CN1315877C - 乙烯的均聚物和共聚物的生产方法 - Google Patents
乙烯的均聚物和共聚物的生产方法 Download PDFInfo
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- CN1315877C CN1315877C CNB018199356A CN01819935A CN1315877C CN 1315877 C CN1315877 C CN 1315877C CN B018199356 A CNB018199356 A CN B018199356A CN 01819935 A CN01819935 A CN 01819935A CN 1315877 C CN1315877 C CN 1315877C
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- Prior art keywords
- compound
- hydroxyl
- silane
- ester
- methyl
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- 238000004519 manufacturing process Methods 0.000 title claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract description 19
- 239000005977 Ethylene Substances 0.000 title abstract description 6
- 229920001577 copolymer Polymers 0.000 title abstract 3
- -1 ester compound Chemical class 0.000 claims abstract description 54
- 239000010936 titanium Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 19
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 5
- 239000005049 silicon tetrachloride Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 claims description 4
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 4
- OMSUIQOIVADKIM-UHFFFAOYSA-N rac-3-Hydroxybutyric acid ethyl ester Natural products CCOC(=O)CC(C)O OMSUIQOIVADKIM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 3
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 claims description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 2
- LSWRBVSEWBWTDR-UHFFFAOYSA-N 2-hydroxyethyl benzoate Chemical compound OCCOC(=O)C1=CC=CC=C1 LSWRBVSEWBWTDR-UHFFFAOYSA-N 0.000 claims description 2
- GILMNGUTRWPWSY-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(O)COC(=O)C=C GILMNGUTRWPWSY-UHFFFAOYSA-N 0.000 claims description 2
- DGZIMLVEXGVYDW-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(=O)C=C DGZIMLVEXGVYDW-UHFFFAOYSA-N 0.000 claims description 2
- WBPAQKQBUKYCJS-UHFFFAOYSA-N 2-methylpropyl 2-hydroxypropanoate Chemical compound CC(C)COC(=O)C(C)O WBPAQKQBUKYCJS-UHFFFAOYSA-N 0.000 claims description 2
- FWIBCWKHNZBDLS-UHFFFAOYSA-N 3-hydroxyoxolan-2-one Chemical compound OC1CCOC1=O FWIBCWKHNZBDLS-UHFFFAOYSA-N 0.000 claims description 2
- FWIQGIQRNBVZEN-UHFFFAOYSA-N 4-ethoxy-2-(2-ethoxy-2-oxoethyl)-2-hydroxy-4-oxobutanoic acid Chemical compound CCOC(=O)CC(O)(C(O)=O)CC(=O)OCC FWIQGIQRNBVZEN-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical group CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 2
- UYXLOULABOHUAJ-UHFFFAOYSA-N CO[SiH](OC)CCC1=CC=CC=C1 Chemical compound CO[SiH](OC)CCC1=CC=CC=C1 UYXLOULABOHUAJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- YSAVZVORKRDODB-UHFFFAOYSA-N Diethyl tartrate Chemical compound CCOC(=O)C(O)C(O)C(=O)OCC YSAVZVORKRDODB-UHFFFAOYSA-N 0.000 claims description 2
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 claims description 2
- LDLDJEAVRNAEBW-UHFFFAOYSA-N Methyl 3-hydroxybutyrate Chemical class COC(=O)CC(C)O LDLDJEAVRNAEBW-UHFFFAOYSA-N 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 2
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- PXKHGMGELZGJQE-ILBGXUMGSA-N chloramphenicol palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](NC(=O)C(Cl)Cl)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 PXKHGMGELZGJQE-ILBGXUMGSA-N 0.000 claims description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
- PCYQQSKDZQTOQG-NXEZZACHSA-N dibutyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCCCOC(=O)[C@H](O)[C@@H](O)C(=O)OCCCC PCYQQSKDZQTOQG-NXEZZACHSA-N 0.000 claims description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 2
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-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
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical group C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- OANIYCQMEVXZCJ-UHFFFAOYSA-N ditert-butyl(dimethoxy)silane Chemical compound CO[Si](OC)(C(C)(C)C)C(C)(C)C OANIYCQMEVXZCJ-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- MRYSSTRVUMCKKB-UHFFFAOYSA-N ethyl 2-hydroxyhexanoate Chemical compound CCCCC(O)C(=O)OCC MRYSSTRVUMCKKB-UHFFFAOYSA-N 0.000 claims description 2
- HYXRUZUPCFVWAH-UHFFFAOYSA-N ethyl 6-hydroxyhexanoate Chemical compound CCOC(=O)CCCCCO HYXRUZUPCFVWAH-UHFFFAOYSA-N 0.000 claims description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical group CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 2
- SAXHIDRUJXPDOD-UHFFFAOYSA-N ethyl hydroxy(phenyl)acetate Chemical compound CCOC(=O)C(O)C1=CC=CC=C1 SAXHIDRUJXPDOD-UHFFFAOYSA-N 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N isobutyric acid methyl ester Natural products COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical group C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 229960000969 phenyl salicylate Drugs 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 claims description 2
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 2
- 229960003415 propylparaben Drugs 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 claims description 2
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000011777 magnesium Substances 0.000 abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 abstract description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- 230000026030 halogenation Effects 0.000 description 12
- 238000005658 halogenation reaction Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001350 alkyl halides Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
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Classifications
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
-
- 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
Abstract
本发明提供一种乙烯均聚物和共聚物的生产方法,更具体地提供在以下物质存在下生产乙烯均聚物和共聚物的方法:(a)通过以下方法生产的固体钛催化剂:使卤化镁化合物与醇接触反应制备镁溶液;使之与有至少一个羟基的酯类化合物和有至少一个烷氧基的硅化合物反应;和加入钛化合物和硅化合物的混合物;(b)周期表中第II或III族有机金属化合物;和(c)烷氧基硅烷化合物和卤烷化合物。按本发明生产的用于乙烯均聚和共聚的催化剂是高活性的,用所述催化剂通过本发明方法生产的聚合物具有堆积密度高和分子量分布窄的优点。
Description
技术领域
本发明提供一种乙烯的均聚物和共聚物的生产方法,更具体地提供一种利用高活性催化剂生产乙烯的均聚物和共聚物的方法,以生产高堆积密度和窄分子量分布的所述聚合物。
发明背景
已知用于乙烯聚合或共聚的含镁催化剂有极高的催化活性并产生高堆积密度的聚合物,它们适合于液相或气相聚合。乙烯的液相聚合指在例如本体乙烯、异戊烷或己烷等介质中进行的聚合过程,该方法中所用催化剂有以下重要特性:高催化活性、所得聚合物的堆积密度等。其中,所述催化活性被认为是最重要的催化剂特性。
已报导许多用于烯烃聚合的含镁的钛基催化剂及其制造方法。特别地,已知许多利用镁溶液获得可产生高表观堆积密度的烯烃聚合物的催化剂的方法。有一种方法是通过镁化合物与醇、胺、环醚、或有机羧酸等电子给体在烃类溶剂存在下反应获得镁溶液。关于使用醇的情况公开在US4,330,649和5,106,807中。此外,通过所述液相镁溶液与卤代化合物如四氯化钛反应生产含镁催化剂的方法是公知的。还试图通过添加酯类化合物控制聚合活性或分子量分布。此催化剂使所得聚合物具有高堆积密度,但在其催化活性或聚合物的分子量分布方面还有待改进。此外,US4,477,639和4,518,706中用四氢呋喃(环酯)作为镁化合物的溶剂。
同时,US4,847,227、4,816,433、4,829,037、4,970,186、和5,130,284报导用诸如邻苯二甲酸二烷基酯、邻苯二甲酰氯等电子给体与氯化钛化合物反应生产聚合活性优异的烯烃聚合催化剂,其能提高所得聚合物的堆积密度。
US5,459,116报导一种通过使包含有至少一个羟基的酯作为电子给体的镁溶液与钛化合物接触反应生产固体钛催化剂的方法。用此方法可获得高聚合活性的催化剂,使所述聚合物具有高堆积密度,但仍有进一步改进的余地。
在α-烯烃聚合特别是丙烯聚合方面,用外电子给体提高立构规整度的技术在该领域是公知的而且在工业中广泛采用。至于外电子给体,广泛已知的是烷氧基硅烷化合物。在这些情况下,虽然聚合物的立构规整度提高,但分子量分布相对变宽。韩国专利公布号93-665公开了在丙烯聚合过程中用有机硅烷作为外电子给体使分子量分布变宽的方法及其益处。
发明概述
本发明的目的是提供一种利用催化活性优异的催化剂生产乙烯均聚物和共聚物的方法,其中所述聚合物有高堆积密度和窄粒度分布。更具体地,本发明提供一种有窄分子量分布的乙烯均聚物和共聚物的生产方法,它涉及聚合物粒子形态的控制和使用高聚合活性的催化剂。
参考以下描述和权利要求书,本发明的其它目的和实用性将是显而易见的。
优选实施方案详述
本发明所述乙烯均聚物和共聚物的生产方法包括在以下物质存在下进行乙烯的均聚或共聚:(a)通过简单有效的生产方法用镁、钛、卤素和电子给体生产的固体钛络合物催化剂,包括(i)使卤化镁化合物与醇接触反应制备镁溶液;(ii)使所述溶液与有至少一个羟基的酯类化合物和有至少一个烷氧基的硅化合物反应;和(iii)加入钛化合物和硅化合物的混合物;(b)周期表第II或III族有机金属化合物;和(c)烷氧基硅烷化合物和卤代烷化合物。
为生产本发明所用催化剂,其中所用卤化镁化合物的类型如下:二卤化镁如氯化镁、碘化镁、氟化镁和溴化镁;卤化烷基镁如卤化甲基镁、卤化乙基镁、卤化丙基镁、卤化丁基镁、卤化异丁基镁、卤化己基镁、和卤化戊基镁;卤化烷氧基镁如卤化甲氧基镁、卤化乙氧基镁、卤化异丙氧基镁、卤化丁氧基镁、卤化辛氧基镁;和卤化芳氧基镁如卤化苯氧基镁和卤化甲基-苯氧基镁。上述镁化合物中,两或多种化合物可以混合物形式使用。此外,上述镁化合物可有效地以与其它金属的配位化合物形式使用。
以上所列举的化合物中,某些可用简式表示,但有些不能如此表示,取决于镁化合物的生产方法。在后一情况下,一般可视为一些所列化合物的混合物。例如,以下化合物可用于本发明:镁化合物与聚硅氧烷化合物、含卤素的硅烷化合物、酯或醇反应得到的此类化合物;和镁金属与醇、酚或醚在卤代硅烷、五氯化磷或亚硫酰氯存在下反应得到的此类化合物。但优选的镁化合物是卤化镁、特别是氯化镁或氯化烷基镁、优选分别有1~10个碳的烷基的那些;氯化烷氧基镁、优选分别有1~10个碳的那些;和氯化芳氧基镁、优选分别有6~20个碳的那些。本发明所用镁溶液可用上述镁化合物在烃类溶剂存在下、或者在不存在烃类溶剂的情况下在醇类溶剂中以溶液形式生产。
本发明所用烃类溶剂的类型包括脂族烃如戊烷、己烷、庚烷、辛烷、癸烷、和煤油;脂环烃如环戊烷、甲基环戊烷、环己烷、和甲基环己烷;芳烃如苯、甲苯、二甲苯、乙苯、枯烯、和繖花烃;和卤代烃如二氯丙烷、二氯乙烯、三氯乙烯、四氯化碳、和氯苯。
使卤化镁化合物转化成镁溶液时,在存在或不存在上述烃的情况下使用醇。醇的类型包括含1~20个碳原子的那些,如甲醇、乙醇、丙醇、丁醇、戊醇、己醇、辛醇、癸醇、十二烷醇、十八烷醇、苄醇、苯乙醇、异丙基苄醇、和枯醇,但优选含1~12个碳原子的醇。目标催化剂的平均尺寸及其粒子分布可随醇的类型、总含量、镁化合物的类型、和镁与醇之比等改变。不过,获得所述镁溶液所需醇的总量为至少0.5mol/mol镁化合物、优选约1.0~20mol、更优选约2.0~10mol。
生产镁溶液的过程中,卤化镁化合物与醇的反应优选在烃类介质存在下进行。所述反应温度虽然可随醇的类型和量而改变,但至少为约-25℃、优选-10~200℃、更优选约0~150℃。所述反应优选进行约15分钟~5小时、更优选约30分钟~4小时。
本发明所用催化剂的生产中使用的电子给体中,所述分别含有至少一个羟基的酯类化合物包括分别有至少一个羟基的不饱和脂族酸酯,如丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯、甲基丙烯酸2-羟丙酯、丙烯酸4-羟丁酯、三丙烯酸季戊四醇酯;分别含有至少一个羟基的脂族单酯或多酯,如乙酸2-羟乙酯、3-羟丁酸甲酯、3-羟丁酸乙酯、2-羟异丁酸甲酯、2-羟异丁酸乙酯、3-羟基-2-甲基丙酸甲酯、2,2-二甲基-3-羟基丙酸酯、6-羟己酸乙酯、2-羟异丁酸叔丁酯、3-羟戊二酸二乙酯、乳酸乙酯、乳酸异丙酯、乳酸丁基异丁酯、乳酸异丁酯、扁桃酸乙酯、酒石酸二甲基乙酯、酒石酸乙酯、酒石酸二丁酯、柠檬酸二乙酯、柠檬酸三乙酯、2-羟己酸乙酯、二(羟甲基)丙二酸二乙酯;分别有至少一个羟基的芳族酯,如苯甲酸2-羟乙酯、水杨酸2-羟乙酯、4-(羟甲基)苯甲酸甲酯、4-羟基苯甲酸甲酯、3-羟基苯甲酸乙酯、4-甲基水杨酸酯、水杨酸乙酯、水杨酸苯酯、4-羟基苯甲酸丙酯、3-羟基萘烷酸苯酯(pheny 1 3-hydroxy naphthanoate)、单乙二醇单苯甲酸酯、二甘醇单苯甲酸酯、三甘醇单苯甲酸酯;分别有至少一个羟基的脂环族酯,如羟丁内酯等。含有至少一个羟基的酯类化合物的量应为0.001~5mol/mol镁、或优选0.01~2mol/mol镁。
关于生产本发明所用催化剂时可用作另一种电子给体的有至少一个烷氧基的硅化合物,优选以下通式所示化合物:RnSi(OR)4-n其中R为有1~12个碳的烃,n为0或1至3的整数。特别地,可使用以下化合物:二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、二苯基二甲氧基硅烷、甲基苯基甲氧基硅烷、二苯基二乙氧基硅烷、乙基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基三甲氧基硅烷、苯基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三乙氧基硅烷、乙烯基三乙氧基硅烷、丁基三乙氧基硅烷、苯基三乙氧基硅烷、乙基三异丙氧基硅烷、乙烯基三丁氧基硅烷、硅酸乙酯、硅酸丁酯、甲基三芳氧基硅烷等。所述化合物的量优选为0.05~3mol/mol镁、或更优选0.1~2mol。关于所述镁溶液、有至少一个羟基的酯类化合物和烷氧基硅化合物接触反应的温度,0~100℃的温度是适合的、更优选10~70℃。
为使催化剂粒子重结晶,使已与所述电子给体反应的所述镁化合物溶液与通式Ti(OR)aX4-a(其中R为烃基,X为卤原子,“a”为0或1至4的自然数)所示液体钛化合物和通式RnSiCl4-n(其中R为氢,有1~10个碳的烷基、烷氧基、卤代烷基或芳基,卤代甲硅烷基,或有1~8个碳的卤代甲硅烷基烷基,“n”为0或1至3的自然数)所示化合物的混合物反应。
满足通式Ti(OR)aX4-a的钛化合物的类型包括4-卤化钛如TiCl4、TiBr4、和TiI4;3-卤化烷氧基钛如Ti(OCH3)Cl3、Ti(OC2H5)Cl3、Ti(OC2H5)Br3、和Ti(O(i-C4H9))Br3;2-卤化烷氧基钛化合物如Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2、Ti(O(i-C4H9))2Cl2、和Ti(OC2H5)2Br2;和四烷氧基钛如Ti(OCH3)4、Ti(OC2H5)4、和Ti(OC4H9)4。本发明中也可使用上述钛化合物的混合物。但优选的钛化合物是分别含有卤素的那些、更优选四氯化钛。
满足以上通式RnSiCl4-n(其中R为氢,有1~10个碳的烷基、烷氧基、卤代烷基或芳基,卤代甲硅烷基,或有1~8个碳的卤代甲硅烷基烷基,“n”为0或1至3的自然数)的硅化合物的类型包括四氯化硅;三氯硅烷如甲基三氯硅烷、乙基三氯硅烷、苯基三氯硅烷;二氯硅烷如二甲基二氯硅烷、二乙基二氯硅烷、二苯基二氯硅烷、和甲基苯基二氯硅烷;一氯硅烷如三甲基氯硅烷;这些硅化合物的混合物也可用于本发明,更优选使用四氯化硅。
镁化合物溶液重结晶过程中钛化合物和硅化合物的混合物的用量适合地为0.1~200mol/mol镁化合物、优选0.1~100mol、更优选0.2~80mol。混合物中硅化合物与钛化合物之摩尔比适合地为0.05~0.95、更优选0.1~0.8。所述镁化合物溶液与钛化合物和硅化合物的混合物反应时,所得重结晶固体组分的形态和大小很大程度地随反应条件而改变。因而,所述镁化合物溶液与钛化合物和硅化合物的混合物的反应优选在足以导致形成固体组分的低温下进行。更优选所述反应通过在-70~70℃、最优选-50~50℃下的接触反应而进行。所述接触反应之后,使所述反应温度缓慢地升高以在50~150℃下充分反应0.5~5小时。
可使以上过程中得到的所述固体催化剂粒子进一步与钛化合物反应。这些钛化合物是卤化钛或分别有1~20个碳的烷氧基官能团的卤化烷氧基钛。有时也可使用这些化合物的混合物。但这些化合物中,适合使用卤化钛或有1~8个碳的烷氧基官能团的卤化烷氧基钛化合物,更优选使用四卤化钛。
按本发明方法生产的催化剂可用于乙烯的均聚或共聚。特别地,所述催化剂用于乙烯的均聚,也用于乙烯与有三或更多碳的α-烯烃如丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、或1-己烯的共聚。
本发明所述聚合反应涉及在以下物质存在下生产乙烯的均聚物和共聚物:(a)上述包含镁、钛、卤素、和电子给体的固体钛络合物催化剂;(b)周期表中第II或III族有机金属化合物;和(c)作为添加剂的烷氧基硅烷化合物和卤代烷化合物。
所述固体钛催化剂组分可在与乙烯或α-烯烃预聚后在所述聚合反应中用作一种组分。所述预聚可在烃类溶剂如己烷存在下、在足够低的温度下、用加压的乙烯或α-烯烃、在上述催化剂组分和诸如三乙基铝等有机铝化合物存在下进行。所述预聚通过使催化剂粒子被聚合物包围以保持催化剂的形态而有助于生产良好质量的后聚合形态的聚合物。聚合物与预聚后催化剂的重量比通常为0.1∶1~20∶1。
本发明中所述有机金属化合物可用以下通式表示:MRn,其中M代表周期表中第II或IIIA族金属组分,如镁、钙、锌、硼、铝、和镓,R代表有1~20个碳的烷基,如甲基、乙基、丁基、己基、辛基、或癸基,n代表所述金属组分的原子价。至于更优选的有机金属化合物,可使用有1~6个碳的烷基的三烷基铝,如三乙基铝和三异丁基铝、或其混合物。有时,也可使用有一或多个卤素或氢化物基的有机铝化合物,如二氯化乙基铝、氯化二乙基铝、倍半氯化乙基铝、或氢化二异丁基铝。
为在极高催化活性下生产窄分子量分布的乙烯聚合物,作为第三组分的添加剂应为有烷氧基的有机硅化合物或烷氧基硅烷和卤代烷化合物。
所述烷氧基硅烷化合物可用以下通式表示:RnSi(OR)4-n,其中R为有1~20个碳的烃,n为0或1至3的整数。特别地,所述烷氧基硅烷化合物的类型包括芳族硅烷如二苯基二甲氧基硅烷、苯基三甲氧基硅烷、苯基乙基二甲氧基硅烷、和苯基甲基二甲氧基硅烷;脂族硅烷如异丁基三甲氧基硅烷、二异丁基二甲氧基硅烷、二异丙基二甲氧基硅烷、二叔丁基二甲氧基硅烷、叔丁基三甲氧基硅烷、环己基甲基二甲氧基硅烷、二环戊基二甲氧基硅烷、二环己基二甲氧基硅烷、2-降菠烷-三乙氧基硅烷、2-降菠烷-甲基二甲氧基硅烷、和乙烯基三乙氧基硅烷;及其混合物。特别地,上述硅烷化合物中,支链烷基二烷氧基硅烷如二异丁基二甲氧基硅烷和环烷基二烷氧基硅烷如二环戊基二甲氧基硅烷被证明是有效的。
卤代烷化合物是有1~20个碳原子和至少一个卤素的化合物,可使用其混合物。例子包括一氯甲烷、二氯甲烷、三氯甲烷、四氯甲烷、一氯乙烷、1,2-二氯乙烷、一氯丙烷、一氯丁烷、一氯仲丁烷、一氯叔丁烷、一氯环己烷、氯苯、一溴甲烷、一溴丙烷、一溴丁烷、和一碘甲烷。
关于所述聚合反应,可在不存在有机溶剂的情况下进行气相或本体聚合,或在有机溶剂存在下进行液相淤浆聚合。但这些聚合方法都在不存在氧、水、或可起催化毒物作用的其它化合物的情况下进行。
在液相淤浆聚合的情况下,所述固体钛络合物催化剂(a)相对于聚合反应体系的浓度为每升溶剂约0.001~5mmol(按催化剂中的钛原子计)、更优选约0.001~0.5mmol。关于所述溶剂,可使用以下化合物或其混合物:烷烃如戊烷、己烷、庚烷、正辛烷、异辛烷、环己烷、甲基环己烷;烷基芳烃如甲苯、二甲苯、乙苯、异丙基苯、乙基甲苯、正丙基苯、二乙基苯;卤代芳烃如氯苯、氯萘、邻二氯苯;及其混合物。
在气相聚合的情况下,所述固体钛络合物催化剂(a)的量应为每升聚合反应器约0.001~5mmol(按催化剂中的钛原子计)、优选约0.001~1.0mmol、更优选约0.01~0.5mmol。
所述有机金属化合物(b)的优选浓度(按有机金属原子计)为约1~2,000mol/mol催化剂(a)中的钛原子、更优选约5~500mol。
为确保高聚合反应速率,不管聚合方法如何,本文所述聚合都在足够高的温度下进行。一般地,约20~200℃的温度是适合的,更优选约20~95℃。聚合时单体的压力适合地为常压至100atm、更优选2~50atm。
本发明中所述聚合物的分子量用本领域公知的熔体指数(ASTM D1238)表示。所述熔体指数值一般随分子量减小而变大。此外,用凝胶渗透色谱法(GPC)测量聚合物的分子量分布,该测量方法为本领域公知。
通过本发明聚合方法所得产品是固态乙烯均聚物或乙烯与α-烯烃的共聚物,它有极好的堆积密度和流动性。由于聚合物的产率足够高,所以不需除去催化剂残渣。
实施例和对比例
通过以下实施例和对比例进一步描述本发明,但不应限于这些实施例。
实施例1
催化剂的生产
通过以下三个步骤生产固体钛络合物催化剂:
步骤(i):镁化合物溶液的生产
在配有机械搅拌器的用氮气氛置换的1.0L反应器中,放入9.5gMgCl2和400ml癸烷。以500rpm搅拌后,加入77ml 2-乙基己醇。使温度升至110℃,然后使反应持续3小时。使反应后所得均匀溶液冷却至室温(25℃)。
步骤(ii):使镁溶液与含有羟基的酯和烷氧基硅烷化合物接触反
应
向上述冷却至25℃的镁化合物溶液中,加入1.2ml甲基丙烯酸2-羟乙酯和14.0ml四乙氧基硅,然后使所述反应持续1小时。
步骤(iii):用钛化合物和硅化合物的混合物处理
将所述溶液的温度调至室温(25℃)后,用1小时的时间向上述溶液中滴加50ml四氯化钛和50ml四氯化硅的混合溶液。所述滴加过程结束后,使反应器的温度升至80℃,并在此温度保持1小时。搅拌后,使之冷却至室温,然后除去所述溶液的上层清液,用200ml癸烷和200ml四氯化钛连续地滴注剩余的固体层。使温度升至100℃并在此温度保持2小时。所述反应之后,使之冷却至室温,然后用400ml己烷洗涤直至脱除游离的未反应TiCl4。如此生产的固体催化剂的钛含量为5.2wt%。
聚合
在烘箱内使一个2升高压反应器干燥并在热时组装。为使反应器内部处于氮气氛下,交替地使反应器内充氮气和抽空三遍。然后用1000ml正己烷滴注,然后向其中加入1mmol三乙基铝、0.1mmol环己基甲基二甲氧基硅烷、0.05mmol氯仿(CHCl3)和0.03mmol(按钛原子计)上述固体催化剂。然后加入5000ml氢气。使反应器温度升至80℃,同时用搅拌器以700rpm的速度搅拌。将乙烯压力调至80psi,使所述聚合持续1小时。聚合后,使反应器温度降至室温,向所述聚合物中加入过量的乙醇溶液。分离收集所生产的聚合物,在真空烘箱内于50℃下干燥至少6小时,从而得到白色粉末形式的聚乙烯。
以所生产聚合物重量(kg)/所用催化剂用量(g)之比的形式计算聚合活性(kg聚乙烯/g催化剂)。聚合结果与聚合物的堆积密度(g/ml)、熔体指数(g/10min)和分子量分布(Mw/Mn)一起示于表1中。
实施例2~10
在改变烷氧基硅烷和卤代烷的情况下,分别以与实施例1相同的方式用实施例1中生产的催化剂进行聚合,结果示于表1中。
对比例1
用实施例1中生产的催化剂,以与实施例1中相同的方式进行聚合,但在实施例1的聚合过程中不使用烷氧基硅烷和卤代烷,结果示于表1中。
对比例2
用实施例1中生产的催化剂,以与实施例1中相同的方式进行聚合,但在实施例1的聚合过程中使用烷氧基硅烷而不使用卤代烷,结果示于表1中。
对比例3
用实施例1中生产的催化剂,以与实施例1中相同的方式进行聚合,但在实施例1的聚合过程中使用卤代烷而不使用烷氧基硅烷,结果示于表1中。
表1
实施例 | 烷氧基硅烷化合物 | 卤代烷 | 活性(kgPE/g催化剂) | 堆积密度(g/ml) | 分子量分布(Mw/Mn) | ||
化合物 | 量(mmol) | 化合物 | 量(mmol) | ||||
1 | A | 0.1 | CH-1 | 0.05 | 8.3 | 0.36 | 3.8 |
2 | B | 0.1 | CH-1 | 0.05 | 8.7 | 0.37 | 3.9 |
3 | C | 0.1 | CH-1 | 0.05 | 8.5 | 0.37 | 4.2 |
4 | B | 0.1 | CH-2 | 0.3 | 8.4 | 0.36 | 4.0 |
5 | B | 0.1 | CH-3 | 0.1 | 8.6 | 0.36 | 3.7 |
6 | B | 0.1 | CH-4 | 0.1 | 8.7 | 0.36 | 3.9 |
7 | B | 0.1 | CH-5 | 0.05 | 9.2 | 0.37 | 4.1 |
8 | B | 0.1 | CH-6 | 0.05 | 8.3 | 0.36 | 3.8 |
9 | C | 0.05 | CH-5 | 0.05 | 8.9 | 0.38 | 4.2 |
10 | B | 0.05 | CH-1 | 0.05 | 9.0 | 0.38 | 4.0 |
CE1 | - | - | - | - | 6.0 | 0.36 | 6.7 |
CE2 | - | - | - | - | 7.1 | 0.36 | 4.1 |
CE3 | - | - | - | - | 4.8 | 0.35 | 6.5 |
*烷氧基硅烷的类型-A:环己基二甲氧基硅烷,B:二环戊基二甲氧基硅烷,C:二异丙基二甲氧基硅烷;
*卤代烷的类型-CH-1:氯仿,CH-2:乙基氯,CH-3:叔丁基氯,CH-4:二氯甲烷,CH-5:环己基氯,CH-6:氯苯;
*CE:对比例。
如上所示,用本发明乙烯均聚物和共聚物的生产方法,可以高聚合活性获得有高堆积密度和窄分子量分布的乙烯均聚物和共聚物。
Claims (6)
1.一种乙烯均聚物和共聚物的生产方法,包括在以下物质存在下进行聚合:
(a)通过以下方法生产的固体钛催化剂:
(i)使卤化镁化合物与醇接触反应制备镁化合物溶液;
(ii)使所述镁化合物溶液与具有至少一个羟基的酯类化合物和具有至少一个烷氧基的硅化合物反应,其中所述具有至少一个羟基的酯类化合物选自具有至少一个羟基的不饱和脂族酸酯、具有至少一个羟基的脂族单酯或多酯、具有至少一个羟基的芳族酯和具有至少一个羟基的脂环族酯,所述具有至少一个烷氧基的硅化合物由通式RnSi(OR)4-n表示,其中R是具有1-12个碳原子的烃基,n是0-3的整数;和
(iii)使所得溶液与钛化合物和硅化合物反应,其中所述钛化合物用以下通式表示:Ti(OR)aX4-a,其中R代表烃基,X代表卤原子,a代表0或1至4的自然数;其中所述硅化合物用以下通式表示:RnSiCl4-n其中R代表氢,有1~10个碳的烷基、烷氧基、卤代烷基或芳基,或卤代甲硅烷基,或有1~8个碳的卤代甲硅烷基烷基,n代表0或1至3的自然数;
(b)周期表中第II或III族有机金属化合物;和
(c)烷氧基硅烷化合物和卤代烷化合物,其中所述烷氧基硅烷化合物用以下通式表示:RnSi(OR)4-n其中R为有1~20个碳的烃,n为0至3的整数;其中所述卤代烷化合物是有1~20个碳原子和至少一个卤素的化合物;
其中,相对于组分(a)中每摩尔的Ti原子,组分(b)的用量为1-2000mol。
2.权利要求1的乙烯均聚物和共聚物的生产方法,其中所述有至少一个羟基的酯类化合物选自丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯、甲基丙烯酸2-羟丙酯、丙烯酸4-羟丁酯、三丙烯酸季戊四醇酯、乙酸2-羟乙酯、3-羟丁酸甲酯、3-羟丁酸乙酯、2-羟异丁酸甲酯、2-羟异丁酸乙酯、3-羟基-2-甲基丙酸甲酯、2,2-二甲基-3-羟基丙酸酯、6-羟己酸乙酯、2-羟异丁酸叔丁酯、3-羟戊二酸二乙酯、乳酸乙酯、乳酸异丙酯、乳酸丁基异丁酯、乳酸异丁酯、扁桃酸乙酯、酒石酸二甲基乙酯、酒石酸乙酯、酒石酸二丁酯、柠檬酸二乙酯、柠檬酸三乙酯、2-羟己酸乙酯、二(羟甲基)丙二酸二乙酯、苯甲酸2-羟乙酯、水杨酸2-羟乙酯、4-(羟甲基)苯甲酸甲酯、4-羟基苯甲酸甲酯、3-羟基苯甲酸乙酯、4-甲基水杨酸酯、水杨酸乙酯、水杨酸苯酯、4-羟基苯甲酸丙酯、3-羟基萘烷酸苯酯、单乙二醇单苯甲酸酯、二甘醇单苯甲酸酯、三甘醇单苯甲酸酯或羟丁内酯;其中所述有至少一个烷氧基的硅化合物选自二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、二苯基二甲氧基硅烷、甲基苯基二甲氧基硅烷、二苯基二乙氧基硅烷、乙基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基三甲氧基硅烷、苯基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三乙氧基硅烷、乙烯基三乙氧基硅烷、丁基三乙氧基硅烷、苯基三乙氧基硅烷、乙基三异丙氧基硅烷、乙烯基三丁氧基硅烷、硅酸乙酯、硅酸丁酯、甲基三芳氧基硅烷和四乙氧基硅烷。
3.权利要求1的乙烯均聚物和共聚物的生产方法,其中所述钛化合物为4-卤化钛,选自TiCl4、TiBr4、和TiI4;3-卤化烷氧基钛,选自Ti(OCH3)Cl3、Ti(OC2H5)Cl3、Ti(OC2H5)Br3、和Ti(O(i-C4H9))Br3;2-卤化烷氧基钛,选自Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2、Ti(O(i-C4H9))2Cl2、和Ti(OC2H5)2Br2;或四烷氧基钛,选自Ti(OCH3)4、Ti(OC2H5)4、和Ti(OC4H9)4;其中所述硅化合物为四氯化硅;三氯硅烷,选自甲基三氯硅烷、乙基三氯硅烷、和苯基三氯硅烷;二氯硅烷,选自二甲基二氯硅烷、二乙基二氯硅烷、二苯基二氯硅烷、和甲基苯基二氯硅烷;或一氯硅烷。
4.权利要求1的乙烯均聚物和共聚物的生产方法,其中所述钛化合物为四氯化钛,所述硅化合物为四氯化硅。
5.权利要求1的乙烯均聚物和共聚物的生产方法,其中所述固体钛催化剂是通过使步骤(a)(iii)的产物进一步与钛化合物反应生产的。
6.权利要求5的乙烯均聚物和共聚物的生产方法,其中所述烷氧基硅烷化合物为芳族硅烷,选自二苯基二甲氧基硅烷、苯基三甲氧基硅烷、苯基乙基二甲氧基硅烷、和苯基甲基二甲氧基硅烷;脂族硅烷,选自异丁基三甲氧基硅烷、二异丁基二甲氧基硅烷、二异丙基二甲氧基硅烷、二叔丁基二甲氧基硅烷、叔丁基三甲氧基硅烷、环己基甲基二甲氧基硅烷、二环戊基二甲氧基硅烷、二环己基二甲氧基硅烷、2-降菠烷-三乙氧基硅烷、2-降菠烷-甲基二甲氧基硅烷、和乙烯基三乙氧基硅烷;或其混合物;其中所述卤代烷化合物选自一氯甲烷、二氯甲烷、三氯甲烷、四氯甲烷、一氯乙烷、1,2-二氯乙烷、一氯丙烷、一氯丁烷、一氯仲丁烷、一氯叔丁烷、一氯环己烷、氯苯、一溴甲烷、一溴丙烷、一溴丁烷、一碘甲烷、及其混合物。
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2000
- 2000-11-09 KR KR10-2000-0066412A patent/KR100389476B1/ko not_active IP Right Cessation
-
2001
- 2001-11-09 DE DE60127293T patent/DE60127293T2/de not_active Expired - Lifetime
- 2001-11-09 EP EP01983846A patent/EP1339761B1/en not_active Expired - Lifetime
- 2001-11-09 US US10/416,359 patent/US7129303B2/en not_active Expired - Fee Related
- 2001-11-09 WO PCT/KR2001/001903 patent/WO2002038624A1/en active IP Right Grant
- 2001-11-09 AT AT01983846T patent/ATE356835T1/de not_active IP Right Cessation
- 2001-11-09 CN CNB018199356A patent/CN1315877C/zh not_active Expired - Fee Related
- 2001-11-09 AU AU2002215243A patent/AU2002215243A1/en not_active Abandoned
- 2001-11-09 JP JP2002541955A patent/JP3689406B2/ja not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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KR20020036288A (ko) | 2002-05-16 |
JP2004513993A (ja) | 2004-05-13 |
EP1339761B1 (en) | 2007-03-14 |
JP3689406B2 (ja) | 2005-08-31 |
US20040063875A1 (en) | 2004-04-01 |
KR100389476B1 (ko) | 2003-06-27 |
ATE356835T1 (de) | 2007-04-15 |
DE60127293T2 (de) | 2007-07-12 |
WO2002038624A1 (en) | 2002-05-16 |
EP1339761A4 (en) | 2005-01-12 |
DE60127293D1 (de) | 2007-04-26 |
EP1339761A1 (en) | 2003-09-03 |
CN1478102A (zh) | 2004-02-25 |
AU2002215243A1 (en) | 2002-05-21 |
US7129303B2 (en) | 2006-10-31 |
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