CN108341902B - Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization - Google Patents
Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization Download PDFInfo
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- CN108341902B CN108341902B CN201710050947.7A CN201710050947A CN108341902B CN 108341902 B CN108341902 B CN 108341902B CN 201710050947 A CN201710050947 A CN 201710050947A CN 108341902 B CN108341902 B CN 108341902B
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- catalyst component
- compound
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- titanium
- organic
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 48
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000005977 Ethylene Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 aromatic alkoxy ester compounds Chemical class 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 14
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003701 inert diluent Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- XRZZOPVYBXOXCN-UHFFFAOYSA-N 2-methoxyethyl benzoate Chemical compound COCCOC(=O)C1=CC=CC=C1 XRZZOPVYBXOXCN-UHFFFAOYSA-N 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- MVGPIOMIIRAWPI-UHFFFAOYSA-N [Mg]OCl Chemical compound [Mg]OCl MVGPIOMIIRAWPI-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 claims description 4
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QLSUGJQAAUGJHE-UHFFFAOYSA-N 2-propan-2-yloxyethyl benzoate Chemical compound CC(C)OCCOC(=O)C1=CC=CC=C1 QLSUGJQAAUGJHE-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- MZBMPBAJNYTJRR-UHFFFAOYSA-N 1-methoxypropan-2-yl 4-ethoxybenzoate Chemical compound CCOC1=CC=C(C(=O)OC(C)COC)C=C1 MZBMPBAJNYTJRR-UHFFFAOYSA-N 0.000 claims description 2
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- KPHLTQOKDPSIGL-UHFFFAOYSA-N 2-ethoxyethyl benzoate Chemical compound CCOCCOC(=O)C1=CC=CC=C1 KPHLTQOKDPSIGL-UHFFFAOYSA-N 0.000 claims description 2
- KOKDCEFCPJHCOB-UHFFFAOYSA-N 2-methoxyethyl 4-ethoxybenzoate Chemical compound CCOC1=CC=C(C(=O)OCCOC)C=C1 KOKDCEFCPJHCOB-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 claims description 2
- ZPHMYHCMBKTAND-UHFFFAOYSA-N CCCCC(CC)CO[Mg] Chemical compound CCCCC(CC)CO[Mg] ZPHMYHCMBKTAND-UHFFFAOYSA-N 0.000 claims description 2
- ZKCNZMISGOLOOY-UHFFFAOYSA-N CCCCCCCCO[Mg] Chemical group CCCCCCCCO[Mg] ZKCNZMISGOLOOY-UHFFFAOYSA-N 0.000 claims description 2
- MBDDNIAGMALXQK-UHFFFAOYSA-N CCOCC(C)C(C=CC=C1)=C1C(O)=O Chemical compound CCOCC(C)C(C=CC=C1)=C1C(O)=O MBDDNIAGMALXQK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 claims description 2
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 2
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- PNHBLDCCSXTBPP-UHFFFAOYSA-N ethyl 1-butyl-6-methoxycyclohexa-2,4-diene-1-carboxylate Chemical compound C(CCC)C1(C(=O)OCC)C(C=CC=C1)OC PNHBLDCCSXTBPP-UHFFFAOYSA-N 0.000 claims description 2
- HORZTLJIITVKGO-UHFFFAOYSA-N ethyl 1-ethyl-6-methoxycyclohexa-2,4-diene-1-carboxylate Chemical compound CCC1(C=CC=CC1OC)C(=O)OCC HORZTLJIITVKGO-UHFFFAOYSA-N 0.000 claims description 2
- UEESBHNOMVAXLN-UHFFFAOYSA-N ethyl 1-tert-butyl-6-methoxycyclohexa-2,4-diene-1-carboxylate Chemical compound C(C)(C)(C)C1(C(=O)OCC)C(C=CC=C1)OC UEESBHNOMVAXLN-UHFFFAOYSA-N 0.000 claims description 2
- CNGIWMGKIUPABV-UHFFFAOYSA-N ethyl 6-methoxy-1-(2-methylpropyl)cyclohexa-2,4-diene-1-carboxylate Chemical compound C(C(C)C)C1(C(=O)OCC)C(C=CC=C1)OC CNGIWMGKIUPABV-UHFFFAOYSA-N 0.000 claims description 2
- WLJROKUYJRNCCL-UHFFFAOYSA-N ethyl 6-methoxy-1-propan-2-ylcyclohexa-2,4-diene-1-carboxylate Chemical compound C(C)(C)C1(C(=O)OCC)C(C=CC=C1)OC WLJROKUYJRNCCL-UHFFFAOYSA-N 0.000 claims description 2
- RRFCVPLNRIAMEM-UHFFFAOYSA-N ethyl 6-methoxy-1-propylcyclohexa-2,4-diene-1-carboxylate Chemical compound C(CC)C1(C(=O)OCC)C(C=CC=C1)OC RRFCVPLNRIAMEM-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- FSLSJTZWDATVTK-UHFFFAOYSA-N tris(6-methylheptyl) phosphate Chemical compound CC(C)CCCCCOP(=O)(OCCCCCC(C)C)OCCCCCC(C)C FSLSJTZWDATVTK-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims 1
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- WIBBNISPGCZGET-UHFFFAOYSA-N magnesium;octan-1-olate Chemical compound CCCCCCCCO[Mg]OCCCCCCCC WIBBNISPGCZGET-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 28
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229940050390 benzoate Drugs 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 235000011147 magnesium chloride Nutrition 0.000 description 8
- 239000011949 solid catalyst Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FQFDSBPNECVJTP-UHFFFAOYSA-N 1-methoxypropane;1-phenylethyl benzoate Chemical compound CCCOC.C=1C=CC=CC=1C(C)OC(=O)C1=CC=CC=C1 FQFDSBPNECVJTP-UHFFFAOYSA-N 0.000 description 1
- HQRVWLQLIRIIGV-UHFFFAOYSA-N 2-methoxyethyl 2,4,6-trichlorobenzoate Chemical compound COCCOC(=O)C1=C(Cl)C=C(Cl)C=C1Cl HQRVWLQLIRIIGV-UHFFFAOYSA-N 0.000 description 1
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 description 1
- SRDCEXFMRBFEPK-UHFFFAOYSA-M CCC[Al](CCl)Cl Chemical compound CCC[Al](CCl)Cl SRDCEXFMRBFEPK-UHFFFAOYSA-M 0.000 description 1
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- KTFSKSJNPRMGEW-UHFFFAOYSA-N [Mg]OCCl Chemical compound [Mg]OCCl KTFSKSJNPRMGEW-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ISFMCQATCMRFPY-UHFFFAOYSA-M chloro(diphenyl)alumane Chemical compound [Cl-].C=1C=CC=CC=1[Al+]C1=CC=CC=C1 ISFMCQATCMRFPY-UHFFFAOYSA-M 0.000 description 1
- LKRBKNPREDAJJQ-UHFFFAOYSA-M chloro-di(propan-2-yl)alumane Chemical compound [Cl-].CC(C)[Al+]C(C)C LKRBKNPREDAJJQ-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-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
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- OAFMYIADTCIEFV-UHFFFAOYSA-N hexane;triethylalumane Chemical compound CCCCCC.CC[Al](CC)CC OAFMYIADTCIEFV-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- C08F10/02—Ethene
-
- 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
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 relates to the technical field of catalysts for ethylene polymerization, and provides a catalyst component for ethylene polymerization, a preparation method thereof and a catalyst for ethylene polymerization, wherein the catalyst component comprises a reaction product of the following components: magnesium compounds, organic epoxy compounds, organic alcohol compounds, organic phosphorus compounds, polyvinylpyrrolidone, titanium-containing compounds and aromatic alkoxy ester compounds; the structure of the aromatic alkoxy ester compound is shown as a general formula (I); the method comprises the following steps: contacting a magnesium halide, an organic epoxy compound, an organic alcohol compound and an organic phosphorus compound to form a homogeneous solution; reacting it with polyvinylpyrrolidone; after cooling, the obtained solution is contacted with a titanium-containing compound to obtain a solid; and (3) contacting the solid with an aromatic alkoxy ester compound to form a mixture to obtain the catalyst component. The catalyst component obtained by the invention has the advantages of increased particle size, obviously narrowed particle size distribution, high bulk density of the obtained polymer and good hydrogen regulation sensitivity.
Description
Technical Field
The invention relates to the technical field of catalysts for ethylene polymerization, in particular to a catalyst component for ethylene polymerization, a preparation method thereof and a catalyst for ethylene polymerization.
Background
It is known that a catalyst system containing a Ti/Mg complex is dominant in the industrial production of polyolefins, and the core of the research is not limited to the polymerization activity of the catalyst, the particle morphology and particle size distribution of the catalyst, the hydrogen response and copolymerization performance of the catalyst, and the like. In the prior art, in order to obtain catalysts with uniform particle diameter and better particle morphology, one generally prepares the catalyst using different magnesium feedstocks.
The first method is to dissolve magnesium chloride as a raw material in a certain solvent to obtain a uniform solution, then mix the solution with a titanium compound and an optional electron donor, obtain a solid containing magnesium, titanium and an optional electron donor by a precipitation method, and treat the solid with an excessive amount of a liquid titanium compound to obtain catalyst particles. For example, in the preparation methods disclosed in patent documents CN1099041A and CN1229092A, the catalyst is obtained by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound, adding an electron donor to form a homogeneous solution, and reacting with at least one precipitation aid and a halide of transition metal titanium or a derivative thereof. The disadvantages of this conventional method are: the particle size and particle size distribution of the catalyst particles are completely controlled by a precipitation process, i.e., a recrystallization process of the magnesium carrier component, and the stability of the catalyst particles is difficult to control.
The second method is to directly load the active components of the catalyst on an inert carrier (such as silica gel and the like) because of the particles of the silica gelThe particle diameter is easy to control, and the particle morphology is good, so that the catalyst particles with uniform particles can be obtained. However, the catalyst prepared by this method has a low titanium content and a low polymerization activity because the amount of the active component supported on the carrier is limited. For example: in patent document CN1268520A, magnesium chloride and silica are used as carriers, titanium tetrachloride is used as an active component, and the preparation method of the catalyst is as follows: mixing MgCl2With TiCl in tetrahydrofuran4Reacting with the SiO treated with the aluminum alkyl2Mixing, and removing tetrahydrofuran to obtain the catalyst component. When the catalyst is used for ethylene polymerization, the titanium content in the catalyst is low, so that the polymerization activity is low. Thus, such catalyst systems, while useful in gas phase fluidized bed polymerization processes of ethylene, are difficult to apply in slurry polymerization processes of ethylene due to their relatively low catalytic activity.
In slurry polymerization of ethylene, the catalyst should have high catalytic activity and good particle size distribution, as well as high bulk density and good hydrogen response. Among them, the bulk density of the polymer is one of the indexes showing the good and bad comprehensive performance of the catalyst. The higher bulk density of the polymer is beneficial to increasing the fluidity of powder, is equivalent to increasing the effective volume of a polymerization kettle, is beneficial to improving the production load of a device, reduces the production cost of resin, and achieves the effects of cost reduction and efficiency improvement. The bulk density of the catalyst systems obtained by the two methods described above is not yet satisfactory. In addition, although the catalyst systems have good performance for olefin polymerization, the catalyst systems adopt a method of adding a precipitation aid in order to obtain a catalyst solid product in the preparation process, and a large amount of titanium tetrachloride is used, which causes great trouble in waste liquid treatment in the post-treatment stage.
Disclosure of Invention
The invention aims to provide a catalyst component for ethylene polymerization, a preparation method thereof and a catalyst for ethylene polymerization aiming at the defects of the catalyst component prepared in the prior art, so that the obtained catalyst component has good particle shape and narrow particle size distribution, and shows higher polymerization activity and better bulk density when used for ethylene polymerization; the catalyst has simple preparation method and less titanium consumption, and is beneficial to simplifying the post-treatment work.
In order to achieve the above object, the present invention provides a catalyst component for ethylene polymerization, comprising the reaction product of: (1) a magnesium compound; (2) an organic epoxy compound; (3) an organic alcohol compound; (4) an organic phosphorus compound; (5) polyvinylpyrrolidone; (6) a titanium-containing compound; (7) aromatic alkoxy ester compounds; wherein,
the structure of the aromatic alkoxy ester compound is shown as a general formula (I),
in the formula, R1Is C1-C20 alkyl or C1-C20 substituted alkyl; r2And R3The same or different, each is independently selected from hydrogen, alkyl of C1-C20, substituted alkyl of C1-C20, cycloalkyl of C3-C20, and aryl of C6-C20; r4，R5And R6The same or different, each is independently selected from hydrogen, hetero atom, C1-C20 alkyl, C1-C20 substituted alkyl, or C1-C20 alkoxy.
According to the catalyst component provided by the present invention, preferably, the magnesium compound has the general formula of Mg (OR)7)nX2-n(ii) a In the formula, R7Is a saturated or unsaturated linear chain alkyl, branched chain alkyl or C3-C20 cyclic chain alkyl of C1-C20; x is halogen, preferably chlorine, n is an integer and 0. ltoreq. n.ltoreq.2;
the magnesium compound is preferably selected from at least one of magnesium chloride, magnesium bromide, chloromethoxymagnesium, monochlorooxymagnesium, monochloroisopropoxygmagnesium, chlorochlorochlorochlorobutoxymagnesium, monochlorooxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dioctoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octyloxymagnesium, and 2-ethylhexyloxymagnesium, more preferably from at least one of magnesium chloride, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, and dioctoxymagnesium, and further preferably from magnesium chloride and/or diethoxymagnesium.
According to the catalyst component provided by the invention, preferably, the organic epoxy compound is selected from at least one of oxides, glycidyl ethers and internal ethers of C2-C8 aliphatic olefin, C2-C8 aliphatic diolefin, C2-C8 halogenated aliphatic olefin or C2-C8 halogenated aliphatic diolefin; more preferably at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene dioxide, epichlorohydrin, tetrahydrofuran, methyl glycidyl ether and diglycidyl ether; further preferred is epichlorohydrin and/or tetrahydrofuran.
According to the catalyst component provided by the invention, preferably, the organic alcohol compound is at least one of C1-C10 alkyl alcohol and C6-C20 aromatic alcohol, wherein the alkyl in the alkyl alcohol is straight-chain alkyl, branched-chain alkyl or cyclic alkyl; the hydrogen atom in the organic alcohol compound is optionally substituted with a halogen atom in addition to the hydrogen atom of the hydroxyl group; the organic alcohol compound is preferably at least one selected from the group consisting of ethanol, propanol, butanol, 2-ethylhexanol, and glycerol. The ratio of each alcohol in the organic alcohol compound is not particularly limited.
In accordance with the catalyst component provided by the present invention, preferably, the organophosphorus compound is selected from at least one of a hydrocarbyl ester of orthophosphoric acid, a hydrocarbyl ester of phosphorous acid, a halogenated hydrocarbyl ester of orthophosphoric acid, and a halogenated hydrocarbyl ester of phosphorous acid; preferably at least one selected from the group consisting of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.
According to the catalyst component provided by the invention, preferably, the number average relative molecular mass of the polyvinylpyrrolidone is 8000-400000, preferably 10000-360000, and more preferably 10000 or 40000.
According to the catalyst component provided by the present invention, preferably, in the general formula (I), R1Is C1-C10 alkyl or C1-C10 substituted alkyl, more preferably methyl, ethyl, propyl or butyl; preferably, R2And R3Each independently selected from hydrogen, C1-C10 alkyl, C1-C10 substituted alkylA C3-C10 cycloalkyl group, a C6-C10 aryl group, more preferably hydrogen, methyl, ethyl, propyl, butyl or phenyl; preferably, R4，R5And R6Each independently selected from hydrogen, heteroatoms, C1-C10 alkyl groups, C1-C10 substituted alkyl groups, or C1-C10 alkoxy groups, more preferably hydrogen, chlorine atoms, methyl, ethyl, propyl, butyl, pentyl, methoxy, ethoxy, propoxy, or butoxy groups.
Preferably, the aromatic alkoxy ester compound is selected from the group consisting of 2-ethoxy-1-methylethylbenzoate, 2-methoxyethylbenzoate, 2-ethoxyethylbenzoate, 2-isopropoxyethylbenzoate, 1-methoxypropane-2-benzoate, 1-ethoxypropane-2-benzoate, 1-methoxypropane-1-phenethylbenzoate, 1-methoxy-3, 3-dimethylbutane-2-benzoate, 1-methoxy-2-methylpropane-2-benzoate, 3- (methoxymethyl) pentane-3-benzoate, 2-methoxyethyl-2, 4, 6-trichlorobenzoate, 2-methoxyethyl-4-ethoxybenzoate, 1-methoxypropan-2 yl-4-ethoxybenzoate, ethyl 1-ethyl-2-methoxybenzoate, ethyl 1-propyl-2-methoxybenzoate, ethyl 1-isopropyl-2-methoxybenzoate, ethyl 1-tert-butyl-2-methoxybenzoate, ethyl 1-isobutyl-2-methoxybenzoate, ethyl 1-n-butyl-2-methoxybenzoate, methyl 1-ethyl-2-methoxyethyl 2-benzoate, ethyl 1-ethyl-2-methoxyethyl 2-benzoate, propyl 1-ethyl-2-methoxyethyl 2-benzoate, isopropyl 1-isopropyl-2-ethoxybenzoate, isopropyl 1-tert-butyl-2-methoxybenzoate, isopropyl 1-isopropyl-2-methoxybenzoate, isopropyl 1-ethyl-2-ethoxybenzoate, isopropyl 1-2-ethoxybenzoate, isopropyl 2-ethoxy, 1-ethyl-2-methoxyethyl-2-benzoic acid butyl ester, 1-propyl-2-methoxyethyl-2-benzoic acid methyl ester, 1-propyl-2-methoxyethyl-2-benzoic acid ethyl ester, 1-propyl-2-methoxyethyl-2-benzoic acid propyl ester, 1-propyl-2-methoxyethyl-2-benzoic acid butyl ester, 1-ethyl-2-methoxyethyl-3-benzoic acid methyl ester, 1-ethyl-2-methoxyethyl-3-benzoic acid ethyl ester, 1-ethyl-2-methoxyethyl-3-benzoic acid propyl ester, 1-ethyl-2-methoxyethyl-3-benzoic acid butyl ester, at least one of methyl 1-propyl-2-methoxyethyl 3-benzoate, ethyl 1-propyl-2-methoxyethyl 3-benzoate, propyl 1-propyl-2-methoxyethyl 3-benzoate, butyl 1-propyl-2-methoxyethyl 3-benzoate, methyl 1-ethyl-2-methoxyethyl 4-benzoate, ethyl 1-ethyl-2-methoxyethyl 4-benzoate, propyl 1-ethyl-2-methoxyethyl 4-benzoate, and butyl 1-ethyl-2-methoxyethyl 4-benzoate.
According to the catalyst component provided by the invention, preferably, the titanium-containing compound has a general formula of Ti (OR)8)aX1 bIn the formula, R8Is C1-C14 aliphatic hydrocarbon group or C6-C14 aromatic hydrocarbon group, X1Is halogen, a is 0, 1 or 2, b is an integer from 0 to 4, and a + b is 3 or 4; the titanium-containing compound is preferably at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, titanium trichloride, dichlorodiethoxytitanium and trichloromonoethoxytitanium, and more preferably titanium tetrachloride.
The hydrocarbyl group can be at least one of alkyl, alkenyl and alkynyl and aryl.
According to the catalyst component provided by the present invention, preferably, the content of the organic epoxy compound is 0.0001 to 1 mole, the content of the organic alcohol compound is 0.0001 to 6 moles, the content of the organic phosphorus compound is 0.0001 to 1 mole, the content of the polyvinylpyrrolidone is 0.0001 to 1 mole, the content of the aromatic alkoxy ester compound is 0.0001 to 1 mole, and the content of the titanium-containing compound is 0.001 to 20 moles per mole of magnesium.
The present invention also provides a process for the preparation of a catalyst component as described above, which process comprises: in the presence of an inert diluent, contacting magnesium halide, an organic epoxy compound, an organic alcohol compound and an organic phosphorus compound, and reacting to form a uniform solution; contacting the uniform solution with polyvinylpyrrolidone for reaction at the temperature of-20-100 ℃; cooling to-40-10 ℃, and then contacting the obtained solution with a titanium-containing compound for reaction to obtain a solid; and (3) contacting the solid with an aromatic alkoxy ester compound to form a mixture, and slowly heating the mixture for reaction to obtain the catalyst component.
According to the method provided by the present invention, preferably, the magnesium compound is dissolved in a system containing an organic epoxy compound, an organic alcohol compound and an organic phosphorus compound; the dissolving temperature is 0-110 ℃, and the reaction time for forming the uniform solution is 0.5-6 hours, preferably 2-5 hours.
According to the method provided by the invention, preferably, the reaction time of the homogeneous solution and polyvinylpyrrolidone as a high molecular surfactant is 0.1-5 hours, more preferably 2-4 hours; the reaction temperature is preferably 0 to 90 ℃.
According to the method provided by the invention, preferably, after the temperature is reduced to-40-0 ℃, the obtained solution is contacted with a titanium-containing compound for reaction to obtain a solid.
According to the method provided by the invention, the solid and the aromatic alkoxy ester compound are contacted to form a mixture, preferably, the mixture is slowly heated to 50-120 ℃, the reaction time is 0.5-10 hours, more preferably 1-6 hours, unreacted materials and the solvent are removed, and the mixture is washed for several times by adopting an inert diluent, so that the catalyst component is obtained.
In order to make the components added in the preparation process dissolve more fully, an inert diluent can be optionally added in the preparation process, and generally the inert diluent is selected from at least one of aromatic compounds, alkane compounds, halogenated aromatic compounds and halogenated alkane compounds. The aromatic hydrocarbon compound and the halogenated alkane compound are selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorobenzene and derivatives thereof; the alkane compound and haloalkane compound are selected from at least one of linear alkanes of C3-C20, linear haloalkanes of C3-C20, branched alkanes of C3-C20, branched haloalkanes of C3-C20, cycloalkanes of C3-C20 and haloalkcycloalkanes of C3-C20, preferably at least one selected from butane, pentane, hexane, cyclohexane, heptane and 1, 2-dichloroethane, as long as an inert diluent which helps the dissolution of the organomagnesium compound can be used. The above inert diluents may be used alone or in combination.
In the preparation process of the catalyst component, the reaction vessel is fully replaced by inert gas. The inert gas used is preferably nitrogen.
The present invention also provides a catalyst for ethylene polymerization, comprising:
(1) the catalyst component for ethylene polymerization as described above or the catalyst component produced by the production method as described above;
(2) the general formula is AlR9 nX2 3-nIn the formula (II), R9Is hydrogen or a C1-C20 hydrocarbon radical, X2Is halogen, n is an integer and is not less than 0 and not more than 3.
The organoaluminum compound is preferably at least one member selected from the group consisting of triethylaluminum, diethylaluminum monochloride, ethylaluminum dichloroide, ethylaluminum sesqui, isobutylaluminum dichloride, triisobutylaluminum, diisopropylaluminum monochloride, chloromethyl-n-propylaluminum monochloride and chlorodiphenylaluminum; more preferably at least one selected from diethylaluminum monochloride, ethylaluminum dichloride and triethylaluminum.
When the catalyst is used for ethylene polymerization, slurry polymerization or gas phase polymerization can be adopted.
The medium adopted by the slurry polymerization is an inert solvent, and is selected from at least one of saturated aliphatic hydrocarbon or aromatic hydrocarbon such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene and the like.
In order to adjust the molecular weight of the final polymer, hydrogen is used as a molecular weight regulator during the polymerization.
In the ethylene polymerization process, inert gas is adopted to fully replace the reaction kettle. The inert gas used is preferably nitrogen.
The technical scheme of the invention has the following beneficial effects: the particle size of the catalyst component obtained by the invention is increased, the purpose of controlling the particle size is achieved, and the particle size distribution of the catalyst component is obviously narrowed; when the obtained catalyst component is used for ethylene polymerization, the obtained polymer has high bulk density while keeping high catalytic activity and good hydrogen regulation sensitivity, and is suitable for slurry polymerization process and gas phase polymerization process of ethylene.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below with reference to examples. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Test mode
1. The particle size distribution of the catalyst is as follows: the measurement was carried out on a MASTER SIZE2000 particle SIZE distribution apparatus manufactured by Markov, UK, and n-hexane was used as a dispersant. D (10), D (50) and D (90) are respectively the particle diameters of 10 percent, 50 percent and 90 percent (from small to large) cumulative particle sizes, and the Span value is the ratio of D (90) -D (10)/D (50).
2. Determination of the bulk density of the polymer: measured according to ASTM-D1895.
3. Determination of the melt index of the polymer: the measurement was carried out according to ASTM-D1238 standard method on a melt index apparatus of 6983, CEAST, Italy, Inc. 6932, at a temperature of 190 ℃ and under a load of 2.16 kg.
Example 1
(1) Preparation of the catalyst component
Adding 4.0g magnesium dichloride, 120ml toluene, 3.0ml epichlorohydrin, 6.0ml 2-ethyl hexanol and 8.0ml tributyl phosphate into a reactor fully replaced by high-purity nitrogen in sequence, heating to 70 ℃ under stirring, reacting for 2 hours at 70 ℃, and adding polyvinylpyrrolidone (M) after the solid is completely dissolved to form a uniform solutionw10000)0.2g, and the reaction was continued for 0.5 hour. The reaction system was cooled to-15 ℃ and 25ml of titanium tetrachloride was slowly added dropwise, the temperature was kept constant for 0.5 hour, then 0.2g of 2-methoxyethyl benzoate was added, the temperature was slowly raised to 85 ℃ and the reaction was carried out at this temperature for 2 hours. And then stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing with hexane for four times, and drying by high-purity nitrogen to obtain the solid catalyst component with good fluidity.
(2) Ethylene polymerization
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of 1M triethylaluminum hexane solution (containing 1.0ml of triethylaluminum) is added, the prepared solid catalyst component is added, the temperature is raised to 80 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.6Mpa, ethylene is introduced to ensure that the total pressure in the kettle reaches 1.0Mpa (gauge pressure), and the polymerization is carried out for 2 hours at the temperature of 90 ℃, wherein the polymerization result is shown in Table 1.
Example 2
(1) The solid catalyst component was prepared in the same manner as in example 1 except that 2-methoxyethyl benzoate was changed to 2-isopropoxyethyl benzoate in an amount of 0.4 g.
(2) Ethylene polymerization example 1. The polymerization results are shown in Table 1.
Example 3
(1) The solid catalyst component was prepared in the same manner as in example 1 except that polyvinylpyrrolidone (M) was usedw40000) was changed to 0.3g, and 2-methoxyethylbenzoate was changed to 1-methoxy-2-methylpropane-2-benzoate, and the amount was 0.4 g.
(2) Ethylene polymerization example 1. The polymerization results are shown in Table 1.
Example 4
(1) The solid catalyst component was prepared in the same manner as in example 1 except that polyvinylpyrrolidone (M) was usedw40000) was changed to 0.4g, and 2-methoxyethyl benzoate was changed to 3- (methoxymethyl) pentane-3-benzoate, and the amount was 0.6 g.
(2) Ethylene polymerization example 1. The polymerization results are shown in Table 1.
Comparative example 1
(1) 4.0g of magnesium dichloride, 120ml of toluene, 3.0ml of epichlorohydrin, 6.0ml of 2-ethylhexanol and 8.0ml of tributyl phosphate are sequentially added into a reactor which is fully replaced by high-purity nitrogen, and the temperature is raised to 70 ℃ under stirring for reaction for 2 hours at 70 ℃. Cooling to 30 deg.C when the solid is completely dissolved to form a uniform solution, and adding polyvinylpyrrolidone (M)w10000)0.15g, and the reaction was continued for 0.5 hour. The reaction system is cooled to-15 ℃, 25ml of titanium tetrachloride is slowly dropped, 3.0ml of ethyl silicate is added, the temperature is kept for 0.5 hour, the temperature is slowly raised to 85 ℃, and the reaction is carried out for 2 hours. Then stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing with hexane for four times, and blow-drying with high-purity nitrogen to obtain the solid catalyst group with good fluidityAnd (4) dividing.
(2) Ethylene polymerization example 1. The polymerization results are shown in Table 1.
Comparative example 2
(1) 4.0g of magnesium dichloride, 120ml of toluene, 3.0ml of epichlorohydrin, 6.0ml of 2-ethylhexanol and 8.0ml of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 70 ℃ under stirring, the reaction is carried out for 2 hours at 70 ℃, after the solid is completely dissolved to form a uniform solution, the reaction system is cooled to-15 ℃, 25ml of titanium tetrachloride is slowly dripped, the temperature is kept for 0.5 hour, 0.2g of 2-methoxyethyl benzoate is added, the temperature is slowly raised to 85 ℃, and the reaction is carried out for 2 hours at the temperature. And then stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing with hexane for four times, and drying by high-purity nitrogen to obtain the solid catalyst component with good fluidity.
(2) Ethylene polymerization example 1. The polymerization results are shown in Table 1.
TABLE 1 Properties of the polymers obtained by polymerization
TABLE 2 Properties of the catalyst components obtained
As can be seen from the experimental data of the examples and the comparative examples in tables 1 and 2, the preparation process of the catalyst component of the present invention is simple, the high molecular surfactant polyvinylpyrrolidone added in the preparation process plays a role in controlling the particle morphology of the catalyst component, the particles are concentrated, and the improvement of the load of the ethylene polymerization apparatus is facilitated; in addition, the addition of the aromatic alkoxy ester enables the catalyst to keep higher activity, improves hydrogen regulation sensitivity, has high polymer bulk density, and is suitable for slurry polymerization process and gas phase polymerization process of ethylene.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (25)
1. A catalyst component for the polymerization of ethylene, characterized in that it comprises the reaction product of: (1) a magnesium compound; (2) an organic epoxy compound; (3) an organic alcohol compound; (4) an organic phosphorus compound; (5) polyvinylpyrrolidone; (6) a titanium-containing compound; (7) aromatic alkoxy ester compounds; wherein,
the structure of the aromatic alkoxy ester compound is shown as a general formula (A)
) As shown in the drawings, the above-described,
（
）
in the formula, R1Is C1-C20 alkyl or C1-C20 substituted alkyl; r2And R3The same or different, each is independently selected from hydrogen, alkyl of C1-C20, substituted alkyl of C1-C20, cycloalkyl of C3-C20, and aryl of C6-C20; r4，R5And R6The same or different, each is independently selected from hydrogen, heteroatoms, C1-C20 alkyl, C1-C20 substituted alkyl, or C1-C20 alkoxy;
the preparation method of the catalyst component comprises the following steps: in the presence of an inert diluent, contacting a magnesium compound, an organic epoxy compound, an organic alcohol compound and an organic phosphorus compound, and reacting to form a uniform solution; contacting the uniform solution with polyvinylpyrrolidone for reaction at the temperature of-20-100 ℃; cooling to-40-10 ℃, and then contacting the obtained solution with a titanium-containing compound for reaction to obtain a solid; and (3) contacting the solid with an aromatic alkoxy ester compound to form a mixture, and slowly heating the mixture for reaction to obtain the catalyst component.
2. The catalyst component according to claim 1 in which the magnesium compound has the general formula Mg (OR)7)nX2-n(ii) a In the formula, R7Is a saturated or unsaturated linear chain alkyl, branched chain alkyl or C3-C20 cyclic chain alkyl of C1-C20; x is halogen, n is an integer and is not less than 0 and not more than 2.
3. The catalyst component according to claim 2 in which X is chlorine.
4. The catalyst component according to claim 2 in which the magnesium compound is selected from at least one of magnesium chloride, magnesium bromide, monochloromoxymagnesium, monochlorooxymagnesium, monochloroisopropoxygagnesium, monochlorooxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dioctoxymagnesium, isopropoxymagnesium and 2-ethylhexyloxymagnesium.
5. The catalyst component according to claim 4 in which the magnesium compound is selected from at least one of magnesium chloride, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium and dioctoxymagnesium.
6. The catalyst component according to claim 5 in which the magnesium compound is selected from magnesium chloride and/or diethoxymagnesium.
7. The catalyst component according to claim 4 or 5 in which the dioctyloxymagnesium is n-octyloxymagnesium.
8. The catalyst component according to claim 1 in which the organic epoxy compound is selected from at least one of the oxides, glycidyl ethers and internal ethers of C2-C8 aliphatic olefins, C2-C8 aliphatic dienes, C2-C8 halogenated aliphatic olefins or C2-C8 halogenated aliphatic dienes.
9. The catalyst component according to claim 8 in which the organic epoxide is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene dioxide, epichlorohydrin, tetrahydrofuran, methyl glycidyl ether and diglycidyl ether.
10. The catalyst component according to claim 1 in which the organic alcohol compound is at least one of C1-C10 alkyl alcohol in which the alkyl group is a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and C6-C20 aromatic alcohol; the hydrogen atom in the organic alcohol compound is optionally substituted with a halogen atom in addition to the hydrogen atom of the hydroxyl group.
11. The catalyst component according to claim 10 in which the organic alcohol compound is selected from at least one of ethanol, propanol, butanol, 2-ethylhexanol and glycerol.
12. The catalyst component according to claim 1 in which the organophosphorus compound is selected from at least one of a hydrocarbyl ester of orthophosphoric acid, a hydrocarbyl ester of phosphorous acid, a halogenated hydrocarbyl ester of orthophosphoric acid and a halogenated hydrocarbyl ester of phosphorous acid.
13. The catalyst component according to claim 12 in which the organophosphorus compound is selected from at least one of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.
14. The catalyst component according to claim 1 in which the polyvinylpyrrolidone has a number-average relative molecular mass of 8000 to 400000.
15. The catalyst component according to claim 14 in which the polyvinylpyrrolidone has a number average relative molecular mass of 10000 to 360000.
16. The catalyst component according to claim 15 in which the polyvinylpyrrolidone has a number average relative molecular mass of 10000 or 40000.
17. The catalyst component according to claim 1 in which the aromatic alkoxy ester compounds are selected from the group consisting of 2-ethoxy-1-methylethylbenzoate, 2-methoxyethylbenzoate, 2-ethoxyethylbenzoate, 2-isopropoxyethylbenzoate, 1-methoxypropane-2-benzoate, 1-ethoxypropane-2-benzoate, 1-methoxy-3, 3-dimethylbutane-2-benzoate, 1-methoxy-2-methylpropane-2-benzoate, 3- (methoxymethyl) pentane-3-benzoate, 2-methoxyethyl-4-ethoxybenzoate, methyl acetate, ethyl acetate, 1-methoxypropan-2-yl-4-ethoxybenzoate, ethyl 1-ethyl-2-methoxybenzoate, ethyl 1-propyl-2-methoxybenzoate, ethyl 1-isopropyl-2-methoxybenzoate, ethyl 1-tert-butyl-2-methoxybenzoate, ethyl 1-isobutyl-2-methoxybenzoate and ethyl 1-n-butyl-2-methoxybenzoate.
18. The catalyst component according to claim 1 in which the titanium-containing compound has the general formula Ti (OR)8)aX1 bIn the formula, R8Is C1-C14 aliphatic hydrocarbon group or C6-C14 aromatic hydrocarbon group, X1Is halogen, a is 0, 1 or 2, b is an integer from 0 to 4, and a + b =3 or 4.
19. The catalyst component of claim 18 in which the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium trichloride, dichlorodiethoxytitanium, and trichloromonoethoxytitanium.
20. The catalyst component according to claim 19 in which the titanium-containing compound is titanium tetrachloride.
21. The catalyst component according to claim 1 in which the content of the organic epoxy compound is 0.0001 to 1 mole, the content of the organic alcohol compound is 0.0001 to 6 moles, the content of the organic phosphorus compound is 0.0001 to 1 mole, the content of the polyvinylpyrrolidone is 0.0001 to 1 mole, the content of the aromatic alkoxy ester compound is 0.0001 to 1 mole, and the content of the titanium-containing compound is 0.001 to 20 moles per mole of magnesium.
22. A process for the preparation of the catalyst component according to any one of claims 1 to 21, characterized in that it comprises: in the presence of an inert diluent, contacting a magnesium compound, an organic epoxy compound, an organic alcohol compound and an organic phosphorus compound, and reacting to form a uniform solution; contacting the uniform solution with polyvinylpyrrolidone for reaction at the temperature of-20-100 ℃; cooling to-40-10 ℃, and then contacting the obtained solution with a titanium-containing compound for reaction to obtain a solid; and (3) contacting the solid with an aromatic alkoxy ester compound to form a mixture, and slowly heating the mixture for reaction to obtain the catalyst component.
23. The method of claim 22, wherein the homogeneous solution is reacted with the polyvinylpyrrolidone for a reaction time of 0.1 to 5 hours; the reaction temperature is 0-70 ℃.
24. The method of claim 23, wherein the homogeneous solution is reacted with the polyvinylpyrrolidone for a reaction time of 2-4 hours.
25. A catalyst for the polymerization of ethylene, comprising:
(1) the catalyst component for the polymerization of ethylene according to any one of claims 1 to 21 or the catalyst component produced according to the process of any one of claims 22 to 24;
(2) the general formula is AlR9 nX2 3-nIn the formula (II), R9Is hydrogen or a C1-C20 hydrocarbon radical, X2Is halogen, n is an integer and is not less than 0 and not more than 3.
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| CN103772554A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
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| CN103772554A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
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