CN102399328A - Catalyst component for olefin polymerization and catalyst thereof - Google Patents
Catalyst component for olefin polymerization and catalyst thereof Download PDFInfo
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- CN102399328A CN102399328A CN2010102830615A CN201010283061A CN102399328A CN 102399328 A CN102399328 A CN 102399328A CN 2010102830615 A CN2010102830615 A CN 2010102830615A CN 201010283061 A CN201010283061 A CN 201010283061A CN 102399328 A CN102399328 A CN 102399328A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- -1 2, 2, 3-butane tricarboxylate compound Chemical class 0.000 claims abstract description 33
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- 150000003609 titanium compounds Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 6
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 claims 5
- 150000007524 organic acids Chemical group 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 150000003890 succinate salts Chemical class 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 150000003377 silicon compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000003701 inert diluent Substances 0.000 description 3
- 235000011147 magnesium chloride Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XZKPFRIEWDWYDH-UHFFFAOYSA-N 1-(methoxymethyl)-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(COC)=CC=C2 XZKPFRIEWDWYDH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-UHFFFAOYSA-N 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
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 description 1
- CADAOKXOWMHTKV-UHFFFAOYSA-N C(C)O[Ti](OCC)OCC.[Cl] Chemical compound C(C)O[Ti](OCC)OCC.[Cl] CADAOKXOWMHTKV-UHFFFAOYSA-N 0.000 description 1
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 description 1
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-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
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- TZSQRHNPVPIZHV-UHFFFAOYSA-M [Mg]OC1=CC=CC=C1 Chemical compound [Mg]OC1=CC=CC=C1 TZSQRHNPVPIZHV-UHFFFAOYSA-M 0.000 description 1
- 125000004416 alkarylalkyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 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 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 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
- 230000033912 thigmotaxis Effects 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 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
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a catalyst component and a catalyst for olefin polymerization, and application thereof in olefin homopolymerization and copolymerization. More particularly, it relates to a solvent system containing organic epoxy compound and organic phosphorus compound, and a solid catalyst obtained after the contact reaction of 2, 2, 3-butane tricarboxylate compound containing specific structure and titanium-containing compound, and the application of said catalyst in olefin polymerization reaction. The catalyst has good catalytic activity, and the obtained polymer has higher melt index. Before the inventor finds that the 2, 2, 3-butyl tricarboxylate compound disclosed by the invention has never been used as an internal electron donor in a catalyst for olefin polymerization.
Description
Technical field
The present invention relates to a kind of catalyst component and catalyzer of for olefines polymerization, and its application in alkene homopolymerization and copolymerization.More particularly, relate to and contain 2,2 of a kind of general formula (I), the solid catalyst of 3-fourth tricarboxylic ester compounds component, and the application of this catalyzer in olefinic polyreaction.
Technical background
As everyone knows, internal electron donor is one of important component of Ziegler-Natta catalyst, and the stereotaxis ability and the activity of profound influence catalyzer are being played the part of important effect in the development course of Ziegler-Natta catalyst.Different internal electron donors have very big difference owing to its chemical constitution and structure is different to the catalyst system Effect on Performance.
In USP4861847, be the solution that solvent makes magnesium chloride at first with epoxy chloropropane and tributyl phosphate, add the precipitation additive phthalic anhydride, use titanium tetrachloride to handle and obtain ingredient of solid catalyst.In this system, use conventional binary aromatic carboxylic acid's ester compound, for example the catalyzer that obtains such as n-butyl phthalate or diisobutyl phthalate be used for polyacrylic synthetic, active high, the polymkeric substance degree of isotacticity is high.After this, have some patents in this system, to use different internal electron donors again, with improve catalyzer one or more performance.As in CN1298887, use a kind of diether compound to improve the hydrogen response of catalyzer.In CN1542024, a kind of diol-lipid compound is used in said system, resulting catalyzer also has high reactivity.
The inventor herein finds to use 2 of general formula (I) in research process; 2; 3-fourth tricarboxylic ester compounds is used for olefinic polymerization as internal electron donor synthetic catalyzer; Especially the polymeric of propylene the time, catalyzer has good catalytic activity, and the polymkeric substance that obtains has higher melting index.And before the inventor herein found, of the present invention 2,2,3-fourth tricarboxylic ester compounds also never was used as internal electron donor and is applied in the olefinic polymerization in the catalyzer.
Summary of the invention
A kind of catalyst component that is used for olefinic polymerization prepares through following steps:
A) magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, forms homogeneous solution.Described homogeneous solution adds or does not add inert solvent.
B) above-mentioned solution and at least a titanium compound are carried out contact reacts.
C) in above-mentioned arbitrary step, introduce at least a compound shown in the formula (I) that is selected from.
R in the general formula (I)
1～R
4Can be identical or inequality, be C
1～C
14The alkyl of straight or branched, C
3～C
10Naphthenic base, C
6～C
10Aryl, C
7～C
10Alkaryl or aralkyl.
The present invention is dissolved in magnesium halide in the solvent system that contains organic epoxy compounds and organo phosphorous compounds; Can prepare magnesium halide solution according to disclosed method among the Chinese patent CN85100997, and disclosed associated viscera is all introduced the present invention as a reference among the CN85100997.
Described magnesium halide is selected from the complex compound, magnesium dihalide molecular formula of water or alcohol of magnesium dihalide, magnesium dihalide one of them or two halogen atoms by alkyl or halogen-oxyl institute metathetical verivate.Particular compound is like magnesium dichloride, dibrominated magnesium, chlorination phenoxy magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.
Wherein said organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Described organic epoxy compounds concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether or THF etc.
Wherein said organo phosphorous compounds is the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl etc.
In order to make magnesium halide dissolve more fully, in this solvent system, can randomly add a certain amount of inert diluent.Described inert diluent can adopt hexane, heptane, octane, benzene,toluene,xylene, 1 usually, and 2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound and other help other solvent of magnesium halide dissolved.Inert diluent can use separately, use also capable of being combined.
Said halogenated magnesium compound can separately or mix and use.
Solvent temperature is suitable to be chosen between 10～150 ℃, and wherein ceiling temperature should not surpass the boiling point of solvent for use.
Dissolution time is as the criterion to dissolve fully.
In the process of preparation magnesium halide solution, the order of each component of adding solution in no particular order.
Separate out titaniferous solid catalytic ingredient after above-mentioned magnesium halide solution and the reaction of at least a titanium compound.Wherein said titanium compound is selected from general formula Ti (OR
5)
4-nX
nAt least a in the shown compound, R in the formula
5For carbonatoms is 1～20 alkyl, preferred C
1～C
14Aliphatic group, X is identical or different, is F, Cl or Br, n is selected from 1～4 integer.Particular compound is like a kind of or its mixture in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium; Described titanium compound should be a completely soluble liquefied compound under application of temperature, in the non-polar solvent, preferred titanium tetrachloride.
The temperature of reaction of said titanium compound and magnesium halide solution is preferably :-40～0 ℃.
In the reaction system temperature-rise period, separate out solid catalyst particle, and can regulate the form of titaniferous solid catalyst through the speed of heat-up rate.The ceiling temperature that heats up should be controlled at below the boiling point of solvent.
Described general formula (I) electron donor compound can prepare in the arbitrary steps in the process at catalyst component and add reaction system, preferably forms the back at granules of catalyst and adds.Can pass through conventional washing, drying and other steps for the granules of catalyst that forms, obtain the solid catalyst of flowable state.In order to regulate the content of titanium in the catalyzer, also can randomly use fresh titanium compound that granules of catalyst is carried out one or many and handle.
At described general formula (I) 2,2, in the internal electron donor compound structure of 3-fourth tricarboxylic ester compounds, preferred group is: R
1～R
3For methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, phenmethyl, to methylbenzyl or styroyl; R
4Be sec.-propyl.Concrete compound comprises: 2,2, and 3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1,2,4-triethyl ester; 2,2,3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1-methyl, 2,4-diethyl ester; 2,2,3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1-propyl group, 2,4-diethyl ester; 2,2,3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1-butyl, 2,4-diethyl ester etc.
In above-mentioned general formula (I) compound, preferred especially group is: R
1～R
3Identical, be methyl, ethyl, n-propyl or sec.-propyl.Preferred especially compound is 2,2,3-fourth tricarboxylic acid, and 3-(1-methylethyl)-, 1,2,4-triethyl ester.
The compound of described general formula (I) can use separately also and can specifically use like succinate compounds, phthalate compound, diether compound, diol-lipid compound etc. with other electron donor compound.
In preparation ingredient of solid catalyst process, wherein in every mole of magnesium halide: organic epoxy compounds: 0.2-10mol, preferred 0.5～4mol; Organo phosphorous compounds: 0.1～3mol, preferred 0.3～1.0mol; Precipitation additive is 0.03～1.0 mole, and titanium compound is 0.5～150 mole, and the compound of general formula (I) is 0.02～0.4 mole.
In addition, the present invention also provides a kind of CH of being used for
2=CHR
6The catalyzer of olefinic polyreaction, wherein R
6Be hydrogen or C
1～C
12Alkyl or aryl, this catalyzer comprise following a), b), c) reaction product of three kinds of components:
A) ingredient of solid catalyst that is used for olefinic polymerization that the present invention is above-mentioned;
B) alkylaluminium cpd; Its general formula is AlR
7 3, R
7Be C identical or inequality
1～C
8Alkyl, one of them or two alkyl can be replaced by chlorine, can select for use one or more aluminum alkyls mix to use, preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination aluminum alkyls, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc., its consumption are the said alkylaluminium cpds of 50～1000 uses with the Al/Ti mol ratio generally;
C) randomly, a kind of external electron donor compound, for example list or polyfunctional carboxylic acids, carboxylic acid anhydride and carboxylicesters, ketone, ether, alcohol, lactone, and organophosphorus and silicoorganic compound.Preferably have organic silicon compound.Its consumption is 0.005～0.5 mole of every mole of aluminum alkyl compound, 0.01～0.25 mole of preferred every mole of aluminum alkyl compound.
Said external electron donor preferably contains at least one Si-OR
10The general formula of key is R
8 aR
9 bSi (OR
10) silicon compound of c, wherein a and b are 0,1 or 2 integer, c be 1～3 integer and (a+b+c) and be 4; R
8, R
9And R
10Be C
1-C
18Alkyl, randomly contain heteroatoms.Preferred especially silicon compound, wherein a is 1, and b is 1, and c is 2, R
8And R
9In have at least one to be to be selected from branched-alkyl, alkenyl, alkylidene group, naphthenic base or aromatic yl group with 3～10 carbon atoms, optional heteroatoms and the R of containing
10Be C
1-C
10Alkyl group, particularly methyl.The example of preferred silicon compound has cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane; Second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane; Dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and (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.
In addition, preferred silicon compound also has, and wherein a is 0, and c is 3, R
9Be branched-alkyl or group of naphthene base, optional heteroatoms and the R of containing
10Be methyl.The example of optional silicon compound has cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and uncle's hexyl Trimethoxy silane like this.
Also can select diether compound in addition, 2-sec.-propyl-2-isopentyl-1 wherein, the 3-Propanal dimethyl acetal, 9, two (methoxymethyl) fluorenes of 9-are preferred especially.
Above-mentioned alkylaluminium cpd can carry out contact reacts separately or as two kinds of mixture of ingredients and above-mentioned catalyst component with optional external electron donor compound.
Above-mentioned catalyzer is suitable for alkene CH
2=CHR
6(R wherein
6Be the alkyl or aryl of hydrogen or 1～12 carbon) and the polyreaction that contains the mixture of (if necessary) a small amount of diolefine.
Catalyst olefinic polymerization provided by the present invention can be adopted the whole bag of tricks of the prior art, does not have special qualification.The polymerization of alkene is carried out according to currently known methods, in the liquid phase of liquid monomer or the solution of monomer in inert solvent, or in gas phase, or through operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferred 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher.
It should be noted that the inventor herein at research process first with a kind of 2,2 of ad hoc structure that contains; 3-fourth tricarboxylic ester compounds is applied to propylene polymerization as the internal electron donor synthetic catalyst, finds to use 2 of general formula (I); 2,3-fourth tricarboxylic ester compounds is used for olefinic polymerization as internal electron donor synthetic catalyzer, especially the polymeric of propylene the time; Catalyzer has excellent activity, and the polymkeric substance that obtains has higher high fusion index.
Embodiment
Following Example is used for explaining the present invention, is not to be used for limiting scope of the present invention.
Testing method:
1, melt index: measure according to ASTM D1238-99.
2, polymkeric substance isotactic index: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant polymer samples; Be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.
3, polymericular weight and MWD MWD (MWD=Mw/Mn): adopt the gel permeation chromatography method; Use PL-GPC220 to measure (standard specimen as solvent down at 150 ℃ with trichlorobenzene; PS, flow velocity: 1.0ml/min, pillar: 3xPlgel 10 μ m MIXED-B 300x7.5nm)
Embodiment 1
1, catalyzer is synthetic: in the double glazing reaction flask of 300ML, add the anhydrous MgCl of 5.0 grams successively
2, 120ml toluene, 8.0ml epoxy chloropropane, 10.0ml tributyl phosphate after dissolving fully under 60 ℃, are cooled to-25 ℃ with this solution, Dropwise 5 0ml titanium tetrachloride; Under-25 ℃, keep half a hour, slowly be warming up to 90 ℃, add 2,2,3-fourth tricarboxylic acid; 3-(1-methylethyl)-, 1,2,4-triethyl ester 5mmol, reaction 1h; With the titanium tetrachloride washing of 40ml, use toluene and hexane wash 2 times after the filtration respectively again, vacuum-drying obtains solid catalyst.
2, propylene polymerization: in the 5L autoclave, 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 above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 1L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Embodiment 2
1, catalyzer is synthetic: in the double glazing reaction flask at 300ML, add the anhydrous MgCl of 5.0 grams successively
2, 120ml toluene, 8.0ml epoxy chloropropane, 10.0ml tributyl phosphate after dissolving fully under 60 ℃, are cooled to-25 ℃ with this solution, Dropwise 5 0ml titanium tetrachloride; Under-25 ℃, keep half a hour, slowly be warming up to 90 ℃, add 2,2; 3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1,2; 4-triethyl ester and 9, two (methoxymethyl) fluorenes of 9-are 5mmol altogether, and mol ratio is 1, reaction 1h; With the titanium tetrachloride washing of 40ml, use toluene and hexane wash 2 times after the filtration respectively again, vacuum-drying obtains solid catalyst.
2, propylene polymerization: in the 5L autoclave, 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 above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 1L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Embodiment 3
Preparation of catalysts is with embodiment 2
In the 5L autoclave, 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 above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas.Close autoclave, introduce hydrogen 6L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1.
Comparative Examples 1
With embodiment 1, just diisobutyl phthalate is replaced 2,2,3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1,2,4-triethyl ester (consumption 5mmol).
The performance of table 1 catalyzer
Claims (9)
1. a solids containing titanium catalyst component that is used for olefinic polymerization is characterized in that, prepares through following steps:
A) magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, forms homogeneous solution;
B) above-mentioned solution and at least a titanium compound are carried out contact reacts after, obtain the solids containing titanium catalyst component;
C) in above-mentioned arbitrary step, introduce at least a compound shown in the formula (I) that is selected from;
In the general formula (I), R
1～R
4Identical or different, represent C
1～C
10Straight or branched alkyl, C
3～C
10Naphthenic base, C
6～C
20Aryl, C
7～C
20Alkaryl or C
7～C
20Aralkyl.
Described titanium compound is selected from general formula Ti (OR
5)
4-nX
nAt least a in the shown compound, R in the formula
5Be C
1～C
14Aliphatic group, X is identical or different, is F, Cl or Br, n is selected from 1～4 integer;
Described precipitation additive is organic acid anhydride, organic acid, ether or ketone compounds.
2. solids containing titanium catalyst component according to claim 1 is characterized in that, the usage quantity of various raw materials; In every mole of magnesium halide; Organic epoxy compounds is 0.2～10 mole, and organo phosphorous compounds is 0.1～3 mole, and precipitation additive is 0.03～1.0 mole; Titanium compound is 0.5～150 mole, and the compound of general formula (I) is 0.02～0.4 mole.
3. solids containing titanium catalyst component according to claim 1 is characterized in that, in the described general formula (I), and R
1～R
4Identical or different, be C
1～C
4The alkyl of straight or branched.
4. solids containing titanium catalyst component according to claim 1 is characterized in that, in the described general formula (I), and R
4Substituting group be the substitution in side chain base.
5. solids containing titanium catalyst component according to claim 1 is characterized in that, in the described general formula (I), and R
1～R
3Identical or different, be methyl, ethyl, n-propyl or sec.-propyl.
6. solids containing titanium catalyst component according to claim 1 is characterized in that, the compound of described general formula (I) is 2,2,3-fourth tricarboxylic acid, and 3-(1-methylethyl)-, 1,2,4-triethyl ester; 2,2,3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1-methyl, 2,4-diethyl ester; 2,2,3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1-propyl group, 2,4-diethyl ester; 2,2,3-fourth tricarboxylic acid, 3-(1-methylethyl)-, 1-butyl, 2,4-diethyl ester a kind of or their mixture.
7. solids containing titanium catalyst component according to claim 1 is characterized in that, the compound of described general formula (I) is 2,2,3-fourth tricarboxylic acid, and 3-(1-methylethyl)-, 1,2,4-triethyl ester.
8. solids containing titanium catalyst component according to claim 1; It is characterized in that the compound of described general formula (I) randomly uses separately or uses with succinate compounds, phthalate compound, diether compound, diol-lipid compound.
9. one kind is used for CH
2=CHR
6The catalyzer of olefinic polyreaction, wherein R
6Be hydrogen or C
1～C
6Alkyl, this catalyzer comprises the reaction product of following component:
A) the described solids containing titanium catalyst component of one of claim 1～8;
B) alkylaluminium cpd;
C) randomly, external electron donor component;
The alkylaluminium cpd general formula is AlR
7 3, R
7Be identical or different C
1～C
8Alkyl, one of them or two alkyl can be replaced by chlorine, are 50～1000 to use the abovementioned alkyl aluminum compounds with the Al/Ti mol ratio;
The external electron donor component is a general formula R
8 aR
9 bSi (OR
10)
cSilicon compound, wherein a and b are respectively 0,1 or 2 integer, c is 1～3 integer, and a+b+c's and be 4; R
8, R
9And R
10Be C
1～C
18Alkyl, randomly contain heteroatoms, its consumption is that every mole of aluminum alkyl compound is counted 0.005～0.5 mole.
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| CN101759564A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Ester compound and application thereof in catalyst for olefin polymerization |
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| CN101759564A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Ester compound and application thereof in catalyst for olefin polymerization |
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