CN101423566B - Solid catalytic component and catalyst thereof - Google Patents
Solid catalytic component and catalyst thereof Download PDFInfo
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- CN101423566B CN101423566B CN2007101766696A CN200710176669A CN101423566B CN 101423566 B CN101423566 B CN 101423566B CN 2007101766696 A CN2007101766696 A CN 2007101766696A CN 200710176669 A CN200710176669 A CN 200710176669A CN 101423566 B CN101423566 B CN 101423566B
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- dioctyl phthalate
- ester
- methoxyphenyl
- tolyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 239000007787 solid Substances 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 20
- -1 isobutyl- Chemical group 0.000 claims description 19
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 125000003944 tolyl group Chemical group 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 150000002240 furans Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 150000004820 halides Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 5
- XZKPFRIEWDWYDH-UHFFFAOYSA-N 1-(methoxymethyl)-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(COC)=CC=C2 XZKPFRIEWDWYDH-UHFFFAOYSA-N 0.000 claims description 4
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 claims description 4
- FOSCDBCOYQJHPN-UHFFFAOYSA-M Cl[Mg] Chemical compound Cl[Mg] FOSCDBCOYQJHPN-UHFFFAOYSA-M 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 claims description 4
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 4
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 4
- 235000011147 magnesium chloride Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- AZNKQOALFNLHKD-UHFFFAOYSA-N cyclobutylmethyl(dimethoxy)silane Chemical compound CO[SiH](CC1CCC1)OC AZNKQOALFNLHKD-UHFFFAOYSA-N 0.000 claims description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 claims description 2
- CADAOKXOWMHTKV-UHFFFAOYSA-N C(C)O[Ti](OCC)OCC.[Cl] Chemical compound C(C)O[Ti](OCC)OCC.[Cl] CADAOKXOWMHTKV-UHFFFAOYSA-N 0.000 claims description 2
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001399 aluminium compounds Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002680 magnesium Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 4
- 125000005843 halogen group Chemical group 0.000 claims 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 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
- 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 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PPWNCLVNXGCGAF-UHFFFAOYSA-N 3,3-dimethylbut-1-yne Chemical compound CC(C)(C)C#C PPWNCLVNXGCGAF-UHFFFAOYSA-N 0.000 description 1
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical group CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- 101100170601 Drosophila melanogaster Tet gene Proteins 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- VHILMKFSCRWWIJ-UHFFFAOYSA-N dimethyl acetylenedicarboxylate Chemical compound COC(=O)C#CC(=O)OC VHILMKFSCRWWIJ-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
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A solid catalytic component uses at least one furan diacid ester in a general formula as an internal electron donor, and when the catalytic component is used for olefin, particularly propylene (co) polymerization, a polymer with high stereospecificity can be obtained. The invention further discloses a catalyst containing the solid catalytic component.
Description
Technical field
The present invention relates to a kind of solid catalytic component and catalyzer thereof, particularly a kind of solid catalytic component and catalyzer thereof that is used for propylene polymerization.
Background technology
As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component
2=CHR olefinic polyreaction particularly can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atoms.Wherein, electron donor is one of requisite composition in the catalyst component, and along with the development of electron donor compound has caused polyolefin catalyst constantly to update.
Previously, reported multiple electron donor compound in the document in a large number, for example polycarboxylic acid, monobasic or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is binary aromatic carboxylic acid's ester class, as n-butyl phthalate or diisobutyl phthalate (CN85100997A) etc.
In recent years, people attempt adopting other compounds as the electron donor in the olefin polymerization catalyst components, US4971937, US2004014597 and EP728769 have adopted special 1, the 3-diether compound is as electron donor, as 2, and 2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc. also can be referring to CN1042547A, CN1143651A, US2003027715 and WO03076480.The disclosed catalyst component that is used for olefinic polyreaction of CN1054139A, it is special 1 to adopt, and the 3-cyclohexadione compounds is as electron donor, as 2,2,6,6-tetramethyl--3,5-heptadione and 2,2,4,6,6-pentamethyl--3,5-heptadione etc.
Special dibasic aliphatic carboxylic acid esters and the diol-lipid compound of one class disclosed again recently, as (referring to CN1236373A, CN1236374A, CN1552741A, CN1213080C, CN1542024A, CN1552742A and CN1552740A) such as succinate, malonic ester, glutarate, glycol ester, propylene glycol ester, butanediol ester, pentadiol ester and hexylene glycol esters.CN1313869A, US6818583 and WO2004024785 disclose the succinate that replaces is given body as the internal electron of the catalyst component that is used for olefinic polymerization application.The use of these electron donor compounds not only can improve activity of such catalysts, and the polyacrylic molecular weight distribution of gained is obviously widened.But when not adopting the external electron donor component, the degree of isotacticity of resulting polymers is still lower.
Summary of the invention
The object of the present invention is to provide a kind of CH of being used for
2The solid catalytic component of=CHR olefinic polymerization, wherein R is hydrogen or the hydrocarbyl group with 1-12 carbon atom.Another object of the present invention provides the catalyzer that contains above-mentioned catalyst component.
Solid catalytic component of the present invention by weight percentage, comprises 10-25% magnesium, 1-10% titanium, 40-60% halogen and 1-30% internal electron donor, and described internal electron donor is selected from least a furans two acid esters in the general formula (I):
Wherein, radicals R
1And R
2Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, be preferably C
1-C
10Alkyl, cycloalkyl or arylalkyl, further preferred C
1-C
10Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or neo-pentyl, preferred especially ethyl, sec.-propyl, normal-butyl or isobutyl-; Radicals R
3And R
4Be same to each other or different to each other, be hydrogen or C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, preferred aryl groups, arylalkyl or kiki fang alkyl group.
The example of suitable above-mentioned general formula compound includes but not limited to:
2-benzofurane-3,4-dioctyl phthalate dimethyl ester, 2-benzofurane-3, the 4-dicarboxylate, 2-benzofurane-3,4-dioctyl phthalate di-n-propyl ester, 2-benzofurane-3,4-dioctyl phthalate diisopropyl ester, 2-benzofurane-3,4-dioctyl phthalate di-n-butyl, 2-benzofurane-3,4-dioctyl phthalate diisobutyl ester, 2-benzofurane-3,4-dioctyl phthalate two peopentyl esters, 2-o-tolyl furans-3,4-dioctyl phthalate dimethyl ester, 2-o-tolyl furans-3, the 4-dicarboxylate, 2-o-tolyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-o-tolyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-o-tolyl furans-3,4-dioctyl phthalate di-n-butyl, 2-o-tolyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-o-tolyl furans-3,4-dioctyl phthalate two peopentyl esters, tolyl furans-3 between 2-, 4-dioctyl phthalate dimethyl ester, tolyl furans-3 between 2-, the 4-dicarboxylate, tolyl furans-3 between 2-, 4-dioctyl phthalate di-n-propyl ester, tolyl furans-3 between 2-, 4-dioctyl phthalate diisopropyl ester, tolyl furans-3 between 2-, 4-dioctyl phthalate di-n-butyl, tolyl furans-3 between 2-, 4-dioctyl phthalate diisobutyl ester, tolyl furans-3 between 2-, 4-dioctyl phthalate two peopentyl esters, 2-p-methylphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-p-methylphenyl furans-3, the 4-dicarboxylate, 2-p-methylphenyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-p-methylphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-p-methylphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-p-methylphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-p-methylphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-o-methoxyphenyl furans-3, the 4-dicarboxylate, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-m-methoxyphenyl furans-3, the 4-dicarboxylate, oxygen base tolyl furans-3 between 2-, 4-dioctyl phthalate di-n-propyl ester, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-p-methoxyphenyl furans-3, the 4-dicarboxylate, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2,5-phenylbenzene furans-3,4-dioctyl phthalate dimethyl ester, 2,5-phenylbenzene furans-3,4-dicarboxylate, 2,5-phenylbenzene furans-3,4-dioctyl phthalate di-n-propyl ester, 2,5-phenylbenzene furans-3,4-dioctyl phthalate diisopropyl ester, 2,5-phenylbenzene furans-3,4-dioctyl phthalate di-n-butyl, 2,5-phenylbenzene furans-3,4-dioctyl phthalate diisobutyl ester, 2,5-phenylbenzene furans-3,4-dioctyl phthalate two peopentyl esters, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate dimethyl ester, 2,5-diphenyl-methyl furans-3, the 4-dicarboxylate, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate diisopropyl ester, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate di-n-butyl, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate diisobutyl ester or 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate two peopentyl esters.
The synthetic method of furans two acid esters of the present invention can be referring to document: Fan M.; Guo L.; Liu X.; Liu W.; Liang Y.Synthesis 2005, (3), 391.; Fan M.; Yan Z.; Liu W.; LiangY.J.Org.Chem.2005,70 (20), 8204..
Magnesium in the catalyst component can be by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; P is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
Magnesium halide in the magnesium halide alcohol adduct is selected from a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate, preferred magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol, preferred alcohol.
After magnesium halide alcohol adduct adopts magnesium halide and alcohol to be total to heat of solution, high pressure ejection or high-speed stirring, the method that is solidified into microsphere particle in heat-eliminating medium obtains, and concrete grammar is referring to the associated description among the US4399054.
Titanium in the catalyst component can be TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.Concrete compound is as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
The preparation method of solid catalytic component of the present invention comprises: (1) joins spherical magnesium halide alcohol adduct in-40～10 ℃ the titanium compound, reacts 1～4 hour, and the mol ratio of magnesium and titanium is 1: 5～1: 50; (2) be warming up to 30～80 ℃, add the internal electron donor compound, the mol ratio of magnesium and internal electron donor compound is 2: 1～15: 1; (3) be warming up to 100～150 ℃ again, reacted 1～4 hour; (4) add titanium compound with step (1) same amount after filtering again, in 110～130 ℃ of reactions 1～4 hour, more after filtration, washing obtained after the drying.
With above-mentioned solid catalytic component is main ingredient, and the present invention also can further be provided for the catalyzer of olefinic polymerization.Catalyzer specifically comprises:
(a) contain magnesium, titanium, halogen and be selected from the catalyst component of at least a furans two acid esters in the general formula (I);
(b) alkylaluminium cpd;
(c) randomly, external electron donor component.
Wherein, alkylaluminium cpd (b) is selected from trialkyl aluminium compound, as the mixture of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
The external electron donor component can add as required selectively.Obtain the olefin polymer of taxis very high (as isotactic index greater than 99%) for needs, suggestion adds the external electron donor compound.
It is R that external electron donor can be selected general formula
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R ', the optional heteroatoms that contains; R also can be halogen or hydrogen atom.Concrete silicoorganic compound are as the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
1 of the also optional self-drifting of external electron donor (II), 3-two ethers:
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VICan be identical or different, can be hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom; R
VIIAnd R
IIICan be identical or different, can be hydrocarbyl group with 1 to 18 carbon atom; R
1-R
VIIIGroup in one or morely can also link up into ring.Preferably, R
VIIAnd R
VIIIBe selected from C
1-C
4Alkyl group, R
IIIAnd R
IVForm undersaturated condensed ring and R
I, R
II, R
VAnd R
VIBe hydrogen.Especially preferably use 9, two (methoxymethyl) fluorenes of 9-.
With titanium: aluminium: the molar ratio computing between the external electron donor compound (c), the amount ratio in the catalyzer between each component are 1: 5-1000: 0-500; Be preferably 1: 25-100: 25-300.
Catalyzer of the present invention is used for olefinic polymerization, can access the polymkeric substance of very high isotactic index when the equal polymerization of special propylene or the copolymerization of propylene and other alkene.Simultaneously, do not get rid of the copolymerization that is applicable to production polyethylene and ethene and alpha-olefin such as propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene or 1-octene yet.
Can adopt the whole bag of tricks of the prior art when being used for propylene polymerization, can in liquid phase or gas phase, carry out, also can under the combination operation of liquid and gas polymerization stage, carry out.Polymerization is carried out at 0～150 ℃ usually, preferred 40～90 ℃.Polymerization pressure is 0.01～10MPa.The hydrogen of chain-transfer agent effect or other compounds can be played and the molecular weight of controlling polymers can be used for.
The present invention passes through to adopt two ester compounds of novel furan structure as internal electron donor, can obtain the catalyzer of high comprehensive performance, when being used for propylene (being total to) polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, even when not using external electron donor, still can obtain high normal polymkeric substance, catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, and the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Embodiment
Embodiment given below is for the present invention is described better, rather than limits the invention.
Testing method:
1, polymericular weight and molecular weight distribution MWD (MWD=M
w/ M
n): adopting the gel permeation chromatography method, is that solvent is measured down at 135 ℃ with the orthodichlorobenzene with Alliance-GPCV2000.
2, polymkeric substance degree of isotacticity: adopt the heptane extraction process to measure (heptane boiling extracting 8 hours), promptly 1 restrain the exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 8 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 1 ratio.
3, the mensuration of melt index: measure according to μ PXRZ-400C.
4, the mensuration of titanium percentage composition: according to spectrophotometry.
5, the mensuration of internal electron donor percentage composition: according to the Autosystem XL of PE company gas chromatograph for determination.
One, furans two ester compounds is synthetic
Only with 2-benzofurane-3, the 4-dimethyl dicarboxylate synthesizes example, and concrete grammar is as follows:
In the 250ml flask, add 16g bromoacetophenone, 1.6gDABCO, 150ml methylene dichloride and 22g Anhydrous potassium carbonate, drip 10g dimethyl butyn (DMAD) under the stirring at room, add the back and continue stirring at room to reacting 6 hours.Thin up is told organic layer, and salt washing 2 times is washed 1 time, uses anhydrous sodium sulfate drying, filter, and solvent evaporated, column chromatography for separation gets white solid 14.5g, yield 81%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 7.96 (s, 1H, CH); δ 7.37-7.71 (m, 5H, phenyl ring H); δ 3.91 (s, 3H, CH
3); δ 3.84 (s, 3H, CH
3).
Two, the preparation of solid catalytic component
Embodiment 1-12
Under the anhydrous and oxygen-free condition, in 500 milliliter of four neck round-bottomed flask of a process abundant metathetical of high pure nitrogen, add TiCl
4100ml and toluene 60ml are cooled to-20 ℃, add 10.0gMgCl
22.8CH
3CH
2OH ball type carrier (according to the method preparation of USP4399054).Rise to 0 ℃ in 1 hour, continuing to heat up rose to 20 ℃ in 2 hours, and continuing to heat up rose to 40 ℃ in 1 hour, added corresponding furans two ester compounds (self-control) 7.4mmol in the table 1 respectively, was warming up to 100 ℃ in 1 hour, kept venting filtrate 2 hours.Add TiCl
4100ml rose to 120 ℃ in 1 hour, kept venting filtrate 2 hours.Add anhydrous hexane 60ml, boiling attitude washing 5 times adds anhydrous hexane 60ml then, and normal temperature washing 3 times is at last with the ingredient of solid catalyst vacuum-drying that obtains.
Comparative example 1-4
Method by the foregoing description prepares solid catalytic component, just internal electron donor is replaced with n-butyl phthalate, dibutyl succinate, 2 respectively, 3-di-isopropyl ethyl succinate and 2,4-pentanediol dibenzoate.
Three, propylene polymerization experiment
The solid catalytic component of the foregoing description 1-12 and comparative example 1-4 is carried out propylene polymerization respectively.Usually step is: volume is the stainless steel autoclave of 5L, after high pure nitrogen is fully replaced, adds A1Et
32.5mmol external electron donor methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol adds ingredient of solid catalyst 10mg and the 1.2L hydrogen of the foregoing description 1-24 again, feeds liquid propene 2.3L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release to 1 normal atmosphere obtains the PP powder.Polymerization result is listed in table 1.
Table 1. propylene polymerization result
Four, the propylene polymerization result of different external electron donors relatively
Catalyst component is with embodiment 8, and polymerization process is with aforementioned, and just external electron donor changes down the external electron donor described in the tabulation into.
The polymerization result of the different external electron donors of table 2. relatively
| External electron donor | Polymerization activity kgPP/gcat | Degree of isotacticity (%) | Molecular weight distribution | Melting index g/10min |
| Methylcyclohexyl dimethoxy silane | 55 | 98.3 | 7.8 | 0.9 |
| Dicyclopentyl dimethoxyl silane | 53 | 98.1 | 7.5 | 1.0 |
| Diisopropyl dimethoxy silane | 50 | 97.9 | 7.9 | 1.0 |
| Di-n-butyl dimethoxy silane | 47 | 98.7 | 7.6 | 1.1 |
| Second, isobutyl dimethoxy silane | 41 | 99.1 | 7.8 | 1.0 |
| 9, two (methoxymethyl) fluorenes of 9- | 52 | 99.3 | 6.9 | 0.9 |
Five, vinyl polymerization experiment
Volume is the stainless steel autoclave of 4L, after the abundant pump drainage displacement of high pure nitrogen, starts stirring, progressively adds the solid catalytic component and the 2.5mmol promotor AlEt of 1L hexane, 10mg embodiment 8 gained under nitrogen protection in still
3After being warming up to 75 ℃, in still, replenish an amount of high-purity hydrogen, make that hydrogen partial pressure is 0.3Mpa in the still, after 5 minutes in still make-up ethylene gas make its dividing potential drop reach 0.75MPa, the dividing potential drop of keeping ethylene gas is constant, make system temperature keep 80 ℃, after 3 hours, cooling discharge, polymkeric substance except that desolvating, is obtained polyethylene 269g after the thorough drying.
Six, ethene and copolymerization of propylene experimental result
Volume is the stainless steel autoclave of 4L, after the abundant pump drainage displacement of high pure nitrogen, starts stirring, progressively adds the solid catalytic component and the 2.5mmol promotor AlEt of 1L hexane, 10mg embodiment 8 gained under nitrogen protection in still
3Feed liquid propene 2.3L, be warming up to 75 ℃ after, in still, replenish an amount of high-purity hydrogen, making the interior hydrogen partial pressure of still is 0.3MPa, make-up ethylene gas makes its dividing potential drop reach 0.75MPa in still then, and the dividing potential drop of keeping ethylene gas is constant, makes system temperature keep 80 ℃, after 3 hours, cooling discharge except that desolvating, obtains polymer powders 471g with polymkeric substance after the thorough drying.
Claims (20)
1. a solid catalytic component by weight percentage, comprises 10%-25% magnesium, 1%-10% titanium, 40%-60% halogen and 1%-30% internal electron donor, it is characterized in that described internal electron donor is selected from least a furans two acid esters in the general formula (I):
Wherein, radicals R
1And R
2Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching; Radicals R
3And R
4Be same to each other or different to each other, be hydrogen or C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching.
2. catalyst component according to claim 1 is characterized in that in the furans two acid esters general formula compounds R
1And R
2Be C
1-C
10Alkyl, cycloalkyl or arylalkyl.
3. catalyst component according to claim 2 is characterized in that in the furans two acid esters general formula compounds R
1And R
2Be C
1-C
10Alkyl.
4. catalyst component according to claim 3 is characterized in that in the furans two acid esters general formula compounds R
1And R
2Be ethyl, sec.-propyl, normal-butyl or isobutyl-.
5. catalyst component according to claim 1 is characterized in that R in the furans two acid esters general formula compounds
3And R
4Be aryl, arylalkyl or kiki fang alkyl group.
6. catalyst component according to claim 1, it is characterized in that furans two acid esters general formula compounds are 2-benzofurane-3,4-dioctyl phthalate dimethyl ester, 2-benzofurane-3, the 4-dicarboxylate, 2-benzofurane-3,4-dioctyl phthalate di-n-propyl ester, 2-benzofurane-3,4-dioctyl phthalate diisopropyl ester, 2-benzofurane-3,4-dioctyl phthalate di-n-butyl, 2-benzofurane-3,4-dioctyl phthalate diisobutyl ester, 2-benzofurane-3,4-dioctyl phthalate two peopentyl esters, 2-o-tolyl furans-3,4-dioctyl phthalate dimethyl ester, 2-o-tolyl furans-3, the 4-dicarboxylate, 2-o-tolyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-o-tolyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-o-tolyl furans-3,4-dioctyl phthalate di-n-butyl, 2-o-tolyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-o-tolyl furans-3,4-dioctyl phthalate two peopentyl esters, tolyl furans-3 between 2-, 4-dioctyl phthalate dimethyl ester, tolyl furans-3 between 2-, the 4-dicarboxylate, tolyl furans-3 between 2-, 4-dioctyl phthalate di-n-propyl ester, tolyl furans-3 between 2-, 4-dioctyl phthalate diisopropyl ester, tolyl furans-3 between 2-, 4-dioctyl phthalate di-n-butyl, tolyl furans-3 between 2-, 4-dioctyl phthalate diisobutyl ester, tolyl furans-3 between 2-, 4-dioctyl phthalate two peopentyl esters, 2-p-methylphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-p-methylphenyl furans-3, the 4-dicarboxylate, 2-p-methylphenyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-p-methylphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-p-methylphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-p-methylphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-p-methylphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-o-methoxyphenyl furans-3, the 4-dicarboxylate, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-o-methoxyphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-m-methoxyphenyl furans-3, the 4-dicarboxylate, oxygen base tolyl furans-3 between 2-, 4-dioctyl phthalate di-n-propyl ester, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-m-methoxyphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate dimethyl ester, 2-p-methoxyphenyl furans-3, the 4-dicarboxylate, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate diisopropyl ester, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate di-n-butyl, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate diisobutyl ester, 2-p-methoxyphenyl furans-3,4-dioctyl phthalate two peopentyl esters, 2,5-phenylbenzene furans-3,4-dioctyl phthalate dimethyl ester, 2,5-phenylbenzene furans-3, the 4-dicarboxylate, 2,5-phenylbenzene furans-3,4-dioctyl phthalate di-n-propyl ester, 2,5-phenylbenzene furans-3,4-dioctyl phthalate diisopropyl ester, 2,5-phenylbenzene furans-3,4-dioctyl phthalate di-n-butyl, 2,5-phenylbenzene furans-3,4-dioctyl phthalate diisobutyl ester, 2,5-phenylbenzene furans-3,4-dioctyl phthalate two peopentyl esters, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate dimethyl ester, 2,5-diphenyl-methyl furans-3,4-dicarboxylate, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate di-n-propyl ester, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate diisopropyl ester, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate di-n-butyl, 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate diisobutyl ester or 2,5-diphenyl-methyl furans-3,4-dioctyl phthalate two peopentyl esters.
7. catalyst component according to claim 1 is characterized in that magnesium in the catalyst component by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; P is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
8. catalyst component according to claim 7 is characterized in that providing in the magnesium halide alcohol adduct of magnesium, and magnesium halide is a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate; Alcohol in the magnesium halide alcohol adduct is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol.
9. catalyst component according to claim 8, it is characterized in that providing the magnesium halide in the magnesium halide alcohol adduct of magnesium is magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is ethanol.
10. catalyst component according to claim 1 is characterized in that the titanium in the catalyst component is TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.
11. catalyst component according to claim 10 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium.
12. catalyst component according to claim 11 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride.
13. a catalyzer that comprises one of the described catalyst component of claim 1 to 12 is characterized in that catalyzer comprises:
A) one of the described solid catalytic component of claim 1 to 12;
B) alkylaluminium cpd;
C) randomly, external electron donor component.
14. catalyzer according to claim 13 is characterized in that alkylaluminium cpd is a trialkyl aluminium compound.
15. catalyzer according to claim 14 is characterized in that alkylaluminium cpd is triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium.
16. catalyzer according to claim 13 is characterized in that external electron donor is that general formula is R
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R '.
17. olefin polymerization catalysis according to claim 16, it is characterized in that external electron donor is the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
18. olefin polymerization catalysis according to claim 13 is characterized in that external electron donor is 9, two (methoxymethyl) fluorenes of 9-.
19. olefin polymerization catalysis according to claim 13 is characterized in that with titanium: aluminium: the molar ratio computing of external electron donor compound, the consumption between each component are 1: 5-1000: 0-500.
20. olefin polymerization catalysis according to claim 19 is characterized in that with titanium: aluminium: the molar ratio computing of external electron donor compound, the consumption between each component are 1: 25-100: 25-300.
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| US20040014597A1 (en) * | 2001-06-13 | 2004-01-22 | Giampiero Morini | Components and catalysts for the (co) polymerization of olefins |
| CN1506380A (en) * | 2002-12-11 | 2004-06-23 | 北京燕化高新技术股份有限公司 | Efficient loaded catalyst for polymerization of propylene and its prepn process |
| US6818583B1 (en) * | 1999-04-15 | 2004-11-16 | Basell Poliolefine Italia S.P.A. | Components and catalysts for the polymerization of olefins |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst |
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| US6818583B1 (en) * | 1999-04-15 | 2004-11-16 | Basell Poliolefine Italia S.P.A. | Components and catalysts for the polymerization of olefins |
| US20040014597A1 (en) * | 2001-06-13 | 2004-01-22 | Giampiero Morini | Components and catalysts for the (co) polymerization of olefins |
| CN1506380A (en) * | 2002-12-11 | 2004-06-23 | 北京燕化高新技术股份有限公司 | Efficient loaded catalyst for polymerization of propylene and its prepn process |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst |
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