CN116606391B - Olefin polymerization catalyst solid component, preparation method thereof, olefin polymerization catalyst and application - Google Patents
Olefin polymerization catalyst solid component, preparation method thereof, olefin polymerization catalyst and application Download PDFInfo
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- CN116606391B CN116606391B CN202210121148.5A CN202210121148A CN116606391B CN 116606391 B CN116606391 B CN 116606391B CN 202210121148 A CN202210121148 A CN 202210121148A CN 116606391 B CN116606391 B CN 116606391B
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- Prior art keywords
- silane
- olefin polymerization
- polymerization catalyst
- solid component
- compound
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 144
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 135
- 239000007787 solid Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 94
- -1 ester compound Chemical class 0.000 claims abstract description 77
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 59
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004820 halides Chemical class 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 27
- 239000000460 chlorine Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000012442 inert solvent Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- MBGGFXOXUIDRJD-UHFFFAOYSA-N 4-Butoxyphenol Chemical compound CCCCOC1=CC=C(O)C=C1 MBGGFXOXUIDRJD-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- SXNLMXPRYYYOSO-UHFFFAOYSA-N (2,3-dimethylcyclopentyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1CCC(C)C1C SXNLMXPRYYYOSO-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910010062 TiCl3 Inorganic materials 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- MGGAITMRMJXXMT-UHFFFAOYSA-N cyclopentyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCC1 MGGAITMRMJXXMT-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- IOPAQHDEQBHWEB-UHFFFAOYSA-N trimethoxy-(2-methylcyclopentyl)silane Chemical compound CO[Si](OC)(OC)C1CCCC1C IOPAQHDEQBHWEB-UHFFFAOYSA-N 0.000 claims description 3
- YQXKUILMUQPCPU-UHFFFAOYSA-N 2,2,2-tricyclopentylethoxysilane Chemical compound C1CCCC1C(C1CCCC1)(CO[SiH3])C1CCCC1 YQXKUILMUQPCPU-UHFFFAOYSA-N 0.000 claims description 2
- KKOWXJFINYUXEE-UHFFFAOYSA-N 2-butoxyphenol Chemical compound CCCCOC1=CC=CC=C1O KKOWXJFINYUXEE-UHFFFAOYSA-N 0.000 claims description 2
- RISYVLILTAVNNP-UHFFFAOYSA-N 2-dodecoxyphenol Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1O RISYVLILTAVNNP-UHFFFAOYSA-N 0.000 claims description 2
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 claims description 2
- WTAUMGJJFXKZLQ-UHFFFAOYSA-N 2-hexoxyphenol Chemical compound CCCCCCOC1=CC=CC=C1O WTAUMGJJFXKZLQ-UHFFFAOYSA-N 0.000 claims description 2
- YYLTYJWUTXSVCO-UHFFFAOYSA-N 2-nonoxyphenol Chemical compound CCCCCCCCCOC1=CC=CC=C1O YYLTYJWUTXSVCO-UHFFFAOYSA-N 0.000 claims description 2
- IWNXSYOIVWMSLX-UHFFFAOYSA-N 2-octadecoxyphenol Chemical compound CCCCCCCCCCCCCCCCCCOC1=CC=CC=C1O IWNXSYOIVWMSLX-UHFFFAOYSA-N 0.000 claims description 2
- ITKQCIBIWWMFPM-UHFFFAOYSA-N 2-octoxyphenol Chemical compound CCCCCCCCOC1=CC=CC=C1O ITKQCIBIWWMFPM-UHFFFAOYSA-N 0.000 claims description 2
- KDTZBYPBMTXCSO-UHFFFAOYSA-N 2-phenoxyphenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1 KDTZBYPBMTXCSO-UHFFFAOYSA-N 0.000 claims description 2
- CCZCXFHJMKINPE-UHFFFAOYSA-N 2-phenylmethoxyphenol Chemical compound OC1=CC=CC=C1OCC1=CC=CC=C1 CCZCXFHJMKINPE-UHFFFAOYSA-N 0.000 claims description 2
- JFSVGKRARHIICJ-UHFFFAOYSA-N 2-propoxyphenol Chemical compound CCCOC1=CC=CC=C1O JFSVGKRARHIICJ-UHFFFAOYSA-N 0.000 claims description 2
- VGIJZDWQVCXVNL-UHFFFAOYSA-N 3-butoxyphenol Chemical compound CCCCOC1=CC=CC(O)=C1 VGIJZDWQVCXVNL-UHFFFAOYSA-N 0.000 claims description 2
- VBIKLMJHBGFTPV-UHFFFAOYSA-N 3-ethoxyphenol Chemical compound CCOC1=CC=CC(O)=C1 VBIKLMJHBGFTPV-UHFFFAOYSA-N 0.000 claims description 2
- XPNKJGMHGPTELE-UHFFFAOYSA-N 3-hexoxyphenol Chemical compound CCCCCCOC1=CC=CC(O)=C1 XPNKJGMHGPTELE-UHFFFAOYSA-N 0.000 claims description 2
- ALSGLTSTBIXVFM-UHFFFAOYSA-N 3-nonoxyphenol Chemical compound CCCCCCCCCOC1=CC=CC(O)=C1 ALSGLTSTBIXVFM-UHFFFAOYSA-N 0.000 claims description 2
- QFTTTWKZLOQAFF-UHFFFAOYSA-N 3-octoxyphenol Chemical compound CCCCCCCCOC1=CC=CC(O)=C1 QFTTTWKZLOQAFF-UHFFFAOYSA-N 0.000 claims description 2
- YYMPIPSWQOGUME-UHFFFAOYSA-N 3-propoxyphenol Chemical compound CCCOC1=CC=CC(O)=C1 YYMPIPSWQOGUME-UHFFFAOYSA-N 0.000 claims description 2
- XIIIHRLCKLSYNH-UHFFFAOYSA-N 4-Hexyloxyphenol Chemical compound CCCCCCOC1=CC=C(O)C=C1 XIIIHRLCKLSYNH-UHFFFAOYSA-N 0.000 claims description 2
- IPOLGHIMIPSIJX-UHFFFAOYSA-N 4-nonoxyphenol Chemical compound CCCCCCCCCOC1=CC=C(O)C=C1 IPOLGHIMIPSIJX-UHFFFAOYSA-N 0.000 claims description 2
- HFRUPPHPJRZOCM-UHFFFAOYSA-N 4-octoxyphenol Chemical compound CCCCCCCCOC1=CC=C(O)C=C1 HFRUPPHPJRZOCM-UHFFFAOYSA-N 0.000 claims description 2
- KIIIPQXXLVCCQP-UHFFFAOYSA-N 4-propoxyphenol Chemical compound CCCOC1=CC=C(O)C=C1 KIIIPQXXLVCCQP-UHFFFAOYSA-N 0.000 claims description 2
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 claims description 2
- YRMPTIHEUZLTDO-UHFFFAOYSA-N cyclopentyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCC1 YRMPTIHEUZLTDO-UHFFFAOYSA-N 0.000 claims description 2
- BVNCDRJKUJGGTL-UHFFFAOYSA-N cyclopentyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C1CCCC1 BVNCDRJKUJGGTL-UHFFFAOYSA-N 0.000 claims description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 claims description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 claims description 2
- TUZXHLFJEVFZAF-UHFFFAOYSA-N diethoxy-bis(2-methylphenyl)silane Chemical compound C=1C=CC=C(C)C=1[Si](OCC)(OCC)C1=CC=CC=C1C TUZXHLFJEVFZAF-UHFFFAOYSA-N 0.000 claims description 2
- GBEUGTODHMIIMD-UHFFFAOYSA-N diethoxy-bis(3-methylphenyl)silane Chemical compound C=1C=CC(C)=CC=1[Si](OCC)(OCC)C1=CC=CC(C)=C1 GBEUGTODHMIIMD-UHFFFAOYSA-N 0.000 claims description 2
- WCJFZAFGBBIZAA-UHFFFAOYSA-N diethoxy-bis(4-methylphenyl)silane Chemical compound C=1C=C(C)C=CC=1[Si](OCC)(OCC)C1=CC=C(C)C=C1 WCJFZAFGBBIZAA-UHFFFAOYSA-N 0.000 claims description 2
- AAMBIAPMLISIDH-UHFFFAOYSA-N dimethoxy-bis(2-methylphenyl)silane Chemical compound C=1C=CC=C(C)C=1[Si](OC)(OC)C1=CC=CC=C1C AAMBIAPMLISIDH-UHFFFAOYSA-N 0.000 claims description 2
- IWEAAVHEPCUQHR-UHFFFAOYSA-N dimethoxy-bis(3-methylphenyl)silane Chemical compound C=1C=CC(C)=CC=1[Si](OC)(OC)C1=CC=CC(C)=C1 IWEAAVHEPCUQHR-UHFFFAOYSA-N 0.000 claims description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- PTCWADDVLPYBBZ-UHFFFAOYSA-N tricyclopentylmethoxysilane Chemical compound C1CCCC1C(C1CCCC1)(O[SiH3])C1CCCC1 PTCWADDVLPYBBZ-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- XZFFGKZBTQABBO-UHFFFAOYSA-N ethoxy(dimethyl)silane Chemical compound CCO[SiH](C)C XZFFGKZBTQABBO-UHFFFAOYSA-N 0.000 claims 3
- 150000003608 titanium Chemical class 0.000 claims 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims 2
- NXAGQOMXVXZXNB-UHFFFAOYSA-N CC(CCCCCC)O[Mg] Chemical compound CC(CCCCCC)O[Mg] NXAGQOMXVXZXNB-UHFFFAOYSA-N 0.000 claims 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 claims 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 claims 1
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 claims 1
- CBVJWBYNOWIOFJ-UHFFFAOYSA-N chloro(trimethoxy)silane Chemical compound CO[Si](Cl)(OC)OC CBVJWBYNOWIOFJ-UHFFFAOYSA-N 0.000 claims 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 claims 1
- VNXMGRKUIIJFOL-UHFFFAOYSA-N dicyclopentylmethoxysilane Chemical compound C1CCCC1C(O[SiH3])C1CCCC1 VNXMGRKUIIJFOL-UHFFFAOYSA-N 0.000 claims 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 claims 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims 1
- FODNZYLSKLWBBC-UHFFFAOYSA-N ethoxy(dipentyl)silane Chemical compound CCCCC[SiH](CCCCC)OCC FODNZYLSKLWBBC-UHFFFAOYSA-N 0.000 claims 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 claims 1
- LUWIGHUDKAFTPP-UHFFFAOYSA-N tetrakis(2-ethylhexyl)silane Chemical compound CCCCC(CC)C[Si](CC(CC)CCCC)(CC(CC)CCCC)CC(CC)CCCC LUWIGHUDKAFTPP-UHFFFAOYSA-N 0.000 claims 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 claims 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 63
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 229910052723 transition metal Inorganic materials 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 150000003624 transition metals Chemical class 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
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- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 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 2
- 229940099259 vaseline Drugs 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WOQNPOAPKYFGMB-UHFFFAOYSA-N 2-tetradecoxyphenol Chemical compound CCCCCCCCCCCCCCOC1=CC=CC=C1O WOQNPOAPKYFGMB-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding 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
- FKTMFLUERPVMAS-UHFFFAOYSA-N cyclohexyl(triethoxy)silane;cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1.CCO[Si](OCC)(OCC)C1CCCCC1 FKTMFLUERPVMAS-UHFFFAOYSA-N 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
- FVAXOELGJXMINU-UHFFFAOYSA-N dicyclopentyl(diethoxy)silane Chemical compound C1CCCC1[Si](OCC)(OCC)C1CCCC1 FVAXOELGJXMINU-UHFFFAOYSA-N 0.000 description 1
- WVEWXPQUQZKPJK-UHFFFAOYSA-N dicyclopentylmethyl(methoxy)silane Chemical compound C1CCCC1C([SiH2]OC)C1CCCC1 WVEWXPQUQZKPJK-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-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
- SZIZIGBTHTUEBU-UHFFFAOYSA-N dimethoxy-bis(4-methylphenyl)silane Chemical compound C=1C=C(C)C=CC=1[Si](OC)(OC)C1=CC=C(C)C=C1 SZIZIGBTHTUEBU-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 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
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005922 tert-pentoxy group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F110/02—Ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 discloses an olefin polymerization catalyst solid component, a preparation method thereof, an olefin polymerization catalyst and application thereof. The olefin polymerization catalyst solid component comprises titanium, magnesium and an internal electron donor, wherein the internal electron donor comprises an internal electron donor compound and a silicone ester compound shown in a formula (I):
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, in particular to an olefin polymerization catalyst solid component, a preparation method thereof, an olefin polymerization catalyst and applications thereof.
Background
Through the development of more than 60 years, the Ziegler-Natta type polyethylene catalyst has very good progress in the aspects of activity, bulk density of powder, content of fine powder, oligomer and the like, and basically meets the requirements of the existing industrial production. With the development of new products, when the resin products with double peaks are produced, a large amount of hydrogen is needed to be added into the existing catalyst, so that the problems of reduced catalyst activity, serious ethylene ethane reaction, influence on the production of safety and stability of the device, unstable product quality and the like are easily caused. In order to better meet the requirements of industrial production, a resin product with more excellent performance is produced, and a catalyst product with excellent hydrogen regulation performance needs to be provided on the premise of ensuring the basic performance of the existing catalyst.
In the prior art, introducing some electron donors into olefin polymerization catalyst can improve hydrogen regulation performance of catalyst, for example, chinese patent with publication number CN1958620A, CN103772536A introduces silane electron donors and benzoate electron donors respectively. The introduction of other electron donors can improve the copolymerization performance of the catalyst, for example, chinese patent publication numbers CN1726230A, CN1798774A and CN101050248A respectively introduce electron donors such as alcohol, ketone, amine, amide, nitrile, alkoxy silane, aliphatic ether, aliphatic carboxylic ester and the like. The introduction of certain electron donors into the catalyst may enhance the activity of the catalyst, such as the introduction of haloalkanes in chinese patent publication No. CN102977232 a.
The above-mentioned electron donors can only improve the performance of olefin polymerization catalysts in a certain aspect, and have not been able to meet the demands of industrial production. It is necessary to find an electron donor which can not only improve the high melt index performance of the polyolefin catalyst under the high hydrogen condition, but also maintain the low melt index performance under the low hydrogen condition, thereby meeting the requirements of industrial production devices for producing the double-peak serial brand products.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention proposes a catalyst solid component for olefin polymerization and a catalyst.
The inventors have found through research that: the silicon ester compound and the compound shown in the general formula (I) are introduced as internal electron donors in the preparation process of the olefin polymerization catalyst, and the olefin polymerization catalyst not only can show good activity and copolymerization performance, but also can show high polymer melt index under the polymerization condition of high hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure is more than or equal to 3). Based on this finding, the present invention has been proposed.
In order to achieve the above object, a first aspect of the present invention provides an olefin polymerization catalyst solid component, wherein the olefin polymerization catalyst solid component comprises titanium, magnesium and an internal electron donor comprising an internal electron donor compound represented by formula (I) and a silicone ester compound;
In formula (I), wherein R 1、R2、R3、R4、R5 is optionally one of RO groups, the others are the same or different from each other and are each independently hydrogen, C 1～C20 linear or branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, R is selected from C 1～C20 linear or branched alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl. It is clearly believed that the internal electron donor compound of formula (I) is a phenol, ether difunctional compound.
The general formula of the silicone compound is R 2 xR3 ySi(OR4)z, wherein R 2 and R 3 are each independently C 1～C10 alkyl or halogen, R 4 is C 1～C10 alkyl, wherein x, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 4, and x+y+z=4.
In the solid component of the catalyst, the silicon ester compound accounts for 0.1 to 1 mole per mole of magnesium, the internal electron donor compound accounts for 0.01 to 1 mole, and the titanium accounts for 1 to 25 moles; preferably, the silicon ester compound is 0.1 to 0.8 mole, the internal electron donor compound is 0.01 to 0.6 mole, and the titanium is 1 to 15 mole.
In a second aspect, the present invention provides a process for the preparation of a solid component of an olefin polymerization catalyst, wherein the process comprises the steps of:
(1) Dispersing an alkoxy magnesium compound in an inert solvent under stirring to form a suspension;
(2) The suspension is contacted with an internal electron donor compound shown in a formula (I), a silicone ester compound and a halide of titanium and/or a derivative thereof for reaction, and then solid-liquid separation and washing are carried out to obtain a catalyst solid component;
In formula (I), R 1、R2、R3、R4、R5 is optionally one of RO groups, the others being the same or different from each other, each independently hydrogen, C 1～C20 linear or branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, R is selected from C 1～C20 linear or branched alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl.
The general formula of the silicone compound is R 2 xR3 ySi(0R4)z, wherein R 2 and R 3 are respectively alkyl of C 1～C10 or halogen, R 4 is alkyl of C 1～C10, wherein x, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 4, and x+y+z=4.
The general formula of the alkoxy magnesium compound is Mg (OR 7)a(OR8)2-a, wherein R 7 and R 8 are each independently substituted OR unsubstituted C 1～C10 alkyl, and the substituent is at least one selected from hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, alkoxy and heteroatom, and a is more than OR equal to 0 and less than OR equal to 2.
The general formula of the titanium halide OR the derivative thereof is Ti (OR 9)dXb, wherein R 9 is C 1～C14 alkyl, preferably C 1～C8 alkyl, X is halogen atom, d and b are each independently integers of 1-4, and d+b=3 OR 4).
Preferably, in step (2), the method of the contact reaction comprises:
(a) Reacting the suspension with a portion of the titanium halide and/or derivative thereof at a temperature of from-30 ℃ to 0 ℃ and adding the internal electron donor compound and the silicone-based compound for one or more time periods before, during and after the reaction of the suspension with the titanium halide and/or derivative thereof to obtain a first product;
(b) Heating the first product obtained in the step (a) to 50-120 ℃, reacting for 0.5-4 hours under the stirring condition, standing, layering, pumping out supernatant to obtain a second product, continuously carrying out contact reaction on the obtained second product and the residual titanium halide and/or the derivative thereof under the stirring condition for 0.5-4 hours in the presence of the optionally added inert solvent, and then carrying out solid-liquid separation.
In the step (a), the silicon ester compound is 0.1 to 1mol, the internal electron donor compound is 0.01 to 1mol, and the halide of titanium and/or its derivative is 1 to 20 mol per mol of magnesium.
The molar ratio of the halide of titanium and/or its derivative in step (b) to the halide of titanium and/or its derivative in step (a) is 1 (1-5).
In a third aspect, the present invention provides an olefin polymerization catalyst, wherein the olefin polymerization catalyst comprises:
(A) A catalyst solid component, wherein the catalyst solid component (a) is the olefin polymerization catalyst solid component described above;
(B) A cocatalyst component, wherein the cocatalyst component (B) is at least one organoaluminum compound.
The general formula of the organic aluminum compound is AlR 1 eX1 fHg, wherein R 1 is hydrogen or C l～C20 alkyl, X 1 is halogen atom, preferably fluorine, chlorine or bromine, e, f and g are each independently integers of 0-3, and e+f+g=3.
The molar ratio of the promoter component (B) in terms of aluminum to the catalyst solid component (A) in terms of titanium is (5-500): 1, preferably (20-200): 1.
In a fourth aspect, the present invention provides the use of an olefin polymerization catalyst solid component according to the invention and/or an olefin polymerization catalyst according to the invention in ethylene homo-and/or co-polymerization.
The solid component of the olefin polymerization catalyst provided by the invention is added with the internal electron donor silicon ester compound and the internal electron donor compound shown in the general formula (I), so that the obtained olefin polymerization catalyst not only can show good activity and copolymerization performance, but also can show high polymerization activity and high polymer melt index under the polymerization condition of high hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure is more than or equal to 3), and show low polymer melt index under the polymerization condition of low hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure is less than or equal to 1). The olefin polymerization catalyst provided by the invention has higher catalytic activity and more suitable hydrogen regulation sensitivity when being used for ethylene polymerization. The solid component of the olefin polymerization catalyst and the preparation process of the olefin polymerization catalyst provided by the invention are simple, and are very suitable for ethylene slurry polymerization processes with double kettles or multiple kettles connected in series.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
According to a first aspect of the present invention, there is provided an olefin polymerization catalyst solid component comprising titanium, magnesium and an internal electron donor comprising an internal electron donor compound represented by the formula (I) and a silicone ester compound,
A compound of formula (I) wherein R 1、R2、R3、R4、R5, optionally one of which is an RO group, and the others, equal to or different from each other, are each independently hydrogen, C 1～C20 straight or branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, R is selected from C 1～C20 straight or branched alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl. Preferably, R is selected from the group consisting of linear or branched alkyl of C 1～C20, cycloalkyl of C 3～C20, aryl of C 6～C10, alkylaryl or arylalkyl of C 6～C10.
In the present invention, the straight-chain or branched alkyl group of C 1～C20 may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl and the like. The aryl group of C 6～C10 may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl or naphthyl. The cycloalkyl group of C 3～C20 may be, for example, cyclopentyl, cyclohexyl, or the like.
In the present invention, the RO group may be an alkoxy group having a carbon number of 1～C20, and for example, may be a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a tert-pentoxy group, a neopentoxy group, or the like.
According to a specific embodiment of the present invention, the compound of formula (I) is preferably at least one selected from the group consisting of p-methoxyphenol, o-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, o-propoxyphenol, m-propoxyphenol, p-butoxyphenol, o-butoxyphenol, m-butoxyphenol, p-hexyloxyphenol, o-hexyloxyphenol, m-hexyloxyphenol, p-octyloxyphenol, o-octyloxyphenol, m-octyloxyphenol, p-nonoxyphenol, m-nonoxyphenol, o-nonoxyphenol, dodecyloxyphenol, tetradecyloxy phenol, octadecyloxyphenol, phenoxyphenol, and hydroxyphenyl benzyl ether.
According to the invention, the silicone compound preferably has the general formula R 2 xR3 ySi(OR4)z, wherein R 2 and R 3 are each independently a C 1～C10 hydrocarbon group or a halogen, R 4 is a C 1～C10 hydrocarbon group, wherein x, y, z are positive integers, 0.ltoreq.x.ltoreq.2, 0.ltoreq.y.ltoreq.2, and 0.ltoreq.z.ltoreq.4, and x+y+z=4.
According to a specific embodiment of the present invention, the silicone compound is preferably selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis (2-ethylhexyloxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane cyclopentyl trimethoxy silane, cyclopentyl triethoxy silane, 2-methyl cyclopentyl trimethoxy silane, 2, 3-dimethyl cyclopentyl trimethoxy silane, cyclohexyl triethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, ethyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, cyclopentyl trimethoxysilane, cyclopentyl triethoxysilane, 2-methylcyclopentyl trimethoxysilane, 2, 3-dimethylcyclopentyl trimethoxysilane, cyclohexyl trimethoxy-silane cyclohexyl triethoxysilane, methyl trimethoxysilane, methyl triethoxysilane, ethyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, one or more of dicyclopentyl diethoxy silane, methylcyclopentylbioxy silane, diphenyldimethoxy silane, diphenyldiethoxy silane, methylphenyl diethoxy silane, methylphenyl dimethoxy silane, di-o-tolyldimethoxy silane, di-o-tolyldiethoxy silane, di-m-tolyldimethoxy silane, di-m-tolyldiethoxy silane, di-p-tolyldimethoxy silane, di-p-tolyldiethoxy silane, trimethylmethoxy silane, trimethylethoxy silane, tricyclopentylmethoxy silane, tricyclopentylethoxy silane, dicyclopentylmethylmethoxy silane, and cyclopentyl dimethylmethoxy silane are used in combination. More preferably, the silicone ester compound is selected from at least one of tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.
According to the present invention, although the internal electron donor in the solid component of the olefin polymerization catalyst can achieve the object of the present invention as long as it contains the compound of the general formula (I) and the silicone-based compound described in the present invention, it is preferable that the internal electron donor compound in the general formula (I) is 0.01 to 1 mol, titanium is 1 to 25 mol, preferably 0.1 to 0.8 mol, the internal electron donor compound is 0.01 to 0.6 mol, and titanium is 1 to 15 mol per mol of magnesium in the solid component of the olefin polymerization catalyst in order to better achieve the object of the present invention.
According to the present invention, the above-mentioned olefin polymerization catalyst solid component can be produced by various methods including reacting a magnesium alkoxide compound, an internal electron donor compound, a silicone ester compound, and a halide of titanium and/or a derivative thereof, and preferably, according to the second aspect of the present invention, the production method of the olefin polymerization catalyst solid component includes the steps of:
(1) Dispersing an alkoxy magnesium compound in an inert solvent under stirring to form a suspension;
(2) The suspension is subjected to contact reaction with an internal electron donor compound represented by the formula (I) and a silicone ester compound, and a halide of transition metal titanium and/or a derivative thereof under stirring, and then subjected to solid-liquid separation and washing.
The specific selection of the internal electron donor compound and the silicone compound represented by the general formula (I) has been described above, and will not be described here again.
According to the present invention, the magnesium alkoxide compound may be various solid materials containing magnesium element which are commonly used in the field of olefin polymerization catalysts, and preferably, the magnesium alkoxide compound has a general formula of Mg (OR 7)a(OR8)2-a, wherein R 7 and R 8 are each independently a substituted OR unsubstituted C 1～C10 alkyl group, and the substituent is at least one selected from the group consisting of hydroxyl group, amino group, aldehyde group, carboxyl group, acyl group, halogen atom, alkoxy group and hetero atom, and 0.ltoreq.a.ltoreq.2.
Non-limiting examples of the alkoxy magnesium compound according to the embodiment of the present invention include: one or more of Mg (OEt) 2、Mg(OCH2CH2CH3)2、Mg(OBu)2, 2-octylmagnesium oxide, mg (OEt) a(OEHA)2-a (1.5. Ltoreq.a.ltoreq.2), and Mg (OEt) a(OBu)2-a (1.3. Ltoreq.a.ltoreq.2), wherein EHA is 2-ethylhexyl. More preferably, the alkoxy magnesium compound is Mg (OEt) 2 and/or Mg (OEt) a(OEHA)2-a (1.5.ltoreq.a.ltoreq.2).
According to the present invention, the amount of the inert solvent may be selected according to the amount of the alkoxy magnesium compound. In general, the inert solvent is used in an amount of 0.8 to 10L, preferably 2 to 8L, based on 1mol of the magnesium alkoxide compound. The inert solvent may be any of a variety of liquid media commonly used in the art that do not chemically interact with the reactants and reaction products. For example: the inert solvent may be silicone oil and/or an inert liquid hydrocarbon solvent. Specifically, the inert solvent may be one or more of toluene, kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil.
According to the present invention, the contact reaction of the suspension with the internal electron donor compound and the silicone-based compound, and the halide of transition metal titanium and/or its derivative with stirring can be performed in the same manner as in the prior art, except that the internal electron donor is the internal electron donor compound and the silicone-based compound of the general formula (I) provided in the present invention. For example, the suspension may be mixed with the electron donor compound, the silicone ester compound, the halide of transition metal titanium and/or the derivative thereof in the general formula (I) at-30 to 0 ℃ for reaction for 30 to 180 minutes, then heated to 50 to 120 ℃ and maintained at the reaction temperature for 0.5 to 10 hours, then subjected to solid-liquid separation, and washed to obtain the olefin polymerization catalyst solid component.
Preferably, the addition ratio of the magnesium alkoxide compound, the silicone ester compound, the electron donor compound in the general formula (I), and the halide of transition metal titanium and/or its derivative is 0.1 to 1 mole, the amount of the electron donor compound in the general formula (I) is 0.01 to 1 mole, and the amount of the halide of transition metal titanium and/or its derivative is 1 to 25 moles, per mole of magnesium alkoxide.
Specifically, the electron donor compound in the general formula (I) may be 0.01 mole, 0.05 mole, 0.1 mole, 0.2 mole, 0.3 mole, 0.4 mole, 0.5 mole, 0.6 mole, 0.7 mole, 0.8 mole, 0.9 mole, 1 mole, etc., the silicone compound may be 0.1 mole, 0.2 mole, 0.3 mole, 0.4 mole, 0.5 mole, 0.6 mole, 0.7 mole, 0.8 mole, 0.9 mole, 1 mole, etc., and the halide of transition metal titanium and/or its derivative may be 1 mole, 5 mole, 10 mole, 15 mole, 20 mole, 25 mole, etc., per mole of magnesium alkoxide.
According to the present invention, the transition metal titanium halide and/OR the derivative thereof may be various titanium-containing substances commonly used in the field of olefin polymerization catalysts, and preferably, the transition metal titanium halide OR the derivative thereof has the general formula of Ti (OR 9)dXb, wherein R 9 is a hydrocarbon group of C 1～C14, preferably C 1～C8 alkyl group, X is a halogen atom, a and b are each independently an integer of 1 to 4, and a+b=3 OR 4.
Specifically, the alkyl group of C 1～C8 may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, and the like. Non-limiting examples of the transition metal titanium halide and/or derivative thereof include ：TiCl3、TiCl4、TiBr4、TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4 and Ti (one or more of OC 4H9)4. Preferably, the transition metal titanium halide and/or derivative thereof is selected from one or more of TiCl3、TiCl4、TiBr4、Ti(OC2H5)2Cl2、Ti(OC2H5)Cl3、Ti(OC2H5)3Cl、Ti(OCH3)Cl3、Ti(OC4H9)Cl3 and Ti (OC 4H9)4. TiCl 4 is preferred in embodiments of the present invention).
Preferably, in order to be able to better enhance the activity and copolymerization performance of the olefin polymerization catalyst solid component and the olefin polymerization catalyst prepared therefrom, in the step (2), the halide of transition metal titanium and/or its derivative is added in multiple times, more preferably in two times and a certain contact reaction time is ensured, thereby further enhancing the hydrogen sensitivity and polymerization activity of the olefin polymerization catalyst solid component, specifically, the contact reaction method comprises:
(a) Reacting the suspension with a first transition metal titanium halide and/or derivative thereof at a temperature of-30 ℃ to 0 ℃ and adding an electron donor compound and a silicone compound of formula (I) for one or more time periods before, during and after the reaction of the suspension with the transition metal titanium halide and/or derivative thereof to obtain a first product;
(b) Heating the first product obtained in the step (1) to 50-120 ℃, reacting for 0.5-4 hours under the stirring condition, standing, layering, pumping out supernatant, continuously carrying out contact reaction on the obtained second product and the halide and/or derivative of the second transition metal titanium under the stirring condition for 0.5-4 hours in the presence of the optionally added inert solvent, and then carrying out solid-liquid separation and washing.
According to the invention, in step (a), the suspension is stirred and mixed with the halide of the first transition metal titanium and/or the derivative thereof at a temperature of from-30 ℃ to 0 ℃ for a reaction of from 10 to 60 minutes, and the electron donor compound and the silicone compound in the general formula (I) are added during one or more time periods before, during and after the reaction of the suspension with the halide of the first transition metal titanium and/or the derivative thereof, preferably during the time period before the reaction of the suspension with the halide of the first transition metal titanium and/or the derivative thereof. The period of time before the suspension reacts with the halide of the first transition metal titanium and/or the derivative thereof means a period of time after the suspension is added to the reactor and before the temperature is raised to the reaction temperature of step (b).
According to the present invention, although the halide of transition metal titanium and/or its derivative is/are added in multiple times, more preferably in two times and a certain contact reaction time is ensured and a certain temperature rising trend is controlled, the hydrogen regulation sensitivity and polymerization activity of the solid component of the olefin polymerization catalyst can be improved, and the obtained olefin polymerization catalyst exhibits higher catalytic activity, better hydrogen regulation sensitivity and good copolymerization performance when used for ethylene polymerization. However, in order to obtain an olefin polymerization catalyst solid component and an olefin polymerization catalyst having more excellent overall properties, the amount of the silicon ester compound used in the step (a) is preferably 0.1 to 1 mol, and the amount of the compound of the general formula (I) is preferably 0.01 to 1 mol, and the amount of the halide of the first transition metal titanium and the derivative thereof is preferably 1 to 20 mol, per mol of the magnesium alkoxide. The molar ratio of the halide of the second transition metal titanium and its derivative to the halide of the first transition metal titanium and its derivative may be selected in a wide range, and more preferably, in order to achieve the above object better, the molar ratio of the halide of the second transition metal titanium and its derivative to the halide of the first transition metal titanium and its derivative is 1 (1 to 5).
According to the present invention, the solid-liquid separation method of the final product obtained in step (b) may be any of various existing methods capable of achieving solid-liquid separation, such as suction filtration, pressure filtration or centrifugal separation, and preferably, the solid-liquid separation method is a pressure filtration method. The conditions for press filtration are not particularly limited in the present invention, so long as the separation of the solid phase and the liquid phase is achieved as sufficiently as possible.
According to the present invention, in the step (b), in order that the reaction can be more sufficiently performed, the step (b) may be further performed in the presence of an inert solvent, and the amount of the inert solvent may be conventionally selected according to the amount of the second product and the halide of the second transition metal titanium and/or the derivative thereof. The inert solvent may be silicone oil and/or an inert liquid hydrocarbon solvent. Specifically, the inert solvent may be one or more of toluene, kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil.
A third aspect of the present invention provides an olefin polymerization catalyst, wherein the olefin polymerization catalyst contains: (A) A catalyst solid component, (B) a cocatalyst component, said (B) cocatalyst component being at least one organoaluminum compound. The olefin polymerization catalyst contains the solid component of the olefin polymerization catalyst provided by the invention, so that the catalyst not only has excellent hydrogen sensitivity, but also has higher polymerization activity.
The type and amount of the organoaluminum compound according to the invention may be any conventional choice in the art. For example, the organoaluminum compounds have the general formula AlR 1 eX1 fHg, wherein R 1 is hydrogen or C l～C20 hydrocarbyl, X 1 is a halogen atom, preferably fluorine, chlorine or bromine, e, f, g are each independently integers from 0 to 3, and e+f+g=3. Specifically, examples of the organoaluminum compound include, but are not limited to, at least one of ：AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3 and AlEt 2 Cl. Generally, in the olefin polymerization catalyst, the molar ratio of the (B) promoter component in terms of aluminum to the (A) olefin polymerization solid catalyst component in terms of titanium is (5 to 500): 1, preferably (20 to 200): 1, and may be, for example, 5:1, 10:1, 20:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, or the like.
In a fourth aspect, the present invention provides the use of an olefin polymerization catalyst solid component according to the invention and/or an olefin polymerization catalyst according to the invention in ethylene homo-and/or co-polymerization.
The olefin polymerization catalyst provided by the invention is suitable for homo-polymerization of ethylene or copolymerization of ethylene and other alpha-olefins, wherein the alpha-olefins can be at least one selected from propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methylpentene-1. Slurry polymerization or gas phase polymerization may be used for the polymerization, and the polymerization temperature may be 0 to 150 ℃, preferably 60 to 90 ℃.
The slurry polymerization medium comprises: and inert solvents such as saturated aliphatic hydrocarbons or aromatic hydrocarbons, e.g., isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.
In order to adjust the molecular weight of the final polymer, hydrogen may also be used as a molecular weight regulator.
The present invention will be described in detail by examples.
The experimental test methods in the following examples and comparative examples include:
1. the solid catalyst component comprises the following titanium elements in percentage by weight: spectrophotometry is used.
2. Polymer Melt Index (MI): according to ASTM D1238-99, load 2.16kg, 190 ℃.
Example 1
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component A1 of olefin polymerization catalyst
To the reactor fully replaced with high purity nitrogen, 4.8g of ethoxymagnesium and 60mL of toluene were added in this order, and a suspension was formed with stirring at 300 rpm. The system is cooled to-20 ℃, 1.0g of p-methoxyphenol, 4mL of tetraethoxysilane and 40mL of titanium tetrachloride are sequentially added in sequence, the temperature is kept for 30 minutes, and then the temperature is raised to 80 ℃ for reaction for 2 hours. The stirring was stopped, the suspension was allowed to stand, and the supernatant was removed by suction. 60mL of toluene and 20mL of titanium tetrachloride were added, and the temperature was raised to 80℃and kept constant for 2 hours. Stopping stirring, standing, and removing supernatant. And (3) washing the catalyst for olefin polymerization for multiple times by toluene and hexane, and drying the catalyst for olefin polymerization for multiple times to obtain the solid component A1 with good fluidity.
(2) Homo-polymerization
① Polymerization with low hydrogen/ethylene ratio
After the stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of triethylaluminum with the concentration of 1M are added, then the solid component A1 (containing 0.4mg of titanium) of the olefin polymerization catalyst prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to enable the pressure in the kettle to reach 0.28MPa, ethylene is introduced to enable the total pressure in the kettle to reach 0.73MPa, and polymerization is carried out for 2 hours at 80 ℃, and the polymerization result is shown in Table 1.
② Polymerization with high hydrogen/ethylene ratio
After the stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of triethylaluminum with the concentration of 1M are added, then the solid component A1 (containing 0.4mg of titanium) of the olefin polymerization catalyst prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to enable the pressure in the kettle to reach 0.58MPa, ethylene is introduced to enable the total pressure in the kettle to reach 0.73MPa, and the polymerization result is shown in Table 2 under the condition of 80 ℃.
Example 2
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component A2 of olefin polymerization catalyst
An olefin polymerization catalyst solid component A2 was prepared in the same manner as in example 1 except that p-methoxyphenol was only replaced with p-ethoxyphenol.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A2 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 3
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component A3 of olefin polymerization catalyst
An olefin polymerization catalyst solid component A3 was prepared in the same manner as in example 1 except that only p-methoxyphenol was replaced with p-butoxyphenol.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A3 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 4
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of olefin polymerization catalyst solid component A4
An olefin polymerization catalyst solid component A4 was prepared in the same manner as in example 1 except that the addition amount of p-methoxyphenol alone was adjusted to 500mg.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A4 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 5
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component A5 of olefin polymerization catalyst
An olefin polymerization catalyst solid component A5 was prepared in the same manner as in example 2 except that the amount of p-ethoxyphenol added was adjusted to 500mg only.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A5 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 6
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component A6 of olefin polymerization catalyst
An olefin polymerization catalyst solid component A6 was prepared in the same manner as in example 3 except that the addition amount of p-butoxyphenol alone was adjusted to 500mg.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A6 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 7
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component A7 of olefin polymerization catalyst
An olefin polymerization catalyst solid component A7 was prepared in the same manner as in example 1 except that the addition amount of p-methoxyphenol alone was adjusted to 200mg.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A7 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 8
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component A8 of olefin polymerization catalyst
An olefin polymerization catalyst solid component A8 was prepared in the same manner as in example 2 except that the amount of p-ethoxyphenol added was adjusted to 200mg only.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A8 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 9
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of olefin polymerization catalyst solid component A9
An olefin polymerization catalyst solid component A9 was prepared in the same manner as in example 3 except that the addition amount of p-butoxyphenol alone was adjusted to 200mg.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A9 of the olefin polymerization catalyst prepared in this example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Example 10
This example is for explaining the preparation of the solid component of the olefin polymerization catalyst provided by the present invention and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of olefin polymerization catalyst solid component A10
To the reactor fully replaced with high purity nitrogen, 4.8g of ethoxymagnesium and 60mL of toluene were added in this order, and a suspension was formed with stirring at 300 rpm. The system is cooled to-20 ℃, 0.5g of p-methoxyphenol, 3.5mL of tetraethoxysilane and 60mL of titanium tetrachloride are sequentially added in sequence, the temperature is kept for 30 minutes, and then the temperature is raised to 80 ℃ for reaction for 2 hours. The stirring was stopped, the suspension was allowed to stand, and the supernatant was removed by suction. 60mL of toluene and 40mL of titanium tetrachloride were added, and the temperature was raised to 80℃and kept constant for 2 hours. Stopping stirring, standing, and removing supernatant. And washing with toluene and hexane for multiple times, and drying to obtain the olefin polymerization catalyst solid component A10 with good fluidity.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component A10 of the olefin polymerization catalyst prepared in this example, the amount of triethylaluminum added was adjusted to 2ml, and the polymerization results were shown in Table 1 and Table 2, respectively.
Comparative example 1
This comparative example is for explaining the preparation of a solid component of a reference olefin polymerization catalyst and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component B1 of olefin polymerization catalyst
To the reactor fully replaced with high purity nitrogen, 4.8g of ethoxymagnesium and 60mL of toluene were added in this order, and a suspension was formed with stirring at 300 rpm. The system is cooled to-20 ℃, 40mL of titanium tetrachloride is slowly added dropwise, the temperature is kept constant for 30 minutes, the temperature is raised to 80 ℃, and the reaction is carried out for 2 hours. The stirring was stopped, the suspension was allowed to stand, and the supernatant was removed by suction. 60mL of toluene and 20mL of titanium tetrachloride were added, and the temperature was raised to 80℃and kept constant for 2 hours. Stopping stirring, standing, and removing supernatant. And (3) washing the catalyst for olefin polymerization for multiple times by toluene and hexane, and drying the catalyst for olefin polymerization for obtaining the solid component B1 with good fluidity.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component of the olefin polymerization catalyst B1 prepared in this comparative example, and the polymerization results were shown in Table 1 and Table 2, respectively.
Comparative example 2
This comparative example is for explaining the preparation of a solid component of a reference olefin polymerization catalyst and the polymerization reaction using the olefin polymerization catalyst thus obtained.
(1) Preparation of solid component B2 of olefin polymerization catalyst
To the reactor fully replaced with high purity nitrogen, 4.8g of ethoxymagnesium and 60mL of toluene were added in this order, and a suspension was formed with stirring at 300 rpm. The system was cooled to-20℃and 4mL of ethyl orthosilicate was added thereto, 40mL of titanium tetrachloride was slowly added dropwise thereto, and after keeping the temperature for 30 minutes, the temperature was raised to 80℃and the reaction was carried out for 2 hours. The stirring was stopped, the suspension was allowed to stand, and the supernatant was removed by suction. 60mL of toluene and 20mL of titanium tetrachloride were added, and the temperature was raised to 80℃and kept constant for 2 hours. Stopping stirring, standing, and removing supernatant. And (3) washing the catalyst for olefin polymerization for multiple times by toluene and hexane, and drying the catalyst for olefin polymerization for obtaining the solid component B2 with good fluidity.
(2) Homo-polymerization
A homopolymerization was conducted in the same manner as in example 1 except that the solid component of the olefin polymerization catalyst was the solid component B2 of the olefin polymerization catalyst prepared in comparative example 2, and the polymerization results were shown in Table 1 and Table 2, respectively.
TABLE 1
As can be seen from the data in Table 1, after the electron donor compound and the silicon ester compound in the general formula (I) are added for compounding, the olefin polymerization catalyst of the invention has the advantages of improved catalyst activity and increased titanium content under the condition of low-hydrogen polymerization. At lower hydrogen/olefin ratios, the resulting polymer has a lower melt index.
TABLE 2
As can be seen from the data in Table 2, after the electron donor compound and the silicone ester compound in the general formula (I) are added, the catalyst of the invention has high catalyst activity under the condition of high-hydrogen polymerization, and the polymer has higher melt index. It can be seen that the polymer obtained under the coaction of the electron donor compound and the silicone ester compound in the general formula (I) has a larger melt index under the condition of higher hydrogen-ethylene ratio, and the polymer obtained under the condition of lower hydrogen-ethylene ratio has the characteristic of smaller melt index. This feature is advantageous for the production of bimodal polyethylene products in slurry polymerization processes, and for the production of high melt index products in gas phase polymerization processes.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.
Claims (15)
1. An olefin polymerization catalyst solid component comprising a halide of titanium and/or a derivative thereof, a magnesium alkoxide compound, and an internal electron donor, wherein the internal electron donor comprises an internal electron donor compound represented by the formula (I):
In the formula (I), R 1、R2、R3、R4、R5 is optionally one RO group, and the rest are the same or different and are each independently C 1～C20 linear or branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, R is selected from linear or branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl of C 1～C20;
the general formula of the silicone compound is R 2 xR3 ySi(OR4)z, wherein R 2 and R 3 are respectively and independently alkyl of C 1～C10 and halogen, R 4 is alkyl of C 1～C10, x, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 4, and x+y+z=4;
the silicon ester compound is 0.1 to 1 mole, the internal electron donor compound is 0.01 to 1 mole, and the halide and/or derivative of titanium is 1 to 25 moles per mole of magnesium.
2. The olefin polymerization catalyst solid component according to claim 1, characterized in that: the internal electron donor compound is selected from at least one of p-methoxyphenol, o-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, o-propoxyphenol, m-propoxyphenol, p-butoxyphenol, o-butoxyphenol, m-butoxyphenol, p-hexyloxyphenol, o-hexyloxyphenol, m-hexyloxyphenol, p-octyloxyphenol, o-octyloxyphenol, m-octyloxyphenol, p-nonoxyphenol, m-nonoxyphenol, o-nonoxyphenol, dodecyloxyphenol, tetradecoxyphenol, octadecyloxyphenol, phenoxyphenol and hydroxyphenyl benzyl ether;
The silicon ester compound is selected from tetramethoxy silane, tetraethoxy silane, tetrapropoxy silane, tetrabutoxy silane, tetra (2-ethylhexyl) silane, ethyltrimethoxy silane, ethyltriethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, n-propyltriethoxy silane, n-propyltrimethoxy silane, decyltrimethoxy silane, decyltriethoxy silane, cyclopentyltrimethoxy silane, cyclopentyltriethoxy silane, 2-methylcyclopentyltrimethoxy silane, 2, 3-dimethylcyclopentyltrimethoxy silane, cyclohexyltrimethoxy silane, cyclohexyltriethoxy silane, ethyltriethoxy silane, vinyltrimethoxy silane, vinyltriethoxy silane, t-butyltriethoxy silane, n-butyltrimethoxy silane, n-butyltriethoxy silane, isobutyltrimethoxy silane, phenyltrimethoxy silane, phenyltriethoxy silane, monochlorotrimethoxy silane, monochlorotriethoxy silane, ethyltriisopropoxy silane, vinyltrimethoxy silane, trimethylphenoxy silane, methyltrimethoxy silane, vinyltriacetoxy silane, dimethyldimethoxy silane, dimethyldiethoxy silane, dimethyldimethoxy silane, di-propyl dimethoxy silane, di-t-butyltriethoxy silane, di-methyl-ethoxy silane, di-t-butyltriethoxy silane, di-methyl-ethoxy silane, di-amyl-ethoxysilane, di-methyl-ethoxy silane, at least one of methylphenyl dimethoxy silane, di-o-tolyldimethoxy silane, di-o-tolyldiethoxy silane, di-m-tolyldimethoxy silane, di-m-tolyldiethoxy silane, di-p-tolyldiethoxy silane, trimethylmethoxy silane, trimethylethoxy silane, tricyclopentylmethoxy silane, tricyclopentylethoxy silane, dicyclopentylmethoxy silane, and cyclopentyldimethylmethoxy silane.
3. The olefin polymerization catalyst solid component according to claim 1, characterized in that:
The silicon ester compound is 0.1 to 0.8 mole, the internal electron donor compound is 0.01 to 0.6 mole, and the halide and/or derivative of titanium is 1 to 15 mole per mole of magnesium.
4. A process for preparing a solid component of an olefin polymerization catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) Dispersing a magnesium alkoxide compound in an inert solvent to form a suspension;
(2) And (3) carrying out contact reaction on the suspension liquid and an internal electron donor compound, a silicone ester compound and a halide and/or derivative of titanium, and then carrying out solid-liquid separation to obtain the catalyst solid component.
5. The method of manufacturing according to claim 4, wherein:
The general formula of the alkoxy magnesium compound is Mg (OR 7)a(OR8)2-a, wherein R 7 and R 8 are each independently substituted OR unsubstituted C 1～C10 alkyl, and the substituent is at least one selected from hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, alkoxy and heteroatom, 0 is less than OR equal to a is less than OR equal to 2, and/OR,
The general formula of the titanium halide and/OR the derivative thereof is Ti (OR 9)dXb, wherein R 9 is C 1～C14 alkyl, X is halogen atom, d and b are each independently integers of 1-4, and d+b=3 OR 4).
6. The method of manufacturing according to claim 5, wherein:
The alkoxy magnesium compound is at least one selected from Mg (OEt) 2、Mg(OCH2CH2CH3)2、Mg(OBu)2, 2-octoxymagnesium and Mg (OEt) a(OEHA)2-a、Mg(OEt)a(OBu)2-a, wherein EHA is 2-ethylhexyl; and/or the number of the groups of groups,
The halide of titanium and/or its derivative is selected from at least one of TiCl3、TiCl4、TiBr4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4、Ti(OC4H9)4.
7. The process according to claim 4, wherein in the step (2), the method of the contact reaction comprises:
(a) Reacting the suspension with a portion of the titanium halide and/or derivative thereof at a temperature of from-30 ℃ to 0 ℃ and adding the internal electron donor compound and the silicone-based compound for one or more time periods before, during and after the reaction of the suspension with the titanium halide and/or derivative thereof to obtain a first product;
(b) Heating the first product obtained in the step (a) to 50-120 ℃, reacting under stirring, standing, layering, pumping out supernatant to obtain a second product, continuously carrying out contact reaction on the obtained second product and the residual titanium halide and/or the derivative thereof and the optional inert solvent under stirring, and then carrying out solid-liquid separation.
8. The method of manufacturing according to claim 7, wherein:
in the step (a), the silicon ester compound is 0.1 to 1 mol, the internal electron donor compound is 0.1 to 1 mol, and the halide of titanium and/or the derivative thereof is 1 to 20 mol per mol of magnesium;
The molar ratio of the halide of titanium and/or its derivative in step (b) to the halide of titanium and/or its derivative in step (a) is 1 (1-5).
9. An olefin polymerization catalyst solid component produced by the production process according to any one of claims 4 to 8.
10. An olefin polymerization catalyst comprising:
(A) A catalyst solid component, wherein (a) the catalyst solid component is the olefin polymerization catalyst solid component according to any one of claims 1 to 3, 9;
(B) A cocatalyst component, wherein the cocatalyst component (B) is at least one organoaluminum compound.
11. The olefin polymerization catalyst according to claim 10, characterized in that:
The general formula of the organic aluminum compound is AlR 1 eX1 fHg, wherein R 1 is hydrogen or C l～C20 alkyl, X 1 is halogen atom, e, f and g are each independently integers of 0-3, and e+f+g=3.
12. The olefin polymerization catalyst according to claim 11, characterized in that:
X 1 is fluorine, chlorine or bromine;
The organic aluminum compound is at least one selected from AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl.
13. The olefin polymerization catalyst according to any one of claims 10 to 12, characterized in that:
The molar ratio of the promoter component (B) in terms of aluminum to the catalyst solid component (A) in terms of titanium is (5-500): 1.
14. The olefin polymerization catalyst according to claim 13, characterized in that:
The molar ratio of the promoter component (B) in terms of aluminum to the catalyst solid component (A) in terms of titanium is (20-200): 1.
15. Use of the olefin polymerization catalyst solid component according to any one of claims 1 to 3, 9, the olefin polymerization catalyst according to any one of claims 10 to 14 in ethylene homo-and/or co-polymerization.
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| CN102295715A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
| CN112759682A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst composition, catalyst and preparation method thereof, composite catalyst and olefin polymerization method |
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| EP0773241B1 (en) * | 1994-01-31 | 2001-09-12 | Toho Titanium Co., Ltd. | Solid catalyst component for polymerizing olefins and catalyst for polymerization of olefins |
| US6469112B2 (en) * | 2000-08-22 | 2002-10-22 | Engelhard Corporation | (Cycloalkyl)methyl silanes as external donors for polyolefin catalysts |
| CN100513433C (en) * | 2005-10-31 | 2009-07-15 | 中国石油化工股份有限公司 | Catalyst components in use for polymerizing ethylene, and catalyst |
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| CN112759682A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst composition, catalyst and preparation method thereof, composite catalyst and olefin polymerization method |
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