CN114524890B - Method for preparing catalyst by using hydration reagent - Google Patents

Method for preparing catalyst by using hydration reagent Download PDF

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CN114524890B
CN114524890B CN202210166466.3A CN202210166466A CN114524890B CN 114524890 B CN114524890 B CN 114524890B CN 202210166466 A CN202210166466 A CN 202210166466A CN 114524890 B CN114524890 B CN 114524890B
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acid
containing compound
titanium
mixture
acidic
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CN114524890A (en
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M·P·麦克丹尼尔
K·S·克莱尔
J·M·普雷托里亚斯
E·D·施韦特费格尔
M·D·雷夫维克
M·L·哈维卡
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Chevron Phillips Chemical Co LLC
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Chevron Phillips Chemical Co LLC
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    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/22—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of chromium, molybdenum or tungsten
    • C08F4/24—Oxides
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a method for preparing a catalyst by using a hydration reagent. A method comprising a) contacting a solvent, a carboxylic acid, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.

Description

Method for preparing catalyst by using hydration reagent
The present application is a divisional application, the application date of the original application is 2021, 1, 26, 202180004668.1, and the name of the invention is "method for preparing a catalyst by using a hydration reagent".
Technical Field
The present disclosure relates to catalyst compositions. More specifically, the present disclosure relates to methods of preparing olefin polymerization catalyst compositions and polymers prepared from the olefin polymerization catalyst compositions.
Background
One class of olefin polymerization catalysts of economic importance includes chromium-silica-titanium (Cr/Si-Ti) catalysts prepared from silica-based catalyst supports. The rigorous drying of the water-sensitive catalyst components used to produce Cr/Si-Ti catalysts increases production time and cost. The development of aqueous solutions suitable for depositing titanium onto silica-based catalyst supports will reduce the production costs of olefin polymerization catalysts. Thus, there is a continuing need to develop new methods of producing olefin polymerization catalysts.
Disclosure of Invention
Disclosed herein is a procatalyst composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support, b) a chromium containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica, c) a titanium containing compound, wherein the amount of titanium is in the range of about 0.1wt% to about 20wt%, based on the amount of silica, d) a carboxylic acid, wherein the equivalent molar ratio of titanium containing compound to carboxylic acid is in the range of about 1:1 to about 1:10, and e) a nitrogen containing compound having the formula containing at least one nitrogen atom, wherein the equivalent molar ratio of titanium containing compound to nitrogen containing compound is in the range of about 1:0.5 to about 1:10.
Also disclosed herein is a procatalyst composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt% based on the total weight of the silica support, b) a chromium containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt% based on the amount of silica, and c) a titanium organic salt, wherein the titanium organic salt comprises titanium, a protonated nitrogen-containing compound, and carboxylate, and wherein i) the amount of titanium is in the range of about 0.1wt% to about 20wt% based on the amount of silica, ii) the equivalent molar ratio of titanium to carboxylate is in the range of about 1:1 to about 1:10, and iii) the equivalent molar ratio of titanium to protonated nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.
Also disclosed herein is a procatalyst composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt% based on the total weight of the silica support, b) a chromium containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt% based on the amount of silica, c) a titanium containing compound, wherein the amount of titanium is in the range of about 0.01wt% to about 0.1wt% based on the amount of silica, d) a carboxylic acid, wherein the equivalent molar ratio of titanium containing compound to carboxylic acid is in the range of about 1:1 to about 1:10, and e) a nitrogen containing compound having the formula containing at least one nitrogen atom, wherein the equivalent molar ratio of titanium containing compound to nitrogen containing compound is in the range of about 1:0.5 to about 1:10.
Also disclosed herein is a procatalyst composition prepared by a process comprising: a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting a titanium-containing compound and the acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting a nitrogen-containing compound and the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5.5, and d) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and forming the addition product by heating the addition product to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the addition product at the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about the catalyst to about 6 minutes.
Also disclosed herein is a process comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting a titanium-containing compound and the acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting a nitrogen-containing compound and the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5.5, and d) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and forming the addition product by heating the addition product to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the addition product at the temperature in the range of from about 150 ℃ to about 150 ℃ for a period of from about 30 minutes to about the catalyst to about 150 minutes.
Also disclosed herein is a method comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting a titanium-containing compound and the acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting a nitrogen-containing compound and the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4.5, d) contacting a silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form a titanated support, and drying the titanium-containing support at least one catalyst selected from the group consisting of forming the titanated support by heating the titanated support to a temperature in the range of from about 50 ℃ to about 150 ℃ and drying the titanated support at least about 150 minutes at a temperature in the range of about 150 ℃ to about the titanium support.
Also disclosed herein is a process comprising a) contacting a titanium-containing compound and a nitrogen-containing compound to form a basic mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the basic mixture is from about 1:1 to about 1:4, b) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, c) contacting the basic mixture and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4.5, and d) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and forming the addition product by heating the addition product to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the addition product at the temperature in the range of from about 150 ℃ to about 6 minutes for a period of from about 30 minutes to about the catalyst.
Also disclosed herein is a method comprising a) contacting a titanium-containing compound and a nitrogen-containing compound to form an alkaline mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the alkaline mixture is in the range of about 1:1 to about 1:4, b) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is in the range of about 1:1 to about 100:1, c) contacting the alkaline mixture and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is in the range of about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of about 3.5 to about 4.5, d) contacting a silica support comprising about 0.1wt% to about 20wt% water with the solubilized titanium mixture to form a titanated support, and drying the titanium-containing support at least one catalyst selected from the group consisting of forming the titanated support by heating the titanated support to a temperature in the range of about 50 ℃ to about 150 ℃ and drying the titanated support at a time period of about 150 minutes and drying the titanated support at least about 150 minutes.
Also disclosed herein is a process comprising a) contacting a solvent, a carboxylic acid, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
Also disclosed herein is a process comprising a) contacting a solvent, at least two carboxylic acids, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, and wherein the at least two carboxylic acids comprise at least one simple carboxylic acid and at least one complex carboxylic acid; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
Also disclosed herein is a process comprising a) contacting a solvent, at least two carboxylic acids, and a nitrogen-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
Also disclosed herein is a process comprising a) contacting a solvent, at least two carboxylic acids, a nitrogen-containing compound, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
Also disclosed herein is a process comprising a) contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the solubilized titanium mixture is from about 1:to about 1:5; and wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
Also disclosed herein is a process comprising a) contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the solubilized titanium mixture is from about 1:to about 1:5; and wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; c) Contacting the solubilized titanium mixture with a chromium-containing compound to form a chromium-titanium mixture; d) Contacting the chromium titanium mixture with a silica support comprising silica to form an addition product, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; and e) drying the addition product by heating to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form a procatalyst.
Also disclosed herein is a method comprising a) preparing an acidic mixture comprising a solvent and at least two components selected from the group consisting of one or more carboxylic acids, one or more acidic phenols, one or more peroxy-containing compounds, and one or more nitrogen-containing compounds, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting the acidic mixture with a chromium-containing compound, a titanium-containing compound, and a silica support to form an addition product, wherein: (i) an equivalent molar ratio of titanium-containing compound to carboxylic acid when present in the acidic mixture is from about 1:1 to about 1:4, (ii) an equivalent molar ratio of titanium-containing compound to acidic phenol when present in the acidic mixture is from about 1:to about 1:5, and (iii) an equivalent molar ratio of titanium-containing compound to peroxy-containing compound when present in the acidic mixture is from about 1:1 to about 1:20; and c) drying the addition product by heating to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form a procatalyst.
Also disclosed herein is a composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.1wt% to about 20wt%, based on the amount of silica; d) A carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is in the range of about 1:1 to about 1:10; and e) a peroxy-containing compound, wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound is in the range of about 1:1 to about 1:20.
Also disclosed herein is a composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; and c) a titanium organic salt, wherein the titanium organic salt comprises titanium, carboxylate, and peroxy-containing compound, and wherein the titanium organic salt comprises i) the amount of titanium is in the range of about 0.1wt% to about 20wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to the peroxy-containing compound is in the range of about 1:0.5 to about 1:20.
Also disclosed herein is a composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.01wt% to about 0.1wt%, based on the amount of silica; d) At least two carboxylic acids, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is in the range of about 1:1 to about 1:10; and e) a peroxy-containing compound, wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound is in the range of about 1:1 to about 1:10.
Also disclosed herein is a composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium organic salt, wherein the titanium organic salt comprises titanium, a protonated nitrogen-containing compound, and a carboxylate, and wherein the titanium organic salt comprises: i) The amount of titanium ranges from about 0.1wt% to about 20wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound in the range of from about 1:0.5 to about 1:10; and d) a peroxy-containing compound, wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound is from about 1:1 to about 1:20.
Also disclosed herein is a composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; and c) a titanium organic salt, wherein the titanium organic salt comprises titanium, a protonated nitrogen-containing compound, and a carboxylate, and wherein the titanium organic salt comprises i) the amount of titanium ranges from about 0.1wt% to about 20wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound in the range of from about 1:0.5 to about 1:10; and d) an acidic phenol, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the acidic titanium mixture is from about 1:1 to about 1:5.
Also disclosed herein is a composition comprising a) at least two components selected from the group consisting of one or more carboxylic acids, one or more acidic phenols, one or more peroxy-containing compounds, and one or more nitrogen-containing compounds; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.01wt% to about 0.1wt%, based on the amount of silica; and (i) wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid when present is in the range of about 1:1 to about 1:10; (ii) Wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound when present is in the range of about 1:1 to about 1:10; (iii) Wherein the equivalent molar ratio of titanium-containing compound to acidic phenol, when present, in the acidic titanium mixture is from about 1:1 to about 1:5; and (iv) wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound when present is in the range of about 1:0.5 to about 1:5.
Drawings
The following drawings form a part of the present specification and are included to further demonstrate certain aspects of the present disclosure. The subject matter of the present disclosure may be more fully understood by reference to the accompanying drawings in combination with the detailed description of specific aspects presented herein.
The figure illustrates the relationship between zeta potential and pH of silica and titania.
While the subject matter disclosed herein is susceptible to various modifications and alternative forms, only a few specific aspects have been shown by way of example in the drawings and are described in detail below. The figures and the detailed description of these specific aspects are not intended to limit the breadth or scope of the disclosed subject matter or appended claims in any way. Rather, the figures and detailed written description are provided to explain the present disclosure to those skilled in the art and to enable those skilled in the art to make and use the concepts disclosed herein.
Detailed Description
The present disclosure encompasses olefin polymerization catalysts and procatalysts thereof, methods of preparing olefin polymerization catalysts and procatalysts thereof, and methods of utilizing olefin polymerization catalysts. In one aspect, a method of the present disclosure includes contacting a silica support or a chromium-silica support (i.e., support) with titanium to produce a Cr/Si-Ti catalyst. The methods disclosed herein contemplate the use of a Solubilized Titanium Mixture (STM) to facilitate association of titanium with a carrier in the presence of water. Herein, a method for preparing an olefin polymerization catalyst includes contacting a chromium-silica support with an STM under conditions suitable to form a catalyst composition. An alternative method for preparing an olefin polymerization catalyst includes contacting a silica support with STM and chromium under conditions suitable to form a catalyst composition. Although these aspects may be disclosed under specific headings, the headings are not limited to the disclosure found therein. In addition, the various aspects and embodiments disclosed herein may be combined in any manner.
Aspects of the present disclosure relate to catalyst compositions and procatalyst compositions. In one aspect, the catalyst composition comprises an olefin polymerization catalyst. In another aspect, an olefin polymerization catalyst comprises a treated procatalyst composition. In another aspect, the treated procatalyst composition comprises a procatalyst that has been subjected to an activation treatment (e.g., calcination) as disclosed herein.
Procatalyst compositions are disclosed herein. In one aspect, the procatalyst composition includes a silica support, a chromium containing compound, a titanium containing compound, a carboxylic acid, and a nitrogen containing compound. Alternatively, the procatalyst composition includes a silica support, a chromium containing compound and a titanium organic salt. Alternatively, the procatalyst composition comprises a silica support, a chromium containing compound, a titanium containing compound, a carboxylic acid, a nitrogen containing compound, and a peroxy containing compound. Alternatively, the procatalyst composition comprises a silica support, a chromium containing compound, a titanium containing compound, a carboxylic acid, and a peroxy containing compound. Alternatively, the procatalyst composition comprises a silica support, a chromium containing compound, a titanium containing compound, an acidic phenol, and a peroxy containing compound. In some aspects, the procatalyst composition comprises a silica support, a chromium-containing compound, a titanium-containing compound, one or more carboxylic acids, one or more nitrogen-containing compounds, one or more acidic phenols, one or more peroxy-containing compounds, or any combination thereof.
In one aspect, the olefin polymerization catalyst of the present disclosure and procatalysts thereof comprise a silica support. The silica support may be any silica support suitable for preparing the olefin polymerization catalysts and procatalysts thereof as disclosed herein. In another aspect, the preparation of olefin polymerization catalysts and their procatalysts precludes heat treatment of the silica support prior to contact with any other catalyst components. Thus, silica supports suitable for use in the present disclosure may be referred to as hydrated silica supports. Without wishing to be bound by theory, the hydrated silica support comprises a silica support, wherein water evolution occurs when the silica support is heated under vacuum in the range of about 180 ℃ to about 200 ℃ for a period of time in the range of about 8 hours to about 20 hours. In another aspect, the silica support thus treated may emit from about 0.1wt% to about 20wt% water, based on the total weight of the silica support; alternatively, about 1wt.% to about 20 wt.% water; alternatively, about 1wt% to about 10wt% water; or alternatively, from about 0.1wt% to about 10wt% water.
Silica supports suitable for use in the present disclosure may have a surface area and pore volume effective to provide for the production of active olefin polymerization catalysts. In one aspect of the disclosure, the silica support has a particle size of between about 100m 2 /g to about 1000m 2 /g; alternatively, about 250m 2 /g to about 1000m 2 /g; alternatively, about 250m 2 /g to about 700m 2 /g; alternatively, about 250m 2 /g to about 600m 2 In the range of/g; or alternatively, greater than about 250m 2 Surface area per gram. The silica support may also be characterized as having a length of greater than about 0.9cm 3 /g; alternatively, greater than about 1.0cm 3 /g; or alternatively, greater than about 1.5cm 3 Pore volume per gram. In one aspect of the disclosure, the silica support is characterized as having a particle size of about 1.0cm 3 /g to about 2.5cm 3 Pore volume in the range of/g. The silica support may also be characterized as having a particle size of between about 10 microns and about 500 microns; alternatively, about 25 microns to about 300 microns; or alternatively, an average particle size in the range of about 40 microns to about 150 microns. Typically, the average pore size of the silica support may range from about 10 angstroms (Angstrom) to about 1000 angstroms. In one aspect of the disclosure, the silica support has an average pore size of from about 50 angstroms to about 500 angstroms; alternatively, in the range of about 75 angstroms to about 350 angstroms.
Silica supports suitable for use in the present disclosure may contain greater than about 50wt% silica, based on the total weight of the silica support; alternatively, greater than about 80wt% silica; or alternatively, greater than about 95 weight percent silica. In one aspect, the silica support comprises silica in an amount ranging from about 70wt% to about 95wt% based on the total weight of the silica support. The silica support may be prepared using any suitable method, for example, by hydrolysis of tetrachlorosilane (SiCl) 4 ) Or by contacting sodium silicate with a mineral acid. In a particular aspect, the silica support may be a hydrogel or a preformed silica support, wherein the preformed silica support optionally has been dried prior to contact with any other catalyst components. Silica support mayIncluding additional components that do not adversely affect the catalyst, such as zirconia, alumina, thoria, magnesia, fluoride, sulfate, phosphate, or combinations thereof. In a particular aspect, the silica support of the present disclosure comprises alumina. Non-limiting examples of silica supports suitable for use in the present disclosure include ES70, a commercially available from PQ Corporation, having a mass of 300m 2 Surface area per gram and 1.6cm 3 Silica support material of pore volume/g; and V398400, which is a silica support material commercially available from Evonik.
In a particular aspect of the present disclosure, a silica support suitable for use in the present disclosure comprises chromium. The silica support comprising chromium may be referred to as a chromated silica support or a chromium-silica support. In another aspect, the chromium-silica support comprises the features disclosed herein for the silica support while additionally containing chromium. One non-limiting example of a chromated silica support is HW30A, which is a chromium-silica support material commercially available from W.R. Grace and Company.
The silica support may be in the range of about 50wt% to about 99wt%; or alternatively, in the range of from about 80wt% to about 99wt% is present in the olefin polymerization catalyst and its procatalyst. Herein, the silica support percentage refers to the weight percent (wt%) of the silica support associated with the olefin polymerization catalyst based on the total weight of the olefin polymerization catalyst after all processing steps are completed (i.e., after activation by calcination). Alternatively, the percentage of silica support refers to the weight percent (wt%) of silica support associated with the procatalyst based on the total weight of the procatalyst after completion of all relevant processing steps excluding activation by calcination.
In another aspect, the olefin polymerization catalyst and procatalyst of the present disclosure comprise chromium. The source of chromium may be any chromium-containing compound capable of providing sufficient chromium to the olefin polymerization catalyst and its procatalyst. In one aspect, the chromium-containing compound may be a water-soluble chromium compound or a hydrocarbon-soluble chromium compound. Examples of water-soluble chromium compounds include chromium trioxide, chromium acetate, chromium nitrate, or combinations thereof. Examples of hydrocarbon soluble chromium compounds include t-butyl chromate, bis-cyclopentadienyl chromium (II), chromium (III) acetylacetonate, or combinations thereof. In one aspect of the present disclosure, the chromium-containing compound may be a chromium (II) compound, a chromium (III) compound, or a combination thereof. Suitable chromium (III) compounds include, but are not limited to, chromium (III) carboxylates, chromium (III) naphthenates, chromium (III) halides, chromium (III) sulfates, chromium (III) nitrates, chromium (III) diketonates, or combinations thereof. Specific chromium (III) compounds include, but are not limited to, chromium (III) sulfate, chromium (III) chloride, chromium (III) nitrate, chromium (III) bromide, chromium (III) acetylacetonate, and chromium (III) acetate. Suitable chromium (II) compounds include, but are not limited to, chromium (II) chloride, chromium (II) bromide, chromium (II) iodide, chromium (II) sulfate, chromium (II) acetate, or combinations thereof.
The amount of chromium present in the olefin polymerization catalyst may be from about 0.01wt% to about 10wt%, based on the total weight of the olefin polymerization catalyst; alternatively, about 0.5wt% to about 5wt%; alternatively, about 1wt% to about 4wt%; or alternatively, in the range of about 2wt% to about 4wt% chromium. In another aspect, the amount of chromium present in the olefin polymerization catalyst may be in the range of about 1wt% to about 5wt% chromium, based on the total weight of the olefin polymerization catalyst. Herein, the percentage of chromium refers to the weight percent (wt%) of chromium associated with the olefin polymerization catalyst based on the total weight of the olefin polymerization catalyst after all processing steps are completed (i.e., after activation by calcination). In another aspect, the amount of chromium present in the procatalyst may be from about 0.01wt% to about 10wt% based on the total weight of silica within the procatalyst; alternatively, about 0.1wt% to about 5wt%; alternatively, about 0.2wt% to about 2wt%; or alternatively, from about 0.5wt% to about 1.5wt% chromium. Herein, the percentage of chromium refers to the weight percent (wt%) of chromium associated with the procatalyst based on the total weight of silica within the procatalyst after completion of all processing steps excluding activation by calcination.
In another aspect, the olefin polymerization catalyst of the present disclosure and procatalyst thereof comprise titanium. The source of titanium may be any titanium-containing compound capable of providing sufficient titanium to the olefin polymerization catalyst and its procatalyst. In another aspect, the titanium-containing compound includes a tetravalent titanium (Ti (IV)) compound or a trivalent titanium (Ti (III)) compound. The Ti (IV) compound may be any compound comprising Ti (IV); alternatively, the Ti (IV) compound may be any compound capable of releasing Ti (IV) species upon dissolution into solution. The Ti (III) compound may be any compound comprising Ti (III); alternatively, the Ti (III) compound may be any compound capable of releasing Ti (III) species upon dissolution into solution.
In one aspect, titanium-containing compounds suitable for use in the present disclosure include those having at least one alkoxy group; or alternatively, at least two alkoxy groups. Ti (IV) compounds suitable for use in the present disclosure include, but are not limited to, those having the general formula TiO (OR) K ) 2 、Ti(OR K ) 2 (acac) 2 、Ti(OR K ) 2 (oxy), ti (IV) compounds of combinations thereof, wherein R K May be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or a combination thereof; "acac" is acetylacetonate; and "oxy" is oxalate. Alternatively, the titanium-containing compound comprises a titanium (IV) alkoxide. In one aspect, the titanium (IV) alkoxide may be titanium (IV) ethoxide, titanium (IV) isopropoxide, titanium (IV) n-propoxide, titanium (IV) n-butoxide, titanium (IV) 2-ethylhexoxide, or a combination thereof. In a particular aspect, the titanium-containing compound can be titanium (IV) isopropoxide.
In another aspect, the titanium-containing compound suitable for use in the present disclosure may include hydrated titanium dioxide, titanium hydroxide, titanic acid, titanyl sulfate, titanium acetylacetonate, titanyl acetylacetonate, or a combination thereof.
In another aspect, titanium-containing compounds suitable for use in the present disclosure may include titanium (IV) halides, non-limiting examples of which include titanium tetrachloride, titanium tetrabromide, titanium (IV) dichloride, and titanium (IV) dibromide. In another aspect, the titanium (IV) halide may include a compound having the general formula Ti (OR K ) n Q 4–n Titanium alkoxy halides of (a); wherein R is K May be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or a combination thereof; wherein Q may be fluorine, chlorine, bromine, iodine, or a combination thereofCombining; and wherein n may be an integer from 1 to 4.
The amount of titanium present in the olefin polymerization catalyst may be from about 0.01wt% to about 10wt%, based on the total weight of the olefin polymerization catalyst of the present disclosure; alternatively, about 0.5wt% to about 5wt%; alternatively, about 1wt% to about 4wt%; or alternatively, in the range of about 2wt% to about 4wt% titanium. In another aspect, the amount of titanium present in the olefin polymerization catalyst can be in the range of about 1wt% to about 5wt% titanium, based on the total weight of the olefin polymerization catalyst. In this context, titanium percentage refers to the weight percent (wt%) of titanium associated with the olefin polymerization catalyst based on the total weight of the olefin polymerization catalyst after all processing steps are completed (i.e., after activation by calcination). In another aspect, the amount of titanium present in the procatalyst may be from about 0.01wt% to about 25wt% based on the total weight of silica within the procatalyst of the disclosure; alternatively, about 0.1wt% to about 20wt%; alternatively, about 0.5wt% to about 10wt%; alternatively, about 1wt% to about 6wt%; or alternatively, in the range of about 2wt% to about 4wt% titanium. In this context, the titanium percentage refers to the weight percent (wt%) of titanium associated with the procatalyst based on the total weight of silica within the procatalyst after completion of all processing steps excluding activation by calcination.
In one aspect, the olefin polymerization catalysts of the present disclosure and procatalysts thereof comprise one or more carboxylic acids. The carboxylic acid may be a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, an alpha-hydroxycarboxylic acid, a beta-hydroxycarboxylic acid, an alpha-ketocarboxylic acid, or a combination thereof. In one aspect, the carboxylic acid may be C 1 To C 15 Monocarboxylic acids or C 1 To C 5 A monocarboxylic acid; alternatively, C 3 To C 15 Dicarboxylic acids or C 3 To C 5 A dicarboxylic acid; alternatively, C 1 To C 15 Tricarboxylic acids or C 1 To C 5 A tricarboxylic acid; alternatively, C 1 To C 15 Alpha-hydroxycarboxylic acid or C 1 To C 5 Alpha-hydroxycarboxylic acids; alternatively, C 1 To C 15 Beta-hydroxycarboxylic acid or C 1 To C 5 Beta-hydroxycarboxylic acids; or alternatively, C 1 To C 15 Alpha-ketocarboxylic acid or C 1 To C 5 Alpha-ketocarboxylic acids.
In a particular aspect, the one or more carboxylic acids can be acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, gluconic acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, salicylic acid, catechol, 2- (hydroxymethyl) butyric acid, or a combination thereof. In another aspect, the carboxylic acid may be oxalic acid.
In another aspect, the olefin polymerization catalysts of the present disclosure and procatalysts thereof comprise at least two carboxylic acids. In such aspects, the at least two carboxylic acids may comprise at least one simple carboxylic acid and at least one complex carboxylic acid, wherein the complex carboxylic acid comprises at least one ring structure. For example, the at least two carboxylic acids may be oxalic acid and phenylmalonic acid.
In one aspect, the olefin polymerization catalyst of the present disclosure and procatalysts thereof comprise an acidic phenol. The acidic phenol may be any acidic phenol capable of providing olefin polymerization catalysts and procatalysts of the type disclosed herein. In one aspect, the acidic phenol comprises catechol, salicyl alcohol, salicylic acid, phthalic acid, or derivatives thereof. In some aspects, the olefin polymerization catalysts of the present disclosure and procatalysts thereof comprise a carboxylic acid and an acidic phenol, both of the types disclosed herein.
The procatalyst of the present disclosure is contained within about 1:1 to about 1:10; alternatively, about 1:1 to about 1:5; or alternatively, an equivalent molar ratio of titanium to carboxylic acid in the range of about 1:1.5 to about 1:4. In one aspect, the equivalent molar ratio of titanium to carboxylic acid is in the range of about 1:1 to about 1:2. Alternatively, the procatalyst of the present disclosure is contained within about 1:1 to about 1:10; alternatively, about 1:1 to about 1:5; or alternatively, an equivalent molar ratio of titanium to acidic phenol in the range of about 1:1.5 to about 1:4. In one aspect, the equivalent molar ratio of titanium to acidic phenol is in the range of about 1:1 to about 1:2.
In one aspect, the olefin polymerization catalysts of the present disclosure and procatalysts thereof comprise a nitrogen-containing compound. The nitrogen-containing compound may be any nitrogen-containing compound suitable for providing effective titanation of the olefin polymerization catalyst and its procatalyst. In another aspect, the nitrogen-containing compound can have structure 1, structure 2, structure 3, structure 4, structure 5, structure 6, or a combination thereof.
Figure BDA0003516289270000161
Figure BDA0003516289270000171
R in the nitrogen-containing compounds utilized as described herein 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 And R is 12 Are independent elements of the structure of the nitrogen-containing compounds in which they are present and are described independently herein. R provided herein 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 And/or R 12 Can be utilized without limitation and in any combination to further describe the inclusion of R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 And/or R 12 Any nitrogen-containing compound structure of (a).
Typically, there is R 1 、R 2 、R 3 、R 5 、R 6 、R 9 、R 10 And/or R 11 R of the corresponding nitrogen-containing compound 1 、R 2 、R 3 、R 5 、R 6 、R 9 、R 10 And/or R 11 Each independently may be hydrogen, an organic group, a hydrocarbon group, or an aryl group. In one aspect, R 1 、R 2 、R 3 、R 5 、R 6 、R 9 、R 10 And/or R 11 Can each independently be C 1 To C 30 An organic group; alternatively, C 1 To C 12 An organic group; or alternatively, C 1 To C 6 An organic group. In one aspect, R 1 、R 2 、R 3 、R 5 、R 6 、R 9 、R 10 And/or R 11 Can each independently be C 1 To C 30 A hydrocarbon group; alternatively, C 1 To C 12 A hydrocarbon group; or alternatively, C 1 To C 6 A hydrocarbon group. In other aspects, R 1 、R 2 、R 3 、R 5 、R 6 、R 9 、R 10 And/or R 11 Can each independently be C 6 To C 30 An aryl group; or alternatively, C 6 To C 12 Aryl groups. In another aspect, R in the nitrogen-containing compounds useful as the present disclosure 1 、R 2 、R 3 、R 5 、R 6 、R 9 、R 10 And/or R 11 The organic group, hydrocarbon group or aryl group of (a) may be substituted or unsubstituted. Those skilled in the art will appreciate that the terms "alkyl", "organo", "hydrocarbyl" and "aryl" are used herein in accordance with the definition from IUPAC Compendium of Chemical Terminology, version 2 (1997).
With R 4 R of the corresponding nitrogen-containing compound 4 May be an organic group, a hydrocarbon group or an aryl group. In one aspect, R 4 Can be C 1 To C 30 An organic group; alternatively, C 1 To C 12 An organic group; or alternatively, C 1 To C 6 An organic group. In one aspect, R 4 Can be C 1 To C 30 A hydrocarbon group; alternatively, C 1 To C 12 A hydrocarbon group; or alternatively, C 1 To C 6 A hydrocarbon group. In other aspects, R 4 Can be C 6 To C 30 An aryl group; or alternatively, C 6 To C 12 Aryl groups. In another aspect, R in the nitrogen-containing compounds useful as the present disclosure 4 The organic group, hydrocarbon group or aryl group of (a) may be substituted or unsubstituted.
In a particular aspect, can be used as R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 9 、R 10 And/or R 11 Any of the substituted organic groups, substituted hydrocarbyl groups, or substituted aryl groups of (a) may contain one or more non-hydrogen substituents. Suitable non-hydrogen substituents herein may be halogen, C 1 To C 12 Hydrocarbon radicals, C 1 To C 12 Hydrocarbyloxy groups, or combinations thereof. In one aspect, the halogen used as the non-hydrogen substituent may be fluorine, chlorine, bromine or iodine. C suitable for use herein 1 To C 12 Non-limiting examples of hydrocarbyloxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, phenoxy, tolyloxy, dimethylphenoxy, trimethylphenoxy and benzoyloxy.
With R 7 And/or R 8 R of the corresponding nitrogen-containing compound 7 And/or R 8 May each independently be hydrogen or methyl.
With R 12 R of the corresponding nitrogen-containing compound 12 Can be branched alkyl or straight chain alkyl. In one aspect, R 12 Can be C 1 To C 30 Branched alkyl; alternatively, C 1 To C 12 Branched alkyl; or alternatively, C 1 To C 6 Branched alkyl groups. In another aspect, R 12 Can be C 1 To C 30 A linear alkyl group; alternatively, C 1 To C 12 A linear alkyl group; or alternatively, C 1 To C 6 A linear alkyl group.
In another aspect, the nitrogen-containing compounds of the present disclosure having structure 2 can have x, where x is an integer from 1 to 4. In one aspect, the nitrogen-containing compound having structure 3 can have y, where y is an integer from 1 to 12. In another aspect, the nitrogen-containing compound having structure 5 can have Z, wherein Z is oxygen or sulfur.
In one aspect, the nitrogen-containing compounds suitable for use in the present disclosure may be alkanolamines, amides, amines, alkylamines, ammonium hydroxides, anilines, hydrazides, hydroxylamines, imines, urea, or combinations thereof. In another aspect, as nitrogen-containing Alkanolamines, amides, amines, ammonium hydroxides, hydrazides, hydroxylamines, imines and/or ureas of the compounds may contain one or more substituents. In one aspect, any substituent contained within any nitrogen-containing compound of the present disclosure may be halogen, C 1 To C 12 An organic group, C 1 To C 12 Hydrocarbon radicals, C 1 To C 12 Hydrocarbyloxy groups, or combinations thereof. The halogen used as a substituent for any of the aspects disclosed herein may be fluorine, chlorine, bromine or iodine. C suitable for use herein 1 To C 12 Non-limiting examples of hydrocarbyloxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, phenoxy, tolyloxy, dimethylphenoxy, trimethylphenoxy and benzoyloxy.
In another aspect, non-limiting examples of specific nitrogen-containing compounds suitable for use in the present disclosure include acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, t-butylamine, N '-dibutylurea, creatine, creatinine, diethanolamine, diethylhydroxylamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N' -dimethylurea, ethanolamine, ethylamine, ethyleneglycol amine, hexylamine, hydroxylamine, imidazole, isopropanolamine, methacrylamide, methylamine, N-methylaniline, N-methyl-2-propanolamine, methyldiethanolamine, methylformamide, propylamine, 2-propanolamine, pyrazole, pyrrolidine, pyrrolidone, succinimide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, 1, 8-diazabicyclo [5.4.0] undec-7-ene, or combinations thereof.
The procatalyst of the present disclosure is contained within about 2:1 to about 1:10; alternatively, about 1:1 to about 1:5; or alternatively, an equivalent molar ratio of titanium to nitrogen-containing compound in the range of about 1:1.5 to about 1:4. In one aspect, the equivalent molar ratio of titanium to nitrogen-containing compound is in the range of about 1:1 to about 1:2.
In a particular aspect, the procatalyst composition of the present disclosure includes a titanium organic salt. In one aspect, the procatalyst composition comprising the titanium organic salt further comprises a silica support and a chromium containing compound, both of the types previously disclosed herein. In another aspect, titanium organic salts suitable for use herein include titanium, protonated nitrogen-containing compounds, and carboxylates.
In one aspect, the titanium organic salt comprises titanium. The source of titanium may be any titanium-containing compound capable of providing sufficient titanium to the procatalyst as disclosed herein. In another aspect, the source of titanium is a titanium-containing compound of the type previously disclosed herein.
In one aspect, the titanium organic salt comprises a protonated nitrogen-containing compound. The protonated nitrogen-containing compound may be any protonated nitrogen-containing compound capable of providing sufficient titanium to the procatalyst as disclosed herein. In another aspect, the protonated nitrogen-containing compound may include a protonated form of any nitrogen-containing compound of the type previously disclosed herein.
In one aspect, the protonated nitrogen-containing compound includes a protonated alkanolamine, a protonated amide, a protonated amine, a protonated alkylamine, a protonated ammonium hydroxide, a protonated aniline, a protonated hydroxylamine, a protonated urea, or a combination thereof.
In another aspect, the protonated nitrogen-containing compounds include protonated acetamides, protonated acrylamides, protonated allylamines, ammonium, protonated ammonium hydroxides, protonated butylamines, protonated t-butylamines, protonated N, N '-dibutylureas, protonated creatine, protonated creatinine, protonated diethanolamine, protonated diethylhydroxylamine, protonated diisopropylamine, protonated dimethylaminoethanol, protonated dimethylcarbamates, protonated dimethylformamide, protonated dimethylglycine, protonated dimethylisopropanolamines, protonated N, N' -dimethylureas, protonated ethanolamine, protonated ethylamine, protonated ethyleneglycol amines, protonated hexylamines, protonated hydroxylamine, protonated imidazole, protonated isopropanolamines, protonated methacrylamides, protonated methylamines, protonated N-methylanilines, protonated N-methyl-2-propanolamines, protonated methyldiethanolamine, protonated methylformamide, protonated propylamines, protonated 2-propanolamines, protonated pyrazoles, protonated pyrrolidines, protonated pyrrolidones, protonated succinimides, protonated tetraethylammonium hydroxides, tetramethyl ammonium hydroxides, trimethyl ammonium, or a combination of 1, 7, 8, 5-bis-and 3.
In another aspect, the titanium organic salt comprises carboxylate. The carboxylate may be any carboxylate capable of providing a sufficient amount of titanium to the procatalyst as disclosed herein. In one aspect, the carboxylate groups may include the anionic form of any carboxylic acid of the type previously disclosed herein.
In another aspect, the carboxylate group includes C 1 To C 15 Monocarboxylate radical, C 2 To C 15 Dicarboxylic acid radicals, C 3 To C 15 Tricarboxylic acid radical, C 1 To C 15 An alpha-hydroxycarboxylic acid radical, or a combination thereof.
In another aspect, the carboxylate includes acetate, citrate, gluconate, glycolate, lactate, malate, malonate, oxalate, phosphonoacetate, tartrate, or a combination thereof.
In another aspect, the amount of titanium present in the titanium organic salt of the present disclosure can be from about 0.01wt% to about 20wt%, based on the total weight of the silica of the procatalyst as disclosed herein; alternatively, about 0.5wt% to about 10wt%; or alternatively, in the range of about 1wt% to about 6wt% titanium. In another aspect, the titanium organic salt is comprised between about 1:1 and about 1:10; alternatively, about 1:1 to about 1:5; or alternatively, an equivalent molar ratio of titanium to carboxylate in the range of about 1:1.5 to about 1:4. In some aspects, the equivalent molar ratio of titanium to carboxylate may be about 1:2. In another aspect, the titanium organic salt is comprised between about 2:1 and about 1:10; alternatively, about 1:1 to about 1:5; or alternatively, an equivalent molar ratio of titanium to nitrogen-containing compound in the range of about 1:1.5 to about 1:4. In another aspect, the equivalent molar ratio of titanium to nitrogen-containing compound can be about 1:2.
In one aspect, the olefin polymerization catalysts of the present disclosure and procatalysts thereof comprise a peroxy-containing compound. The peroxy-containing compound may be any peroxy-containing compound suitable for providing effective titanation of the olefin polymerization catalyst and its procatalyst. In another aspect, the peroxy-containing compound includes an organic peroxide, a diacyl peroxide, a peroxydicarbonate, a monoperoxycarbonate, a peroxyketal, a peroxyester, a dialkyl peroxide, a hydroperoxide, or any combination thereof. In one aspect, the peroxy-containing compound includes hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or any combination thereof. In one aspect, the peroxy-containing compound includes hydrogen peroxide. In one aspect, the procatalyst of the present disclosure includes an equivalent molar ratio of titanium to the peroxy-containing compound in the range of about 1.0:0.5 to about 1:50, alternatively about 1:2 to about 1:20, or alternatively, about 1:5 to about 1:10. In some aspects, the use of peroxy-containing compounds in olefin polymerization catalysts and procatalysts thereof results in increased solubility of the carboxylic acid-Ti component of STM.
In one aspect of the present disclosure, a method for preparing an olefin polymerization catalyst includes utilizing a dissolved titanium mixture (STM). In a particular aspect, an STM of the present disclosure comprises a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, optionally a peroxy-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, a peroxy-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises a carboxylic acid, a titanium-containing compound, a peroxy-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises an acidic phenol, a titanium-containing compound, a nitrogen-containing compound, a peroxy-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises an acidic phenol, a titanium-containing compound, a nitrogen-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises an acidic phenol, a titanium-containing compound, a peroxy-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises a carboxylic acid, an acidic phenol, a titanium-containing compound, a peroxy-containing compound, and a solvent. In another aspect, an STM of the present disclosure comprises a carboxylic acid, an acidic phenol, a nitrogen-containing compound, a titanium-containing compound, a peroxy-containing compound, and a solvent. In one aspect, an STM comprises carboxylic acids of the type used as components of the procatalyst as disclosed herein, alternatively at least two carboxylic acids of the type used as components of the procatalyst as disclosed herein. In another aspect, an STM comprises a titanium-containing compound of the type used as a component of a procatalyst as disclosed herein. In another aspect, an STM comprises one or more nitrogen-containing compounds of the type used as components of a procatalyst as disclosed herein. In another aspect, an STM comprises one or more peroxy-containing compounds of the type used as components of a procatalyst as disclosed herein. In another aspect, an STM comprises one or more acidic phenols of the type used as components of a procatalyst as disclosed herein.
In another aspect, an STM of the present disclosure comprises a solvent. The solvent may be an aqueous solvent, an alcohol, an organic solvent, a hydrocarbon, or a combination thereof. Non-limiting examples of aqueous solvents suitable for use in the present disclosure include deionized water, distilled water, filtered water, or combinations thereof. Non-limiting examples of alcohols suitable for use as solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, benzyl alcohol, phenol, or combinations thereof. In another aspect, the organic solvent suitable for use in the present disclosure may be an ester, a ketone, or a combination thereof. Non-limiting examples of esters suitable for use as solvents include ethyl acetate, propyl acetate, butyl acetate, isobutyl isobutyrate, methyl lactate, ethyl lactate, or combinations thereof. Non-limiting examples of ketones suitable for use as solvents include acetone, ethyl methyl ketone, methyl isobutyl ketone, or combinations thereof. In a particular aspect, the hydrocarbon suitable for use as a solvent may be a halogenated aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, or a combination thereof. Non-limiting examples of hydrocarbons suitable for use as solvents include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, benzene, toluene, ethylbenzene, xylenes, chlorobenzene, dichlorobenzene, or combinations thereof.
In a particular aspect, a Solubilized Titanium Mixture (STM) as disclosed herein comprises an acidic mixture that can be prepared by contacting one or more carboxylic acids and a solvent, or alternatively, one or more acidic phenols and a solvent. In one aspect, STM is prepared by sequentially adding a titanium-containing compound and a nitrogen-containing compound to an acidic mixture as disclosed herein. In an alternative aspect, a titanium-containing compound and a nitrogen-containing compound may be contacted to form a basic mixture, which is then contacted with an acidic mixture to form an STM as disclosed herein. In another aspect, the nitrogen-containing compound used to form the alkaline mixture may be a component of an aqueous solution.
In another aspect, a Solubilized Titanium Mixture (STM) as disclosed herein comprises an acidic mixture. The acidic mixture may be prepared by contacting a carboxylic acid with a peroxy-containing compound and a solvent. Alternatively, the acidic mixture may be prepared by contacting at least two carboxylic acids with a peroxy-containing compound and a solvent. Alternatively, the acidic mixture may be prepared by contacting an acidic phenol with a peroxy-containing compound and a solvent. Alternatively, the acidic mixture may be prepared by contacting an acidic phenol with one or more carboxylic acids and optionally a peroxy-containing compound and a solvent.
In one aspect, STM is prepared by sequentially adding a titanium-containing compound and a nitrogen-containing compound to an acidic mixture as disclosed herein. In another aspect, an STM is prepared by adding a titanium-containing compound to an acidic mixture as disclosed herein. In some aspects, the order of addition is any order that is compatible with the materials disclosed herein. For example, any STM may comprise any of the components disclosed herein (e.g., acidic phenols, nitrogen-containing compounds, peroxy-containing compounds, carboxylic acids), titanium-containing compounds, and chromium-containing compounds.
In an alternative aspect, a titanium-containing compound and a nitrogen-containing compound may be contacted to form a basic mixture, which is then contacted with an acidic mixture to form an STM as disclosed herein. In another aspect, the nitrogen-containing compound used to form the alkaline mixture may be a component of an aqueous solution.
In one aspect, the STM comprises one or more carboxylic acids, alternatively one or more acidic phenols, alternatively a combination of one or more acidic phenols and one or more carboxylic acids, all of the carboxylic acids and the acidic phenols being of the type disclosed herein. In one aspect, an STM of the present disclosure comprises a liquid crystal display having a ratio of between about 1:1 to about 100:1; alternatively, about 1:1 to about 50:1; or alternatively, an acidic mixture of solvent to carboxylic acid in a weight ratio ranging from about 1:1 to about 10:1. In another aspect, the STM is contained in about 1:0.5 to about 1:20; alternatively, about 1:1 to about 1:10; or alternatively, an equivalent molar ratio of titanium-containing compound to carboxylic acid in the range of about 1:1 to about 1:5. In some aspects, the equivalent molar ratio of titanium-containing compound to carboxylic acid can be about 1:2.5. In another aspect, the STM is contained in about 0.1:1 to about 5:1; alternatively, about 0.5:1 to about 3:1; alternatively, about 1:1 to about 2:1; or alternatively, an equivalent molar ratio of the nitrogen-containing compound to the carboxylic acid in the range of about 1:1 to about 2:1. In another aspect, the STM is contained in about 1:0.5 to about 1:50; alternatively, about 1:1 to about 1:20; alternatively, about 1:5 to about 1:10; or alternatively, an equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the range of about 1:3 to about 1:8. In another aspect, the STM is contained in about 1:0.5 to about 1:10; alternatively, about 1:1 to about 1:5; alternatively, about 1:1 to about 1:3; or alternatively, an equivalent molar ratio of titanium-containing compound to acidic phenol in the range of about 1:1 to about 1:2.5.
In another aspect, the STM is contained in about 1:0.5 to about 1:10; alternatively, about 1:1 to about 1:5; alternatively, about 1:1 to about 1:3; or alternatively, an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the range of about 1:1 to about 1:2.5. In other aspects, the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound can be about 1:2.
In a particular aspect, an STM suitable for use in the present disclosure may be characterized as having a pH of less than about 5.5. Alternatively, an STM may be characterized as having a length between about 2.5 and about 5.5; alternatively, about 3.0 to about 5.0; or alternatively, a pH in the range of about 3.5 to about 4.5.
In one aspect of the present disclosure, the catalyst components disclosed herein may be contacted in any order or manner deemed suitable by one of ordinary skill in the art with the aid of the present disclosure to produce an olefin polymerization catalyst having the features disclosed herein.
In a particular aspect, a process for preparing an olefin polymerization catalyst includes contacting a solvent and one or more carboxylic acids, both of which are of the type disclosed herein, to form an acidic mixture. The method may further include contacting a titanium-containing compound of the type disclosed herein with the acidic mixture to form an acidic titanium mixture. In one aspect, a nitrogen-containing compound of the type disclosed herein and an acidic titanium mixture may be contacted to form an STM as disclosed herein, for example, the nitrogen-containing compound may be added to the acidic titanium mixture to form the STM. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture in a single portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2 within the STM. In a particular aspect, the amount of nitrogen-containing compound to be added to the acidic titanium mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in multiple portions, and wherein a single portion comprises from about 3% to about 10% of the amount of nitrogen-containing compound that constitutes an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. When the green endpoint of the bromocresol green indicator is reached, the addition of multiple portions of nitrogen-containing compound may be stopped. In some aspects, the green endpoint of the bromocresol green indicator is associated with a pH of about 4.0 within the STM. In another aspect, adding the nitrogen-containing compound to the acidic titanium mixture includes partially neutralizing the acidic titanium mixture; or alternatively, the acidic titanium mixture is completely neutralized. The method for preparing an olefin polymerization catalyst may also include contacting a chromium-silica support of the type disclosed herein with an STM to form an addition product. In another aspect, the addition product can be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.
In another aspect, a process for preparing an olefin polymerization catalyst comprises contacting a solvent and one or more carboxylic acids, both of which are of the type disclosed herein, to form an acidic mixture. The method may further include contacting a titanium-containing compound of the type disclosed herein with the acidic mixture to form an acidic titanium mixture. In one aspect, a nitrogen-containing compound of the type disclosed herein and an acidic titanium mixture may be contacted to form an STM as disclosed herein, for example, the nitrogen-containing compound may be added to the acidic titanium mixture to form the STM. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture in a single portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2 within the STM. In a particular aspect, the amount of nitrogen-containing compound to be added to the acidic titanium mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in multiple portions, and wherein a single portion comprises from about 3% to about 10% of the amount of nitrogen-containing compound that constitutes an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. When the green endpoint of the bromocresol green indicator is reached, the addition of multiple portions of nitrogen-containing compound may be stopped. In some aspects, the green endpoint of the bromocresol green indicator is associated with a pH of about 4.0 within the STM. In another aspect, adding the nitrogen-containing compound to the acidic titanium mixture includes partially neutralizing the acidic titanium mixture; or alternatively, the acidic titanium mixture is completely neutralized.
The method for preparing an olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein with an STM to form a titanated support. In another aspect, the titanated support may be prepared by heating the titanated support to a temperature between about 25 ℃ and about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the titanated support is dried at a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form a dried titanated support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein with a dried titanated support to form an addition product by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In an alternative aspect, prior to drying the titanated support as disclosed herein, a chromium-containing compound and titanated support may be contacted to form an addition product, which may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In another alternative aspect, a chromium-containing compound and a silica support may be contacted to form a chromium-silica support, the chromium-silica support may be contacted with an STM to form an addition product, and the addition product may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.
In another aspect, a process for preparing an olefin polymerization catalyst comprises contacting a titanium-containing compound and a nitrogen-containing compound, both of the types disclosed herein, to form a basic mixture. The method may further comprise contacting a solvent and a carboxylic acid, both of the type disclosed herein, to form an acidic mixture. The basic mixture and the acidic mixture may be contacted to form a dissolved titanium mixture (STM) as disclosed herein, for example, the basic mixture may be added to the acidic mixture to form the STM. In some aspects, the basic mixture is added to the acidic mixture in a single portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a particular aspect, the amount of basic mixture to be added to the acidic mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the basic mixture is added to the acidic mixture in multiple portions, and wherein a single portion comprises from about 3% to about 10% of the amount of the basic mixture that constitutes an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. When the green end point of the bromocresol green indicator is reached, the addition of multiple portions of the alkaline mixture can be stopped. In some aspects, the green endpoint of the bromocresol green indicator is associated with a pH of about 4.0 within the STM. In another aspect, adding the alkaline mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or alternatively, the acidic mixture is completely neutralized. The method for preparing an olefin polymerization catalyst may also include contacting a chromium-silica support of the type disclosed herein with an STM to form an addition product. In another aspect, the addition product can be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.
In another aspect, a process for preparing an olefin polymerization catalyst comprises contacting a titanium-containing compound and a nitrogen-containing compound, both of the types disclosed herein, to form a basic mixture. The method may further comprise contacting a solvent and a carboxylic acid, both of the type disclosed herein, to form an acidic mixture. The basic mixture and the acidic mixture may be contacted to form a dissolved titanium mixture (STM) as disclosed herein, for example, the basic mixture may be added to the acidic mixture to form the STM. In some aspects, the basic mixture is added to the acidic mixture in a single portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a particular aspect, the amount of basic mixture to be added to the acidic mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the basic mixture is added to the acidic mixture in multiple portions, and wherein a single portion comprises from about 3% to about 10% of the amount of the basic mixture that constitutes an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. When the green end point of the bromocresol green indicator is reached, the addition of multiple portions of the alkaline mixture can be stopped. In some aspects, the green endpoint of the bromocresol green indicator is associated with a pH of about 4.0 within the STM. In another aspect, adding the alkaline mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or alternatively, the acidic mixture is completely neutralized. The method for preparing an olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein with an STM to form a titanated support. In another aspect, the titanated support may be prepared by heating the titanated support to a temperature between about 25 ℃ and about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the titanated support is dried at a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form a dried titanated support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein with a dried titanated support to form an addition product by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In an alternative aspect, prior to drying the titanated support as disclosed herein, a chromium-containing compound and titanated support may be contacted to form an addition product, which may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In another alternative aspect, a chromium-containing compound and a silica support may be contacted to form a chromium-silica support, the chromium-silica support may be contacted with an STM to form an addition product, and the addition product may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.
In another aspect, a method for preparing an olefin polymerization catalyst comprises contacting a solvent, one or more carboxylic acids, one or more nitrogen-containing compounds, and a peroxy-containing compound to form an acidic mixture, each of which are of the type disclosed herein. Alternatively, a process for preparing an olefin polymerization catalyst comprises contacting a solvent, one or more acidic phenols, a nitrogen-containing compound, and a peroxy-containing compound to form an acidic mixture, each of which is of the type disclosed herein. Alternatively, a process for preparing an olefin polymerization catalyst comprises contacting a solvent, one or more carboxylic acids, one or more acidic phenols, one or more nitrogen-containing compounds, and a peroxy-containing compound to form an acidic mixture, each of the solvent, the carboxylic acid, the acidic phenol, the nitrogen-containing compound, and the peroxy-containing compound being of the type disclosed herein. Alternatively, a process for preparing an olefin polymerization catalyst comprises contacting a solvent, one or more carboxylic acids, one or more acidic phenols, and a peroxy-containing compound to form an acidic mixture, each of which is of the type disclosed herein. Alternatively, a process for preparing an olefin polymerization catalyst comprises contacting a solvent, one or more acidic phenols, one or more nitrogen-containing compounds, and a peroxy-containing compound to form an acidic mixture, each of which is of the type disclosed herein. The method may further include contacting a titanium-containing compound of the type disclosed herein with the acidic mixture to form an acidic titanium mixture.
In one aspect, a nitrogen-containing compound of the type disclosed herein and an acidic titanium mixture may be contacted to form a Solubilized Titanium Mixture (STM) as disclosed herein, for example, the nitrogen-containing compound may be added to the acidic titanium mixture to form the STM. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture in a single portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2 within the STM. In a particular aspect, the amount of nitrogen-containing compound to be added to the acidic titanium mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in multiple portions, and wherein a single portion comprises from about 3% to about 10% of the amount of nitrogen-containing compound that constitutes an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. When the green endpoint of the bromocresol green indicator is reached, the addition of multiple portions of nitrogen-containing compound may be stopped. In some aspects, the green endpoint of the bromocresol green indicator is associated with a pH of about 4.0 within the STM. In another aspect, adding the nitrogen-containing compound to the acidic titanium mixture includes partially neutralizing the acidic titanium mixture; or alternatively, the acidic titanium mixture is completely neutralized. The method for preparing an olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein with an STM to form a titanated support. In another aspect, the titanated support may be prepared by heating the titanated support to a temperature between about 25 ℃ and about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the titanated support is dried at a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form a dried titanated support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein with a dried titanated support to form an addition product by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In an alternative aspect, prior to drying the titanated support as disclosed herein, a chromium-containing compound and titanated support may be contacted to form an addition product, which may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In another alternative aspect, a chromium-containing compound and a silica support may be contacted to form a chromium-silica support, the chromium-silica support may be contacted with an STM to form an addition product, and the addition product may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.
In another aspect, a method for preparing an olefin polymerization catalyst includes contacting a solvent, a carboxylic acid, and a peroxy-containing compound to form an acidic mixture, the solvent, the carboxylic acid, and the peroxy-containing compound each being of the type disclosed herein. Alternatively, a process for preparing an olefin polymerization catalyst comprises contacting a solvent, an acidic phenol, and a peroxy-containing compound to form an acidic mixture, each of which are of the type disclosed herein. Alternatively, a process for preparing an olefin polymerization catalyst comprises contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxy-containing compound to form an acidic mixture, each of the solvent, the carboxylic acid, the acidic phenol, and the peroxy-containing compound being of the type disclosed herein.
The method may further include contacting a titanium-containing compound of the type disclosed herein with the acidic mixture to form an acidic titanium mixture. The method for preparing an olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein with an STM to form a titanated support. In another aspect, the titanated support may be prepared by heating the titanated support to a temperature between about 25 ℃ and about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the titanated support is dried at a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form a dried titanated support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein with a dried titanated support to form an addition product by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In an alternative aspect, prior to drying the titanated support as disclosed herein, a chromium-containing compound and titanated support may be contacted to form an addition product, which may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst. In another alternative aspect, a chromium-containing compound and a silica support may be contacted to form a chromium-silica support, the chromium-silica support may be contacted with an STM to form an addition product, and the addition product may be prepared by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, the addition product is dried at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at about 25 ℃ to about 300 ℃; alternatively, about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.
The use of a dissolved titanium mixture (STM) in the preparation of the olefin polymerization catalysts of the present disclosure may be advantageous because the STM may facilitate the association of titanium with a silica support in the presence of an aqueous solvent (e.g., water). Other advantages may exist when the STM used to form the olefin polymerization catalyst comprises an aqueous solvent (e.g., water). The solubility of titanium in the aqueous solvent may be sufficient to allow the STM and silica support to be contacted using a spray drying process. Spray drying as used herein refers to a process that produces a dry powder from a liquid or slurry by rapid drying with hot gas. The spray drying process can be used to prepare olefin polymerization catalysts in a continuous production process, with the potential to produce large quantities of olefin polymerization catalysts. The spray drying process can also be used to prepare olefin polymerization catalysts having a uniform particle size distribution. The use of STM comprising an aqueous solvent may allow the use of a hydrated silica support and eliminate the heat treatment required for anhydrous catalyst preparation processes (e.g., drying the hydrated silica support prior to contact with any other catalyst components).
As will be appreciated by one of ordinary skill in the art, calcination of the procatalysts disclosed herein may result in emission of Volatile Organic Compounds (VOCs). In various aspects of the present disclosure utilizing peroxides in the absence of nitrogen-containing compounds, VOC emissions are reduced when compared to otherwise similar catalyst preparations conducted in the presence of nitrogen-containing compounds. In one aspect, the VOC emissions achieved by the catalysts of the present disclosure may be reduced by equal to or greater than about 10%, alternatively, equal to or greater than about 20%, or alternatively, equal to or greater than about 30% when compared to an otherwise similar catalyst preparation performed in the presence of a nitrogen-containing compound.
In some aspects of the present disclosure, contacting the components for preparing the olefin polymerization catalyst may be performed in the presence of a reaction medium. In another aspect, the reaction medium may be formed during contact of the components used to prepare the olefin polymerization catalyst. The reaction medium may comprise a solvent (e.g., water) as disclosed herein and one or more liquids associated with the components used to prepare the olefin polymerization catalyst (e.g., water associated with the silica support). In one aspect, the reaction medium excludes any solid components (e.g., silica support and any solids associated therewith) used to prepare the olefin polymerization catalysts disclosed herein. In some aspects, the total amount of water present in the reaction medium can be from about 1wt% to about 99wt%, based on the total weight of the reaction medium; alternatively, about 1wt% to about 50wt%; alternatively, about 1wt% to about 20wt%; or alternatively, in the range of about 1wt% to about 10 wt%. In another aspect, the reaction medium may contain greater than about 20wt% water, based on the total weight of the reaction medium; alternatively, about 40wt% water; alternatively, about 60wt% water; alternatively, about 80wt% water; or alternatively, about 90wt% water, wherein the water may be derived from one or more components used to prepare the olefin polymerization catalyst.
In any aspect of the present disclosure, a method for preparing an olefin polymerization catalyst further comprises activating the procatalyst prepared as disclosed herein by a calcination step. In some aspects, calcination of the procatalyst includes heating the procatalyst in an oxidizing environment to produce the olefin polymerization catalyst. For example, the procatalyst may be prepared by heating it to a temperature of from about 400 ℃ to about 1000 ℃ in the presence of air; alternatively, about 500 ℃ to about 900 ℃; or alternatively, the procatalyst is calcined at a temperature in the range of about 500 ℃ to about 850 ℃. Calcination of the procatalyst may also include maintaining the procatalyst at about 400 ℃ to about 1000 ℃ in the presence of air; alternatively, about 500 ℃ to about 900 ℃; or alternatively, a temperature in the range of about 500 ℃ to about 850 ℃ for about 1 minute to about 24 hours; alternatively, about 1 minute to about 12 hours; alternatively, about 20 minutes to about 12 hours; alternatively, about 1 hour to about 10 hours; alternatively, about 3 hours to about 10 hours; or alternatively, a period of time in the range of about 3 hours to about 5 hours to produce an olefin polymerization catalyst.
The olefin polymerization catalysts of the present disclosure are suitable for use in any olefin polymerization process using various types of polymerization reactors. In one aspect of the present disclosure, the polymers of the present disclosure are produced by any olefin polymerization process using various types of polymerization reactors. As used herein, a "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and/or copolymers. The homopolymer and/or copolymer produced in the reactor may be referred to as a resin and/or polymer. Various types of reactors include, but are not limited to, those that may be referred to as batch reactors, slurry reactors, gas phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, or other reactors and/or reactors of various types. The gas phase reactor may comprise a fluidized bed reactor or a staged horizontal reactor. The slurry reactor may comprise vertical and/or horizontal loops. The high pressure reactor may comprise an autoclave and/or a tubular reactor. The reactor types may include batch and/or continuous processes. Continuous processes may use batch and/or continuous product discharge or transfer. The process may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, olefin polymerization catalyst and/or cocatalyst, diluent, and/or other materials of the polymerization process.
The polymerization reactor system of the present disclosure may comprise one type of reactor in the system, or multiple reactors of the same or different types, operating in any suitable configuration. The production of polymer in a plurality of reactors may comprise several stages in at least two separate polymerization reactors interconnected by a transfer system which makes it possible to transfer the polymer produced by the first polymerization reactor into the second reactor. Alternatively, polymerization in multiple reactors may include manual or automatic transfer of polymer from one reactor to a subsequent reactor or reactors for additional polymerization. Alternatively, the multi-stage or multi-step polymerization may occur in a single reactor, with conditions being changed such that different polymerization reactions occur.
The desired polymerization conditions in one reactor may be the same as or different from the operating conditions of any other reactor involved in the overall process to produce the polymers of the present disclosure. The multiple reactor system may include any combination including, but not limited to, a plurality of loop reactors, a plurality of gas phase reactors, a combination of loop and gas phase reactors, a plurality of high pressure reactors, and a combination of high pressure reactors with loop and/or gas reactors. Multiple reactors may be operated in series or in parallel. In one aspect of the disclosure, any arrangement and/or any combination of reactors may be used to produce the polymers of the disclosure.
According to one aspect of the present disclosure, a polymerization reactor system may comprise at least one loop slurry reactor. Such reactors are common and may include vertical or horizontal loops. In general, a continuous process may include continuously introducing monomer, olefin polymerization catalyst, and/or diluent into a polymerization reactor, and continuously removing from this reactor a suspension comprising polymer particles and diluent. The monomer, diluent, olefin polymerization catalyst, and optionally any comonomer may be continuously fed to a loop slurry reactor where polymerization occurs. The reactor effluent may be flashed to remove the liquid comprising the diluent from the solid polymer, monomer, and/or comonomer. Various techniques may be used for this separation step, including but not limited to flash distillation, which may include any combination of heating and depressurization; separation by cyclonic action in a cyclone or hydrocyclone; separation by centrifugation; or other suitable separation method.
Typical slurry polymerization processes (also known as particle form processes) are disclosed, for example, in U.S. Pat. nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415; each of which is incorporated herein by reference in their entirety.
Suitable diluents for use in slurry polymerization include, but are not limited to, the monomers polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions may occur under bulk conditions in which no diluent is used. An example is the polymerization of propylene monomers as disclosed in U.S. Pat. No. 5,455,314, which is incorporated herein by reference in its entirety.
According to another aspect of the present disclosure, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recycle stream containing one or more monomers that is continuously circulated through a fluidized bed in the presence of an olefin polymerization catalyst under polymerization conditions. The recycle stream may be withdrawn from the fluidised bed and recycled back to the reactor. At the same time, the polymer product may be withdrawn from the reactor and fresh monomer may be added to replace the polymerized monomer. Such gas phase reactors may include processes for multi-step gas phase polymerization of olefins, wherein the olefin is polymerized in the gas phase in at least two separate gas phase polymerization zones while the polymer containing the olefin polymerization catalyst formed in the first polymerization zone is fed to the second polymerization zone. One type of gas phase reactor suitable for use is disclosed in U.S. Pat. nos. 4,588,790, 5,352,749 and 5,436,304, each of which is incorporated herein by reference in its entirety.
According to another aspect of the present disclosure, the high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. The tubular reactor may have several zones in which fresh monomer, initiator or olefin polymerization catalyst is added. The monomer may be entrained in an inert gas stream and introduced in one zone of the reactor. The initiator, olefin polymerization catalyst, and/or catalyst components may be entrained in the gas stream and introduced in another zone of the reactor. The gas streams may be intermixed to effect polymerization. Heat and pressure may be suitably employed to obtain optimal polymerization conditions.
According to another aspect of the present disclosure, the polymerization reactor may comprise a solution polymerization reactor in which the monomer is contacted with the olefin polymerization catalyst composition by suitable stirring or other means. Carriers comprising organic diluents or excess monomers may be employed. If desired, the monomer may be introduced into the vapor phase and contacted with the catalytic reaction product in the presence or absence of a liquid material. The polymerization zone is maintained at a temperature and pressure that will result in the formation of a solution of the polymer in the reaction medium. Agitation can be used to achieve better temperature control and maintain a uniform polymerization mixture throughout the polymerization zone. The polymerization exotherm is dissipated by suitable means.
The polymerization reactor suitable for use in the present disclosure may also comprise any combination of at least one raw material feed system, at least one feed system for an olefin polymerization catalyst or catalyst component, and/or at least one polymer recovery system. Reactor systems suitable for the present disclosure may also include systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, discharge, laboratory analysis, and process control.
The conditions that are controlled to achieve polymerization efficiency and to provide polymer properties include, but are not limited to, temperature, pressure, type and amount of olefin polymerization catalyst or cocatalyst, and concentration of various reactants. The polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. Suitable polymerization temperatures may be any temperature below the depolymerization temperature according to gibbs free energy equation (Gibbs Free Energy Equation). Generally, this includes, for example, from about 60 ℃ to about 280 ℃, and/or from about 70 ℃ to about 110 ℃, depending on the type of polymerization reactor and/or polymerization process.
The suitable pressure will also vary depending on the reactor and polymerization process. The pressure in the loop reactor for liquid phase polymerization is typically less than 1000psig (6.9 MPa). The pressure for gas phase polymerization is typically in the range of about 200psig (1.4 MPa) to 500psig (3.45 MPa). The high pressure polymerization in a tubular or autoclave reactor is typically operated in the range of about 20,000psig (138 MPa) to 75,000psig (518 MPa). The polymerization reactor may also be operated in the supercritical region where it occurs at generally higher temperatures and pressures. Operating at conditions above the critical point (supercritical phase) as indicated by the pressure/temperature diagram may provide advantages.
The concentration of the various reactants can be controlled to produce polymers having certain physical and mechanical properties. The proposed end-use product to be formed from the polymer, as well as the method of forming that product, can be varied to determine the desired end-product properties. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, impact resistance, creep, stress relaxation, and hardness test values. Physical properties include, but are not limited to, density, molecular weight distribution, melting temperature, glass transition temperature, melt crystallization temperature, density, stereoregularity, crack propagation, short chain branching, long chain branching, and rheology measurements.
The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifier and electron donor are generally important in producing a particular polymer property. Comonomers can be used to control product density. Hydrogen can be used to control the molecular weight of the product. Cocatalysts may be used for alkylation, poison scavenging, and/or molecular weight control. The concentration of poisons can be minimized because poisons can affect the reaction and/or otherwise affect the polymer product properties. Modifiers can be used to control product properties, and electron donors can affect stereoregularity.
Polymers, such as polyethylene homopolymers and copolymers of ethylene with other mono-olefins, can be produced in the manner described above using the olefin polymerization catalysts prepared as described herein. The polymers produced as disclosed herein may be formed into articles or end use articles using techniques known in the art such as extrusion, blow molding, injection molding, fiber spinning, thermoforming, and casting. For example, the polymer resin may be extruded into a sheet that is then thermoformed into an end-use article, such as a container, cup, tray, toy, or part of another product. Examples of other end use articles that the polymeric resins may form include pipes, films, and bottles.
A process of the present disclosure includes contacting an olefin polymerization catalyst of the type described with an olefin monomer under conditions suitable to form a polyolefin, and recovering the polyolefin. In one aspect, the olefin monomer is an ethylene monomer and the polyolefin is an ethylene polymer (polyethylene).
The polyethylene prepared as described herein may be characterized as having a molecular weight in the range of about 1g/10min to about 1000g/10min; alternatively, about 3g/10min to about 300g/10min; alternatively, about 6g/10min to about 100g/10min; or alternatively, a High Load Melt Index (HLMI) in the range of about 15g/10min to about 40g/10 min. In another aspect, a polyethylene prepared as described herein can be characterized as having an HLMI that is about 1.5 to about 15 times greater than the HLMI of a polymer produced with an otherwise similar olefin polymerization catalyst that does not contain titanium.
In a particular aspect, polyethylene can be prepared with a titanation-free catalyst produced from a water-extracted procatalyst. In another aspect, the water-extracted procatalyst is a water-extracted procatalyst prior to calcination. For example, a procatalyst prepared as described herein may be extracted with water and subsequently calcined to provide a titanated catalyst (i.e., an olefin polymerization catalyst derived from the water extracted procatalyst). In another aspect, the polyethylene produced with the titanation catalyst may be characterized as having an HLMI in the range of about 1dg/min to about 7 dg/min. Such HMLI values may indicate that the titanation catalyst has an amount of from about 0wt% to about 1wt% based on silica; or alternatively, an amount of titanium in the range of about 0.1wt% to about 0.5 wt%.
Melt Index (MI) represents the flow of molten polymer through an orifice having a diameter of 0.0825 inches when subjected to a force of 2,160 grams at 190℃as determined according to ASTM D1238-82 Condition E. I10 represents the flow of molten polymer through an orifice having a diameter of 0.0825 inches when subjected to a force of 10,000 grams at 190℃as determined according to ASTM D1238-82 Condition N. HLMI (high load melt index) represents the flow of molten polymer through an orifice having a diameter of 0.0825 inches when subjected to a force of 21,600 grams at 190 ℃ as determined according to ASTM D1238-82 condition F.
Examples
The following examples are given as particular aspects of the present disclosure and to illustrate the practice and advantages of the present disclosure. It should be understood that the examples are given by way of illustration and are not intended to limit the specification or the claims that follow in any way.
Those skilled in the art will appreciate a composition comprising silicon dioxide (SiO 2 ) And titanium dioxide (TiO) 2 ) The surface of the oxide of (a) is usually terminated with hydroxyl groups which are protonic groups that can participate in the acid-base reaction. Under strongly acidic conditions, hydroxyl groups can be protonated to create a positive charge on the oxide surface. Under strongly alkaline conditions, the hydroxyl groups can be deprotonated to create a negative charge on the oxide surface. Somewhere between the two limits there is a certain pH at which there is zero net charge on the oxide surface. The pH associated with zero net charge is the isoelectric point. Each oxide has a characteristic acidity and a specific isoelectric point which are controlled by the chemical nature of the metallic or non-metallic element of the oxide.
The figure shows the zeta potential of silica and titania as a function of the pH of the solution and the isoelectric point values of the two oxides. Also shown is a plot of coulombic Si-Ti attraction. The zeta potential is the difference in charge potential that exists between the surface of a solid particle immersed in a conductive liquid (e.g., water) and the bulk of the liquid. The figure shows that in the region of pH values between 3.0 and 5.0, the titanium dioxide is positively charged, while the silicon dioxide is negatively charged. The figure also indicates that coulombic Si-Ti attraction is greatest near a pH of about 4.0. Without wishing to be bound by theory, when the coulombic Si-Ti attraction is maximized by maintaining the pH of the solution at about 4.0, a highly efficient titanation of the olefin polymerization catalyst from the Ti aqueous solution may result. To explore this theory, several series of experiments were performed to establish conditions that lead to the formation of an aqueous Ti solution with a pH of about 4.0.
All silica support materials, chemicals and solvents described herein were used as received and were not dried prior to use.
The catalysts used in the experiments described below include
Figure BDA0003516289270000391
It is a commercial Cr/silica-titania catalyst obtained from w.r.Grace and Company and activated at various temperatures. />
Figure BDA0003516289270000392
Prepared by ternary gelation of Si, ti and Cr, containing 2.5wt% Ti and 1wt% Cr, having a grain size of about 500m 2 Surface area per gram, pore volume of 2.5mL/g, and average particle size of about 130 microns. Another commercial Cr/silica-titania catalyst used was designated C-25305HM, available from Philadelphia Quartz (PQ) Corporation. It also contains 2.5wt% Ti and 1wt% Cr, with a weight of about 500m 2 Surface area per gram, pore volume of 2.7mL/g, and average particle size of about 100 microns. The main basic catalyst for titanation described below is +.>
Figure BDA0003516289270000401
HA30W, a commercial Cr/silica available from w.r.Grace. This catalyst does not contain titanium but does contain 1wt% Cr. It has a thickness of about 500m 2 Surface area per gram, pore volume of about 1.6mL/g, and average particle size of about 100 microns. Three other commercial Cr/silica catalysts were also used; one catalyst is known as EP30X from PQ Corporation; another catalyst is from Asahi Glass Corporation (AGC), under the trade name D-70-150A (LV); and the third catalyst is +.f from W.R.Grace >
Figure BDA0003516289270000402
969MPI. All three of these catalysts do not contain titanium, but do contain 1wt% Cr. All three had a pore volume of about 1.6 mL/g. EP30X and 969MPI have a mean length of about 300m 2 Surface area/g and average particle size of about 100 microns. AGC D-70-150A (LV) has a value of about 400m 2 Surface area/g and average particle size of about 80 microns.
Activity tests were carried out in a 2.2 liter steel reactor equipped with a marine stirrer operating at 400 rpm. The reactor was surrounded by steel jacketed circulating water whose temperature was controlled by using a steam and water heat exchanger. These were connected in an electronic feedback loop so that the reactor temperature could be maintained +/-0.5 ℃ during the reaction.
A small amount (typically 0.01 to 0.10 g) of solid chromium catalyst is first charged to a dry reactor under nitrogen unless otherwise stated. Next, about 0.25g of sulfate treated alumina (600 ℃) was added as a poison scavenger. Then 1.2 liters of isobutane liquid was charged and the reactor was heated to the specified temperature, typically 105 ℃. Finally, ethylene was added to the reactor to reach a fixed pressure, typically 550psig (3.8 MPa), which was maintained during the experiment. Agitation was continued for a specified period of time, typically about one hour, and activity was indicated by recording the flow of ethylene into the reactor to maintain the set pressure.
After the time of dispensing, the ethylene flow was stopped and the reactor was slowly depressurized and opened to recover the granular polymer powder. In all cases, the reactor was clean, without any indication of wall scale, coating or other forms of fouling. The polymer powder was then removed and weighed. Activity was specified as grams of polymer produced per gram of solid catalyst loaded per hour.
Example 1
Several control experiments were performed and the results of the control experiments are listed in table 1. The performance of the experimental catalysts shown in the other examples in terms of productivity, activity and melt index potential can be compared to these control tests. Runs 1.10-1.13 show the performance of two non-titanated catalysts, with the latter HA30W providing a measure of the effectiveness of titanation of runs 1.16-1.18. The titanation shown in runs 1.16-1.18 uses Ti (OiPr) 4 To titanate HA 30W. Titanation in run 1.15 exposes the support to TiCl at 250 ℃ 4 Vapor in an attempt to produce a titanated catalyst that is not contaminated with organic or alcohol byproducts. In both methods, the support must be dried to remove free water from the surface, typically by heat treatment at about 150 ℃ to about 800 ℃. Otherwise, titanium will react with free adsorbed water and be ineffective. In runs 1.15-1.18, the catalyst was dried at 200 ℃ and then titanated by gas phase or anhydrous solvent (typically heptane).
Figure BDA0003516289270000411
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Figure BDA0003516289270000421
Example 2: acidic titanation
The first series of experiments investigated the ability of carboxylic acids to form acidic Ti-containing solutions capable of providing effective titanation to olefin polymerization catalysts (i.e., catalysts) of the type disclosed herein. The results are shown in Table 2. All of these experiments were initiated with a hydrated silica support that was not subjected to heat treatment prior to contact with any other catalyst components. The listed carboxylic acids are mixed with water or an alternative solvent system as listed to form a solution, but in all cases the solvent is not dried and no anhydrous conditions are attempted to be used. Adding Ti (OiPr) 4 And when dissolution occurs, the acidic Ti-containing solution thus formed is impregnated onto a chromium-silica support (HA 30W). The product was then dried and calcined in air at 650 ℃ for three hours and subsequently used in polymerization experiments.
Table 2 summarizes the study of the various carboxylic acids. The carboxylic acid alone (without addition of base) does not produce extremely efficient titanation. Experiment 2.2 using acetic acid in propanol solvent provided the most efficient titanation. Successful results were also observed when HA30W was impregnated with an acidic Ti-containing solution and dripped into a 300 ℃ activation tube ("hot drip", runs 2.12-2.16). This rapid drying process is moderately effective as evidenced by the higher melt index obtained when using this process to produce a catalyst as compared to oven drying. When citric acid is used instead of oxalic acid, the "hot drop" drying method results in more efficient titanation. This result can be due to the first pK of citric acid a (3.13) first pK higher than oxalic acid a (1.23). The lower acidity of citric acid can produce a Ti-containing solution having a higher and closer pH value to 4.0 when compared to Ti-containing solutions produced with oxalic acid.
Figure BDA0003516289270000431
Example 3: alkaline titanation
The next series of experiments investigated the ability of the base to form an alkaline Ti-containing solution that can provide effective titanation to the catalyst. The results are shown in Table 3. The experimental procedure was essentially the same as described in example 2. Ti dissolved in some strong bases such as organic bases is effective, but ammonium hydroxide and alkali metal hydroxide are not. Quaternary ammonium hydroxides solubilize Ti but are less effective as uncharged primary, secondary or tertiary amines. The melt index potential resulting from the use of alkaline solutions is low as is the case for non-titanated supports and therefore does not show evidence of effective titanation of the chromium-silica support.
Figure BDA0003516289270000441
Example 4: adjusting pH with ammonium hydroxide
The results in tables 2 and 3 confirm that attaching titania to silica at both high and low pH can be problematic. The next series of experiments was conducted to explore the theory that maximum coulombic Si-Ti attraction occurs at a pH of about 4.0. Ti (OiPr) 4 To titanium dioxide dissolved in an aqueous oxalic acid solution (2 equivalents oxalic acid/Ti) to produce an acidic Ti-containing solution having a pH of about 1. Ammonium hydroxide or a quaternary ammonium derivative as listed in table 4 was added until a green endpoint of the bromocresol green indicator indicating a pH of about 4.0 was reached to produce a Solubilized Ti Mixture (STM) of the type disclosed herein. The stoichiometry required to partially neutralize the acidic Ti-containing solution, and thereby produce STM, is typically about two equivalents of base/Ti. The HA30W support was impregnated with STM and the product was dried and calcined in air at 650 ℃ for three hours, then used in polymerization experiments.
The results listed in Table 4 refer toThe method was successful. Quaternary ammonium hydroxides are more effective when compared to ammonium hydroxide. This result can be explained by the lower volatility of tetraalkylammonium hydroxides. The results in table 4 also indicate that the amount of base used to prepare STM affects the melt index potential conferred by the resulting catalyst. The method also allowed effective titanation on hydrogels instead of preformed silica supports (run 4.16). The catalyst of trial 4.6 was prepared by reverse addition and showed excellent performance: dissolving Ti in NMe 4 In an aqueous OH solution to form an alkaline solution, which is added to an aqueous oxalic acid solution to prepare an STM for impregnating a HA30W support.
Figure BDA0003516289270000451
Figure BDA0003516289270000461
Example 5: adjustment of pH with urea
The next series of experiments investigated the ability of urea to partially neutralize the acidic Ti-containing solution and produce STM that is capable of providing effective titanation to the catalyst. Urea readily decomposes to volatile products upon heating. The replacement of the carbonaceous catalyst component with a urea compound makes it possible to reduce emissions of volatile organic compounds and highly reactive volatile organic compounds generated during calcination of the catalyst. The experimental procedure was essentially the same as described in example 4, but without the use of bromocresol green indicator. The results are shown in table 5. The addition of urea to the acidic Ti-containing solution provides an increasingly efficient titanation as the amount of urea increases. This effect was not observed in experiments investigating the use of urea in spray drying applications, possibly because urea decomposed and/or evaporated during the spray drying operation. Effective titanation was also observed in the case of N, N' -dimethylurea, which was less volatile than urea.
Figure BDA0003516289270000462
Example 6: adjusting pH with alkanolamines
The next series of experiments investigated the ability of alkanolamines to partially neutralize acidic Ti-containing solutions and produce STMs that can provide effective titanation of the catalyst. Ethanolamine and isopropanolamine are chosen because they generally exhibit low toxicity, have low cost, are readily available from a variety of sources, and have a less odor than most amines. The experimental procedure was essentially the same as described in example 5 and the results are shown in table 6. The results varied and the bulkier amine appeared to perform best. Without wishing to be bound by theory, this may be the result of the lower volatility of the more bulky compounds and/or the lower dielectric constant of Ti ions generated by the more bulky compounds. Dimethylaminoethanol (DMAE) provides a relatively high melt index, is low cost, is available from multiple suppliers, and has a low odor. The catalyst of trial 6.11 was prepared by: titanium dioxide was dissolved into two equivalents of aqueous oxalic acid followed by the addition of two equivalents of DMAE to form a dissolved Ti Solution (STM) of the type disclosed herein. The HA30W support was impregnated with STM to form a titanated support, which was dried under vacuum at 100 ℃ overnight. The resulting dried titanated support was extracted with water, then calcined at 650 ℃ and subjected to polymerization experiments. Melt index data indicate that the catalyst has suffered a significant loss of Ti, presumably during the water extraction step. This observation indicates that after drying at 100 ℃, ti may not be sufficiently attached to the silica and supports previous observations that attachment between Ti and silica occurred at least in part at temperatures greater than 150 ℃.
Figure BDA0003516289270000471
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Figure BDA0003516289270000481
Example 7: adjusting pH with other amines
The next series of experiments investigated the ability of various other amines to partially neutralize the acidic Ti-containing solution and produce STM that can provide effective titanation of the catalyst. The experimental procedure was essentially the same as described in example 5 and the results are shown in table 7. The general trend of higher performance was observed for the bulkier amines, but sometimes suffered from lack of solubility, as in the case of 2-ethylhexyl amine or DABCO. Bases capable of delocalizing the positive charges obtained after protonation show extremely good properties; examples include DBU, creatine, and imidazole.
Figure BDA0003516289270000491
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Figure BDA0003516289270000501
Example 8: pH adjustment with inorganic base
The next series of experiments investigated the ability of the inorganic base to partially neutralize the acidic Ti-containing solution and produce STM that is capable of providing effective titanation to the catalyst. The experimental procedure was essentially the same as described in example 5 and the results are shown in table 8. This approach is often unsuccessful. Without wishing to be bound by theory, the higher dielectric constant may have been an effect, but the presence of divalent or trivalent metal cations may interfere with the delicate balance of surface charges between the silica and the titania. Experiments 8.2 and 8.3 were partially successful and co-incorporated an equal amount of Al ions with Ti ions. Three equivalents of oxalic acid were added to dissolve two equivalents of metal (1 Ti (OiPr) 4 +1Al(OH) 3 ) This is a lower acid/metal ratio than in most other experiments described herein. Run 8.3 included partially neutralizing the acid with tetraethylammonium hydroxide in an amount of 1.5 equivalents base/Ti. Compared with the textIn most of the other experiments described, this is a lower alkali/metal ratio, but an increase in HLMI was observed. Without wishing to be bound by theory, it may be easier to coat titanium dioxide onto aluminum oxide than to coat titanium dioxide onto silicon dioxide. Ti and Al are both metals and the chemistry of both are in many respects more similar than that of Ti and Si.
Figure BDA0003516289270000502
Figure BDA0003516289270000511
Example 9: dissolution of Ti by other acids
The next series of experiments investigated the ability of carboxylic acids other than oxalic acid to be partially neutralized and to produce STM that can provide effective titanation of the catalyst. The experimental procedure was essentially the same as described in example 4 and the results are shown in table 9. Experiments were generally less successful than experiments with oxalic acid. Two equivalents of base/Ti were added for several experiments, which exceeded the number of equivalents needed to obtain a pH of 4.0, as the acid tested was weaker than oxalic acid. In other experiments, base was added until the green endpoint of the bromocresol green indicator was reached, indicating a pH of 4.0. An example of this method is trial 9.7, where the use of citric acid and tetramethylammonium hydroxide produced highly efficient titanation as demonstrated by HLMI values of approximately 30. Run 9.14 indicated that titanyl sulfate could be partially neutralized by DMAE in the absence of carboxylic acid to produce moderately efficient titanation.
Figure BDA0003516289270000512
Figure BDA0003516289270000521
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Example 10: dissolution of Ti with peroxide
The catalysts listed in Table 10 (inventive runs 10.1-10.43) were prepared much like those previously described herein, except that peroxide (typically H 2 O 2 ) Added to the formulation as a replacement for part or all of the amine or acid. In this way, the amount of amine used, and in some experiments the amount of acid used, can be reduced, which in turn reduces costs and emissions, and produces polymers with higher HLMI.
In these experiments, 30g of Cr/silica catalyst sold under the name HA30W by W.R.Grace was weighed out into a bowl. It has a thickness of about 500m 2 Surface area per gram, pore volume of about 1.6mL/g, and it contains 1wt% Cr. It is not predried in any way. To a 100mL beaker was added 50mL deionized water into which the organic acid was dissolved. Peroxide is then added to the solution, typically H, in an inventive test 2 O 2 . Then, 6.65mL of titanium tetraisopropoxide was added to the aqueous solution, which resulted in its immediate precipitation as hydrated titanium dioxide. The amount of titanium added is equal to 3.5wt% Ti based on the weight of dry Cr/silica. The amounts of acid and peroxide used in each experiment were varied, but these amounts are listed in Table 10 as equivalents of acid or peroxide added per equivalent of titanium. The precipitated slurry was stirred until the titanium dioxide dissolved into an orange or dark red solution (when H 2 O 2 In the presence), typically after about 10 minutes. In the case when the titanium dioxide is not readily soluble, stirring is continued for several hours before it is finally concluded that no soluble complex is formed, and the experiment is terminated. These are some of the control tests in table 10.
However, when a soluble complex is indeed formed, the next step is to add a nitrogen compound to the solution in some experiments, while in other experiments no nitrogen compound is used. The nitrogen compound is always dissolved into the titanium solution. Also, the amounts of nitrogen compounds are listed in Table 10 in terms of equivalent amounts of nitrogen compounds per equivalent amount of titanium. Finally, the titanium solution was added to the Cr/silica in the bowl and it was manually stirred for several minutes to produce a consistent moist (rather than wet) powder, that is, to incipient wetness. The bowl was then placed in a vacuum oven set at 100 ℃ overnight. The next day, the dried catalyst powder was poured through a 40 mesh screen to break up any small lumps. Samples of the resulting titanium-containing catalyst were calcined in dry air at 650 ℃ for 3 hours. It is then recovered under dry nitrogen and stored for later use.
Control run 10.2 shows that although two equivalents of oxalic acid can dissolve titania, the HLMI obtained is better than that obtained from a Cr/silica catalyst in the absence of titania (table 1, run 1.12). In other words, in the case of using only oxalic acid, titanation is not effective. Control 10.2 served as the baseline for other later experiments. Any HLMI greater than 5-7 represents an improvement in the efficiency of the titanation procedure.
Referring to Table 10, it was observed that the addition of peroxide resulted in dissolution of titanium dioxide in a number of acids that were insoluble in Ti in the absence of peroxide. Some of these acids produce extremely high HLMI. It was also observed that the addition of peroxide greatly improved the HLMI caused by the catalyst even in the case where the titanium dioxide was soluble in the absence of peroxide. Furthermore, when peroxide is added, the amount of nitrogen compound used may be reduced, or in some cases, the nitrogen compound may be completely eliminated, in many experiments. This reduction is a great improvement because nitrogen compounds lead to undesirable emissions during calcination.
In table 11, various combinations of organic acids (and/or nitrogen compounds) were used in an attempt to further reduce emissions and maximize HLMI. In many of these experiments, H has been further utilized 2 O 2 Dissolving Ti and reducing the aforementioned ability of nitrogen compounds or even acid ligands. In these experiments (inventions 11.44 to 11.60), the catalysts were prepared exactly as described previously herein. That is, 30g of Cr/silica was weighed into a bowl, and 50mL of deionized water was measured into a 100mL beaker. Acid together with H when used 2 O 2 Together dissolve into waterIs a kind of medium. Then 6.65mL of titanium tetraisopropoxide (3.5 wt% Ti based on Cr/silica weight) was added and it immediately precipitated out as hydrated titanium dioxide. However, after a short stirring time of about 10 minutes, ti dissolved. Nitrogen compound, when present, is then added and the solution is added to the dry catalyst to reach incipient wetness. Drying and firing are accomplished as described above.
The protocol was slightly different only in inventive experiment 11.44. Here, 30g of silica was weighed into a bowl (instead of Cr/silica). The silica is EP30X from Philadelphia Quartz Corp. With 300m 2 Surface area per gram. Likewise, 50mL of deionized water was measured into a beaker, after which acid, H, was added thereto 2 O 2 And 6.65mL of titanium isopropoxide. After Ti dissolution, 1.25g of basic chromium acetate was also added to the solution. The silica is then impregnated with the solution as described above. It is dried and calcined as previously described. It should also be noted that acidic phenols may be substituted for organic acids to produce effective ligands. Thus, several experiments with catechol and salicyl instead of carboxylic acid were shown.
In Table 11, some of the large acids were found to be incapable of dissolving titanium dioxide until a small amount of smaller acid was also added. For example, in invention test 11.56 catechol was ineffective until combined with a small amount of oxalic acid. Similarly, salicylic acid alone, which was ineffective, dissolved Ti when one equivalent of oxalic acid was also added, and resulted in high HLMI (invention trial 11.54). Similar results occur in the case of salicyl alcohol in invention runs 11.52 and 11.53, phenylmalonic acid in run 11.51, diglycolic acid in run 11.49, iminodiacetic acid in run 11.48, and methylmalonic acid in run 11.46.
Figure BDA0003516289270000541
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Figure BDA0003516289270000551
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Figure BDA0003516289270000561
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Figure BDA0003516289270000571
The target titanium level was 3.5wt% Ti. This is considered to be 1 equivalent of Ti. Attempts were made to dissolve 1 equivalent of titanium dioxide with the stated equivalent of carboxylic acid and with the stated equivalent of H2O2 and/or base,
after impregnating the Ti solution onto the silica, the resulting mixture was dried in a vacuum oven overnight at 100 ℃, followed by calcination of a portion of the catalyst in dry air at 650 ℃ for 3 hours. DMAE = dimethylaminoethanol, DMF = dimethylformamide
Figure BDA0003516289270000582
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Figure BDA0003516289270000591
The target titanium level was 3.5wt% Ti. This is considered to be 1 equivalent of Ti. Attempts were made to dissolve 1 equivalent of titanium dioxide with the stated equivalent of carboxylic acid and with the stated equivalent of H2O2 and/or base,
after impregnating the Ti solution onto the silica, the resulting mixture was dried in a vacuum oven overnight at 100 ℃, followed by calcination of a portion of the catalyst in dry air at 650 ℃ for 3 hours. DMAE = dimethylaminoethanol, DMF = dimethylformamide
Additional disclosure-part I
The following enumerated aspects of the present disclosure are provided as non-limiting examples.
A first aspect is a process comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4; c) Contacting a nitrogen-containing compound with the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5.5; and d) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
A second aspect is the method of the first aspect, further comprising e) calcining the procatalyst to form a catalyst by heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ and maintaining the temperature of the procatalyst in the range of about 400 ℃ to about 1000 ℃ for a period of about 1 minute to about 24 hours.
A third aspect is the method of any one of the preceding two aspects, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is about 1:2 and the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is about 1:2.
A fourth aspect is the method of any one of the preceding three aspects, wherein the pH of the solubilized titanium mixture is in the range of about 3.5 to about 4.5.
A fifth aspect is the method of any one of the preceding four aspects, wherein (c) comprises neutralizing the acidic titanium mixture, and wherein the neutralizing is partially or fully neutralizing.
A sixth aspect is the method of any one of the preceding five aspects, wherein the nitrogen-containing compound has structure 1, structure 2, structure 3, structure 4, structure 5, or structure 6: wherein R is 1 、R 2 、R 3 、R 9 、R 10 And R is 11 Each independently is hydrogen, C 1 To C 12 Organic group or C 6 To C 12 An aryl group; r is R 4 Is C 1 To C 12 Organic group or C 6 To C 12 An aryl group; r is R 5 And R is 6 Each independently is hydrogen, C 1 To C 6 Organic group or C 6 To C 12 An aryl group; r is R 7 And R is 8 Each independently is hydrogen or CH 3 ；R 12 Is branched C 1 To C 6 Alkyl, cyclic C 1 To C 6 Alkyl or straight-chain C 1 To C 6 An alkyl group; x is an integer from 1 to 4, y is an integer from 1 to 12, and Z is oxygen or sulfur.
Figure BDA0003516289270000601
Figure BDA0003516289270000611
A seventh aspect is the method of any one of the first six aspects, wherein the nitrogen-containing compound comprises an alkanolamine, an amine, an ammonium hydroxide, a hydroxylamine, urea, or a combination thereof.
An eighth aspect is the method of any of the seventh aspects above, wherein the nitrogen-containing compound comprises acetamide, ammonia, ammonium hydroxide, t-butylamine, creatine, N '-dibutylurea, diethanolamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N' -dimethylurea, ethanolamine, ethyleneglycol amine, hexylamine, hydroxylamine, imidazole, isopropanolamine, N-methylaniline, methyldiethanolamine, methylformamide, pyrazole, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, or a combination thereof.
A ninth aspect is the method of any one of the eight preceding aspects, wherein theThe carboxylic acid includes C 1 To C 15 Monocarboxylic acid, C 2 To C 15 Dicarboxylic acids, C 3 To C 15 Tricarboxylic acid, C 1 To C 15 Alpha-hydroxycarboxylic acids, or combinations thereof.
A tenth aspect is the method of any one of the nine preceding aspects, wherein the carboxylic acid comprises acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid, or a combination thereof.
An eleventh aspect is the method of any of the preceding ten aspects, wherein the titanium-containing compound comprises a titanium hydroxide, a titanic acid, a titanyl sulfate, a titanium (IV) alkoxide, a titanyl acetylacetonate, a titanium (IV) halide, or a combination thereof.
A twelfth aspect is the method of any of the preceding eleven aspects, wherein the titanium-containing compound comprises titanium (IV) isopropoxide.
A thirteenth aspect is the method of any one of the first twelve aspects, wherein (d) further comprises spray drying the solubilized titanium mixture onto the chromium-silica support.
A fourteenth aspect is the method of any one of the thirteenth aspects, wherein the chromium-silica support is characterized as having a particle size of about 100m 2 /g to about 1000m 2 Surface area per gram and about 1.0cm 3 /g to about 2.5cm 3 Pore volume per gram.
A fifteenth aspect is the method of any one of the preceding fourteenth aspects, wherein the amount of chromium present in the catalyst is in the range of from about 0.01wt% to about 10wt%, based on the total weight of the catalyst, and the amount of titanium present in the catalyst is in the range of from about 0.01wt% to about 10wt%, based on the total weight of the catalyst.
A sixteenth aspect is the method of any one of the fifteenth aspects, wherein the solvent comprises an aqueous solvent, an alcohol, an organic solvent, or a combination thereof.
A seventeenth aspect is a process for forming an ethylene polymer, the process comprising contacting the catalyst formed by the process of the second aspect with ethylene monomer under conditions suitable for forming the ethylene polymer, and recovering the ethylene polymer.
An eighteenth aspect is the method of the seventeenth aspect, wherein the ethylene polymer has a High Load Melt Index (HLMI) that is about 1.5 to about 15 times greater than the HLMI of an ethylene polymer prepared with an otherwise similar catalyst produced in the absence of the nitrogen-containing compound.
A nineteenth aspect is a method comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4; c) Contacting a nitrogen-containing compound with the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4.5; d) Contacting a silica support comprising about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form a titanated support, and drying the titanated support by heating to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form a dried titanated support; and e) contacting a chromium-containing compound and at least one material selected from the group consisting of the silica support, the titanated support and the dried titanated support to form a procatalyst.
A twentieth aspect is the method of the nineteenth aspect, the method further comprising: f) The procatalyst is calcined by heating to a temperature in the range of about 400 ℃ to about 1000 ℃ and maintaining the temperature in the range of about 400 ℃ to about 1000 ℃ for a period of about 1 minute to about 24 hours to form the catalyst.
A twenty-first aspect is the method of the nineteenth aspect, wherein (c) comprises neutralizing the acidic titanium mixture, and wherein the neutralizing is partially or fully neutralizing.
A twenty-second aspect is a method comprising: a) Contacting a titanium-containing compound and a nitrogen-containing compound to form a basic mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the basic mixture is from about 1:1 to about 1:4; b) Contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; c) Contacting the basic mixture and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4.5; and d) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
A twenty-third aspect is the method of the twenty-second aspect, further comprising: e) The procatalyst is calcined to form a catalyst by heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ and maintaining the temperature of the procatalyst in the range of about 400 ℃ to about 1000 ℃ for a period of about 1 minute to about 24 hours.
A twenty-fourth aspect is a method comprising: a) Contacting a titanium-containing compound and a nitrogen-containing compound to form a basic mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the basic mixture is from about 1:1 to about 1:4; b) Contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; c) Contacting the basic mixture and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4.5; d) Contacting a silica support comprising about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form a titanated support, and drying the titanated support by heating to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form a dried titanated support; and e) contacting a chromium-containing compound and at least one material selected from the group consisting of the silica support, the titanated support and the dried titanated support to form a procatalyst.
A twenty-fifth aspect is the method of the twenty-fourth aspect, the method further comprising: f) The procatalyst is calcined to form a catalyst by heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ and maintaining the temperature of the procatalyst in the range of about 400 ℃ to about 1000 ℃ for a period of about 1 minute to about 24 hours.
A twenty-sixth aspect is a procatalyst composition comprising: a) A silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.1wt% to about 20wt%, based on the amount of silica; d) A carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is in the range of about 1:1 to about 1:10; and e) a nitrogen-containing compound having a formula containing at least one nitrogen atom, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.
A twenty-seventh aspect is the procatalyst composition of the twenty-sixth aspect, wherein the carboxylic acid comprises C 1 To C 15 Monocarboxylic acid, C 2 To C 15 Dicarboxylic acids, C 3 To C 15 Tricarboxylic acid, C 1 To C 15 Alpha-hydroxycarboxylic acids, or combinations thereof.
A twenty-eighth aspect is the procatalyst composition of any one of the twenty-sixth or twenty-seventh aspects, wherein the carboxylic acid comprises acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid, or a combination thereof.
A twenty-ninth aspect is the procatalyst composition of any one of the twenty-sixth through twenty-eighth aspects, wherein the nitrogen-containing compound comprises an alkanolamine, an amide, an amine, an alkylamine, an ammonium hydroxide, an aniline, a hydroxylamine, urea, or a combination thereof.
A thirty-first aspect is the procatalyst composition of any one of the twenty-sixth through twenty-ninth aspects, wherein the nitrogen-containing compound comprises acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, tert-butylamine, N '-dibutylurea, creatine, creatinine, diethanolamine, diethylhydroxylamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N' -dimethylurea, ethanolamine, ethylamine, ethyleneglycol amine, hexylamine, hydroxylamine, imidazole, isopropanolamine, methacrylamide, methylamine, N-methylaniline, N-methyl-2-propanolamine, methyldiethanolamine, methylformamide, propylamine, 2-propanolamine, pyrazole, pyrrolidine, pyrrolidone, succinimide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, 1, 8-diazabicyclo [5.4.0] undec-7-ene, or a combination thereof.
A thirty-first aspect is the procatalyst composition of any one of the twenty-first to thirty-first aspects, wherein the silica support further comprises alumina.
A thirty-second aspect is the procatalyst composition of any one of the twenty-sixth through thirty-first aspects, wherein the silica support is characterized by having about 100m 2 /g to about 1000m 2 Surface area per gram and about 1.0cm 3 /g to about 2.5cm 3 Pore volume per gram.
A thirty-third aspect is the procatalyst composition of any one of the twenty-sixth through thirty-second aspects, wherein the silica support comprises a hydrated silica support.
A thirty-fourth aspect is the procatalyst composition of any one of the twenty-first to thirty-third aspects, wherein the silica support comprises about 1wt% to about 20wt% water, based on the total weight of the silica support.
A thirty-fifth aspect is a procatalyst composition comprising: a) A silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; and c) a titanium organic salt, wherein the titanium organic salt comprises titanium, a protonated nitrogen-containing compound, and a carboxylate, and wherein: i) The amount of titanium ranges from about 0.1wt% to about 20wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound in the range of from about 1:0.5 to about 1:10.
A thirty-sixth aspect is the procatalyst composition of the thirty-fifth aspect, wherein the protonated nitrogen-containing compound comprises a protonated alkanolamine, a protonated amide, a protonated amine, a protonated alkylamine, a protonated ammonium hydroxide, a protonated aniline, a protonated hydroxylamine, a protonated urea, or a combination thereof.
A thirty-seventh aspect is the procatalyst composition of the thirty-fifth aspect, wherein the protonated nitrogen-containing compound comprises a protonated acetamide, a protonated acrylamide, a protonated allylamine, ammonium, a protonated ammonium hydroxide, a protonated butylamine, a protonated tert-butylamine, a protonated N, N '-dibutylurea, a protonated creatine, a protonated creatinine, a protonated diethanolamine, a protonated diethylhydroxylamine, a protonated diisopropanolamine, a protonated dimethylaminoethanol, a protonated dimethylcarbamate, a protonated dimethylformamide, a protonated dimethylglycine, a protonated dimethylisopropanolamine, a protonated N, N' -dimethylurea, a protonated ethanolamine, a protonated ethylamine, a protonated ethyleneglycol amine, a protonated hexylamine, a protonated hydroxylamine, a protonated imidazole, a protonated isopropanolamine, a protonated methacrylamide, a protonated methylamine, a protonated N-methylaniline, a protonated N-methyl-2-propanolamine, a protonated diethanolamine, a protonated methylformamide, a protonated propylamine, a protonated 2-propanolamine, a protonated pyrazole, a pyrrolidinone, a protonated tetraacetic acid, a 5.5-bis-isocyanatomide, a 2-naphtalene, a protonated tetraacetic acid, a 2-naphtalene, a-1, a-naphthyridine, a-1-bis-naphtalene, a-amine, a-bis-naphthas, or a combination thereof.
A thirty-eighth aspect is the procatalyst composition of any one of the thirty-fifth through thirty-seventh aspects, wherein the carboxylate comprises C 1 To C 15 Monocarboxylate radical, C 2 To C 15 Dicarboxylic acid radicals, C 3 To C 15 Tricarboxylic acid radical, C 1 To C 15 An alpha-hydroxycarboxylic acid radical, or a combination thereof.
A thirty-ninth aspect is the procatalyst composition of any one of the thirty-fifth to thirty-eighth aspects, wherein the carboxylate comprises acetate, citrate, glycolate, oxalate, phosphonoacetate, or a combination thereof.
A fortieth aspect is the procatalyst composition of any one of the thirty-fifth through thirty-ninth aspects, wherein the silica support further comprises alumina.
A forty aspect is the procatalyst composition of any of the thirty-fifth through fortieth aspects, wherein the silica support is characterized by having about 100m 2 /g to about 1000m 2 Surface area per gram and about 1.0cm 3 /g to about 2.5cm 3 Pore volume per gram.
A forty-second aspect is the procatalyst composition of any one of the thirty-fifth through fortieth aspects, wherein the silica support comprises a hydrated silica support.
A forty-third aspect is the procatalyst composition of any one of the thirty-fifth through fortieth aspects, wherein the silica support comprises about 1wt% to about 20wt% water, based on the total weight of the silica support.
A forty-fourth aspect is a procatalyst composition comprising: a) A silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.01wt% to about 0.1wt%, based on the amount of silica; d) A carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is in the range of about 1:1 to about 1:10; and e) a nitrogen-containing compound having a formula containing at least one nitrogen atom, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.
A forty-fifth aspect is a procatalyst composition prepared by a process comprising: a) Contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4; c) Contacting a nitrogen-containing compound with the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5.5; and d) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form the procatalyst.
Additional disclosure-part II
The following enumerated aspects of the present disclosure are provided as non-limiting examples.
A first aspect is a process comprising a) contacting a solvent, a carboxylic acid, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
The second aspect is the method of the first aspect, wherein the peroxy-containing compound comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
A third aspect is the method of any one of the first to second aspects, wherein the carboxylic acid comprises C 1 To C 15 Monocarboxylic acid, C 2 To C 15 Dicarboxylic acids, C 3 To C 15 Tricarboxylic acid, C 1 To C 15 Alpha-hydroxycarboxylic acids, or combinations thereof.
A fourth aspect is the method of any one of the first to third aspects, wherein the carboxylic acid comprises acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, gluconic acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
A fifth aspect is a process comprising a) contacting a solvent, a carboxylic acid, a nitrogen-containing compound, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
A sixth aspect is the method of the fifth aspect, wherein the carboxylic acid comprises C 1 To C 15 Monocarboxylic acid, C 1 To C 15 Dicarboxylic acids, C 2 To C 15 Tricarboxylic acid, C 1 To C 15 Alpha-hydroxycarboxylic acids, or combinations thereof.
A seventh aspect is the method of any one of the fifth to sixth aspects, wherein the carboxylic acid comprises acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, gluconic acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
An eighth aspect is the method of any of the fifth to seventh aspects, wherein the nitrogen-containing compound comprises an alkanolamine, an amide, an amine, an alkylamine, an ammonium hydroxide, an aniline, a hydroxylamine, urea, or a combination thereof.
A ninth aspect is the method of any one of the fifth to eighth aspects, wherein the peroxy-containing compound comprises an organic peroxide, a diacyl peroxide, a peroxydicarbonate, a monoperoxycarbonate, a peroxyketal, a peroxyester, a dialkyl peroxide, a hydroperoxide, or a combination thereof.
A tenth aspect is the method of any one of the fifth to ninth aspects, wherein the peroxy-containing compound comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
An eleventh aspect is a process comprising a) contacting a solvent, at least two carboxylic acids, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, and wherein the at least two carboxylic acids comprise at least one simple carboxylic acid and at least one complex carboxylic acid; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
A twelfth aspect is the method of the eleventh aspect, wherein the at least two carboxylic acids comprise C 1 To C 15 Monocarboxylic acid, C 2 To C 15 Dicarboxylic acids, C 3 To C 15 Tricarboxylic acid,C 1 To C 15 Alpha-hydroxycarboxylic acids, or combinations thereof.
A thirteenth aspect is the method of any one of the eleventh to twelfth aspects, wherein the at least two carboxylic acids comprise citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, gluconic acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
A fourteenth aspect is the method of any one of the eleventh to thirteenth aspects, wherein the peroxy-containing compound comprises an organic peroxide, a diacyl peroxide, a peroxydicarbonate, a monoperoxycarbonate, a peroxyketal, a peroxyester, a dialkyl peroxide, a hydroperoxide, or a combination thereof.
A fifteenth aspect is the method of any one of the eleventh to fourteenth aspects, wherein the peroxy-containing compound comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
A sixteenth aspect is a method comprising a) contacting a solvent, at least two carboxylic acids, and a nitrogen-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
A seventeenth aspect is a method comprising a) contacting a solvent, at least two carboxylic acids, a nitrogen-containing compound, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
An eighteenth aspect is a method comprising a) contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the solubilized titanium mixture is from about 1:to about 1:5; and wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1wt% to about 20wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of from about 50 ℃ to about 150 ℃ for a period of from about 30 minutes to about 6 hours to form a procatalyst.
A nineteenth aspect is the method of the eighteenth aspect, wherein the acidic phenol comprises catechol, salicyl, salicylic acid, phthalic acid, or any combination thereof.
A twentieth aspect is a process comprising a) contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the solubilized titanium mixture is from about 1:to about 1:5; and wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; c) Contacting the solubilized titanium mixture with a chromium-containing compound to form a chromium-titanium mixture; d) Contacting the chromium titanium mixture with a silica support comprising silica to form an addition product, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; and e) drying the addition product by heating to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form a procatalyst.
A twenty-first aspect is a process comprising a) preparing an acidic mixture comprising a solvent and at least two components selected from the group consisting of one or more carboxylic acids, one or more acidic phenols, one or more peroxy-containing compounds, and one or more nitrogen-containing compounds, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) Contacting the acidic mixture with a chromium-containing compound, a titanium-containing compound, and a silica support to form an addition product, wherein: (i) an equivalent molar ratio of titanium-containing compound to carboxylic acid when present in the acidic mixture is from about 1:1 to about 1:4, (ii) an equivalent molar ratio of titanium-containing compound to acidic phenol when present in the acidic mixture is from about 1:to about 1:5, and (iii) an equivalent molar ratio of titanium-containing compound to peroxy-containing compound when present in the acidic mixture is from about 1:1 to about 1:20; and c) drying the addition product by heating to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature in the range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form a procatalyst.
A twenty-second aspect is a composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.1wt% to about 20wt%, based on the amount of silica; d) A carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is in the range of about 1:1 to about 1:10; and e) a peroxy-containing compound, wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound is in the range of about 1:1 to about 1:20.
A twenty-third aspect is the composition of the twenty-second aspect, further comprising a nitrogen-containing compound, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.
A twenty-fourth aspect is the composition of any one of the twenty-second to twenty-third aspects, wherein the carboxylic acid comprises C 1 To C 15 Monocarboxylic acid, C 2 To C 15 Dicarboxylic acids, C 3 To C 15 Tricarboxylic acid, C 1 To C 15 Alpha-hydroxycarboxylic acids, or combinations thereof.
A twenty-fifth aspect is the composition of any one of the twenty-second to twenty-fourth aspects, wherein the carboxylic acid comprises citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, gluconic acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
A twenty-sixth aspect is the composition of any one of the twenty-third to twenty-fifth aspects, wherein the nitrogen-containing compound comprises an alkanolamine, an amide, an amine, an alkylamine, an ammonium hydroxide, an aniline, a hydroxylamine, urea, or a combination thereof.
A twenty-seventh aspect is the composition of any one of the twenty-second to twenty-sixth aspects, wherein the peroxy-containing compound comprises an organic peroxide, a diacyl peroxide, a peroxydicarbonate, a monoperoxycarbonate, a peroxyketal, a peroxyester, a dialkyl peroxide, a hydroperoxide, or a combination thereof.
A twenty-eighth aspect is the composition of any one of the twenty-second to twenty-seventh aspects, wherein the peroxy-containing compound comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
A twenty-ninth aspect is the composition of any one of the twenty-second to twenty-eighth aspects, further comprising an acidic phenol.
A thirty-first aspect is a composition comprising a) a silica support comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica support; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; and c) a titanium organic salt, wherein the titanium organic salt comprises titanium, carboxylate, and peroxy-containing compound, and wherein the titanium organic salt comprises i) the amount of titanium is in the range of about 0.1wt% to about 20wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to the peroxy-containing compound is in the range of about 1:0.5 to about 1:20.
A thirty-first aspect is the composition of the thirty-first aspect, further comprising a nitrogen-containing compound, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1:5.
A thirty-second aspect is the composition of any one of the thirty-first to thirty-second aspects, wherein the peroxy-containing compound comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
A thirty-third aspect is the composition of any one of the thirty-third aspects, wherein the carboxylate comprises acetate, citrate, gluconate, glycolate, glyoxylate, lactate, malate, malonate, oxalate, phosphonoacetate, tartrate, or a combination thereof.
A thirty-fourth aspect is a composition comprising a) a silica carrier comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica carrier; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.01wt% to about 0.1wt%, based on the amount of silica; d) At least two carboxylic acids, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is in the range of about 1:1 to about 1:10; and e) a peroxy-containing compound, wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound is in the range of about 1:1 to about 1:10.
A thirty-fifth aspect is the composition of the thirty-fourth aspect, wherein the at least two carboxylic acids comprise at least one simple carboxylic acid and at least one complex carboxylic acid.
A thirty-sixth aspect is the composition of the thirty-fourth to thirty-fifth aspects, wherein the peroxy-containing compound comprises hydrogen peroxide, t-butyl peroxide, or a combination thereof.
A thirty-seventh aspect is the composition of the thirty-fourth to thirty-sixth aspects, further comprising an acidic phenol.
A thirty-eighth aspect is the composition of any one of the thirty-fourth to thirty-seventh aspects, further comprising a nitrogen-containing compound, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.
A thirty-ninth aspect is a composition comprising a) a silica carrier comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica carrier; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium organic salt, wherein the titanium organic salt comprises titanium, a protonated nitrogen-containing compound, and a carboxylate, and wherein the titanium organic salt comprises: i) The amount of titanium ranges from about 0.1wt% to about 20wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound in the range of from about 1:0.5 to about 1:10; and d) a peroxy-containing compound, wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound is from about 1:1 to about 1:20.
A fortieth aspect is a composition comprising a) a silica carrier comprising silica, wherein the amount of silica is in the range of about 70wt% to about 95wt%, based on the total weight of the silica carrier; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; and c) a titanium organic salt, wherein the titanium organic salt comprises titanium, a protonated nitrogen-containing compound, and a carboxylate, and wherein the titanium organic salt comprises i) the amount of titanium ranges from about 0.1wt% to about 20wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound in the range of from about 1:0.5 to about 1:10; and d) an acidic phenol, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the acidic titanium mixture is from about 1:1 to about 1:5.
A fortieth aspect is a composition comprising a) at least two components selected from the group consisting of one or more carboxylic acids, one or more acidic phenols, one or more peroxy-containing compounds, and one or more nitrogen-containing compounds; b) A chromium-containing compound, wherein the amount of chromium is in the range of about 0.1wt% to about 5wt%, based on the amount of silica; c) A titanium-containing compound, wherein the amount of titanium is in the range of about 0.01wt% to about 0.1wt%, based on the amount of silica; and (i) wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid when present is in the range of about 1:1 to about 1:10; (ii) Wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound when present is in the range of about 1:1 to about 1:10; (iii) Wherein the equivalent molar ratio of titanium-containing compound to acidic phenol, when present, in the acidic titanium mixture is from about 1:1 to about 1:5; and (iv) wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound when present is in the range of about 1:0.5 to about 1:5.
A fortieth aspect is a catalyst prepared according to the method of the first aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form an olefin polymerization catalyst.
A forty-third aspect is a catalyst prepared according to the method of the fifth aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form an olefin polymerization catalyst.
A forty-fourth aspect is a catalyst prepared according to the method of the eleventh aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form the olefin polymerization catalyst.
A forty-fifth aspect is a catalyst prepared according to the method of the sixteenth aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form the olefin polymerization catalyst.
A forty-sixth aspect is a catalyst prepared according to the method of the seventeenth aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form the olefin polymerization catalyst.
A forty-seventh aspect is a catalyst prepared according to the method of the eighteenth aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form the olefin polymerization catalyst.
A forty-eighth aspect is a catalyst prepared according to the method of the twentieth aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form an olefin polymerization catalyst.
A forty-ninth aspect is a catalyst prepared according to the method of the twenty-first aspect, wherein the method further comprises heating the procatalyst to a temperature in the range of about 400 ℃ to about 1000 ℃ in the presence of air to form an olefin polymerization catalyst.
The terms "a" and "an" are intended to include plural alternatives, such as at least one, unless specifically indicated otherwise. Although the methods and processes are described herein as "comprising" various components or steps, the methods and processes may also "consist essentially of" or "consist of" the various components or steps. Specific features of the disclosed subject matter can be disclosed as follows: feature X may be A, B or C. It is also contemplated that the recitation may also be recited as a list of alternatives to each feature, such that recitation "feature X is a, alternatively B, or alternatively C" is also an aspect of the present disclosure, whether or not the recitation is explicitly recited.
While various aspects of the present disclosure have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the disclosure. The aspects of the present disclosure described herein are merely exemplary and are not intended to be limiting. Many variations and modifications of the disclosure are possible and are within the scope of the disclosure. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., "about 1 to about 10" includes 2, 3, 4, etc.; "greater than 0.10" includes 0.11, 0.12, 0.13, etc.). Use of the term "optionally" with respect to any element of a claim means that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claims. The use of broad terms such as "comprising," "including," "having," and the like should be understood to provide support for narrow terms such as "consisting of … …," "consisting essentially of … …," "substantially comprising … …," and the like.
The scope of protection is therefore not limited by the description set out above, but is only limited by the claims which follow, the scope of which includes all equivalents of the subject matter of the claims. Each claim is incorporated into the specification as an aspect of the present disclosure. Accordingly, the claims are a further description and are an addition to aspects of the present disclosure. Discussion of a reference in this disclosure is not an admission that it is prior art to the present disclosure, especially any reference that may have a publication date after the priority date of this application. The present disclosure of all patents, patent applications, and publications cited herein are hereby incorporated by reference to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein.
All publications, patent applications, and patents mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. With respect to all ranges disclosed herein, such ranges are intended to include any combination of the recited upper and lower limits, even if the particular combination is not specifically listed.

Claims (27)

1. A method for preparing a procatalyst, comprising:
a) Contacting a solvent, a carboxylic acid, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from 1:1 to 100:1;
b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from 1:1 to 1:4, and the equivalent molar ratio of titanium-containing compound to the peroxy-containing compound in the solubilized titanium mixture is from 1:1 to 1:20;
c) Contacting a chromium-silica support comprising 0.1wt% to 20wt% water with the solubilized titanium mixture to form an addition product; and
d) Drying the addition product by heating to a temperature in the range of 50 ℃ to 150 ℃ and maintaining the temperature in the range of 50 ℃ to 150 ℃ for a period of 30 minutes to 6 hours to form a procatalyst.
2. The method of claim 1, wherein the at least two carboxylic acids comprise acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
3. The method of claim 1, wherein the acidic mixture further comprises a nitrogen-containing compound selected from the group consisting of alkanolamines, amides, alkylamines, ammonium hydroxides, anilines, hydroxylamines, urea, or combinations thereof.
4. The method of claim 1, wherein the acidic mixture further comprises an amine.
5. The method of claim 1, wherein the solvent comprises an aqueous solvent, an alcohol, a hydrocarbon, or a combination thereof.
6. The method of claim 1, wherein the solvent comprises an organic solvent.
7. A method for preparing a procatalyst, comprising:
a) Contacting a solvent, at least two carboxylic acids, a nitrogen-containing compound, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to at least two carboxylic acids in the acidic mixture is from 1:1 to 100:1;
b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to at least two carboxylic acids in the solubilized titanium mixture is from 1:1 to 1:4, and the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from 1:1 to 1:20;
c) Contacting a chromium-silica support comprising 0.1wt% to 20wt% water with the solubilized titanium mixture to form an addition product; and
d) Drying the addition product by heating to a temperature in the range of 50 ℃ to 150 ℃ and maintaining the temperature in the range of 50 ℃ to 150 ℃ for a period of 30 minutes to 6 hours to form a procatalyst.
8. The method of claim 7, wherein the peroxy-containing compound comprises a diacyl peroxide, peroxydicarbonate, monoperoxycarbonate, peroxyketal, peroxyester, dialkyl peroxide, hydroperoxide, or a combination thereof.
9. The method of claim 7, wherein the peroxy-containing compound comprises an organic peroxide.
10. The method of claim 7, wherein the peroxy-containing compound comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
11. The method of claim 7, wherein the at least two carboxylic acids comprise acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
12. The method of claim 7, wherein the nitrogen-containing compound comprises an alkanolamine, an amide, an alkylamine, an ammonium hydroxide, an aniline, a hydroxylamine, urea, or a combination thereof.
13. The method of claim 7, wherein the nitrogen-containing compound comprises an amine.
14. A method for preparing a procatalyst, comprising:
a) Contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxy-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from 1:1 to 100:1;
b) Contacting a titanium-containing compound with the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from 1:1 to 1:4, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the solubilized titanium mixture is from 1:1 to 1:5; and wherein the equivalent molar ratio of titanium-containing compound to peroxy-containing compound in the solubilized titanium mixture is from 1:1 to 1:20;
c) Contacting the solubilized titanium mixture with a chromium-containing compound to form a chromium-titanium mixture;
d) Contacting the chromium titanium mixture with a silica support comprising silica to form an addition product, wherein the amount of silica is in the range of 70wt% to 95wt%, based on the total weight of the silica support; and
e) Drying the addition product by heating to a temperature in the range of 50 ℃ to 150 ℃ and maintaining the temperature in the range of 50 ℃ to 150 ℃ for a period of 30 minutes to 6 hours to form a procatalyst.
15. The method of claim 14, wherein the acidic phenol comprises catechol, salicyl, salicylic acid, or a combination thereof.
16. The method of claim 14, wherein the peroxy-containing compound comprises a diacyl peroxide, peroxydicarbonate, monoperoxycarbonate, peroxyketal, peroxyester, dialkyl peroxide, hydroperoxide, or a combination thereof.
17. The method of claim 14, wherein the peroxy-containing compound comprises an organic peroxide.
18. The method of claim 14, wherein the peroxy-containing compound comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
19. The method of claim 14, wherein the carboxylic acid comprises acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, α -hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
20. A method for preparing a procatalyst, comprising:
a) Preparing an acidic mixture comprising a solvent, one or more peroxy-containing compounds, and at least one component selected from the group consisting of: one or more carboxylic acids, one or more acidic phenols, and one or more nitrogen-containing compounds;
b) Contacting the acidic mixture with a chromium-containing compound, a titanium-containing compound, and a silica support to form an addition product, wherein:
(i) When present in the acidic mixture, the equivalent molar ratio of titanium-containing compound to the one or more carboxylic acids is from 1:1 to 1:4,
(ii) The weight ratio of solvent to carboxylic acid in the acidic mixture is from 1:1 to 100:1,
(iii) When present in the acidic mixture, the equivalent molar ratio of titanium-containing compound to the one or more acidic phenols is from 1:1 to 1:5,
(iv) When present in the acidic mixture, the equivalent molar ratio of titanium-containing compound to one or more peroxy-containing compounds is from 1:1 to 1:20; and
(v) When present in the acidic mixture, the equivalent molar ratio of titanium-containing compound to the one or more nitrogen-containing compounds is in the range of 1:0.5 to 1:10; and
c) Drying the addition product by heating to a temperature in the range of 50 ℃ to 150 ℃ and maintaining the temperature in the range of 50 ℃ to 150 ℃ for a period of 30 minutes to 6 hours to form a procatalyst.
21. The method of claim 20, wherein the one or more acidic phenols comprise catechol, salicyl, salicylic acid, or any combination thereof.
22. The method of claim 20, wherein the one or more peroxy-containing compounds comprises a diacyl peroxide, a peroxydicarbonate, a monoperoxycarbonate, a peroxyketal, a peroxyester, a dialkyl peroxide, a hydroperoxide, or a combination thereof.
23. The method of claim 20, wherein the one or more peroxy-containing compounds comprises an organic peroxide.
24. The method of claim 20, wherein the one or more peroxy-containing compounds comprises hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.
25. The method of claim 20, wherein the one or more carboxylic acids comprise acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, alpha-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.
26. The method of claim 20, wherein the one or more nitrogen-containing compounds comprise alkanolamines, amides, alkylamines, ammonium hydroxides, anilines, hydroxylamines, urea, or combinations thereof.
27. The method of claim 20, wherein the one or more nitrogen-containing compounds comprise an amine.
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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
US20230340166A1 (en) * 2022-04-26 2023-10-26 Chevron Phillips Chemical Company Lp Aqueous methods for titanating a chromium/silica catalyst with an alkali metal
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424320A (en) * 1981-11-25 1984-01-03 Phillips Petroleum Company Polymerization with a silica base catalyst having titanium incorporated through use of peroxide
US4444964A (en) * 1980-12-31 1984-04-24 Phillips Petroleum Company Polymerization process using phosphate supported chromium catalyst
CN101173013A (en) * 2006-10-31 2008-05-07 中国石油化工股份有限公司 Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same
WO2019204076A1 (en) * 2018-04-16 2019-10-24 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst utilizing hydrated reagents

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248179A (en) 1962-02-26 1966-04-26 Phillips Petroleum Co Method and apparatus for the production of solid polymers of olefins
US4364842A (en) * 1980-12-31 1982-12-21 Phillips Petroleum Company Phosphate supported chromium catalyst
US4501885A (en) 1981-10-14 1985-02-26 Phillips Petroleum Company Diluent and inert gas recovery from a polymerization process
US4382022A (en) * 1981-11-25 1983-05-03 Phillips Petroleum Company Silica having titanium incorporated through use of peroxide
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
US5565175A (en) 1990-10-01 1996-10-15 Phillips Petroleum Company Apparatus and method for producing ethylene polymer
US5575979A (en) 1991-03-04 1996-11-19 Phillips Petroleum Company Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator
US5352749A (en) 1992-03-19 1994-10-04 Exxon Chemical Patents, Inc. Process for polymerizing monomers in fluidized beds
US5436304A (en) 1992-03-19 1995-07-25 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5455314A (en) 1994-07-27 1995-10-03 Phillips Petroleum Company Method for controlling removal of polymerization reaction effluent
US6239235B1 (en) 1997-07-15 2001-05-29 Phillips Petroleum Company High solids slurry polymerization
KR100531628B1 (en) 1998-03-20 2005-11-29 엑손모빌 케미칼 패턴츠 인코포레이티드 Continuous slurry polymerization volatile removal
US6262191B1 (en) 1999-03-09 2001-07-17 Phillips Petroleum Company Diluent slip stream to give catalyst wetting agent
ATE274535T1 (en) * 2000-07-05 2004-09-15 Basell Polyolefine Gmbh SUPPORTED, TITANIZED CHROME CATALYST AND ITS USE FOR PRODUCING ETHYLENE HOMOPOLYMERS AND COPOLYMERS
US9988468B2 (en) * 2016-09-30 2018-06-05 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4444964A (en) * 1980-12-31 1984-04-24 Phillips Petroleum Company Polymerization process using phosphate supported chromium catalyst
US4424320A (en) * 1981-11-25 1984-01-03 Phillips Petroleum Company Polymerization with a silica base catalyst having titanium incorporated through use of peroxide
CN101173013A (en) * 2006-10-31 2008-05-07 中国石油化工股份有限公司 Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same
WO2019204076A1 (en) * 2018-04-16 2019-10-24 Chevron Phillips Chemical Company Lp Methods of preparing a catalyst utilizing hydrated reagents

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