Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene

Definitions

• the present invention is in the field of olefin polymerization catalysts and olefin polymerization, and particularly relates to a catalyst for ethylene polymerization or ethylene copolymerization, a method for preparing a catalyst, and a catalyst.
• Olefin polymerization catalysts are the core of polyolefin polymerization technology. From the development of olefin polymerization catalysts, there are two main aspects: (1) Development of polyolefin resin catalysts capable of preparing special properties or properties, such as metallocene catalysts. And non-post-expansion transition metal catalysts; (2) For the production of general-purpose polyolefin resins, on the basis of further improving the performance of the catalyst, simplifying the catalyst preparation process, reducing the catalyst cost, and developing environmentally friendly technologies to improve the efficiency , Increase competitiveness. Before the 1980s, the focus of research on polyethylene catalysts was to pursue catalyst efficiency. After nearly 30 years of efforts, the catalytic efficiency of polyethylene catalysts has been improved, which has simplified the production process of polyolefins and reduced energy consumption and material consumption.
• Patent CN201010186264.2 and CN200910092169.3 disclose that the main components of the supported catalyst are a carrier, a titanium halide and an electron donor, and the titanium halide is directly added to the catalyst component.
• Patent CN201010231403. 9 discloses that a broad distribution of polyolefin can be prepared by adding organosilicon oxime during the preparation of the catalyst.
• the patent discloses that in the preparation of the catalyst, the titanate reacts with the silicon halide in situ to form a titanium halide, and then is supported on a carrier to prepare a main catalyst, and then the catalyst system is combined with the cocatalyst to efficiently catalyze ethylene polymerization or ethylene copolymerization.
• a siloxane electron donor is added to the catalyst component, and the molecular weight distribution of the polyolefin is broadened.
• the main catalyst particles prepared by the invention have good morphology, high loading and high activity, and the catalyst does not fall off from the carrier, and is suitable for a slurry polymerization process, a gas phase polymerization process or a combined polymerization process.
• An object of the present invention is to provide a catalyst for ethylene polymerization or copolymerization of ethylene and a comonomer having high catalytic activity and a process for producing the same.
• the ethylene copolymerization catalyst provided by the present invention is composed of a main catalyst and a cocatalyst; wherein the main catalyst is composed of a carrier, a transition metal halide, an organic alcohol compound and a siloxane electron donor, a carrier, a transition metal halide
• the molar ratio of the organic alcohol compound to the siloxane electron donor is 1: 1-30: 0. 5-30: 0. 01-5; the transition metal halide is formed by in situ reaction of titanate with silicon halide.
• the molar ratio of the carrier to the titanate, the silicon halide is 1: 1-30: 1-40, and the molar ratio of the titanate to the silicon halide is 1: 0.5-2: the cocatalyst is an organoaluminum compound;
• the relationship between the amount of the main catalyst and the cocatalyst is as follows: transition metal halide in the main catalyst and cocatalyst
• the molar ratio of the agent is 1: 30-500.
• the carrier refers to a halide carrier, an inorganic oxide carrier or a polymer carrier;
• the halide carrier is a magnesium dihalide, a water or an alcohol complex of a magnesium dihalide, or a derivative in which one or two halogen atoms of the magnesium dihalide molecular form are replaced by a hydroxyl group or a halohydroxyoxy group.
• the inorganic oxide carrier is selected from the group consisting of At least one of silica, alumina
• the polymeric carrier is selected from the group consisting of polystyrene.
• magnesium dichloride, dibutyl magnesium, and chlorobutyl magnesium are preferred.
• titanate is added during the preparation of the procatalyst, said titanate being selected from the formula
• (1) is at least one of Ti(OR) 4 compounds, wherein R is selected from an aliphatic hydrocarbon group, a C 6 - C 20 cyclopentadienyl group and a derivative thereof, and C 6 - C 2 ()
• the aromatic hydrocarbon group, COR' or COOR', R' is an aliphatic group or an aromatic group having C 6 - C 1Q .
• R may be specifically selected from the group consisting of: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, isobutyl, tert-butyl, isopentyl, tert-amyl , 2-ethylhexyl, phenyl, naphthyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-sulfonylphenyl, formyl, acetyl or benzoyl At least one of an acyl group and the like. Titanium tetrabutoxide is preferred.
• the molar ratio of titanate to carrier is preferably from 1 to 30:1.
• One of the features of the present invention is the addition of a silicon halide during the preparation of the main catalyst, said silicon halide being selected from the group consisting of
• R′ may be specifically selected from the group consisting of: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl , octyl, decyl, decyl, isobutyl, tert-butyl, isopentyl, tert-amyl, 2-ethylhexyl, phenyl, naphthyl, o-methylphenyl, m-methylbenzene At least one of a group, p-methylphenyl, o-sulfonylphenyl, formy
• the molar ratio of the silicon halide to the carrier is preferably from 1 to 40:1.
• One of the features of the present invention is the addition of an organic alcohol during the preparation of the main catalyst, the organic alcohol being selected from the formula
• R 3 is at least one of the compounds of R 3 OH, wherein R 3 is ⁇ .
• An aliphatic hydrocarbon group, a C 6 -C 2 o cyclopentadienyl group and a derivative thereof or a C 6 -C 2 o aromatic hydrocarbon group, and R 3 may be specifically selected from the group consisting of: methyl, ethyl, propyl, butyl , pentyl, hexyl, heptyl, octyl, decyl, decyl, isobutyl, tert-butyl, isopentyl, tert-amyl, At least one of 2-ethylhexyl, benzyl, and the like. Particular preference is given to ethanol, octanol, isooctanol, isopropanol, hexanol, pentanol and the like.
• the molar ratio of organic alcohol to carrier is preferably from 3 to 15:1.
• One of the features of the present invention is the addition of a silicon oxime electron donor during the preparation of the main catalyst, which is in accordance with the general formula (4):
• R 2 , R 3 , and R 4 are (indenyl group of s, cycloalkyl group of C 3 -C 2 , or aryl group of 6 - C 30.
• R 2 , R 3 , R4 And R 5 may be three identical or two identical or four different.
• the siloxane electron donor may be specifically selected from the group consisting of: triethoxyisopropoxysilane, diethoxyisopropoxy tert-butyl Silicon oxysilane, triisopropoxy tert-butoxysilane, diisopropoxy di-tert-butoxysilane, diethoxycyclohexyloxy-tert-butoxysilane, diethoxyphenoxy Mixing of one or more of tert-butoxysilane, monoethoxydiisopropoxy-tert-butoxysilane or ethoxyisopropoxy-tert-butoxycyclohexyloxysilane.
• the molar ratio of the organosiloxane compound to the carrier is preferably 0. 01-5: 1.
• the cocatalyst organoaluminum compound is selected from one or a mixture of two compounds of the formula A1R 5 J 3 _, wherein R 5 is hydrogen or a hydrocarbon group or alkoxy group having from 1 to 20 carbon atoms.
• X is a halogen
• n is an integer of 0 ⁇ n ⁇ 3, specifically selected from the group consisting of: trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-tert-butyl a mixture of one or both of aluminum, trioctyl aluminum, diethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, etc.; methylaluminoxane, ethylaluminoxane Among them, a mixture of one or two of triethyl aluminum or triisobutyl aluminum or methyl aluminoxane is preferred.
• the relationship between the amount of the main catalyst and the cocatalyst is as follows:
• the molar ratio of the transition metal halide to the cocatalyst is from 1:30 to 500.
• the preparation method of the olefin polymerization catalyst provided by the invention comprises the following steps -
• step 3 Add silicon halide to the solution obtained in step 2) at 10-150 ° C, add dropwise, and stir for 1-5 hours. The reaction was stopped, the precipitate was allowed to stand, filtered, washed, and dried.
• step 4) Disperse the product obtained in step 3) in an organic solvent, and add an excess of TiCl 4 at a temperature of -10 ° C to 30 ° C for 1 hour at a temperature of -10 ° C to 30 ° C. The temperature was slowly raised to 60 ° C - 100 ° C for 2-5 hours. After the reaction was completed, the mixture was washed 4 to 6 times with toluene or n-hexane, filtered, and the unreacted product and solvent were removed, and vacuum-dried to obtain a main catalyst.
• 30-500: 1 is mixed to obtain an olefin polymerization catalyst.
• the organic solvent is selected from the group consisting of toluene, xylene, hexane, heptane, octane or decane, or a mixed solvent thereof, preferably toluene, hexanyl, heptane or decane.
• the use of the ethylene polymerization catalyst provided by the present invention is as follows: It can be used as a polymerization catalyst for ethylene or a copolymerization of ethylene and an ⁇ -olefin, wherein the ⁇ -olefin is preferably propylene, 1-butene, 1-hexene, 1- Octene, 1-decene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methyl Styrene and the like.
• the ⁇ -olefin is preferably propylene, 1-butene, 1-hexene, 1- Octene, 1-decene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methyl Styrene and the like.
• the object of the invention is to provide the ethylene copolymerization catalyst with good particle shape and spherical shape; high catalyst activity, wide polyethylene molecular weight distribution obtained by polymerization; suitable for slurry method, gas phase polymerization process or combined polymerization process; Low requirements on equipment and low environmental pollution.
• the obtained solid particles were dispersed in 30 ml of toluene, 20 ml of TiCl 4 was added dropwise at 0 ° C, and maintained at 0 to 10 ° C for 1 h, and reacted at 60 ° C for 3 h. Stirring was stopped, the suspension was allowed to stand, the layers were separated, the supernatant was removed, and the toluene was washed twice, washed twice with nitrogen, and dried by nitrogen to obtain a main catalyst having good fluidity and narrow particle size distribution.
• the obtained solid particles were dispersed in 40 ml of toluene, and 25 ml of TiCl 4 was added dropwise at -5 ° C, and maintained at 0 to 10 ° C for 2 hours, and reacted at 70 ° C for 4 hours. Stirring was stopped, the suspension was allowed to stand, the layers were separated, the supernatant was removed, and the toluene was washed twice, washed twice with nitrogen, and dried by nitrogen to obtain a main catalyst having good fluidity and narrow particle size distribution.
• the obtained solid particles were dispersed in 50 ml of toluene, and 30 ml of TiCl 4 was added dropwise at 0 ° C, and then maintained at 0 to 10 Torr for 1 hour, and reacted at 65 ° C for 3 hours.
• the stirring was stopped, the suspension was allowed to stand, the layers were separated, the supernatant was removed, the toluene was washed twice, and the hexane was washed twice, and dried with nitrogen to obtain a main catalyst having good fluidity and narrow particle size distribution.
• the obtained solid particles were dispersed in 30 ml of toluene, and 20 ml of TiCl 4 was added dropwise at 0 ° C, and then maintained at 0 to 10 ° C for 1 h at 60 ° C for 3 h. The stirring was stopped, the suspension was allowed to stand, the layers were separated, the supernatant was removed, the toluene was washed twice, and the hexane was washed twice, and dried with nitrogen to obtain a main catalyst having good fluidity and narrow particle size distribution.
• the obtained solid particles were dispersed in 30 ml of toluene, 20 ml of TiCl 4 was added dropwise at 0 ° C, and maintained at 0 to 10 ° C for 1 h, and reacted at 60 ° C for 3 h. Stirring was stopped, the suspension was allowed to stand, the layers were separated, the supernatant was removed, and the toluene was washed twice, washed twice with nitrogen, and dried by nitrogen to obtain a main catalyst having good fluidity and narrow particle size distribution.
• the obtained solid particles were dispersed in 30 ml of toluene, 0 ° C ij n 20 ml of TiCl 4 , and maintained at 0-10 ° C for 1 h, 60 ⁇ for 3 h. Stirring was stopped, the suspension was allowed to stand, the layers were separated, the supernatant was removed, and the toluene was washed twice, washed twice with nitrogen, and dried by nitrogen to obtain a main catalyst having good fluidity and narrow particle size distribution.
• the mixture is heated at -10 °C for 1 h, at 0 °C for 1 h, at 20 °C for 1 h, and at a constant temperature of 60 °C, 10 ml of hexane is added dropwise, and the temperature is reacted for 2 h.
• the stirring was stopped, the suspension was allowed to stand, the layer was separated, the supernatant liquid was removed, the toluene was washed twice, the hexane was washed twice, and the nitrogen was blown dry to obtain a main catalyst component having good fluidity and narrow particle size distribution;
• the ethylene copolymerization catalyst provided by the invention has good particle shape and spherical shape; high catalyst activity, wide molecular weight distribution of polyethylene obtained by polymerization; suitable for slurry method, gas phase polymerization process or combined polymerization process; simple preparation method and equipment requirements Low, less environmental pollution.

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