CN114805647B - Catalyst composition for olefin polymerization and application thereof - Google Patents
Catalyst composition for olefin polymerization and application thereof Download PDFInfo
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- CN114805647B CN114805647B CN202210386118.7A CN202210386118A CN114805647B CN 114805647 B CN114805647 B CN 114805647B CN 202210386118 A CN202210386118 A CN 202210386118A CN 114805647 B CN114805647 B CN 114805647B
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- CN
- China
- Prior art keywords
- benzoate
- compound
- butyl
- malonate
- heptanediol
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 44
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 239000011949 solid catalyst Substances 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 150000002170 ethers Chemical class 0.000 claims abstract description 3
- -1 alkyl aluminum compound Chemical class 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 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 5
- RDAWEBNAEYZNNL-UHFFFAOYSA-N 4-ethylheptane-3,5-diol Chemical compound CCC(O)C(CC)C(O)CC RDAWEBNAEYZNNL-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 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
- 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 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- QKXKUNZWVMVMAL-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,7-dimethyloctane Chemical compound COCC(CC(C)C)(COC)CCC(C)C QKXKUNZWVMVMAL-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- WKNTTWKXLKQFIX-UHFFFAOYSA-N bis(2-methylpropyl) 2,3-bis(2-methylpropyl)butanedioate Chemical compound CC(C)COC(=O)C(CC(C)C)C(CC(C)C)C(=O)OCC(C)C WKNTTWKXLKQFIX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000007519 polyprotic acids Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 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
- VLNWOAXHHCJYKZ-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2-methylhexane Chemical compound CCCC(COC)(COC)C(C)C VLNWOAXHHCJYKZ-UHFFFAOYSA-N 0.000 claims description 2
- DYBLSSRNAVRHCO-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2-methylheptane Chemical compound CCCC(COC)(COC)CC(C)C DYBLSSRNAVRHCO-UHFFFAOYSA-N 0.000 claims description 2
- SYHQXEMTUUJSQS-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2-methylnonane Chemical compound CCCCCC(COC)(COC)CC(C)C SYHQXEMTUUJSQS-UHFFFAOYSA-N 0.000 claims description 2
- KXNSSSBEJVRWCG-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2-methyloctane Chemical compound CCCCC(COC)(COC)CC(C)C KXNSSSBEJVRWCG-UHFFFAOYSA-N 0.000 claims description 2
- JEBVXRABSSMSGU-UHFFFAOYSA-N 4,4-bis(methoxymethyl)octane Chemical compound CCCCC(CCC)(COC)COC JEBVXRABSSMSGU-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
- 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 2
- URCWVERZGIEEQN-UHFFFAOYSA-N 5,5-bis(methoxymethyl)-2-methylnonane Chemical compound CCCCC(COC)(COC)CCC(C)C URCWVERZGIEEQN-UHFFFAOYSA-N 0.000 claims description 2
- LMEDZKRKRMGCAS-UHFFFAOYSA-N 5,5-bis(methoxymethyl)-2-methyloctane Chemical compound CCCC(COC)(COC)CCC(C)C LMEDZKRKRMGCAS-UHFFFAOYSA-N 0.000 claims description 2
- SYQQENUCDWAZKU-UHFFFAOYSA-N 7-ethyl-5,5-bis(methoxymethyl)-2-methylnonane Chemical compound C(CC(C)C)C(COC)(COC)CC(CC)CC SYQQENUCDWAZKU-UHFFFAOYSA-N 0.000 claims description 2
- HPLKIGUFDPCPKV-UHFFFAOYSA-N bis(2-methylpropyl) 2,3-dibutylbutanedioate Chemical compound C(CCC)C(C(=O)OCC(C)C)C(C(=O)OCC(C)C)CCCC HPLKIGUFDPCPKV-UHFFFAOYSA-N 0.000 claims description 2
- ZNMIGSMSMLEKGI-UHFFFAOYSA-N bis(2-methylpropyl) 2,3-dipropylbutanedioate Chemical compound CC(C)COC(=O)C(CCC)C(CCC)C(=O)OCC(C)C ZNMIGSMSMLEKGI-UHFFFAOYSA-N 0.000 claims description 2
- IBQZHKUFRSQWEJ-UHFFFAOYSA-N bis(2-methylpropyl) 4-bromobenzene-1,2-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(Br)C=C1C(=O)OCC(C)C IBQZHKUFRSQWEJ-UHFFFAOYSA-N 0.000 claims description 2
- HVTZPAKTPAZTBQ-UHFFFAOYSA-N bis(2-methylpropyl) 4-methylbenzene-1,2-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(C)C=C1C(=O)OCC(C)C HVTZPAKTPAZTBQ-UHFFFAOYSA-N 0.000 claims description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 2
- MOYILVSDIVNUDO-UHFFFAOYSA-N dibutyl 4-bromobenzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=C(Br)C=C1C(=O)OCCCC MOYILVSDIVNUDO-UHFFFAOYSA-N 0.000 claims description 2
- QFDIPTVSUHQNNT-UHFFFAOYSA-N dibutyl 4-methylbenzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C)C=C1C(=O)OCCCC QFDIPTVSUHQNNT-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
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 2
- NNDOHYGFLASMFR-UHFFFAOYSA-N diethyl 2,2-dipropylpropanedioate Chemical compound CCOC(=O)C(CCC)(CCC)C(=O)OCC NNDOHYGFLASMFR-UHFFFAOYSA-N 0.000 claims description 2
- AVLHXEDOBYYTGV-UHFFFAOYSA-N diethyl 2,3-bis(2-methylpropyl)butanedioate Chemical compound CCOC(=O)C(CC(C)C)C(CC(C)C)C(=O)OCC AVLHXEDOBYYTGV-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
- RPFNAJGCHRWCRI-UHFFFAOYSA-N diethyl 2,3-dibutylbutanedioate Chemical compound CCCCC(C(=O)OCC)C(CCCC)C(=O)OCC RPFNAJGCHRWCRI-UHFFFAOYSA-N 0.000 claims description 2
- WWIDLUJSQINFMG-UHFFFAOYSA-N diethyl 2,3-dipropylbutanedioate Chemical compound CCOC(=O)C(CCC)C(CCC)C(=O)OCC WWIDLUJSQINFMG-UHFFFAOYSA-N 0.000 claims description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 150000008379 phenol ethers Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- BQWORYKVVNTRAW-UHFFFAOYSA-N heptane-3,5-diol Chemical compound CCC(O)CC(O)CC BQWORYKVVNTRAW-UHFFFAOYSA-N 0.000 claims 8
- ZQVKTHRQIXSMGY-UHFFFAOYSA-M 4-ethylbenzoate Chemical compound CCC1=CC=C(C([O-])=O)C=C1 ZQVKTHRQIXSMGY-UHFFFAOYSA-M 0.000 claims 1
- GUNIIZNPUZBGEZ-UHFFFAOYSA-N 4-methylheptane-3,5-diol Chemical compound CCC(O)C(C)C(O)CC GUNIIZNPUZBGEZ-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 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 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 150000003609 titanium compounds Chemical class 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 6
- 150000002681 magnesium compounds Chemical class 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002690 malonic acid derivatives Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YVVDKVRIXQXQGL-UHFFFAOYSA-N (5-benzoyloxy-4-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(C)C(CC)OC(=O)C1=CC=CC=C1 YVVDKVRIXQXQGL-UHFFFAOYSA-N 0.000 description 1
- ZQGWBPQBZHMUFG-UHFFFAOYSA-N 1,1-dimethylthiourea Chemical compound CN(C)C(N)=S ZQGWBPQBZHMUFG-UHFFFAOYSA-N 0.000 description 1
- SLWNWODQXZGDES-UHFFFAOYSA-N 1,3-dimethoxy-5-methylheptane Chemical compound CC(CC(CCOC)OC)CC SLWNWODQXZGDES-UHFFFAOYSA-N 0.000 description 1
- NZLADODZCMJITO-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)O.C(C1=CC=CC=C1)(=O)O.CCC(CCCC)O Chemical compound C(C1=CC=CC=C1)(=O)O.C(C1=CC=CC=C1)(=O)O.CCC(CCCC)O NZLADODZCMJITO-UHFFFAOYSA-N 0.000 description 1
- MVJSLTMEEOSFIE-UHFFFAOYSA-N CC[AlH]CC.Cl Chemical compound CC[AlH]CC.Cl MVJSLTMEEOSFIE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LYUUVYQGUMRKOV-UHFFFAOYSA-N Diethyl diallylmalonate Chemical compound CCOC(=O)C(CC=C)(CC=C)C(=O)OCC LYUUVYQGUMRKOV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 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 description 1
- UKDMOYCITFFGNN-UHFFFAOYSA-N bis(2-methylpropyl) 2-methylpropanedioate Chemical compound CC(C)COC(=O)C(C)C(=O)OCC(C)C UKDMOYCITFFGNN-UHFFFAOYSA-N 0.000 description 1
- SWBJZPDGKVYSLT-UHFFFAOYSA-N bis(2-methylpropyl) propanedioate Chemical compound CC(C)COC(=O)CC(=O)OCC(C)C SWBJZPDGKVYSLT-UHFFFAOYSA-N 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- BDGJRWFEEJVDBX-UHFFFAOYSA-N but-1-ene;4-methylpent-1-ene Chemical compound CCC=C.CC(C)CC=C BDGJRWFEEJVDBX-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- MJUPCHKLIXLNHM-UHFFFAOYSA-N butyl-dimethoxy-propan-2-ylsilane Chemical compound CCCC[Si](OC)(OC)C(C)C MJUPCHKLIXLNHM-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- YRMPTIHEUZLTDO-UHFFFAOYSA-N cyclopentyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCC1 YRMPTIHEUZLTDO-UHFFFAOYSA-N 0.000 description 1
- PYKIHPRFFNLVMF-UHFFFAOYSA-N dibutyl 2-methylpropanedioate Chemical compound CCCCOC(=O)C(C)C(=O)OCCCC PYKIHPRFFNLVMF-UHFFFAOYSA-N 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- UELKSYXXNGHTSE-UHFFFAOYSA-N diethyl 2,2-dimethylpropanedioate Chemical compound CCOC(=O)C(C)(C)C(=O)OCC UELKSYXXNGHTSE-UHFFFAOYSA-N 0.000 description 1
- VQAZCUCWHIIFGE-UHFFFAOYSA-N diethyl 2-ethylpropanedioate Chemical compound CCOC(=O)C(CC)C(=O)OCC VQAZCUCWHIIFGE-UHFFFAOYSA-N 0.000 description 1
- NQSVPQIOJRYMGQ-UHFFFAOYSA-N diethyl 2-methyl-2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C)(C(C)C)C(=O)OCC NQSVPQIOJRYMGQ-UHFFFAOYSA-N 0.000 description 1
- DTHLCPJSRSNVLX-UHFFFAOYSA-N diethyl 2-methyl-2-propylpropanedioate Chemical compound CCOC(=O)C(C)(CCC)C(=O)OCC DTHLCPJSRSNVLX-UHFFFAOYSA-N 0.000 description 1
- UPQZOUHVTJNGFK-UHFFFAOYSA-N diethyl 2-methylpropanedioate Chemical compound CCOC(=O)C(C)C(=O)OCC UPQZOUHVTJNGFK-UHFFFAOYSA-N 0.000 description 1
- BYQFBFWERHXONI-UHFFFAOYSA-N diethyl 2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C(C)C)C(=O)OCC BYQFBFWERHXONI-UHFFFAOYSA-N 0.000 description 1
- GRRSDGHTSMJICM-UHFFFAOYSA-N diethyl 2-propylpropanedioate Chemical compound CCOC(=O)C(CCC)C(=O)OCC GRRSDGHTSMJICM-UHFFFAOYSA-N 0.000 description 1
- FGYDHYCFHBSNPE-UHFFFAOYSA-N diethyl phenylmalonate Chemical compound CCOC(=O)C(C(=O)OCC)C1=CC=CC=C1 FGYDHYCFHBSNPE-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 description 1
- GRRSIURPYQMDIG-UHFFFAOYSA-N dipropan-2-yl 2-methylpropanedioate Chemical compound CC(C)OC(=O)C(C)C(=O)OC(C)C GRRSIURPYQMDIG-UHFFFAOYSA-N 0.000 description 1
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 1
- RZSUKLPCTYXZSU-UHFFFAOYSA-N dipropyl 2-ethylpropanedioate Chemical compound CCCOC(=O)C(CC)C(=O)OCCC RZSUKLPCTYXZSU-UHFFFAOYSA-N 0.000 description 1
- XYTCGJMKSLBRMP-UHFFFAOYSA-N dipropyl 2-methylpropanedioate Chemical compound CCCOC(=O)C(C)C(=O)OCCC XYTCGJMKSLBRMP-UHFFFAOYSA-N 0.000 description 1
- LWIWFCDNJNZEKB-UHFFFAOYSA-N dipropyl propanedioate Chemical compound CCCOC(=O)CC(=O)OCCC LWIWFCDNJNZEKB-UHFFFAOYSA-N 0.000 description 1
- WFALCSMFRJIZOX-UHFFFAOYSA-N ditert-butyl 2-ethylpropanedioate Chemical compound CC(C)(C)OC(=O)C(CC)C(=O)OC(C)(C)C WFALCSMFRJIZOX-UHFFFAOYSA-N 0.000 description 1
- GBWGGPUIWKWJIT-UHFFFAOYSA-N ditert-butyl 2-methylpropanedioate Chemical compound CC(C)(C)OC(=O)C(C)C(=O)OC(C)(C)C GBWGGPUIWKWJIT-UHFFFAOYSA-N 0.000 description 1
- UYQYKBUQBMOSBU-UHFFFAOYSA-N ditert-butyl 2-propylpropanedioate Chemical compound CC(C)(C)OC(=O)C(CCC)C(=O)OC(C)(C)C UYQYKBUQBMOSBU-UHFFFAOYSA-N 0.000 description 1
- CLPHAYNBNTVRDI-UHFFFAOYSA-N ditert-butyl propanedioate Chemical compound CC(C)(C)OC(=O)CC(=O)OC(C)(C)C CLPHAYNBNTVRDI-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-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
Abstract
The invention provides a catalyst composition for olefin polymerization and application thereof, the catalyst composition comprises a solid catalyst component a, aluminum alkyl b and a malonate compound C with an external electron donor having a structure of a general formula (I), wherein the solid catalyst component a comprises magnesium, titanium, halogen and at least one of internal electron donors containing lone pair electrons such as ethers and esters; the external electron donor C can also be a mixture of diether compound with a general formula (II) and alkoxysilane with a general formula (III) and malonate with a general formula (I), and the activity of the solid catalyst component a has a high-temperature self-extinguishing effect when the solid catalyst component a is subjected to olefin polymerization in the presence of the external electron donor C.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and relates to a catalyst composition for olefin polymerization and application thereof.
Background
It is known that a solid titanium catalyst component having magnesium, titanium, halogen and an electron donor as essential components can be used for olefin polymerization, particularly in polymerization of alpha-olefins having 3 carbon atoms or more, to obtain a polymer having a high yield and a high isotacticity, wherein an electron donor compound is one of essential components in the catalyst component, and as an internal electron donor compound is developed to cause continuous renewal of a polyolefin catalyst, an external electron donor is also required to be developed in cooperation with an internal electron donor. At present, various electron donor compounds such as mono-OR polycarboxylic acid esters, ketones, mono-OR polyether, amines and the like and derivatives thereof, as well as external electron donors, organosiloxane compounds of the general formula RnSi (OR) 4-n, have been disclosed in large numbers. The external electron donor is matched with the existing solid catalyst, can have higher activity and orientation capability when being applied to catalyzing propylene polymerization, but is applied to certain occasions, particularly gas phase processes, because the gas medium is not uniformly dispersed, the heat transfer effect is not as uniform as that in the liquid phase medium, local hot spots can occur in the polymerization process, and the catalyst still has higher activity at high temperature, so that the explosion polymerization phenomenon can occur.
The invention patent CN101835812A discloses an external electron donor with high-temperature self-extinguishing function, but the use amount of the external electron donor is large, if the ratio of the required aluminum alkyl to the use amount of the external electron donor is smaller than 4, the orientation capability is not high, and the activity is still to be improved.
Disclosure of Invention
By the general formula R 1 R 2 C(COOR 3 )(COOR 4 ) When the malonate compound (I) is matched with the existing solid catalyst, the malonate compound has the function of self-extinguishing at high temperature, namely the activity at high temperature is far lower than that of the existing catalyst system at normal temperature, and meanwhile, the malonate compound (I) is small in dosage and high in catalyst orientation capability and activity.
The invention further provides the use of the catalyst composition of the invention in the polymerization of olefins.
To achieve the above object, according to a first aspect of the present invention, there is provided a catalyst composition for preparing an olefin polymer, comprising the following components:
a. a solid catalyst component comprising Mg, ti, halogen and an internal electron donor compound comprising a lone pair of electrons, such as O, N, P, S;
b. an alkyl aluminum compound;
c. having the general formula R as external electron donor 1 R 2 C(COOR 3 )(COOR 4 ) Malonate compounds of (I).
Wherein R is 1 、R 2 、R 3 And R is 4 May be the same or different, substituted or unsubstituted C 1 -C 20 Is a hydrocarbon group of (2); in addition R 1 And R is 2 Is optionally selected from hydrogen and halogen.
For R 3 And R is 4 Preferably substituted or unsubstituted C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 3 ～C 10 Cycloalkyl, C 6 ～C 10 Aryl, C 7 ～C 10 Alkylaryl or C 7 ～C 10 Aralkyl, more preferably substituted or unsubstituted C 2 ～C 8 Straight chain alkyl, C 3 ～C 8 Branched alkyl, C 3 ～C 10 Cycloalkyl or C 7 ～C 10 Aralkyl groups.
R 1 And R is 2 May preferably be selected from hydrogen, halogen and substituted or unsubstituted C 1 ～C 10 Alkyl, C 1 ～C 10 Alkylene, C 3 ～C 10 Cycloalkyl, C 6 ～C 10 Aryl and C 7 ～C 10 Alkylaryl or arylalkyl radicals; more preferably, R 1 And R is 2 Selected from hydrogen, halogen and substituted or unsubstituted C 1 ～C 8 Alkyl, C 2 ～C 8 Alkylene, C 3 ～C 10 Cycloalkyl, C 6 ～C 10 Aryl and C 7 ～C 10 Alkylaryl groups.
The malonate compounds specifically include: diethyl malonate, dipropyl malonate, diisopropyl malonate, dibutyl malonate, diisobutyl malonate, di-tert-butyl malonate, diethyl methylmalonate, dipropyl methylmalonate, diisopropyl methylmalonate, di-n-butyl methylmalonate, diisobutyl methylmalonate, di-tert-butyl methylmalonate, diethyl ethyl malonate, dipropyl ethyl malonate, diisopropyl ethyl malonate, di-n-butyl ethyl malonate, diisobutyl ethyl malonate, di-tert-butyl ethyl malonate, diethyl propyl malonate, dipropyl propyl malonate, diisopropyl propyl malonate, di-n-butyl propyl malonate, diisobutyl propyl malonate, di-tert-butyl propyl malonate, diethyl isopropyl malonate isopropyl malonate, diisopropyl isopropyl malonate, di-n-butyl isopropyl malonate, diisobutyl isopropyl malonate, di-t-butyl isopropyl malonate, diethyl phenyl malonate, dipropyl phenyl malonate, di-n-butyl phenyl malonate, diisobutyl phenyl malonate, di-t-butyl phenyl malonate, diethyl benzyl malonate, dipropyl benzyl malonate, diisobutyl benzyl malonate, diethyl dimethyl malonate, diethyl methyl propyl malonate, diethyl methyl isopropyl malonate, diethyl di-n-propyl malonate, diethyl diisopropyl malonate, and diethyl diallyl malonate.
For the C component of the catalyst combination, it is also possible to contain a compound of the formula R 5 R 6 C(CH 2 OR 7 ) 2 (II) a 1, 3-diether compound.
In the general formula (II), R 5 And R is 6 May be the same or different, and is substituted or unsubstituted C 1 ～C 10 Straight chain alkyl, C 3 ～C 15 Branched alkyl, C 3 ～C 15 Cycloalkyl, C 6 ～C 20 Aryl or C 7 ～C 20 Alkylaryl or arylalkyl groups, preferably substituted or unsubstituted C 2 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 3 ～C 10 Cycloalkyl, C 6 ～C 15 Aryl or C 7 ～C 15 Alkylaryl or arylalkyl radicals; r is R 5 And R is 6 Optionally may be bonded to form a ring or not. And R is 7 Methyl or ethyl; the ratio of 1, 3-diether to malonate is from 0.01 to 100 (mol/mol), preferably from 0.1 to 10 (mol/mol), more preferably from 0.2 to 5 (mol/mol).
The 1, 3-diether compound specifically includes 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 9-bis (methoxymethyl) fluorene, 2-dibutyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane and 2-isobutyl-2-isopentyl-1, 3-dimethoxypropane.
In addition, the catalyst composition may contain a component C having the general formula R 1 n Si(OR 2 ) 4-n (III)Alkoxysilane compounds (n=0 or 1 or 2 or 3, r in the general formula (iii) 1 And R is 2 Is substituted or unsubstituted C 1 ～C 10 Alkyl, C 1 ～C 10 Alkylene, C 3 ～C 10 Cycloalkyl, C 6 ～C 10 Aryl and C 7 ～C 10 Alkylaryl or arylalkyl groups); the ratio of alkoxysilane to malonate is 0.01 to 100 (mol/mol), preferably 0.1 to 10 (mol/mol), more preferably 0.2 to 5 (mol/mol);
the alkoxy silane is specifically cyclohexyl methyl dimethoxy silane, diphenyl dimethoxy silane, butyl isopropyl dimethoxy silane, diisopropyl dimethoxy silane, dipropyl dimethoxy silane, dicyclopentyl dimethoxy silane, dibutyl dimethoxy silane, cyclohexyl trimethoxy silane, butyl trimethoxy silane, propyl trimethoxy silane, isopropyl trimethoxy silane, phenyl trimethoxy silane, cyclopentyl trimethoxy silane and ethyl trimethoxy silane.
For the solid catalyst component a in the catalyst composition, the internal electron donor compound is preferably selected from compounds containing an O atom, such as ethers, esters, phenol ethers, phenol esters and ketones, preferably benzoate compounds, phthalate compounds, 1, 3-diethers, polyacid ester compounds, polyol/phenol ester compounds; among them, the 1, 3-diether compounds are specifically 2-propyl-2-isopropyl-1, 3-dimethoxypropane, 2-propyl-2-butyl-1, 3-dimethoxypropane, 2-propyl-2-isobutyl-1, 3-dimethoxypropane, 2-propyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-butyl-2-isobutyl-1, 3-dimethoxypropane, 2-butyl-2-isopentyl-1, 3-dimethoxypropane, 2-isobutyl-2-pentyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopentyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-bis (2-methylbutyl) -1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-dimethoxypropane and 2, 9-dimethoxyfluorene.
And the polybasic acid ester compound is preferably selected from the group consisting of malonate compounds, succinate compounds, glutarate compounds, and phthalate compounds. More preferably, one or more selected from diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, diisooctyl phthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methylphthalate, di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, diethyl 2, 3-di-n-propylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-n-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-di-n-propylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-di-n-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate and the like.
The esters formed for the polyols/phenols are preferably selected from the group consisting of 1, 3-diol ester compounds and 1, 2-diphenol ester compounds, more preferably selected from the group consisting of 2, 4-pentanediol dibenzoate, 2, 4-pentanediol di-n-propyl benzoate, 2, 4-pentanediol di-p-isopropyl benzoate, 2, 4-pentanediol di-p-isobutyl benzoate, 2, 4-pentanediol di-n-butyl benzoate, 2, 4-pentanediol di-p-tert-butyl benzoate, 3, 5-heptanol dibenzoate, 3, 5-heptanol di-p-methyl benzoate, 3, 5-heptanol di-p-ethyl benzoate, 3, 5-heptanol di-n-propyl benzoate, 3, 5-heptanol di-p-isopropyl benzoate, 3, 5-heptanol di-p-isobutyl benzoate, 3, 5-heptanol di-p-butyl benzoate 3, 5-heptanediol di-tert-butyl benzoate, 4-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol di-p-methyl benzoate, 4-ethyl-3, 5-heptanediol di-p-ethyl benzoate, 4-ethyl-3, 5-heptanediol di-p-propyl benzoate, 4-ethyl-3, 5-heptanediol di-p-tert-butyl benzoate, 4-propyl-1, 2-diphenol dibenzoate, 1, 2-diphenol di-p-n-propyl benzoate, 1, 2-diphenol di-p-isopropyl benzoate, 1, 2-diphenol di-p-isobutyl benzoate, one or more of 1, 2-diphenol di-n-butyl benzoate, 1, 2-diphenol di-p-tert-butyl benzoate, 4-tert-butyl-1, 2-diphenol di-p-n-propyl benzoate, 4, 5-dipropyl-1, 2-diphenol di-p-isopropyl benzoate, 4-ethyl-1, 2-diphenol di-p-isobutyl benzoate, 4-isopropyl-1, 2-diphenol di-p-n-butyl benzoate, 4-isopentyl-1, 2-diphenol di-p-tert-butyl benzoate, 2-ethyl-1, 2-diphenol di-p-n-propyl benzoate, 4-isobutyl-5-ethyl-1, 2-diphenol di-p-isobutyl benzoate and the like.
The preferred components of the catalyst composition for preparing olefin polymers provided by the invention comprise the following:
a. a solid catalyst component containing Mg, ti, halogen, and an internal electron donor compound selected from one or more of a phthalate compound, a 1, 3-diether compound, a 1, 3-malonate compound, a succinate compound, a 1, 3-diol ester compound, and a 1, 2-diphenol ester compound;
b. an alkyl aluminum compound;
C. having the general formula R as external electron donor 1 R 2 C(COOR 3 )(COOR 4 ) Malonate compound of (I) (in the general formula I, R 1 、R 2 、R 3 And R is 4 May be the same or different, substituted or unsubstituted C 1 -C 20 Preferably selected from hydrogen, halogen and substituted or unsubstituted C 1 -C 10 Is a hydrocarbon group of (2); in addition R 1 And R is 2 Is optionally selected from hydrogen and halogen) and of the formula R n Si(OR') 4-n An alkoxysilane compound of the formula (III) (in the formula (III), n=0 or 1 or 2 or 3, R and R' are substituted or unsubstituted C 1 ～C 10 Alkyl, C 1 ～C 10 Alkylene, C 3 ～C 10 Cycloalkyl, C 6 ～C 10 Aryl and C 7 ～C 10 Alkylaryl or arylalkyl). The ratio of malonate to alkoxysilane is 0.01 to 100 (mol/mol), preferably 0.1 to 10 (mol/mol).
In the solid catalyst component a in the catalyst composition, the content of titanium is 1 to 7 weight percent and the content of magnesium is 8 to 20 weight percent based on the total weight of the solid catalyst component a; preferably, the content of the titanium is 1.5-4.5 wt% and the content of the magnesium is 15-20 wt%.
For component b of the catalyst composition, the alkyl aluminum compound has the formula AlRbnX3-n, wherein Rb is hydrogen or C 1 ～C 20 X is halogen, n is more than 1 and less than or equal to 3.
In the catalyst system, the molar ratio of the component a to the component b is 1 (5-1000), preferably 1 (20-250) in terms of titanium to aluminum; the molar ratio of component a to component C, calculated as titanium, is 1 (0.1 to 200), preferably 1 (0.2 to 50), more preferably 1 (0.2 to 10), where the amount of component C is the sum of the compounds of the formulae (I), (II) and (III). In addition component C may also be diluted with an alkane, preferably selected from C 6 ～C 10 More specifically selected from one or more of hexane, heptane, octane, nonane and decane, and the molar ratio of the external electron donor to the diluent alkane is from 1:0.1 to 10.
The invention also provides a method for polymerizing olefin, wherein the olefin is polymerized under the action of the catalyst composition or the catalyst composition. And the olefin has the general formula CH 2 =chr, wherein R is hydrogen or C 1 ～C 12 A hydrocarbyl or aryl group of (a); preferably the olefin is propylene. The olefin polymerization process of the present invention is particularly suitable for being carried out in a gas phase polymerization process. The most commonly used gas phase polymerization processes of olefin, especially propylene, at present are fluidized bed processes such as UNIPO propylene polymerization process, vertical stirred tank processes such as Novolen propylene polymerization process, horizontal stirred tank processes such as Innovene propylene polymerization process and the like, and particularly in the UNIPO and Novolen processes, the catalyst combination provided by the invention has a high-temperature self-extinguishing function, so that the possibility of caking or bursting is greatly reduced, and the continuous operation time of the device is prolonged.
The solid catalyst component a for olefin polymerization according to the present invention preferably comprises the reaction product of a titanium compound, a magnesium compound and the above-mentioned internal electron donor compound. The amounts of the titanium compound, the magnesium compound and the internal electron donor compound used for preparing the catalyst solid component are not particularly limited, and may be conventional amounts in the art, respectively.
Wherein the magnesium compound is selected from magnesium dihalide, alkoxymagnesium, alkyl magnesium, hydrate or alkoxide of magnesium dihalide, and derivative of magnesium dihalide in which one halogen atom is replaced by hydrocarbyloxy or halohydrocarbonoxy; preferably magnesium dihalide or an alkoxide of magnesium dihalide. Specific examples are magnesium dichloride, magnesium dibromide, magnesium diiodide, and alcohol compounds thereof.
Wherein the titanium compound is TiX m (OR 1 ) 4-m Wherein R is 1 Is C 1 ～C 20 X is halogen, m is more than or equal to 1 and less than or equal to 4. For example: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium trichloromonoethoxide, preferably titanium tetrachloride.
The solid catalyst component a described in the present invention can be prepared by the following method.
The method comprises the following steps: the catalyst component was prepared as disclosed in patent CN 1506384. Firstly, mixing a magnesium compound, an organic alcohol compound and an inert solvent, heating to dissolve, and then adding phthalic anhydride for mixing. Then contacting with precooled titanium compound, heating to a certain temperature, adding internal electron donor compound, reacting for a period of time at a certain temperature, treating the obtained solid with titanium compound, washing solid particles with inert solvent for many times, and drying to obtain the catalyst component.
The second method is as follows: firstly, dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, mixing the uniform solution with a titanium compound, and separating out a solid in the presence of a precipitation aid; the solid is contacted with an internal electron donor compound to be supported on the solid, and if necessary, the solid is treated with titanium tetrahalide and an inert diluent.
And a third method: the titanium compounds according to the invention are, in particular, tiCl 4 And the general formula is MgCl 2. PROH adducts to prepare the solid catalyst component. In MgCl 2 In pROH, p is a number from 0.1 to 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having from 1 to 18 carbon atoms. The adducts may be formed into spheres by different methods. The catalyst component may be prepared in particular according to the method disclosed in patent CN 1091748.
The method four: the magnesium dialkoxide can also be added into the aromatic hydrocarbon compound to be stirred to form suspension; treating the suspension with tetravalent titanium chloride, adding an internal electron donor for reaction, and washing the obtained solid with aromatic hydrocarbon compounds; then the mixture is treated by tetravalent titanium chloride, and finally the mixture is washed by inert solvent and pumped to dryness, thus obtaining the solid catalyst component.
And a fifth method: the catalyst component is prepared according to the method disclosed in patent US 4540679. Firstly, magnesium alkoxide reacts with carbon dioxide to prepare a magnesium carbonate hydrocarbonate carrier. Then, a transition metal compound (preferably a tetravalent titanium compound) and a magnesium carbonate hydrocarbylcarbonate carrier are reacted with an internal electron donor in a certain ratio in an inert solvent to obtain a solid catalyst.
The solid catalyst component a may be obtained by, for example, forming an emulsion of a magnesium compound, an electron donor, etc. in a diluent, adding a titanium compound to fix the emulsion to obtain a spherical solid, and then treating the spherical solid. In any of the above preparation methods, the desired internal electron donor compound may be added in the form of a compound; it may also be added in other ways, as may be obtained in situ by using suitable precursors of the internal electron donor compounds, which precursors are capable of becoming the desired electron donor compounds by, for example, known chemical reactions such as esterification reactions and the like.
According to the present invention, in the above catalyst composition of the present invention, the alkyl aluminum compound b has the formula AlRbnX3-n, wherein Rb is hydrogen or C 1 ～C 20 X is halogen, n is more than 1 and less than or equal to 3.
In one embodiment of the present invention, the alkyl aluminum compound includes triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, triisobutyl aluminum, diethyl aluminum monohydride, diisobutyl aluminum monohydride, diethyl aluminum monohydrochloride, diisobutyl aluminum monochloride, sesquiethyl aluminum chloride, and ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminum, and the like.
According to the invention, in the catalyst composition, the molar ratio of component a to component b is in titanium: aluminum is 1 (5-1000). Preferably 1 (20-250). The molar ratio of the component a to the component C is as titanium: c is 1 (0.1-100). Preferably 1 (0.5-50).
According to a second aspect of the present invention there is provided a prepolymerized catalyst composition for the polymerization of olefins comprising at least one prepolymer obtained by prepolymerization of the above catalyst composition with an olefin, preferably propylene, said prepolymer having a prepolymerization multiple of from 0.1 to 1000g of olefin polymer per g of component a. In the present invention, "prepolymerized catalyst" means a catalyst which has undergone a polymerization step at a low degree of conversion. According to the present invention, the same alpha-olefin as the olefin used for the polymerization can be used for the prepolymerization, wherein propylene is preferred as the olefin to be subjected to the prepolymerization. In particular, it is particularly preferred to carry out the prepolymerization with propylene or a mixture thereof with one or more alpha-olefins in an amount of up to 20 mol%. Preferably, the degree of conversion of the prepolymerized catalyst component is from about 0.2 to 500 g polymer per g solid catalyst component a.
The prepolymerization step can be carried out in liquid or gas phase at a temperature of-20 to 80 ℃, preferably 0 to 50 ℃. The prepolymerization step can be carried out in-line as part of a continuous polymerization process or separately in a batch operation. For the preparation of polymers having a catalyst component content of from 0.5 to 20g/g, the batch prepolymerization of the catalyst according to the invention with propylene is particularly preferred. The polymerization pressure is 0.01-10 MPa.
According to a third aspect of the present invention there is provided a process for the polymerisation of olefins by the action of the above catalyst composition or the above pre-polymerised catalyst composition.
In the present invention, the olefin has the general formula CH 2 =chr, wherein R is hydrogen or C 1 ～C 12 Is a hydrocarbon group or an aryl group. For example, the olefins include ethylene, propylene, 1-butene4-methyl-1-pentene and 1-hexene, preferably the olefin is propylene.
In a specific embodiment of the present invention, the above catalyst composition or the above catalyst composition of the present invention may be used in the homopolymerization of propylene and or the copolymerization of other olefins of propylene.
The catalyst of the invention can be directly added into a reactor for use in the polymerization process, or the catalyst and olefin are prepolymerized to obtain a prepolymerized catalyst and then added into the reactor.
The olefin polymerization of the present invention can be carried out according to a known polymerization method, in a liquid phase or a gas phase, or in a combination of liquid phase and gas phase polymerization stages. Conventional techniques such as slurry processes, gas-phase fluidized beds, and the like are employed. The following reaction conditions are preferably employed: the polymerization temperature is 0 to 150℃and preferably 60 to 90 ℃.
The inventors of the present invention have made many experiments to have a high-temperature self-extinguishing effect by using a malonate compound having the general formula (I) as an external electron donor for polymerization of olefins, particularly propylene.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in more detail with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention, and the specific experimental methods not mentioned in the following examples are generally carried out in accordance with conventional experimental methods.
The testing method comprises the following steps:
the polymer isotactic index was measured by heptane extraction (heptane boiling extraction for 6 hours): 2g of the dried polymer sample was extracted with boiling heptane in an extractor for 6 hours, and the residue was dried to constant weight to give a polymer weight (g) to 2 ratio, i.e.isotactic index.
Examples
EXAMPLES 1 to 19 propylene slurry atmospheric polymerization experiments
Specifically, the experimental method for propylene slurry atmospheric polymerization comprises the following steps:
a250 ml reaction flask was used with purified nitrogenAfter the gas was fully replaced, 150ml of decane which had been fully dried was added, and then the nitrogen in the reaction flask was fully saturated with polymerization-grade propylene and fully replaced, the reaction system was carried out completely under the atmosphere of propylene, and after the system temperature was raised to the reaction temperature, a certain amount of triethylaluminum and an external electron donor (triethylaluminum was used as AlEt were added 3 Ti=100 mol/mol, ti being the content of AlEt in the solid catalyst component a added 3 External electron donor=20mol/mol), adding about 60mg of solid catalyst component a, starting propylene polymerization, continuously introducing propylene in the process, keeping the pressure of a reaction bottle at 0.01MPa, maintaining the set reaction temperature for 1 hour, adding 30ml of ethanol to terminate the reaction, filtering to obtain a solid, and fully drying to obtain a polymer, wherein the activity of the catalyst is the ratio of the obtained polymer to the amount of the added solid catalyst.
The propylene polymerization results are shown in tables 1 and 2.
TABLE 1 propylene polymerization results for examples 1-10 and comparative examples 1-3
* CS-1-G is a barrage Yang Ke group product; SHAC (short hand alternating current) 20 1 is a Dow chemical product; NG and BCND-II-04 are products of China petrochemical catalyst Limited company; a is that C100 /A C67 Is the ratio of catalyst activities at 100 ℃ and 67 ℃; the molar ratios of the external electron donor 1 and the external electron donor 2 in examples 3,5, 8, 9, 10 and comparative example 3 were 1:2, 1:1, 3:2, 1:1 and 2:1, respectively.
As can be seen from Table 1, the present application provides a reaction system of a catalyst composition using the silicon compound of the present invention as an external electron donor, as compared with the prior art silane C100 /A C67 The catalyst composition provided by the application has lower value, namely, the activity of the catalyst composition at high temperature is reduced more rapidly, and the explosion polymerization during high-temperature polymerization can be avoided.
TABLE 2 propylene polymerization results for example 20 and comparative examples 4-5
Note that: the number of the external electron donor columns in the table is the ratio (mol/mol) of the two external electron donors; comparative example 5, al/external electron donor=5 (mol/mol).
As can be seen from Table 2, the catalyst combinations of the present invention have higher catalytic activity, higher directing ability, and require a small amount of external electron donor.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A process for the polymerization of olefins, characterized in that it is used for the preparation of propylene polymers,
the olefin polymerization method adopts a process of UNIPOL,
the catalyst composition employed in the olefin polymerization process comprises the following components:
a. a solid catalyst component comprising Mg, ti, halogen, and an internal electron donor compound comprising a lone pair of electrons, including O, N, P and S;
b. an alkyl aluminum compound;
c. the external electron donor is malonate and alkoxysilane or malonate and general formula R 5 R 6 C(CH 2 OR 7 ) 2 (II) 1, 3-diether compounds in which R 5 And R is 6 May be the same or different, and is substituted or unsubstituted C 1 ～C 10 Straight chain alkyl, C 3 ～C 15 Branched alkyl, C 3 ～C 15 Cycloalkyl, C 6 ～C 20 Aryl or C 7 ～C 20 Alkylaryl or arylalkyl radicals;
the ratio of the alkoxy silane to the malonate is 0.2-5 (mol/mol);
the ratio of the 1, 3-diether compound to the malonate is 0.2-5 (mol/mol);
the malonate compound is one or more selected from diethyl malonate, diethyl dipropyl malonate and dibutyl malonate;
the alkoxy silane is selected from one or more of dicyclopentyl dimethoxy silane, methylcyclohexyl dimethoxy silane, diisopropyl dimethoxy silane and propyl trimethoxy silane;
the 1, 3-diether compound is 2-isopropyl-2-isopentyl-1, 3-dimethoxy propane.
2. The process for the polymerization of olefins according to claim 1, wherein,
in the solid catalyst component a, the internal electron donor compound contains compounds of O atoms, including ethers, esters, phenol ethers, phenol esters and ketones.
3. The process for the polymerization of olefins according to claim 2, wherein,
in the solid catalyst component a, the internal electron donor compound is selected from 1, 3-diether compounds, and the 1, 3-diether compounds are selected from 2-propyl-2-isopropyl-1, 3-dimethoxy propane, 2-propyl-2-butyl-1, 3-dimethoxy propane, 2-propyl-2-isobutyl-1, 3-dimethoxy propane, 2-propyl-2-isopentyl-1, 3-dimethoxy propane, 2-isopropyl-2-isobutyl-1, 3-dimethoxy propane, 2-isopropyl-2-isopentyl-1, 3-dimethoxy propane, 2-butyl-2-isobutyl-1, 3-dimethoxy propane, 2-butyl-2-isopentyl-1, 3-dimethoxy propane, 2-isobutyl-2-pentyl-1, 3-dimethoxy propane, 2-isobutyl-2-isopentyl-1, 3-dimethoxy propane, 2-isopentyl-2- (2-ethylbutyl) -1, 3-dimethoxy propane, 2-dimethyl-1, 3-dimethoxy propane, 2-dimethyl-9-dimethoxy propane or 9-dimethyl-fluorene.
4. The process for the polymerization of olefins according to claim 2, wherein,
in the solid catalyst component a, the internal electron donor compound is selected from polybasic acid esters; the polybasic acid ester is selected from one or more of malonate compound, succinate compound, glutarate compound and phthalate compound; the malonate compound, the succinate compound, the glutarate compound, and the phthalate compound are selected from one or more of diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, diisooctyl phthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methylphthalate, di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, diethyl 2, 3-di-n-propylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-n-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-di-n-propylsuccinate, diisobutyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-di-n-butylsuccinate, and diisobutyl 2, 3-diisobutylsuccinate.
5. The process for the polymerization of olefins according to claim 2, wherein,
in the solid catalyst component a, the internal electron donor compound is selected from esters of polyols or phenols; the polyol or phenol forms an ester selected from one or more of 1, 3-diol ester compounds and 1, 2-diphenol ester compounds selected from 2, 4-pentanediol dibenzoate, 2, 4-pentanediol di-n-propyl benzoate, 2, 4-pentanediol di-p-isopropyl benzoate, 2, 4-pentanediol di-isobutyl benzoate, 2, 4-pentanediol di-n-butyl benzoate, 2, 4-pentanediol di-p-butyl benzoate, 3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methyl benzoate, 3, 5-heptanediol diethylbenzoate, 3, 5-heptanediol di-n-propyl benzoate, 3, 5-heptanediol di-p-isopropyl benzoate, 3, 5-heptanediol di-p-isobutyl benzoate, 3, 5-heptanediol di-n-butyl benzoate, 3, 5-heptanediol di-p-butyl benzoate, 4-methyl-3, 5-heptanediol di-n-butyl benzoate, 4-ethyl-3, 5-heptanediol di-p-n-butyl benzoate, 4-ethyl-2, 5-heptanediol di-p-ethyl benzoate, 3, 5-ethyl-p-ethyl benzoate, 3, 5-heptanediol di-p-ethyl benzoate, 3, 5-ethyl-p-heptanediol di-p-isopropyl benzoate, 3, 5-heptanediol di-p-n-ethyl benzoate, 3, 4-ethyl benzoate, 4-p-ethyl benzoate, one or more of 1, 2-diphenol di-p-isobutyl benzoate, 1, 2-diphenol di-n-butyl benzoate, 1, 2-diphenol di-p-tert-butyl benzoate, 4-tert-butyl-1, 2-diphenol di-p-n-propyl benzoate, 4, 5-dipropyl-1, 2-diphenol di-p-isopropyl benzoate, 4-ethyl-1, 2-diphenol di-p-isobutyl benzoate, 4-isopropyl-1, 2-diphenol di-p-n-butyl benzoate, 4-isopentyl-1, 2-diphenol di-p-tert-butyl benzoate, 2-ethyl-1, 2-diphenol di-p-isopropyl benzoate, 4-tert-butyl-5-ethyl-1, 2-diphenol di-p-isobutyl benzoate.
6. The olefin polymerization process according to claim 1, wherein in the solid catalyst component a, the titanium is contained in an amount of 1 to 7wt% and the magnesium is contained in an amount of 8 to 20wt% based on the total weight of the solid catalyst component a.
7. The process for the polymerization of olefins according to claim 1, wherein said alkylaluminum compound has the general formula AlRbnX3-n, wherein Rb is hydrogen or C 1 ～C 20 X is halogen, n is more than 1 and less than or equal to 3.
8. The process for the polymerization of olefins according to claim 1 wherein the molar ratio of component a to component b is from 1:5 to 1000 in terms of titanium to aluminum; the molar ratio of the component a to the component c is 1:0.1-100 calculated by the titanium to the external electron donor compound.
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