 2 to 20 carbon atoms means a linear double bond-containing alkylene group having 2 to 20 carbon atoms or a branched double bond-containing alkylene group having 3 to 20 carbon atoms.
The aryl group having 6 to 20 carbon atoms includes phenyl, biphenyl and the like.
Preferably, in the formula (I) or the formula (II), R1、R2、R3、R4、R1、R2、R3The same or different, each is selected from linear or branched alkyl with 1-10 carbon atoms, linear or branched alkene with double structure with 2-10 carbon atoms, cycloalkyl with 3-6 carbon atoms, aryl with 6-10 carbon atoms, and alkylaryl or arylalkyl with 7-12 carbon atoms.
In the present invention, non-limiting examples of the linear or branched alkyl group having 1 to 10 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, dimethylhexyl and n-decyl.
Examples of the linear or branched alkylene group having a double bond having 2 to 10 carbon atoms may include, but are not limited to: vinyl, allyl, and propenyl.
Examples of the cycloalkyl group having 3 to 6 carbon atoms may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl.
Examples of the aryl group having 6 to 10 carbon atoms may include, but are not limited to: phenyl, 4-methylphenyl and 4-ethylphenyl.
Examples of the aralkyl group having 7 to 12 carbon atoms may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.
Examples of the alkylaryl group having 7 to 12 carbon atoms may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl and isopropylphenyl groups.
According to the present invention, specific examples of the tetraoxyl compound include, but are not limited to: tetramethoxyethane, tetraethoxyethane, tetrapropoxyethane, tetrabutoxyethane, tetraisopropoxyethane, tetraisobutoxyethane, 1-dimethoxy-3, 3-diethoxyethane, tetraethoxyethane, tetrapropyloxyethane, tetracyclopropoxyethane, tetracyclobutoxyethane, tetracyclopentoxyethane, tetracyclohexyloxyethane, tetraphenoxyethane, tetraphenylmethoxyethane, tetraphenoxyethane, tetra-p-methylphenoxyethane, tetra-p-ethylphenoxyethane, tetra-o-methylphenoxyethane, tetra-o-ethylphenoxyethane, tetra-m-methylphenoxyethane, tetra-m-ethylphenoxyethane, 1, 3, 3-tetramethoxypropane, 1, 3, 3-tetraethoxypropane, 1, 3, 3-tetrapropoxypropane, 1, 1, 3, 3-tetrabutoxypropane, 1, 3, 3-tetraisopropoxypropane, 1, 3, 3-tetraisobutoxypropane, 1-dimethoxy-3, 3-diethoxypropane, 1, 3, 3-tetraenyloxypropane, 1, 3, 3-tetraenyloxypropylene, 1, 3, 3-tetrapropyleneoxypropane, 1, 3, 3-tetracyclopropoxypropane, 1, 3, 3-tetracyclobutoxypropane, 1, 3, 3-tetracyclopentoxypropane, 1, 3, 3-tetracyclohexyloxypropane, 1, 3, 3-tetraphenyloxypropane, 1, 3, 3-tetraphenylmethoxypropane, 1, 3, 3-tetraphenethoxypropane, 1, 1, 3, 3-tetra-p-methylphenoxypropane, 1, 3, 3-tetra-p-ethylphenoxypropane, 1, 3, 3-tetra-o-methylphenoxypropane, 1, 3, 3-tetra-o-ethylphenoxypropane, 1, 3, 3-tetra-m-methylphenoxypropane, 1, 3, 3-tetra-m-ethylphenoxypropane, 1, 3, 3-tetramethoxybutane, 1, 3, 3-tetraethoxybutane, 1, 3, 3-tetrapropoxybutane, 1, 3, 3-tetrabutoxybutane, 1, 3, 3-tetraisopropoxybutane, 1, 3, 3-tetraisobutoxybutane, 1-dimethoxy-3, 3-diethoxybutane, 1, 3, 3-tetraethoxybutane, 1, 3-tetraethoxy-ne, 1, 1, 3, 3-tetraallyloxybutane, 1, 3, 3-tetrapropyloxybutane, 1, 3, 3-tetracyclopropoxybutane, 1, 3, 3-tetracyclobutoxybutane, 1, 3, 3-tetracyclopentoxybutane, 1, 3, 3-tetracyclohexyloxybutane, 1, 3, 3-tetraphenoxybutane, 1, 3, 3-tetraphenylmethoxybutane, 1, 3, 3-tetraphenylethoxybutane, 1, 3, 3-tetra-p-methylphenoxybutane, 1, 3, 3-tetra-p-ethylphenoxybutane, 1, 3, 3-tetra-o-methylphenoxybutane, 1, 3, 3-tetra-o-ethylphenoxybutane, 1, 3, 3-tetra-m-methylphenoxybutane, 1, 3, 3-tetra-m-methylphenoxybutane, 1, 1, 3, 3-tetra-m-ethylphenoxybutane, 2, 3, 3-tetramethoxybutane, 2, 3, 3-tetraethoxybutane, 2, 3, 3-tetrapropoxybutane, 2, 3, 3-tetrabutoxybutane, 2, 3, 3-tetraisopropoxybutane, 2, 3, 3-tetraisobutoxybutane, 2-dimethoxy-3, 3-diethoxybutane, 2, 3, 3-tetraethoxybutane, 2, 3, 3-tetraallyloxybutane, 2, 3, 3-tetracyclopropoxybutane, 2, 3, 3-tetracyclobutoxybutane, 2, 3, 3-tetracyclopentoxybutane, 2, 2, 3, 3-tetracyclohexyloxybutane, 2, 3, 3-tetraphenoxybutane, 2, 3, 3-tetraphenylmethoxybutane, 2, 3, 3-tetraphenylethoxybutane, 2, 3, 3-tetra-p-methylphenoxybutane, 2, 3, 3-tetra-p-ethylphenoxybutane, 2, 3, 3-tetra-o-methylphenoxybutane, 2, 3, 3-tetra-o-ethylphenoxybutane, 2, 3, 3-tetra-m-methylphenoxybutane, 2, 3, 3-tetra-m-ethylphenoxybutane, 1, 5, 5-tetramethoxypentane, 1, 5, 5-tetraethoxypentane, 1, 5, 5-tetrapropoxypentane, 1, 5, 5-tetrabutoxypentane, 2, 1, 5, 5-tetrabutoxypentane, 2, 3, 3-tetramethylphenoxybutane, 1, 5, 5-n, 2, 3-tetramethoxypentane, 3-n, and mixtures thereof, 1, 1, 5, 5-tetraisopropoxypentane, 1, 5, 5-tetraisobutoxypentane, 1-dimethoxy-5, 5-diethoxypentane, 1, 5, 5-tetraethyleneoxypentane, 1, 5, 5-tetraallyloxypentane, 1, 5, 5-tetrapropyloxypentane, 1, 5, 5-tetracyclopropoxypentane, 1, 5, 5-tetracyclobutoxypentane, 1, 5, 5-tetracyclopentoxypentane, 1, 5, 5-tetracyclohexyloxypentane, 1, 5, 5-tetraphenoxypentane, 1, 5, 5-tetraphenylmethoxypentane, 1, 5, 5-tetraphenylethoxypentane, 1, 5, 5-tetra-p-methylphenoxypentane, 1, 1, 5, 5-tetra-p-ethylphenoxypentane, 1, 5, 5-tetra-o-methylphenoxypentane, 1, 5, 5-tetra-o-ethylphenoxypentane, 1, 5, 5-tetra-m-methylphenoxypentane, 1, 5, 5-tetra-m-ethylphenoxypentane, 1, 3, 3-tetramethoxy-2-methylpropane, 1, 3, 3-tetrapropoxy-2-methylpropane, 1, 3, 3-tetrabutoxy-2-methylpropane, 1, 3, 3-tetramethoxy-2-ethylpropane, 1, 3, 3-tetraethoxy-2-ethylpropane, 1, 1, 3, 3-tetrapropoxy-2-ethylpropane, 1, 3, 3-tetrabutoxy-2-ethylpropane, 1, 3, 3-tetramethoxy-2-propylpropane, 1, 3, 3-tetraethoxy-2-propylpropane, 1, 3, 3-tetrapropoxy-2-propylpropane, 1, 3, 3-tetrabutoxy-2-propylpropane, 1, 3, 3-tetramethoxy-2-isopropylpropane, 1, 3, 3-tetraethoxy-2-isopropylpropane, 1, 3, 3-tetrapropoxy-2-isopropylpropane, 1, 3, 3-tetrabutoxy-2-isopropylpropane, 1, 1, 3, 3-tetramethoxy-2-butylpropane, 1, 3, 3-tetraethoxy-2-butylpropane, 1, 3, 3-tetrapropoxy-2-butylpropane and 1, 1, 3, 3-tetrabutoxy-2-butylpropane.
Preferably, the tetraoxyl compound is at least one selected from tetramethoxyethane, 1, 3, 3-tetramethoxypropane, 1, 3, 3-tetraethoxy-2-methylpropane and tetraallyloxyethane.
In the invention, the tetrahydroxy compound can be prepared by a conventional synthesis method, and can also be purchased by a method for purchasing general chemical products.
During the polymerization process, the external electron donor compound may be added after pre-contacting with the solid catalyst component for a certain period of time, may be added after being mixed with the solid catalyst component for a short time, or may be added at different stages of the polymerization.
According to the invention, the tetraoxyl compound is used in an amount of 0.001 to 5.0 moles per mole of aluminum in the alkyl aluminum compound.
In the invention, the solid catalyst component can be obtained by contacting and reacting a titanium compound, a magnesium compound and an internal electron donor compound. Specifically, the solid catalyst component can be prepared according to conventional methods in the prior art, for example, the solid catalyst component is prepared by selecting the following method one or method two:
the first method comprises the steps of contacting a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an optional silane compound in an inert diluent to form a uniform solution, and then contacting and reacting the uniform solution with a titanium compound and an internal electron donor compound in the presence of a precipitation assistant to obtain a solid catalyst component.
In the first method, the magnesium compound may be selected from at least one of magnesium halide, water or alcohol complex of magnesium halide, and derivative in which one halogen atom in magnesium halide molecule is substituted by hydrocarbyloxy group or halohydrocarbyloxy group. Preferably, the magnesium compound is a magnesium halide, for example, magnesium chloride, magnesium bromide, magnesium iodide; further preferred is magnesium chloride.
The organic epoxy compound can be selected from compounds such as oxides, glycidyl ethers and internal ethers of aliphatic olefins with 2-8 carbon atoms, dienes or halogenated aliphatic olefins or dienes. Specific examples include, but are not limited to: ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
The precipitation aid can be selected from at least one of organic acid anhydride, organic acid, ether and ketone; preferably at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, and amyl ether.
The inert diluent in the first process is not particularly limited in the present invention, and may be conventionally selected in the art. The inert diluent can adopt benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbons or halogenated hydrocarbon compounds; toluene and/or xylene are preferred. In addition, the organic phosphorus compound and the silane compound are also selected from those conventional in the art.
The specific operation of the first method can be carried out according to the preparation method of the solid catalyst disclosed in patent documents CN102464746A and CN1258684A, the relevant disclosure content of which is fully incorporated into the present invention by reference.
The second method, 1) mixing the titanium compound and the magnesium halide alcohol compound carrier at the temperature of-30 ℃ to 0 ℃ to obtain a carrier suspension; 2) heating the carrier suspension to 80-130 ℃, adding the internal electron donor compound in the heating process, and reacting at constant temperature for 0.2-2h to obtain a solid precipitate; 3) and washing and drying the solid precipitate to obtain the solid catalyst component.
Optionally, in step 3), the solid precipitate is treated with a titanium compound before washing. The treatment may be performed one or more times. The inert solvent used for washing can be one or more selected from hexane, heptane, octane, decane and toluene. Further, in step 1), the mixing is optionally carried out in the presence of an inert solvent.
In the second method, the structural formula of the magnesium halide alcoholate carrier is MgX2P (ROH), wherein X is Cl, Br or I, preferably Cl; r is C1-C18Alkyl, preferably C2-C4The linear alkyl group of (1); p is 0.1-6.
The preparation method of the magnesium halide alcoholate carrier of the invention can comprise the following steps: mixing magnesium halide and low-carbon alcohol, heating to react to generate magnesium halide alcoholate melt, wherein the reaction temperature is 90-140 ℃, putting the magnesium halide alcoholate melt into a cooled inert medium after high shear action in a dispersion medium to form magnesium halide alcoholate particles, and washing and drying to obtain the magnesium halide alcoholate carrier. The high shear effect can be obtained by a conventional method such as a high-speed stirring method (for example, patent document CN00109216.2), a spraying method (for example, patent document US6020279), and a super-gravity rotating bed (for example, patent document CN1580136) and an emulsifier method (for example, patent document CN 1463990). The dispersant system (dispersion medium) can be hydrocarbon inert solvent such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert cooling medium can be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc.
The magnesium halide alcoholate carrier in the second method can be obtained by the preparation methods of patent documents CN1091748, CN1330086A, CN101050245, US6020279, CN1580136 and CN1463990, and the disclosures of which are incorporated herein by reference.
In the present invention, the internal electron donor compound may be at least one selected from mono-or poly-aliphatic carboxylic acid ester compounds and aromatic carboxylic acid ester compounds, phosphoric acid ester compounds, acid anhydrides, ketones, alcohols, amines, ether compounds and derivatives thereof, and glycol ester compounds.
According to different synthesis processes of solid catalyst components, different catalyst systems with different performances can be obtained by using different internal electron donors.
When the internal electron donor compound is a carboxylate compound, the internal electron donor compound may be selected from benzoate, phthalate, malonate, succinate, glutarate, and the like. Preferably, said internal electron donor compound is selected from the group consisting of ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl phthalate, di-octyl phthalate, di-n-butyl phthalate, di-butyl succinate, di-2, di-n-butyl succinate, di-2, di-butyl succinate, di-n-phthalate, di-butyl succinate, di-n-butyl succinate, di-n-butyl succinate, di-phthalate, di-butyl succinate, di-n-butyl succinate, di-2, di-butyl succinate, di-n-butyl succinate, di-n-2, di-butyl succinate, di-n-butyl succinate, di-n-succinate, di-succinate and di-n-butyl succinate and di-butyl succinate, At least one of diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, tributyltrimellitate, triethyl hemitrimellitate, tributyl hemitrimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate. More preferably, the internal electron donor compound is dibutyl phthalate or diisobutyl phthalate.
When the internal electron donor compound is a phosphate-based compound, non-limiting examples of the internal electron donor compound include: trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl dimethylphenyl phosphate, phenyl diisopropylphenyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, o-tolyl-p-di-tert-butylphenyl phosphate. Preferably, the internal electron donor compound is tributyl phosphate.
When the internal electron donor compound is an ether compound, it is preferable that the internal electron donor compound is selected from the group consisting of 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (, diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-methyl-propyl-2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-propyl-methyl-2-methyl-propyl-2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-propyl-2-methyl-2, 2-methyl-ethyl-2-methyl-2-ethyl-propyl-methyl-2-methyl-2, 2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-, 2, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-propyl, 2-isopropylpropane, 2-dimethoxypropane, 2-isopropylpropane, 2-isopropylpropane, 2-dimethoxypropane, 2-dimethoxypropane, 2, or a, At least one of 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene; more preferably 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane.
When the internal electron donor compound is a glycol ester compound, non-limiting examples of the internal electron donor compound include: 2-isopropyl-2-isoamyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 9-bis (phenylmethylcarboxymethyl) fluorene, etc., and 2, 4-pentanediol dibenzoate is preferable.
When the internal electron donor compound is an anhydride compound, the internal electron donor compound is preferably phthalic anhydride.
In the preparation process of the solid catalyst component, if two or more internal electron donors are contained, the used internal electron donor compounds can be used together in various ways, can be used in different steps and under different conditions, and can also be added simultaneously, and the addition of the used internal electron donor compounds is not in sequence.
According to the invention, the titanium compound has the general formula Ti (OR)w)4-kX′kWherein R iswIs C1-C20Alkyl, X' is Cl, Br or I, and k is an integer of 0 to 4.
Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
According to the invention, the molar ratio of the titanium compound to the magnesium compound in the solid catalyst component, calculated as the element Ti/Mg, is between 1: 0.5 and 150.
According to the invention, the alkylaluminum compound has the general formula AlR'dX1 3-dWherein R' is C1-C8Alkyl radical, X1Is halogen, 0 < d.ltoreq.3, identical or different when two or three R' "are present.
Preferably, the alkyl aluminium compound is triethyl aluminium, triisobutyl aluminium, tri-n-butyl aluminium, tri-n-hexyl aluminium, Al (n-C)6H13)3、Al(n-C8H17)3And AlEt2At least one of Cl.
In the present invention, the molar ratio of the aluminum in the aluminum alkyl compound to the titanium in the solid catalyst component may be 1 to 1000: 1, preferably 1 to 500: 1.
According to the invention, the alkylaluminum compound and the external electron donor compound can be contacted with the solid catalyst component either individually or as a mixture of the two components.
According to different requirements on polymer performance, the catalyst system can be directly used for olefin polymerization; or the catalyst system can be prepolymerized with olefin to generate a prepolymerized catalyst system, and then the prepolymerized catalyst system and the olefin are polymerized.
According to a second aspect of the present invention, there is provided an olefin polymerisation process comprising: contacting one or more olefins with the catalyst system described above under olefin polymerization conditions.
In the present invention, the olefin may have the general formula CH2＝CH-RVWherein R isVIs hydrogen or C1-C6An alkyl group.
Non-limiting examples of the olefins include: ethylene, propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene. The olefin is preferably propylene and/or ethylene, more preferably propylene.
In addition, the olefin may be polymerized in the presence of small amounts of diolefins, depending on the particular application.
In the present invention, the olefin polymerization reaction may be carried out in a liquid phase (liquid phase monomer or monomer dissolved in an inert solvent) or a gas phase, or may be carried out in an operation in which liquid phase and gas phase polymerization stages are combined. The olefin polymerization may be carried out according to known polymerization techniques, for example, using conventional techniques such as slurry processes, gas phase fluidized beds, and the like.
The olefin polymerization reaction conditions include: the polymerization temperature is from 0 to 150 ℃ and preferably from 60 to 90 ℃ and the polymerization pressure is normal pressure or higher.
The remaining parameters not defined in the present invention can be routinely selected according to the state of the art.
The present invention will be further described with reference to the following examples. But is not limited by these examples.
In the following examples and comparative examples:
1) the isotactic index of the polymer is determined by the n-heptane extraction method, according to GB/T2412-2008, a 2g dried polymer sample is placed in an extractor and extracted with boiling n-heptane for 6 hours, and then the residue is dried to constant weight; the ratio of the weight (g) of the resulting polymer to 2 is the isotactic index.
2) Polymer melt index: measured according to GB3682-2000 at 230 ℃ under a load of 2.16 kg.
Preparation examples 1 to 4 are intended to illustrate the preparation of the solid catalyst component of the present invention.
Preparation example 1
Into a 300mL glass reaction flask with stirring which was sufficiently purged with high-purity nitrogen gas was charged 90mL (820mmol) of titanium tetrachloride and cooled to-20 ℃ C, 37mmol of magnesium chloride alcoholate as magnesium element (prepared as disclosed in example 1 of CN 1330086A) was added thereto, followed by warming to 110 ℃ C, and during the warming, 0.3mmol of tributyl phosphate and 7.3mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added, and after maintaining at 110 ℃ C for 30min, the liquid was filtered off, washed 2 times with titanium tetrachloride, washed 5 times with hexane, and dried under vacuum to obtain solid catalyst component A for olefin polymerization.
Preparation example 2
A300 mL stirred glass reaction flask fully purged with high purity nitrogen was charged with 90mL of titanium tetrachloride and 10mL of hexane, cooled to-20 ℃ and charged with 8g of a magnesium chloride alcoholate carrier (prepared according to CN1330086A example 1, having a molar ratio of ethanol to magnesium chloride of 2.62). Then, while stirring, the temperature was gradually increased in stages, and when the temperature reached 40 ℃, 4.9mmol of 2, 4-pentanediol dibenzoate and 4.5mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added. Continuing to heat to 110 ℃, keeping the temperature constant for 0.5h to obtain a solid precipitate, filtering out liquid, adding 100mL of titanium tetrachloride into the solid each time, treating at 110 ℃ for 1 hour, and repeating the treatment step for 3 times; and then washed with hexane 5 times, and finally dried in vacuum to obtain a solid catalyst component B.
Preparation example 3
A300 mL stirred glass reaction flask fully purged with high purity nitrogen was charged with 100mL of titanium tetrachloride, cooled to-20 ℃ and charged with 8g of magnesium chloride alcoholate carrier (prepared according to CN1330086A example 1, molar ratio of ethanol to magnesium chloride in carrier was 2.62). Gradually heating to 110 ℃, adding 2.5mmol of 2, 4-pentanediol dibenzoate prepared in preparation example 1 and 3.9mmol of dibutyl phthalate in the heating process, keeping the temperature at 110 ℃ for 0.5h to obtain a solid precipitate, filtering out liquid, adding 100mL of titanium tetrachloride for treatment twice, washing with hexane five times, and drying in vacuum to obtain a solid catalyst component C.
Preparation example 4
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 50 ℃ under stirring, the mixture is maintained for 2.5 hours to completely dissolve the solid, 1.4g of phthalic anhydride is added, and the mixture is maintained for 1 hour. Cooling the solution to below-25 ℃, and dripping TiCl within 1 hour4And (2) slowly heating to 80 ℃, gradually separating out a solid in the heating process, adding 6mmol of 2, 4-pentanediol dibenzoate, maintaining the temperature for 1 hour, filtering, adding 70mL of toluene, and washing twice to obtain a solid precipitate. Then 60mL of toluene, TiCl, was added to the solid440mL, warmed to 100 ℃ for 2 hours, and the filtrate was drained and the treatment was repeated. Adding 60mL of toluene, washing for three times in a boiling state, adding 60mL of hexane, and washing for two times in the boiling state to obtain a solid catalyst component D.
Examples 1-46 are intended to illustrate the catalyst system and olefin polymerization process of the present invention.
Examples 1 to 7
In a 5 l autoclave, purged with a stream of nitrogen at 70 ℃ for 1 hour, then the polymerization vessel was replaced 3 times with gaseous propylene, and 5mL of a hexane solution of Triethylaluminum (TEAL) (the concentration of triethylaluminum is 0.5mmol/mL), a hexane solution of an external electron donor (the concentration of the external electron donor is 0.1mmol/mL), 10mL of anhydrous hexane and 4 to 12mg of the solid catalyst component A were introduced under nitrogen protection. The autoclave was closed, and a set amount of hydrogen and 1.0 to 1.2kg of liquid propylene were introduced; the temperature in the kettle was rapidly raised to 70 ℃ with stirring. After polymerization was carried out at 70 ℃ for 1 hour (see remarks for polymerization time test), stirring was stopped, unpolymerized propylene monomer was removed, and the polymer was collected and vacuum-dried at 70 ℃ for 2 hours, to thereby obtain polypropylene. Wherein the added external electron donors are 1, 1, 3, 3-Tetramethoxypropane (TMOP) respectively. The amount of hydrogen added, the amount of external electron donor added, the polymerization time, the polymerization activity of the catalyst system and the polypropylene properties are shown in Table 1.
Examples 8 to 15
Propylene polymerization was conducted in the same manner as in examples 1 to 7 except that the solid catalyst component B was used as a main catalyst in the polymerization. The hydrogenation amount, the external electron donor amount, the polymerization time, the polymerization temperature, the polymerization activity of the catalyst system and the polypropylene properties are shown in Table 1.
Examples 16 to 21
Propylene polymerization was conducted in the same manner as in examples 1 to 7 except that the solid catalyst component C was used as a main catalyst in the polymerization. The hydrogenation amount, the external electron donor amount, the polymerization activity of the catalyst system and the polypropylene performance are shown in Table 1.
Examples 22 to 27
Propylene polymerization was conducted in the same manner as in examples 1 to 7 except that the solid catalyst component D was used as a main catalyst in the polymerization. The hydrogenation amount, the external electron donor amount, the polymerization activity of the catalyst system and the polypropylene performance are shown in Table 1.
Examples 28 to 30
Propylene polymerization was conducted in the same manner as in examples 1 to 7 except that 1, 1, 3, 3-tetraethoxy-2-methylpropane (TEOMP) was used as an external electron donor. The amount of hydrogenation, the polymerization time, the polymerization activity of the catalyst system and the properties of the polypropylene are shown in Table 1.
Examples 31 to 33
Propylene polymerization was conducted in the same manner as in examples 28 to 30 except that the solid catalyst component B was used as a main catalyst in the polymerization. The amount of hydrogenation, the polymerization time, the polymerization activity of the catalyst system and the properties of the polypropylene are shown in Table 1.
Examples 34 to 36
Propylene polymerization was conducted in the same manner as in examples 28 to 30 except that the solid catalyst component C was used as a main catalyst in the polymerization. The amount of hydrogenation, the polymerization time, the polymerization activity of the catalyst system and the properties of the polypropylene are shown in Table 1.
Example 37
Propylene polymerization was carried out in the same manner as in examples 1 to 7 except that Tetraallyloxyethane (TAOE) was used as an external electron donor. The amount of hydrogenation, the polymerization activity of the catalyst system and the polypropylene properties are shown in Table 1.
Examples 38 to 40
Propylene polymerization was conducted in the same manner as in example 37 except that the solid catalyst component B was used as a main catalyst in the polymerization. The amount of hydrogenation, the polymerization activity of the catalyst system and the polypropylene properties are shown in Table 1.
Examples 41 to 42
Propylene polymerization was conducted in the same manner as in example 37 except that the solid catalyst component C was used as a main catalyst in the polymerization. The amount of hydrogenation, the polymerization activity of the catalyst system and the polypropylene properties are shown in Table 1.
Examples 43 to 46
Propylene polymerization was conducted in the same manner as in example 37 except that the solid catalyst component D was used as a main catalyst in the polymerization. The amount of hydrogenation, the polymerization time, the polymerization activity of the catalyst system and the properties of the polypropylene are shown in Table 1.
Comparative examples 1 to 4
The polymerization process was the same as in examples 1-7, except that the solid catalyst component A was used as a main catalyst during polymerization, and the added external electron donor was changed to a hexane solution of methylcyclohexyldimethoxysilane (C-doror) at a concentration of 0.1mmol/mL, to thereby obtain polypropylene. The amount of hydrogenation, polymerization time, polymerization activity and properties of polypropylene are shown in Table 1.
Comparative examples 5 to 8
The polymerization process was the same as in examples 1-7, except that the catalyst B was used as a main catalyst during the polymerization, and the added external electron donor was changed to a hexane solution of methylcyclohexyldimethoxysilane (C-doror) at a concentration of 0.1mmol/mL, thereby obtaining polypropylene. The amount of hydrogenation, polymerization time, polymerization activity and properties of polypropylene are shown in Table 1.
Comparative examples 9 to 15
The polymerization process was the same as in examples 1 to 7, except that the catalyst C was used as a main catalyst during the polymerization, and the added external electron donor was changed to methylcyclohexyldimethoxysilane (C-donor) or dicyclopentyldimethoxysilane (D-donor) in hexane solution (the concentrations of C-donor and D-donor were 0.1mmol/mL), thereby obtaining polypropylene. The amount of hydrogenation, polymerization time, polymerization activity and properties of polypropylene are shown in Table 1.
Comparative examples 16 to 21
The polymerization process was the same as in examples 1 to 7, except that the catalyst D was used as a main catalyst during the polymerization, and the added external electron donor was changed to methylcyclohexyldimethoxysilane (C-donor) or dicyclopentyldimethoxysilane (D-donor) in hexane solution (the concentrations of C-donor and D-donor were 0.1mmol/mL), thereby obtaining polypropylene. The amount of hydrogenation, polymerization activity and properties of polypropylene are shown in Table 1.
TABLE 1
*: al represents triethyl aluminum, and Si represents an external electron donor; the remarks are the polymerization times or polymerization temperatures of the corresponding examples.
As can be seen from the data in Table 1, the use of the external electron donor of the present invention can obtain a polymer with better performance by using different main catalysts in combination with different external electron donors while maintaining the good overall performance of the catalyst. For A, B, C, D four-system catalyst, the invention can obtain a catalyst system with better hydrogen regulation sensitivity, and the polymerization activity of the catalyst is slowly attenuated.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A catalyst system for the polymerization of olefins, the catalyst system comprising the reaction product of:
1) a solid catalyst component comprising titanium, magnesium, a halogen and an internal electron donor compound;
2) an alkyl aluminum compound;
3) an external electron donor compound selected from at least one of the tetrahydrocarbyloxy compounds represented by formula (I) or formula (II):
in the formula (I) and the formula (II), R1、R2、R3、R4、R1、R2、R3The same or different, each is selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched double bond-containing alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl or arylalkyl group having 7 to 20 carbon atoms.
2. The catalyst system for olefin polymerization according to claim 1, wherein R in the formula (I) or (II)1、R2、R3、R4、R1、R2、R3The same or different, each is selected from linear or branched alkyl with 1-10 carbon atoms, linear or branched alkene with double structure with 2-10 carbon atoms, naphthenic base with 3-6 carbon atoms, aryl with 6-10 carbon atoms, alkylaryl or arylalkyl with 7-12 carbon atoms;
the tetraoxyl compound is used in an amount of 0.001 to 5.0 moles per mole of aluminum in the alkyl aluminum compound.
3. The catalyst system for olefin polymerization according to claim 1 or 2, wherein the tetraoxyl compound is selected from tetramethoxyethane, tetraethoxyethane, tetrapropoxyethane, tetrabutoxyethane, tetraisopropoxyethane, tetraisobutoxyethane, 1-dimethoxy-3, 3-diethoxyethane, tetraethoxyethane, tetrapropoxyethane, tetracyclopropoxyethane, tetracyclobutoxyethane, tetracyclopentoxyethane, tetracyclohexyloxyethane, tetraphenoxyethane, tetraphenylmethoxyethane, tetraphenylethoxyethane, tetra-p-methylphenoxyethane, tetra-p-ethylphenoxyethane, tetra-o-methylphenoxyethane, tetra-m-ethylphenoxyethane, 1, 3, 3-tetramethoxypropane, tetrakis-methoxypropane, tetrakis-methoxyphenoxyethane, tetra-n-ethylphenoxyethane, tetra-m-methylphenoxyethane, tetra-m-phenoxyethane, 1, 3, 3-tetramethoxypropane, and a, 1, 1, 3, 3-tetraethoxypropane, 1, 3, 3-tetrapropoxypropane, 1, 3, 3-tetrabutoxypropane, 1, 3, 3-tetraisopropoxypropane, 1, 3, 3-tetraisobutoxypropane, 1-dimethoxy-3, 3-diethoxypropane, 1, 3, 3-tetraenyloxypropane, 1, 3, 3-tetraallyloxypropylene, 1, 3, 3-tetrapropyloxypropane, 1, 3, 3-tetracyclopropoxypropane, 1, 3, 3-tetracyclobutoxypropane, 1, 3, 3-tetracyclopentoxypropane, 1, 3, 3-tetracyclohexyloxypropane, 1, 3, 3-tetraphenoxypropane, 1, 1, 3, 3-tetraphenylmethoxypropane, 1, 3, 3-tetraphenylethoxypropane, 1, 3, 3-tetra-p-methylphenoxypropane, 1, 3, 3-tetra-p-ethylphenoxypropane, 1, 3, 3-tetra-o-methylphenoxypropane, 1, 3, 3-tetra-o-ethylphenoxypropane, 1, 3, 3-tetra-m-methylphenoxypropane, 1, 3, 3-tetra-m-ethylphenoxypropane, 1, 3, 3-tetramethoxybutane, 1, 3, 3-tetraethoxybutane, 1, 3, 3-tetrapropoxybutane, 1, 3, 3-tetrabutoxybutane, 1, 3, 3-tetraisopropoxybutane, 1, 3, 3-tetraisobutoxybutane, 1, 1-dimethoxy-3, 3-diethoxybutane, 1, 3, 3-tetraethyleneoxybutane, 1, 3, 3-tetraallyloxybutane, 1, 3, 3-tetrapropyloxybutane, 1, 3, 3-tetracyclopropoxybutane, 1, 3, 3-tetracyclobutoxybutane, 1, 3, 3-tetracyclopentoxybutane, 1, 3, 3-tetracyclohexyloxybutane, 1, 3, 3-tetraphenoxybutane, 1, 3, 3-tetraphenylmethoxybutane, 1, 3, 3-tetraphenylethoxybutane, 1, 3, 3-tetra-p-methylphenoxybutane, 1, 3, 3-tetra-o-methylphenoxybutane, 1, 1, 3, 3-tetra-o-ethylphenoxybutane, 1, 3, 3-tetra-m-methylphenoxybutane, 1, 3, 3-tetra-m-ethylphenoxybutane, 2, 3, 3-tetramethoxybutane, 2, 3, 3-tetraethoxybutane, 2, 3, 3-tetrapropoxybutane, 2, 3, 3-tetrabutoxybutane, 2, 3, 3-tetraisopropoxybutane, 2, 3, 3-tetraisobutoxybutane, 2-dimethoxy-3, 3-diethoxybutane, 2, 3, 3-tetraethoxybutane, 2, 3, 3-tetraallyloxybutane, 2, 3, 3-tetrapropyloxybutane, 2, 3, 3-tetracyclopropoxybutane, 2, 2, 3, 3-tetracyclobutoxybutane, 2, 3, 3-tetracyclopentoxybutane, 2, 3, 3-tetracyclohexyloxybutane, 2, 3, 3-tetraphenoxybutane, 2, 3, 3-tetraphenylmethoxybutane, 2, 3, 3-tetraphenoxyethobutane, 2, 3, 3-tetra-p-methylphenoxybutane, 2, 3, 3-tetra-p-ethylphenoxybutane, 2, 3, 3-tetra-o-methylphenoxybutane, 2, 3, 3-tetra-o-ethylphenoxybutane, 2, 3, 3-tetra-m-methylphenoxybutane, 2, 3, 3-tetra-m-ethylphenoxybutane, 1, 5, 5-tetramethoxypentane, 1, 5, 5-tetraethoxypentane, 1, 1, 1, 5, 5-tetrapropoxypentane, 1, 5, 5-tetrabutoxypentane, 1, 5, 5-tetraisopropoxypentane, 1, 5, 5-tetraisobutoxypentane, 1-dimethoxy-5, 5-diethoxypentane, 1, 5, 5-tetraenyloxypentane, 1, 5, 5-tetraallyloxypentane, 1, 5, 5-tetrapropyloxypentane, 1, 5, 5-tetracyclopropoxypentane, 1, 5, 5-tetracyclobutoxypentane, 1, 5, 5-tetracyclopentoxypentane, 1, 5, 5-tetracyclohexyloxypentane, 1, 5, 5-tetraphenoxypentane, 1, 5, 5-tetraphenmethoxypentane, 1, 1, 5, 5-tetraphenylethoxypentane, 1, 5, 5-tetra-p-methylphenoxypentane, 1, 5, 5-tetra-p-ethylphenoxypentane, 1, 5, 5-tetra-o-methylphenoxypentane, 1, 5, 5-tetra-o-ethylphenoxypentane, 1, 5, 5-tetra-m-methylphenoxypentane, 1, 5, 5-tetra-m-ethylphenoxypentane, 1, 3, 3-tetramethoxy-2-methylpropane, 1, 3, 3-tetraethoxy-2-methylpropane, 1, 3, 3-tetrapropoxy-2-methylpropane, 1, 3, 3-tetrabutoxy-2-methylpropane, 1, 3, 3-tetramethoxy-2-ethylpropane, 1, 1, 3, 3-tetraethoxy-2-ethylpropane, 1, 3, 3-tetrapropoxy-2-ethylpropane, 1, 3, 3-tetrabutoxy-2-ethylpropane, 1, 3, 3-tetramethoxy-2-propylpropane, 1, 3, 3-tetraethoxy-2-propylpropane, 1, 3, 3-tetrapropoxy-2-propylpropane, 1, 3, 3-tetrabutoxy-2-propylpropane, 1, 3, 3-tetramethoxy-2-isopropylpropane, 1, 3, 3-tetraethoxy-2-isopropylpropane, 1, 3, 3-tetrapropoxy-2-isopropylpropane, At least one of 1, 1, 3, 3-tetrabutoxy-2-isopropyl propane, 1, 3, 3-tetramethoxy-2-butyl propane, 1, 3, 3-tetraethoxy-2-butyl propane, 1, 3, 3-tetrapropoxy-2-butyl propane, and 1, 1, 3, 3-tetrabutoxy-2-butyl propane;
preferably, the tetraoxyl compound is at least one selected from tetramethoxyethane, 1, 3, 3-tetramethoxypropane, 1, 3, 3-tetraethoxy-2-methylpropane and tetraallyloxyethane.
4. The catalyst system for the polymerization of olefins according to claim 1, wherein the solid catalyst component is prepared by the following method: the method comprises the following steps of (1) carrying out contact reaction on a titanium compound, a magnesium compound and an internal electron donor compound to obtain a solid catalyst component;
the internal electron donor compound is at least one selected from mono-element or multi-element aliphatic carboxylic ester compounds and aromatic carboxylic ester compounds, phosphate ester compounds, acid anhydrides, ketones, alcohols, amines, ether compounds and derivatives thereof, and glycol ester compounds.
5. The catalyst system for olefin polymerization according to claim 1 or 4, wherein the internal electron donor compound is selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl phthalate, Diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl hemimellitate, tributyl hemimellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phenyl phosphate, phenyl dimethyl phosphate, cresyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl dimethyl phosphate, phenyl diisopropyl phenyl phosphate, p-cresyl dibutyl phosphate, m-cresyl dibutyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, dimethyl naphthalene phosphate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl phosphate, tributyl naphthalene phosphate, triethyl naphthalene dicarboxylate, triethyl naphthalene phosphonate, and the like, O-tolylp-di-tert-butylphenyl phosphate, 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-dimethyl-2-propyl-dimethoxypropane, 2-dimethyl-propyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-2-propyl-dimethoxypropane, 2-propyl-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-dimethyl-1, 2-dimethyl-propyl-dimethyl-propyl, 2, and the same, 2, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 2-cyclohexyl-2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-propanediol dibenzoate, 3, 5-heptanediol dibenzoate, 2-methyl-2-propyl-2-isopentyl-1, 3-propanediol dibenzoate, 2, 3, 5-propanediol dibenzoate, 2-methyl-ethyl-carbonate, 2-butyl-2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-methyl-1, 3-dimethoxypropane, 3-diol dibenzoate, 3-methyl-dimethyl-one, 2-dimethyl-one, 2, or a, 2, or a, 2, or a, 2, or a, 2, or a, 2, or a, At least one of 4-ethyl-3, 5-heptanediol dibenzoate and 9, 9-bis (phenylmethylcarboxymethyl) fluorene;
preferably, the internal electron donor compound is at least one selected from the group consisting of dibutyl phthalate, diisobutyl phthalate, tributyl phosphate, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane and 2, 4-pentanediol dibenzoate.
6. The catalyst system for the polymerization of olefins according to claim 4 in which the titanium compound has the general formula Ti (OR)w)4-kX′kWherein R iswIs C1-C20Alkyl, X' is Cl, Br or I, and k is an integer of 0-4;
preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, and trichloromonoethoxytitanium;
in the solid catalyst component, the molar ratio of the titanium compound to the magnesium compound is 1: 0.5-150 calculated by element Ti/Mg.
7. Catalyst system for the polymerization of olefins according to claim 1 in which the alkylaluminum compound has the general formula AlR'dX1 3-dWherein R' "is C1-C8Alkyl radical, X1Is halogen, d is more than 0 and less than or equal to 3, and when two or three R's are contained, each R' is the same or different;
preferably, the alkyl aluminium compound is triethyl aluminium, triisobutyl aluminium, tri-n-butyl aluminium, tri-n-hexyl aluminium, Al (n-C)6H13)3、Al(n-C8H17)3And AlEt2At least one of Cl;
the molar ratio of aluminium in the aluminium alkyl compound to titanium in the solid catalyst component is from 1 to 1000: 1, preferably from 1 to 500: 1.
8. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst system of any of claims 1-7 under olefin polymerization conditions.
9. The olefin polymerization process of claim 8, wherein the olefin has the general formula CH2＝CH-RVWherein R isVIs hydrogen or C1-C6An alkyl group; the olefin is preferably propylene and/or ethylene, more preferably propylene.
10. The olefin polymerization process of claim 8, wherein the olefin polymerization reaction conditions comprise: the polymerization temperature is from 0 to 150 ℃ and preferably from 60 to 90 ℃ and the polymerization pressure is normal pressure or higher.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042157A (en) * | 1988-09-30 | 1990-05-16 | 希蒙特公司 | Olefin polymerization catalysis |
| CN1316442A (en) * | 2000-03-30 | 2001-10-10 | 住友化学工业株式会社 | Method of preparing catalyst for olefines polymerizing and preparation method of olefin polymer |
| CN109096416A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The preparation method of catalyst component for olefin polymerization and preparation method thereof and olefin polymerization catalysis and olefin polymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042157A (en) * | 1988-09-30 | 1990-05-16 | 希蒙特公司 | Olefin polymerization catalysis |
| CN1316442A (en) * | 2000-03-30 | 2001-10-10 | 住友化学工业株式会社 | Method of preparing catalyst for olefines polymerizing and preparation method of olefin polymer |
| CN109096416A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The preparation method of catalyst component for olefin polymerization and preparation method thereof and olefin polymerization catalysis and olefin polymer |
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