KR950704372A - PROCESS FOR POLYMERIZING ALPHA-OLEFIN - Google Patents

Abstract

A method of polymerizing C ₂₀ or less of at least one α-olephine consisting of contacting at least one α-olefin under polymerization conditions having a catalyst system consisting of: (a) Magnesium compounds of the general formula MgR'R "in the presence of a polycarboxylic acid ester electron donor with or without halo hydrocarbons, wherein R 'and R" are each independently an alkoxide group, an aryloxide group or a halogen; Titanium halide-containing, magnesium-containing procatalyst component obtained by contacting a tetravalent titanium halide compound with (b) an organoaluminum promoter component, and (c) general formula (i) where R ¹ is C ₁₃ -C ₃₀ alkyl group, C ₁₆ -C ₃₆ alkylyl group, or C ₁₆ -C ₃₆ aralkyl group, R ² and R ³ are each independently methyl or C ₁₃ -C ₃₀ alkyl group or C ₁ -C ₆ hydrocarbyloxy group; R ⁴ is a C ₁ -C ₆ hydrocarbyloxy group), the method yields a high catalyst yield, retains low oligomer content properties, and produces polymer products having a broad molecular weight distribution.

Description

PROCESS FOR POLYMERIZING ALPHA-OLEFIN

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Claims (18)

A method of polymerizing C ₂₀ or less at least one sil-olefin consisting of contacting at least one α-olefin under neutral conditions having a catalyst system consisting of: (a) a magnesium compound of the general formula MgR'R ", wherein R ′ and R ″ are halogenated magnesium-containing procatalyst components obtained by halogenating a C ₁ -C ₁₀ alkoxide group) with a halogenated tetravalent titanium compound; (b) organoaluminum promoter components; And (c) a general formula Wherein R ¹ is a C ₁₃ -C ₃₀ alkyl group, a C ₁₆ -C ₃₆ alkylyl group, or a C ₁₆ -C ₃₆ aralkyl group; R ² and R ³ are each independently methyl or a C ₁₃ -C ₃₀ alkyl group or C ₁ -C ₆ hydrocarbyloxy group; R ⁴ is a C ₁ -C ₆ hydrocarbyloxy group. The method of claim 1, wherein the organosilane selectivity modifier is present in an amount such that the molar ratio of selectivity modifier to titanium present in the procatalyst component is about 0.5 to about 80. 3. The compound of claim 2, wherein R ¹ is a C ₁₆ -C ₃₀ alkyl group, a C ₁₉ -C ₃₀ alkaryl group, or a C ₁₉ -C ₃₀ aralkyl group; R ² and R ³ are individually methyl or a C ₁₆ -C ₃₀ alkyl group or a C ₁ -C ₄ alkoxy group, and R ⁴ is a C ₁ -C ₄ alkoxy group. The organosilane selectivity modifier according to claim 3, wherein the organosilane selectivity modifier is n-octadecyltriethoxysilane, n-octadecyltrimethoxysilane, n-triacyltrimethoxysilane, n-triacyltriethoxysilane, methyl-n Octadecyldimethoxysilane, methyl-n-octadecyldiethoxysilane or mixtures thereof. The method of claim 4, wherein the organosilane is n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, methyl-n-octadecyldiethoxysilane, or methyl-n-octadecyldimethoxysilane. The method of claim 5, wherein the tetravalent titanium halide compound is titanium tetrachloride. The method of claim 6, wherein the magnesium compound is magnesium ethoxide. 8. The method of claim 7, wherein the polycarboxylic ester electron donor is diisobutyl phthalate. The method of claim 8, wherein the α-olefins are propylene and ethylene. The method of claim 9, wherein the α-olefin is propylene. A method of polymerizing C ₂₀ or less of at least one α-olefin consisting of contacting at least one α-olefin under polymerization conditions with a catalyst system; (a) Halogenated tetravalent magnesium compounds of the general formula MgR'R ", with or without halohydrocarbons, wherein R 'and R" are each independently an alkoxide group or an aryloxide group. Magnesium halide-containing procatalyst obtained by halogenation with a titanium compound, (b) organoaluminum cocatalyst, and (c) organosilane selectivity modifier, wherein the organosilane selectivity modifier is Wherein R ¹ is a C ₁₃ -C ₃₀ alkyl group, a C ₁₆ -C ₃₆ alkaryl group, or a C ₁₆ -C ₃₆ aralkyl group; R ² and R ³ are individually a methyl and a C ₁₃ -C ₃₀ alkyl group or C ₁ -C ₆ hydrocarbyloxy group; R ⁴ is a C ₁ -C ₆ hydrocarbyloxy group. The compound of claim 11, wherein R ¹ is a C ₁₆ -C ₃₀ alkyl group, a C ₁₉ -C ₃₀ alkaryl group, or a C ₁₉ -C ₃₀ aralkyl group; R ² and R ³ are individually methyl or a C ₁₆ -C ₃₀ alkyl group or a C ₁ -C ₄ alkoxy group, and R ⁴ is a C ₁ -C ₄ alkoxy group. 13. The process of claim 12, wherein R ³ and R ⁴ are C ₁ -C ₂ alkoxy groups, The organosilane selectivity modulator according to claim 13, wherein the organosilane selectivity modifier is n-octadecyltriethoxysilane, n-octadecyltriethoxysilane, n-triacyltrimethoxysilane, n-triacyltriethoxysilane, methyl-n Octadecyldimethoxysilane, methyl-n-octadecyldiethoxysilane or mixtures thereof. An olefin polymerization catalyst system composed of: (a) a magnesium halide containing procatalyst component obtained by halogenating a magnesium compound with a halogenated tetravalent titanium compound in the presence of a polycarboxylic acid ester compound, with or without halogenated hydrocarbons, (b) an organoaluminum promoter catalyst, and (c) General formula Wherein R ¹ is a C ₁₃ -C ₃₀ alkyl group, a C ₁₆ -C ₃₆ alkaryl group, or a C ₁₆ -C ₃₆ aralkyl group; R ² and R ³ are individually a methyl and a C ₁₃ -C ₃₀ alkyl group or C ₁ -C ₆ hydrocarbyloxy group; R ⁴ is a C ₁ -C ₆ hydrocarbyloxy group. 16. The olefin polymerization catalyst system of claim 15, wherein the molar ratio of selectivity regulator to titanium present in the procatalyst component is about 0.5 to about 80. 17. The olefin polymerization catalyst system of claim 16, wherein the magnesium compound is magnesium alkoxide, the halogenated tetravalent titanium compound contains four or more halogen atoms and the organoaluminum promoter is a trialkylaluminum compound. 18. The olefin polymerization catalyst system of claim 17, wherein the magnesium compound is magnesium diethoxide, the polycarboxylic acid ester compound is diisobutyl phthalate, and the halohydrocarbon is chlorobenzene or 0-chlorotoluene. ※ Note: The disclosure is based on the initial application.