TH43992B - Catalyst system for (co) polymerization of olefins - Google Patents

Abstract

DC60 (15/01/44) This invention relates to a catalytic system for the (co)polymerization of propylene composed of the following components: (A) a solid catalytic component consisting of titanium, magnesium, halogen, and 1,3-diether; (B) an organic aluminum compound; and, alternatively, (C) an organic silicon compound. Compared to previous scientific advances, the stereospecificity of the polymer prepared using the catalytic system of this invention is greater than 99%, even without an external electron donor, and the activity of the catalytic system and the adjustability of hydrogen gas per molecular weight of the polymer are not significantly reduced. This invention relates to a catalytic system. For the co-polymerization of propylene with the following components: (A) a solid-state catalyst composed of titanium, magnesium, halogen, and 1,3-diether; (B) an organic aluminum compound; and, alternatively, (C) an organic silicon compound, in comparison to previous methods, the stereospecificity of the polymers prepared using the catalytic system of this invention is higher than 99% even without an external electron donor, and the activity of the catalytic system and the adjustability of hydrogen gas per molecular weight of the polymer are not significantly reduced.

Claims (13)

1. The catalytic system for the copolymerization of olefins consists of the following components: (A) a solid catalyst component consisting of titanium, magnesium, halogen, and 1,3-diether, prepared by dissolving magnesium halide in a solvent system containing organic epoxy compounds, organic phosphorus compounds, and, optionally, an inert diluent to form a homogeneous solution: mixing the homogeneous solution with titanium tetrahalide or its derivatives to form a mixture; precipitation of the solid from the mixture in the presence of at least one precipitating agent; treatment of the solid with 1,3-diether to deposit diether onto the solid, where the solid treatment step may be omitted when the precipitating agent contains 1,3-diether; and treatment of the diether deposited onto the solid with titanium tetrahalide or its derivatives and an inert diluent. (B) organic aluminum compounds; And, as an alternative, (C) organosilicone compounds. 2. The catalytic system described in Patent 1 exhibits the characteristic that the precipitating agent is selectively chosen from organic anhydrides, acid anhydrides, ethers, aldehydes, and ketones. 3. The catalytic system according to Patent 1 exhibits the characteristic that the precipitating agent is selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromelitic dianehydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, di-ethyl ether, dipropyl ether, dibutyl ether, diamyl, 1,3-diether, and a mixture of any one of these. 4. The catalytic system under claim 1 exhibits the characteristic that the aforementioned 1,3-diether is selected from... Compounds of the general formula: (chemical formula) where each R independently is hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkyl and C7-C20 straight-chain or branched-chain aralkyl, with the condition that all R cannot be hydrogen or CH3; each R1 independently is hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkyl and C7-C20 straight-chain or branched-chain aralkyl; each R2 independently is hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkyl and C7-C20 straight-chain or branched-chain aralkyl. C7-C20 straight-chain or branched R alkyl radicals, both R and R can be crosslinked to form saturated or unsaturated condensed cyclic structures, alternatively replaced by radicals selected from halogenated groups, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl and C7-C20 straight-chain or branched R alkyl radicals; and based on the molar of magnesium halide, the amount of 1,3-diether ranges from 0.04 to 1 mol. 5. The catalytic system according to claim 1 exhibits the characteristic that the aforementioned 1,3-diotheres are selected from compounds of the general formula: (chemical formula) where each R is independently hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl, and C7-C20 straight-chain or branched-chain R1; and each R1 is independently hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl, and C7-C20 straight-chain or branched-chain R1; Each R2 radical is independent of the following: hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl, and C7-C20 straight-chain or branched R2 alkyl groups; two or more R2 radicals can be linked together to form saturated or unsaturated condensed cyclic structures, alternatively replaced by radicals selected from groups containing halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl, and C7-C20 straight-chain or branched R2 alkyl groups. 6. The catalytic system under claim 1 exhibits the characteristic that the aforementioned 1,3-diotherm is selected from. Compounds of the general formula: (chemical formula) where each R independently is hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl and C7-C20 straight-chain or branched-chain aralkyl; each R1 independently is hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl and C7-C20 straight-chain or branched-chain aralkyl; each R2 independently is hydrogen, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl and C7-C20 straight-chain or branched-chain aralkyl; both R's Or, more than one can be linked together to form saturated or unsaturated cyclic condensed structures, alternatively replaced by radicals selected from halogenated groups, C1-C20 alkyls, C3-C20 cycloalkyls, C6-C20 aryls, C7-C20 alkaryls, and C7-C20 aralkyl straight-chain or branched chains. 7. The catalytic system under claim 1 exhibits the characteristic that the aforementioned 1,3-diether is selected from groups consisting of: 2-(2-ethylhexyl)-1,3-dimethoxypropane; 2-isopropyl-1,3-dimethoxypropane; 2-butyl-1,3-dimethoxypropane; 2-sec-butyl-1,3-dimethoxypropane; 2-cyclohexyl-1,3-dimethoxypropane; 2-phenyl-1,3-dimethoxypropane; 2-cumyl-1,3-dimethoxypropane; 2-(2-phenyl ethyl)-1,3-dimethoxypropane; 2-(2-cyclohexyl ethyl)-1,3-dimethoxypropane; 2-(para-chlorophenyl)-1,3-dimethoxypropane; 2-(diphenylmethyl)-1,3-dimethoxypropane; 2-(1-naptyl)-1,3-dimethoxypropane; 2-(2-fluorophenyl)-1,3-dimethoxypropane; 2-(1-decahedronaphthalinyl)-1,3-dimethoxypropane; 2-(para-tert-butylphenyl)-1,3-dimethoxypropane; 2,2-dicyclohexyl-1,3-dimethoxypropane; 2,2-dicyclopentyl-1,3-dimethoxypropane; 2,2-diethyl-1,3-dimethoxypropane; 2,2-dipropyl-1,3-dimethoxypropane; 2,2-diisopropyl-1,3-dimethoxypropane; 2,2-dibutyl-1,3-dimethoxypropane; 2-methyl-2-propyl-1,3-dimethoxypropane; 2-methyl-2-benzyl-1,3-dimethoxypropane; 2-methyl-2-ethyl-1,3-dimethoxypropane; 2-methyl-2-isopropyl-1,3-dimethoxypropane; 2-methyl-2-phenyl-1,3-dimethoxypropane; 2-methyl-2-cyclohexyl-1,3-dimethoxypropane; 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane; 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane; 2-methyl-2-isobutyl-1,3-dimethoxypropane; 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane; 2,2-diisobutyl-1,3-dimethoxypropane; 2,2-diphenyl-1,3-dimethoxypropane; 2,2-dibenzyl-1,3-dimethoxypropane; 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane; 2-Isobutyl-2-Isopropyl-1,3-Dimethoxypropane; 2,(1-Methyl butyl)-2-Isopropyl-1,3-Dimethoxypropane; 2,(1-Methyl butyl)-2-Sec-Butyl-1,3-Dimethoxypropane; 2,2-Di-Sec-Butyl-1,3-Dimethoxypropane; 2,2-Di-Tert-Butyl-1,3-Dimethoxypropane; 2,2-Di-Neopentyl-1,3-Dimethoxypropane; 2-Isopropyl-2-Isopentyl-1,3-Dimethoxypropane; 2-Phenyl-2-Isopentyl-1,3-Dimethoxypropane; 2-phenyl-2-sec-butyl-1,3-dimethoxypropane; 2-benzyl-2-isopentyl-1,3-dimethoxypropane; 2-benzyl-2-sec-butyl-1,3-dimethoxypropane; 2-phenyl-2-benzyl-1,3-dimethoxypropane; 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane; 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane; 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane; 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane; 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane; 2-cyclohexyl-2-cyclohexyl-1,3-dimethoxypropane; 1,1-bis(methoxymethyl)-cyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-bis(methoxymethyl)-3,4,-dicyclopentylcyclopentadiene; 1,1-bis(methoxymethyl)-indine; 1,1-bis(methoxymethyl)-2,3-dimethylidine; 1,1-bis(methoxymethyl)-4,5-6,7-tetrahydroindine; 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindine; 1,1-bis(methoxymethyl)-4,7-dimethylidine; 1,1-bis(methoxymethyl)-3,6-dimethylidine; 1,1-bis(methoxymethyl)-4-phenylidine; 1,1-bis(methoxymethyl)-4-phenyl-2-methylidine; 1,1-bis(methoxymethyl)-4-cyclohexilidine; 1,1-bis(methoxymethyl)-7-(3,3,3,3-trifluoropropyl)indine; 1,1-bis(methoxymethyl)-7-trimethylxylindine; 1,1-bis(methoxymethyl)-7-trifluoromethilidine; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindine; 1,1-bis(methoxymethyl)-7-methylindine; 1,1-bis(methoxymethyl)-7-cyclopentylindine; 1,1-bis(methoxymethyl)-7-isopropylindine; 1,1-bis(methoxymethyl)-7-cyclohexylindine; 1,1-bis(methoxymethyl)-7-tert-butylindine; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindine; 1,1-bis(methoxymethyl)-7-phenylindine; 1,1-bis(methoxymethyl)-2-phenylindine; 9,9-bis(methoxymethyl)-fluorine; 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorine; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorine; 9,9-bis(methoxymethyl)-2,3-benzofluorine; 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorine; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorine; 9,9-bis(methoxymethyl)-1,8-dichlorofluorine; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorine; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorine; 9,9-bis(methoxymethyl)-1,8-difluorofluorine; 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorine; 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorine; 9,9-bis(methoxymethyl)-4-ter-butylfluorine; 1,1-bis(1'-butoxyethyl)-cyclopentadiene; 1,1-bis(1'-isopropoxy-(eta)-propyl)-cyclopentadiene; 1-methoxymethyl-1-(1'-methoxyethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(alpha-methoxybenzyl)-indine; 1,1-bis(phenoxymethyl)indine; 1,1-bis(1'-methoxyethyl)-5,6-dichloroindine; 1,1-bis(phenoxymethyl)-3,6-dicyclohexilidine; 1-methoxymethyl-1-(1'-methoxyethylene)-7-tert-butylidine; 1,1-bis[2-(2'-methoxypropyl)]-2-methylidine; 9,9-bis(alpha-methoxybenzyl)fluorine; 9,9-bis(1' isopropoxy-eta-butyl-4,5-diphenylfluorine; 9,9-bis(1'-methoxyethylene)fluorine; 9-(methoxymethyl)-9-(1'-methoxyethyl)-2,3,6,7-tetrafluorofluorine; 9-methoxymethyl-9-pentoxymethylfluorine; 9-methoxymethyl-9-ethoxymethylfluorine; 9-methoxymethyl-9-(1'-methoxypropyl)-fluorine; 9-methoxymethyl-9-[2-(2'-methoxypropyl)]-fluorine; 1,1-bis(methoxymethyl)-2,5-cyclohexadiene; 1,1-bis(methoxymethyl)benzonaphthene; 7,7-bis(methoxymethyl)-2,5-norbornene; 9,9-bis(methoxymethyl)-1,4-methane-dihydronaphthalene; 9,9-bis(methoxymethyl)-9,10-dihydroanthrazine; 1,1-bis(methoxymethyl)-1,2-dihydronaphthalene; 4,4-bis(methoxymethyl)-1-phenyl-3,4-dihydronaphthalene; 4,4-bis(methoxymethyl)-1-phenyl-1,4-dihydronaphthalene; 5,5-bis(methoxymethyl)-1,3,6-cyclohepatatrine 8. The catalytic system according to claim 1 is characterized as follows: Component (B) is an organic aluminum compound with the formula AIRnX3-n, where each R independently is a hydrogen, or a hydrocarbon group with 1-20 carbon atoms, X is a halogen, and n is a number ranging from 1 to 3. 9. The catalytic system according to claim 1 is characterized as follows: Component (B) is trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tri-isobutyl aluminum and trioctyl aluminum; hydrogenated alkyl aluminum such as diethyl aluminum hydride and di-isobutyl aluminum hydride; halogenated alkyl aluminum such as diethyl aluminum chloride, di-isobutyl aluminum chloride, sesquiethyl aluminum sesquichloride, ethyl aluminum dichloride and a mixture of these substances. 10. The catalytic system according to claim 1 is characterized as follows: Component (B) is triethyl aluminum and tri-isobutyl aluminum. 11. The catalytic system according to claim 1 is characterized as follows: Component (C) is an organo-silicon compound with the formula RnSi(OR')4-n, where R and R' are independently alkyl, cycloalkyl, aryl, or haloalkyl groups, and n is an integer ranging from 0 to 3. 12. The catalytic system according to claim 1 is characterized as follows: Component (C) is: Trimethyl methoxysilane, Trimethyl ethoxysilane, Methyl cyclohexyl dimethoxysilane, Dibutyl dimethoxysilane, Dimethyl dimethoxysilane, Dimethyl diethoxysilane, Diphenyl dimethoxysilane, Diphenyl diethoxysilane, Phenyl triethoxysilane, Phenyl trimethoxysilane, and a mixture of these substances. 13. The catalytic system under claim 1 exhibits the characteristic that component (C) may be replaced by 1,3-diether.