CN1318457C - Catalyst component for olefinic polymerization and its catalyst - Google Patents
Catalyst component for olefinic polymerization and its catalyst Download PDFInfo
- Publication number
- CN1318457C CN1318457C CNB2004100736223A CN200410073622A CN1318457C CN 1318457 C CN1318457 C CN 1318457C CN B2004100736223 A CNB2004100736223 A CN B2004100736223A CN 200410073622 A CN200410073622 A CN 200410073622A CN 1318457 C CN1318457 C CN 1318457C
- Authority
- CN
- China
- Prior art keywords
- catalyst component
- electron donor
- alkyl
- olefinic polymerization
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- -1 benzoic acid ester compound Chemical class 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical class CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 150000003900 succinic acid esters Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical class CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 125000002877 alkyl aryl group Chemical group 0.000 abstract 2
- 239000005711 Benzoic acid Substances 0.000 abstract 1
- 235000010233 benzoic acid Nutrition 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 14
- 239000004615 ingredient Substances 0.000 description 11
- 239000011949 solid catalyst Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 235000011147 magnesium chloride Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 5
- FNODWEPAWIJGPM-UHFFFAOYSA-N ethyl 2-methoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OC FNODWEPAWIJGPM-UHFFFAOYSA-N 0.000 description 5
- PFYHAAAQPNMZHO-UHFFFAOYSA-N Methyl 2-methoxybenzoate Chemical class COC(=O)C1=CC=CC=C1OC PFYHAAAQPNMZHO-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 4
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- PEPUAWXAGBAMGU-UHFFFAOYSA-N butyl 2-methoxybenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1OC PEPUAWXAGBAMGU-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 210000001835 viscera Anatomy 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- GOHPTLYPQCTZSE-UHFFFAOYSA-N 2,2-dimethylsuccinic acid Chemical compound OC(=O)C(C)(C)CC(O)=O GOHPTLYPQCTZSE-UHFFFAOYSA-N 0.000 description 1
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 1
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 1
- VHEWAHGOEWDLJK-UHFFFAOYSA-N 2-methylpropyl 2-ethoxybenzoate Chemical compound CCOC1=CC=CC=C1C(=O)OCC(C)C VHEWAHGOEWDLJK-UHFFFAOYSA-N 0.000 description 1
- ODCRXIIYCSXTLW-UHFFFAOYSA-N 2-methylpropyl 2-methoxybenzoate Chemical compound COC1=CC=CC=C1C(=O)OCC(C)C ODCRXIIYCSXTLW-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- IHVVZSPWQJWRDV-UHFFFAOYSA-N Butyl ethyl malonate Chemical compound CCCCOC(=O)CC(=O)OCC IHVVZSPWQJWRDV-UHFFFAOYSA-N 0.000 description 1
- NTHKCSDJQGWPJY-UHFFFAOYSA-N CCCC[SiH](OC)OC Chemical group CCCC[SiH](OC)OC NTHKCSDJQGWPJY-UHFFFAOYSA-N 0.000 description 1
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- ONKUXPIBXRRIDU-UHFFFAOYSA-N Diethyl decanedioate Chemical compound CCOC(=O)CCCCCCCCC(=O)OCC ONKUXPIBXRRIDU-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- RQRAFBDBIOAJDS-UHFFFAOYSA-N bis(2-methylpropyl) 2-ethyl-2-methylbutanedioate Chemical compound CC(C)COC(=O)C(C)(CC)CC(=O)OCC(C)C RQRAFBDBIOAJDS-UHFFFAOYSA-N 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- DJHQJVJMROPIHP-UHFFFAOYSA-N diethyl 2-ethyl-2-methylbutanedioate Chemical compound CCOC(=O)CC(C)(CC)C(=O)OCC DJHQJVJMROPIHP-UHFFFAOYSA-N 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XHEDLZYGAQSNTR-UHFFFAOYSA-N ethene;hexanedioic acid Chemical compound C=C.C=C.OC(=O)CCCCC(O)=O XHEDLZYGAQSNTR-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- OUZCDRGUTZLAGO-UHFFFAOYSA-N ethyl 2-ethoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OCC OUZCDRGUTZLAGO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FGPBPUHIXVUSGJ-UHFFFAOYSA-N heptyl 2-methoxybenzoate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1OC FGPBPUHIXVUSGJ-UHFFFAOYSA-N 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QAYQKAPOTVSWLS-UHFFFAOYSA-N methyl 2-ethoxybenzoate Chemical class CCOC1=CC=CC=C1C(=O)OC QAYQKAPOTVSWLS-UHFFFAOYSA-N 0.000 description 1
- AUGBGGJZVFLTSZ-UHFFFAOYSA-N octyl 2-methoxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1OC AUGBGGJZVFLTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- TYLMQMJLOUNOGK-UHFFFAOYSA-N pentyl 2-methoxybenzoate Chemical compound CCCCCOC(=O)C1=CC=CC=C1OC TYLMQMJLOUNOGK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- LZRFQYZCMVMADF-UHFFFAOYSA-N phenyl 2-methoxybenzoate Chemical compound COC1=CC=CC=C1C(=O)OC1=CC=CC=C1 LZRFQYZCMVMADF-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-M pivalate Chemical class CC(C)(C)C([O-])=O IUGYQRQAERSCNH-UHFFFAOYSA-M 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- DXFQVUJFXYGTNP-UHFFFAOYSA-N propan-2-yl 2-ethoxybenzoate Chemical compound CCOC1=CC=CC=C1C(=O)OC(C)C DXFQVUJFXYGTNP-UHFFFAOYSA-N 0.000 description 1
- WHVIVRXGERGYGC-UHFFFAOYSA-N propan-2-yl 2-methoxybenzoate Chemical compound COC1=CC=CC=C1C(=O)OC(C)C WHVIVRXGERGYGC-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- RJIFVNWOLLIBJV-UHFFFAOYSA-N tributyl benzene-1,2,4-tricarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C(C(=O)OCCCC)=C1 RJIFVNWOLLIBJV-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a catalyst component and a catalyst thereof for olefinic polymerization. The catalyst component contains titanium, magnesium, halogen and at least two electron donor compounds, wherein at least one electron donor compound is selected from a benzoic acid ester compound which is replaced by adjacent position alkoxy shown in a general formula (I). In the formula (I), R<1> to R<2> are identical or different straight chains or branched chains of alkyl C1 to C20, cycloalkyl C3 to C20, aryl C6 to C20, alkaryl C7 to C20 and aralkyl C7 to C20; R<3> to R<6> are identical or different hydrogen, halogen, nitro, straight chains or branched chains of alkyl C1 to C20, cycloalkyl C3 to C20, aryl C6 to C20, alkaryl C7 to C20 and aralkyl C7 to C20. When used for olefin polymerization, particularly propylene polymerization, the catalyst of the present invention has high catalytic activity and good hydrogen regulating sensitivity, and can obtain a polymer with good particle shapes.
Description
Technical field
The present invention relates to a kind of catalyst component and catalyzer of for olefines polymerization, and it is at alpha-olefin CH
2Application in the polyreaction of=CHR and composition thereof, wherein R is the alkyl of hydrogen or 1～12 carbon atom.More particularly, relate to a kind of catalyst component and catalyzer and application thereof that contains the benzoate compounds of ortho position alkoxyl group replacement.
Technical background
Containing the titanium compound that is loaded on the magnesium halide in active and the catalyzer of electron donor compound is well known in the prior art.
U.S. Pat 4544717 discloses, and by add electron donor compound (being the internal electron donor compound) in the solid ingredient that contains titanium compound, can improve the stereospecificity of catalyzer.Up to now, existing many patent disclosures the multiple internal electron donor compound that is applicable to the preparation Ziegler-Natta catalyst, and the catalyzer that is used for olefinic polymerization that comprises these internal electron donor compounds.
These internal electron donor compounds mainly comprise: used a kind of electron donor compound that is selected from phthalate in the European patent EP 0045977 described catalyzer, European patent EP 0361493, describe among the EP0728724 1, the 3-diether compound, describe among the Chinese patent CN1105671A 1, the 3-cyclohexadione compounds, Chinese patent CN1236732, CN1236733, CN1236734, the malonic ester compounds of the special replacement of describing among the CN1292800, the international succinate compounds of describing among the WO0063261 of asking of PCT, the beta substitution glutarate compounds of describing in the PCT International Application No. WO 0055215, the cyano group ester compound of describing among the Chinese patent CN1242780, the two amine electron donor compounds of describing among the Chinese patent CN1087918, the electron donor compound of the maleic acid ester class of describing in the PCT International Application No. WO 03022894, and Chinese patent CN1436766, a kind of special polynary ester compound of describing among the CN1436796 etc.
Owing to adopt different internal electron donor compounds to make prepared catalyzer have different characteristics, for example some catalyzer has higher activity, some catalyzer has better hydrogen regulation sensitivity, the polyolefin resin of some Preparation of Catalyst has wider molecular weight distribution or the like, but in polyolefinic industrial production, be starved of the employed catalyzer of polymerization and have very excellent comprehensive performances.In the prior art, people adopt the method that adds multiple internal electron donor compound in catalyst preparation process to improve the over-all properties of catalyzer usually.In disclosed patent WO9957160, WO0230998, WO03002617, JP2001139621, JP2002249507, KR20000026517 etc., set forth and used two or more internal electron donor compound to prepare catalyst component and the catalyzer that is used for olefinic polymerization simultaneously.But its result can't be satisfactory.Usually, owing to after having used two or more internal electron donor compounds activity of such catalysts is decreased.
Pass through repetition test, the inventor finds to cooperate with the electron donor compound of disclosed routine in the above-mentioned prior art by the benzoate compounds of selecting for use a class ortho position alkoxyl group to replace, use as inner electron donor jointly, can prepare the catalyst component and the catalyzer of high comprehensive performance.It is worthy of note that catalyzer of the present invention is being used for olefinic polymerization, is particularly showing very high catalytic activity and good hydrogen response during propylene polymerization, and can obtain the polymkeric substance of better particle form.
Summary of the invention
The invention provides a kind of catalyst component that is used for olefinic polymerization, this catalyst component comprises titanium, magnesium, halogen and at least two kinds of electron donor compounds, wherein has at least a kind of electron donor compound to be selected from the benzoate compounds (abbreviating compd A as) that the ortho position alkoxyl group replaces that has shown in general formula (I):
In the formula (I), R
1And R
2Identical or inequality, be straight or branched C
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl; R
3～R
6Be identical or inequality, be hydrogen, halogen, nitro, straight or branched C
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl; R
3～R
6Bonding generates one or several condensed ring structure mutually, and this condensed ring structure can by with R
3～R
6The group of identical definition replaces.
Preferably, R
3～R
6Identical or inequality, be selected from hydrogen, halogen, straight or branched C
1～C
4Alkyl.
More preferably, the compound shown in the general formula (I) comprises the compound shown in the following general formula (II):
R wherein
1And R
2The base such as general formula (I) definition.Preferably, R
1And R
2Identical or different, be selected from straight or branched C
1～C
8Alkyl, C
3～C
6Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl or C
7～C
10Aralkyl.More preferably, R
1And R
2Identical or different, be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group, hexyl, heptyl, octyl group, cyclohexyl and phenyl etc.
Particularly, the electron donor compound shown in the general formula (II) can comprise following specific exampless:
The o-methoxybenzoic acid methyl esters, the o-methoxybenzoic acid ethyl ester, the o-methoxybenzoic acid n-propyl, the o-methoxybenzoic acid isopropyl ester, the positive butyl ester of o-methoxybenzoic acid, the o-methoxybenzoic acid isobutyl ester, the o-methoxybenzoic acid pentyl ester, the own ester of o-methoxybenzoic acid, the o-methoxybenzoic acid cyclohexyl, the o-methoxybenzoic acid phenyl ester, the o-methoxybenzoic acid heptyl ester, the o-methoxybenzoic acid monooctyl ester, the o-ethoxybenzoic acid methyl esters, the o-ethoxybenzoic acid ethyl ester, the o-ethoxybenzoic acid n-propyl, the o-ethoxybenzoic acid isopropyl ester, the positive butyl ester of o-ethoxybenzoic acid, o-ethoxybenzoic acid isobutyl ester etc.
Also comprise another kind of electron donor compound (abbreviating compd B as) in the catalyst component of the present invention at least, it can be selected from ester, ether, ketone, amine and silane compound etc. except that compd A.Preferred monobasic or polyhydric aliphatic family carboxylicesters or monobasic or polynary aromatic carboxylic acid esters and diether compound.
Wherein monobasic or polyhydric aliphatic family carboxylicesters or monobasic or polynary aromatic carboxylic acid esters are for example: benzoates, phthalate, malonic ester class, succinate class, glutarate class, pivalate class or carbonats compound etc.Preferred their alkyl ester, concrete as: ethyl benzoate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, dinoctyl phthalate, diethyl malonate, butyl ethyl malonate, 2,3-di-isopropyl ethyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-di-isopropyl dibutyl succinate, 2,3-di-isopropyl succsinic acid dimethyl esters, 2,2-dimethyl succinate diisobutyl ester, 2-ethyl-2-methylsuccinic acid diisobutyl ester, 2-ethyl-2-methylsuccinic acid diethyl ester, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, diethyl maleate, maleic acid n-butyl, the naphthalene dicarboxylic acids diethyl ester, the naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, the benzene-1,2,3-tricarboxylic acid triethyl, the benzene-1,2,3-tricarboxylic acid tri-n-butyl, the pyromellitic acid tetra-ethyl ester, pyromellitic acid four butyl esters etc.
1 shown in the diether compound preferred formula (III) wherein, 3-two ethers, wherein R
I, R
II, R
III, R
IV, R
VAnd R
VIMutually the same or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, 0
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, and R
VIIAnd R
VIIICan be identical or different, be selected from the C of straight or branched
1-
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; R
I-R
VIGroup between can be keyed to ring.Preferably, R wherein
VIIAnd R
VIIIBe selected from C
1-C
4Alkyl.
These 1, the 3-diether compounds has been disclosed among Chinese patent ZL89108368.5 and the Chinese patent CN11411285A.
As above said, except above-mentioned two class electron donor compounds, catalyst component of the present invention also comprises titanium, magnesium and halogen.Particularly preferably, this catalyst component is that load has the titanium compound with at least one Ti-halogen bond and the reaction product of above-mentioned electron donor compound on a kind of halogenide of magnesium, the halogenide of described magnesium preferably has the magnesium dihalide of active state, is more preferably magnesium dichloride.This magnesium dichloride is well-known as the carrier of Ziegler-Natta catalyst in the art.Usually, this magnesium dichloride with active state is characterised in that, in X ray diffracting spectrum, the intensity that appears at the intensive diffraction peak in the diffracting spectrum of nonactive magnesium dichloride reduce and be expanded into one dizzy.
The general formula of described titanium compound is: TiX
n(OR)
4-n, R is C in the formula
1～C
20Alkyl, be preferably normal-butyl/isobutyl-, 2-ethylhexyl, n-octyl and phenyl; X is a halogen, and n is 1～4.Concrete titaniferous compound can be selected titanium tetrahalide, particularly titanium tetrachloride for use; Three chlorocarbon oxygen machine base titanium, particularly trichlorine butoxy and Trichlorophenoxy titaniums; Four titan-alkoxides, particularly four titanium butoxide, purity titanium tetraethoxide.
The preparation of ingredient of solid catalyst of the present invention can be carried out according to various disclosed methods.For example, can use the preparation method of the ingredient of solid catalyst that Chinese patent CN85100997 set forth, at first anhydrous magnesium chloride is dissolved in and forms solution in the solvent system, add titanium tetrachloride and compd A of the present invention and compd B then, in the presence of precipitation additive, by heating up, separate out the ingredient of solid catalyst that contains the active centre again.The described associated viscera of Chinese patent CN85100997 is incorporated herein the present invention as a reference.
Also can at first prepare magnesium dichloride and pure adducts MgCl according to another kind of method
2.nROH particle, preferred this adducts particle is spherical in shape, and wherein n is generally 1.5～4, and preferred 2.0～3.5; R is the alkyl of carbon number 1-4, described alcohol such as ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, isooctyl alcohol etc.Then this adducts particle and multiple electron donor compound of the present invention and titanium compound are reacted, finally obtain the spheric catalyst component.The preparation of relevant this spherical solid catalyst component can be carried out with reference to disclosed method among Chinese patent CN1036011C, the CN1330086A, and disclosed associated viscera is incorporated herein the present invention as a reference.
In any preparation method, with respect to MgCl
2, common mole with 1/500 to 1/20, preferred 1/100 to 1/50 recently uses compd A; Mole with 1/50 to 1/1, preferred 1/20 to 1/2 recently uses compd B.
Compd A and compd B can use in many ways jointly, and preferably the two uses in different steps, under the different condition.With regard to usage quantity, the mol ratio of compd A and compd B is generally 0.01～0.5, and preferred 0.05～0.15.
Ingredient of solid catalyst of the present invention changes into the catalyzer that is used for olefinic polymerization by reacting according to currently known methods and organo-aluminium compound.
In particular, the purpose of this invention is to provide a kind of alkene CH that is used for
2The catalyzer of=CHR polyreaction, wherein R is the alkyl of hydrogen or 1～12 carbon atom, this catalyzer comprises the reaction product between following material:
(1), a kind of above-mentioned ingredient of solid catalyst that contains Mg, Ti and halogen and electron donor compound;
(2), a kind of alkylaluminium cpd, and randomly,
(3), one or more electron donor compounds (external electron donor).
The alkylaluminium cpd preferred formula is AlR
nX
3-nCompound, R is the alkyl of hydrogen or carbonatoms 1～20, particularly alkyl, aralkyl, aryl etc. in the formula; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Alkylaluminium cpd of the present invention comprises: trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum; Alkyl aluminium hydrides such as one hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum; Aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, aluminum alkyls muriates such as ethyl aluminum dichloride wherein are preferably triethyl aluminum and triisobutyl aluminium.
The consumption of aluminum alkyls is: wherein the mol ratio of titanium is 5-5000 in aluminium and the solid constituent (1), is preferably 20-500.
The external electron donor compound is preferably silicoorganic compound.Its general formula is RnSi (OR ')
4-n, 0＜n in the formula≤3, R and R ' they are alkyl of the same race or not of the same race, cycloalkyl, aryl, haloalkyl etc. in the general formula, R also can be halogen or hydrogen atom.Silicoorganic compound of the present invention comprise the trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, two phenoxy group dimethoxy silane, the phenylbenzene diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, (1,1,1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1,1,1-three fluoro-2-propyl group)-methyl dimethoxysilane etc.
In addition, the external electron donor of catalyzer of the present invention also can select for use Chinese patent CN1020448C and CN1141285A disclosed 1,3-diether, and the disclosed succinate of Chinese patent CN1313869A.
The consumption of external electron donor (3) is: the mol ratio of organo-aluminium compound and described external electron donor compound is 0.1～500, and is preferred 1～300, more preferably 3～100.
The polymerization of alkene is carried out according to currently known methods, in liquid monomer or monomer in the liquid phase of the solution in inert solvent, or in gas phase, or by operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferably 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher.
Embodiment
Provide following examples so that the present invention is described better rather than restriction the present invention.
The common step of propylene polymerization:
In 5 liters of autoclaves, adopt stream of nitrogen gas to purge 1 hour down, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.1mmol/ml), 10ml anhydrous hexane and the 9mg ingredient of solid catalyst of 1ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas then at 70 ℃.Close autoclave, introduce the hydrogen of 1.5NL and the liquid propene of 1.5Kg; In under agitation 5 minutes temperature is risen to 70 ℃., stop stirring after 1 hour 70 ℃ of following polyreactions, remove unpolymerized propylene monomer, collected polymer 70 ℃ of following vacuum-dryings 2 hours, is weighed and is calculated catalyst activity (AC); With the degree of isotacticity (I.I) of boiling n-heptane extraction process mensuration polymkeric substance, measure the melting index (M.I) of polymkeric substance by testing standard GB/T3682-2000.
The preparation of electron donor compound-compd A of the present invention:
The preparation of embodiment 1, o-methoxybenzoic acid ethyl ester
In the flat four-hole bottle of the 100mL that stirrer, reflux condensing tube and thermometer are housed, add 12g o-methoxybenzoic acid and 50mL dehydrated alcohol, stir and slowly add the 5mL vitriol oil down, backflow 6h, in reaction solution impouring 200mL water, divide oil-yielding stratum, inferior with the sodium carbonate solution washing oil number of plies, to pH=8～9, wash twice again with water, at last oil reservoir is spent the night with anhydrous magnesium sulfate drying, the elimination siccative, underpressure distillation, collect the cut of 100～101 ℃/200Pa of boiling range, get o-methoxybenzoic acid ethyl ester product 11.6g, yield is 81.6%.Its IR (cm-1) data are as follows:
1727.75，1600.16，1492.20，1305.73，1251.75，1129.06，1079.99，1021.10，751.20
The preparation of embodiment 2, o-methoxybenzoic acid methyl esters
Synthetic method by similarly to Example 1 just replaces ethanol with methyl alcohol, promptly obtains the o-methoxybenzoic acid methyl esters.Its IR (cm-1) data are as follows:
1727.75，1600.16，1492.20，1305.73，1251.75，1133.97，1084.90，1026.01756.11
The preparation of embodiment 3, butyl-o-methoxybenzoate
Synthetic method by similarly to Example 1 just replaces ethanol with methyl alcohol, promptly obtains butyl-o-methoxybenzoate.Its IR (cm-1) data are as follows:
1727.75，1595.26，1497.11，1300.82，1251.75，1129.06，1084.90，1026.01，756.1
Embodiment 4～8 is the preparation of ingredient of solid catalyst:
The common step of ingredient of solid catalyst preparation:
In the glass reaction bottle that the 350ml band stirs, add the 100ml titanium tetrachloride, be cooled to-10 ℃～-20 ℃; Add the spherical magnesium chloride alcohol adducts of 7g (MgCl
22.8C
2H
5OH, its preparation method is referring to CN1330086A) the 5mmol compd A, beginning slowly is warming up to 100 ℃, wherein adds the 5.2mmol compd B when being warming up to 40 ℃, filters liquid at 100 ℃ after keeping 2 hours; Add the 100ml titanium tetrachloride, be warming up to 120 ℃, filter liquid after keeping 0.5 hour at 120 ℃; Add the 100ml titanium tetrachloride again, filter liquid after keeping 0.5 hour at 120 ℃.Use the hexane wash solids at last, 3 times 60 ℃ of heat are washed, and 2 room temperature cold wash, hexane consumption are 60ml/ time; Vacuumize the drying solid thing afterwards, promptly obtain ingredient of solid catalyst.Polymerization result is listed in the table 1.
The comparative example 1
In the glass reaction bottle that the 350ml band stirs, add the 100ml titanium tetrachloride, be cooled to-10 ℃～-20 ℃; Adding the spherical magnesium chloride alcohol of 7g adds and thing (MgCl
22.8C
2H
5OH), beginning slowly is warming up to 100 ℃, wherein adds the 5.2mmol compd B when being warming up to 40 ℃, filters liquid at 100 ℃ after keeping 2 hours; Add the 100ml titanium tetrachloride, be warming up to 120 ℃, filter liquid after keeping 0.5 hour at 120 ℃; Add the 100ml titanium tetrachloride again, filter liquid after keeping 0.5 hour at 120 ℃.Use the hexane wash solids at last, 3 times 60 ℃ of heat are washed, and 2 room temperature cold wash, hexane consumption are 60ml/ time; Vacuumize the drying solid thing afterwards, promptly obtain ingredient of solid catalyst.Polymerization result is listed in the table 1.
Table 1
| Embodiment | Compd A | Compd B | Catalyst activity kgPP/gCat | I.I wt％ | M.I g/10min |
| Example 4 | The o-methoxybenzoic acid methyl esters | DNBP | 55 | 97.6 | 6.9 |
| Example 5 | The o-methoxybenzoic acid ethyl ester | DNBP | 60 | 97.8 | 5.6 |
| Example 6 | The o-methoxybenzoic acid ethyl ester | DIBP | 57 | 96.9 | 6.3 |
| Example 7 | The positive butyl ester of o-methoxybenzoic acid | DNBP | 57 | 98.3 | 5.1 |
| Example 8 | The positive butyl ester of o-methoxybenzoic acid | DIBP | 54 | 97.2 | 5.9 |
| Contrast 1 | ---- | DNBP | 50 | 98.1 | 4.3 |
Annotate: DIBP is that diisobutyl phthalate and NBP are n-butyl phthalate in the table
Embodiment 9:
Use the catalyzer of embodiment 6 preparations, examine, just the add-on of hydrogen is adjusted into 10NL by the common polymerization procedure of propylene.Polymerization result is listed in the table 2.
Comparative Examples 2:
Use the catalyzer of comparative example's 1 preparation, examine, just the add-on of hydrogen is adjusted into 10NL by the common polymerization procedure of propylene.Polymerization result is listed in the table 2.
Table 2
| The embodiment numbering | Catalyzer embodiment numbering | Catalyst activity kgPP/gCat | M.I g/10min | I.I wt％ |
| 9 | 6 | 65 | 30.6 | 96.5 |
| Comparative Examples 2 | Comparative Examples 1 | 56 | 20.3 | 97.0 |
It is worthy of note, used in the present invention activity of such catalysts is reduced, but also be significantly improved, this point from 1 table data as can be seen.In addition, from the data of table 1 and table 2 embodiment and Comparative Examples more as can be seen, catalyzer of the present invention is depressed at identical hydrogen branch, has higher melting index, and when the hydrogen add-on improves, the raising of melting index is more obvious, and this proves absolutely that catalyzer of the present invention has better hydrogen response.
Claims (11)
1, the catalyst component that is used for olefinic polymerization, this catalyst component comprise titanium, magnesium, halogen and at least two kinds of electron donor compounds, and wherein a kind of electron donor compound is selected from the benzoates that the ortho position alkoxyl group replaces that has shown in general formula (I):
In the general formula (I), R
1～R
2Be straight or branched C identical or inequality
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl; R
3～R
6Be hydrogen, halogen, nitro, straight or branched C identical or inequality
1～C
20Alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl; R
3～R
6Bonding generates one or several condensed ring structure mutually, and this condensed ring structure can by with R
3～R
6The group of identical definition replaces.
2, _ and the catalyst component that is used for olefinic polymerization according to claim 1, wherein said benzoates with ortho position alkoxyl group replacement is the compound shown in the following general formula (II):
R wherein
1And R
2The base such as general formula (I) definition.
3, the catalyst component that is used for olefinic polymerization according to claim 2, wherein R
1And R
2Identical or different, be selected from straight or branched C
1～C
8Alkyl, C
3～C
6Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl or C
7～C
10Aralkyl.
4, the catalyst component that is used for olefinic polymerization according to claim 2, wherein R
1And R
2Identical or different, be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group, hexyl, heptyl, octyl group, cyclohexyl or phenyl.
5, the catalyst component that is used for olefinic polymerization according to claim 1, wherein another kind of electron donor compound are selected from least a or several of monobasic or polybasic aliphatic carboxylic acid esters,, monobasic or polybasic aromatic carboxylic acid esters and diether compound.
6, the catalyst component that is used for olefinic polymerization according to claim 5, wherein said monobasic or polybasic aliphatic carboxylic acid esters, or monobasic or polybasic aromatic carboxylic acid esters comprise benzoates, phthalate, malonic ester class, succinate class, glutarate class or pivalate class.
7, the catalyst component that is used for olefinic polymerization according to claim 5, wherein said diether compound are 1 shown in the general formula (III), 3-two ethers:
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VIMutually the same or inequality, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20A kind of in the aralkyl, and R
VIIAnd R
VIIIIdentical or different, be selected from the C of straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20A kind of in the aralkyl; R
I-R
VIGroup between can be keyed to ring.
8, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that describedly having benzoates that the ortho position alkoxyl group replaces and the mol ratio of another kind of electron donor compound is 0.01 one 0.5.
9, the catalyst component that is used for olefinic polymerization according to claim 1 is characterized in that, this catalyst component is at a kind of MgCl
2.nROH load has the titanium compound with at least one Ti-halogen bond and the reaction product of described two kinds of electron donor compounds on the adducts particle, and wherein n is 1.5～4; R is the alkyl of carbon number 1-4.
10, a kind of CH that is used for
2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1-C
6Alkyl or aryl, this catalyzer comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1-9;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
11, be used for alkene CH
2=CHR polymeric method, wherein R is the hydrocarbyl group of hydrogen or 1-12 carbon atom, carries out in the presence of the described catalyzer of claim 10.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100736223A CN1318457C (en) | 2004-09-02 | 2004-09-02 | Catalyst component for olefinic polymerization and its catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100736223A CN1318457C (en) | 2004-09-02 | 2004-09-02 | Catalyst component for olefinic polymerization and its catalyst |
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| CN1318457C true CN1318457C (en) | 2007-05-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004100736223A Expired - Lifetime CN1318457C (en) | 2004-09-02 | 2004-09-02 | Catalyst component for olefinic polymerization and its catalyst |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486776B (en) * | 2008-01-17 | 2010-12-22 | 中国石油化工股份有限公司 | Catalyst component for olefinic polymerization , and catalyst thereof |
| SG177665A1 (en) * | 2009-07-15 | 2012-02-28 | China Petroleum & Chemical | Spherical magnesium halide adduct, catalyst component and catalyst for olefin polymerization prepared therefrom |
| CN102040690A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing polypropylene with low ash content |
| CN103304691B (en) * | 2012-03-08 | 2015-09-16 | 中国石油化工股份有限公司 | A kind of catalyst system for olefinic polyreaction |
| CN103923238B (en) * | 2013-10-31 | 2018-03-02 | 北京利和知信科技有限公司 | Catalytic component and catalyst for olefinic polymerization |
| EP3438083B1 (en) * | 2016-03-28 | 2023-08-16 | Toho Titanium Co., Ltd. | Alkoxy magnesium, method for producing alkoxy magnesium, solid catalyst component for olefin polymerization use, catalyst for olefin polymerization use, and method for producing olefin polymer |
| BR112020001201B1 (en) | 2017-07-19 | 2023-03-21 | Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation | ZIEGLER-NATTA CATALYST SYSTEM FOR OLEFIN POLYMERIZATION, SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION AND OLEFIN POLYMERIZATION PROCESS |
| CN119490612A (en) * | 2023-08-15 | 2025-02-21 | 中国石油化工股份有限公司 | A solid catalyst component for olefin polymerization, catalyst and application thereof |
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|---|---|---|---|---|
| CN1087918A (en) * | 1992-09-24 | 1994-06-15 | 希蒙特公司 | Olefin polymerization catalytic component and catalyst |
| CN1105671A (en) * | 1993-10-01 | 1995-07-26 | 希蒙特公司 | Components and catalysts for olefin polymerization |
| WO1999057160A1 (en) * | 1998-05-06 | 1999-11-11 | Montell Technology Company B.V. | Catalyst components for the polymerization of olefins |
| CN1242780A (en) * | 1997-09-03 | 2000-01-26 | 蒙特尔技术有限公司 | Components and catalysts for the polymerization of olefins |
| CN1292800A (en) * | 1998-11-04 | 2001-04-25 | 蒙特尔技术有限公司 | Catalyst components and catalysts for olefin polymerization |
| WO2002030998A1 (en) * | 2000-10-13 | 2002-04-18 | Basell Technology Company B.V. | Catalyst components for the polymerization of olefins |
| JP2002249507A (en) * | 2001-02-26 | 2002-09-06 | Toho Catalyst Co Ltd | Solid catalyst component for olefin polymerization and catalyst |
| WO2003002617A1 (en) * | 2001-06-26 | 2003-01-09 | Basell Poliolefine Italia S.P.A | Components and catalysts for the polymerization of olefins |
-
2004
- 2004-09-02 CN CNB2004100736223A patent/CN1318457C/en not_active Expired - Lifetime
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|---|---|---|---|---|
| CN1087918A (en) * | 1992-09-24 | 1994-06-15 | 希蒙特公司 | Olefin polymerization catalytic component and catalyst |
| CN1105671A (en) * | 1993-10-01 | 1995-07-26 | 希蒙特公司 | Components and catalysts for olefin polymerization |
| CN1242780A (en) * | 1997-09-03 | 2000-01-26 | 蒙特尔技术有限公司 | Components and catalysts for the polymerization of olefins |
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| CN1292800A (en) * | 1998-11-04 | 2001-04-25 | 蒙特尔技术有限公司 | Catalyst components and catalysts for olefin polymerization |
| WO2002030998A1 (en) * | 2000-10-13 | 2002-04-18 | Basell Technology Company B.V. | Catalyst components for the polymerization of olefins |
| JP2002249507A (en) * | 2001-02-26 | 2002-09-06 | Toho Catalyst Co Ltd | Solid catalyst component for olefin polymerization and catalyst |
| WO2003002617A1 (en) * | 2001-06-26 | 2003-01-09 | Basell Poliolefine Italia S.P.A | Components and catalysts for the polymerization of olefins |
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