CN114524891A

CN114524891A - Method for preparing catalyst by using hydration reagent

Info

Publication number: CN114524891A
Application number: CN202210166553.9A
Authority: CN
Inventors: 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
Original assignee: Chevron Phillips Chemical Co LLC
Current assignee: Chevron Phillips Chemical Co LLC
Priority date: 2020-01-28
Filing date: 2021-01-26
Publication date: 2022-05-24
Also published as: MX2023012169A; CN114524890B; MX2022009166A; BR122022026884B1; CN114409833B; BR122022026872B1; MX2023012167A; MY197765A; CN114478871A; CA3166010A1; CN114524892B; CN114478871B; KR102499046B1; BR112022013017A2; CN114409833A; CN114144439B; MY197764A; CN114478872A; EP4097150A1; CN114524892A

Abstract

The invention provides a method for preparing a catalyst by using a hydration reagent. 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 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 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 0.1 wt% to about 20 wt% water and the dissolved 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 application is a divisional application, and the filing date of the original application is 26/1/2021, application number is 202180004668.1, and the name of the invention is "method for preparing catalyst by using hydration reagent".

Technical Field

The present disclosure relates to catalyst compositions. More specifically, the present disclosure relates to methods of making olefin polymerization catalyst compositions and polymers made from the olefin polymerization catalyst compositions.

Background

An economically important class of olefin polymerization catalysts includes chromium-silica-titanium (Cr/Si-Ti) catalysts prepared from silica-based catalyst supports. Severe drying of the water sensitive catalyst components used to produce Cr/Si-Ti catalysts can increase 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. Therefore, there is a continuing need to develop new methods for 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 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt%, based on the amount of silica, c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.1 wt% to about 20 wt% 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 molecular formula containing at least one nitrogen atom, wherein the equivalent molar ratio of the titanium-containing compound to the 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 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt%, based on the amount of silica, and c) an organic salt of titanium, wherein the titanium organic salt comprises titanium, a protic nitrogen-containing compound, and carboxylates, and wherein i) the amount of titanium is in the range of from about 0.1 wt% to about 20 wt%, based on the amount of silica, ii) the equivalent molar ratio of titanium to carboxylates is in the range of from 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 from 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 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt%, based on the amount of silica, c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.01 wt% to about 0.1 wt% 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 molecular formula containing at least one nitrogen atom, wherein the equivalent molar ratio of the titanium-containing compound to the 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 a 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 an 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 an 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 0.1 wt% to about 20 wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product to form the procatalyst by heating the addition product to a temperature within a range of about 50 ℃ to about 150 ℃ and maintaining the temperature of the addition product within the range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours.

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 dissolved titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the dissolved titanium mixture is from about 1:1 to about 1:4, and the pH of the dissolved titanium mixture is less than about 5.5, and d) contacting a chromium-silicon dioxide support comprising from about 0.1 wt% to about 20 wt% water and the dissolved titanium mixture to form an addition product, and drying the addition product by heating the addition product to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature of the addition product 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 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 in the range of from about 3.5 to about 4.5, d) contacting a silica support comprising from about 0.1 wt% to about 20 wt% water and the solubilized titanium mixture to form a titanated support, and drying the titanated support by heating the titanated support to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature of the titanated support 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 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.

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 0.1 wt% to about 20 wt% water and the solubilized titanium mixture to form an addition product, and drying the addition product by heating the addition product to a temperature in the range of about 50 ℃ to about 150 ℃ and maintaining the temperature of the addition product 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 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, d) contacting a silica support comprising from about 0.1 wt% to about 20 wt% water and the solubilized titanium mixture to form a titanated support, and drying the titanated support by heating the titanated support to a temperature in the range of from about 50 ℃ to about 150 ℃ and maintaining the temperature of the titanated support 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 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.

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 and the acidic mixture to form a solubilized titanium mixture, wherein the solubilized titanium mixture has an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:1 to about 1:4, and the solubilized titanium mixture has an equivalent molar ratio of titanium-containing compound to peroxy-containing compound of about 1:1 to about 1: 20; and c) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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 method 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 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 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 0.1 wt% to about 20 wt% water and the dissolved 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 and the acidic mixture to form a dissolved titanium mixture, wherein the dissolved titanium mixture has an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:1 to about 1: 4; and c) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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 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 and the acidic mixture to form a solubilized titanium mixture, wherein an 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 an 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 0.1 wt% to about 20 wt% water and the dissolved 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 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 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, 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 dissolved titanium mixture is from about 1:1 to about 1: 20; and c) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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 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 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, 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 dissolved titanium mixture is from about 1:1 to about 1: 20; c) contacting the dissolved 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 in an amount in the range of from about 70 wt% to about 95 wt%, based on the total weight of the silica support, to form an addition product; 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 the procatalyst.

Also disclosed herein 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 nitrogenous 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) the 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) the 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) the 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 said temperature in said range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.

Also disclosed herein is a composition comprising a) a silica support comprising silica, wherein the amount of silica ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.1 wt% to about 20 wt% 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 ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; and c) an organic salt of titanium, wherein the organic salt of titanium comprises titanium, a carboxylate, and a peroxy-containing compound, and wherein the organic salt of titanium comprises i) an amount of titanium in a range of from about 0.1 wt% to about 20 wt%, 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 peroxy-containing compound is in the range of from 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 ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.01 wt% to about 0.1 wt% 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 ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; 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) an amount of titanium in a range of about 0.1 wt% to about 20 wt% 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 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 ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; 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) an amount of titanium in a range from about 0.1 wt% to about 20 wt% 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 from about 1:0.5 to about 1: 10; and d) an acidic phenol, wherein the equivalent molar ratio of the titanium-containing compound to the 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.01 wt% to about 0.1 wt% 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 the titanium-containing compound to the 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 the titanium-containing compound to the nitrogen-containing compound, when present, is in the range of about 1:0.5 to about 1: 5.

Drawings

The following drawings form 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 understood more fully by reference to the accompanying drawings, in which detailed description of specific aspects presented herein are taken.

FIG. 1 illustrates the relationship between zeta potential and pH for 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 drawings and detailed description of these specific aspects are not intended to limit the breadth or scope of the disclosed subject matter or the appended claims in any way. Rather, the drawings and detailed written description are provided to illustrate the disclosure to those skilled in the art and to enable such persons to make and use the concepts disclosed herein.

Detailed Description

The present disclosure encompasses olefin polymerization catalysts and procatalysts thereof, methods of making olefin polymerization catalysts and procatalysts thereof, and methods of utilizing olefin polymerization catalysts. In one aspect, one disclosed method includes contacting a silica support or a chromium-silica support (i.e., a 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 support in the presence of water. Herein, a method for preparing an olefin polymerization catalyst comprises contacting a chromium-silica support with an STM under conditions suitable to form a catalyst composition. An alternative process for preparing an olefin polymerisation catalyst comprises contacting a silica support with an STM and chromium under conditions suitable to form a catalyst composition. Although these aspects may be disclosed under specific headings, the headings are not limiting of the disclosure found therein. Additionally, 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 the treated procatalyst composition. In another aspect, the treated procatalyst composition comprises a procatalyst that has been subjected to an activation treatment (e.g., calcined) as disclosed herein.

Disclosed herein are procatalyst compositions. In one aspect, a procatalyst composition comprises a silica support, a chromium-containing compound, a titanium-containing compound, a carboxylic acid, and a nitrogen-containing compound. Alternatively, the procatalyst composition comprises 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 catalysts and procatalysts thereof of the present disclosure comprise a silica support. The silica support may be any silica support suitable for preparing an olefin polymerization catalyst and procatalyst thereof as disclosed herein. In another aspect, the preparation of the olefin polymerization catalyst and its procatalyst excludes heat treatment of the silica support prior to contact with any other catalyst components. Thus, a silica support suitable for use in the present disclosure may be referred to as a hydrated silica support. Without wishing to be bound by theory, the hydrated silica support comprises a silica support, wherein water emission occurs when the silica support is heated in the range of about 180 ℃ to about 200 ℃ under vacuum conditions 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 0.1 wt% to about 20 wt% water, based on the total weight of the silica support; alternatively, from about 1 wt.% to about 20 wt.% water; alternatively, from about 1 wt% to about 10 wt% water; or alternatively, from about 0.1 wt% to about 10 wt% 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 an active olefin polymerization catalyst. In one aspect of the disclosure, the silica support has a particle size of about 100m²G to about 1000m²(ii)/g; alternatively, about 250m²G to about 1000m²(ii)/g; alternatively, about 250m²G to about 700m²(ii)/g; alternatively, about 250m²G to about 600m²In the range of/g; or alternatively, greater than about 250m²Surface area in g. The silica support may also be characterized as having greater than about 0.9cm³(ii)/g; alternatively, greater than about 1.0cm³(iv) g; or alternatively, greater than about 1.5cm³Pore volume in g. In one aspect of the disclosure, the silica support is characterized as having a silica content of about1.0cm³G to about 2.5cm³Pore 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, from about 25 microns to about 300 microns; or alternatively, an average particle size in a range of about 40 microns to about 150 microns. Typically, the average pore diameter of the silica support can range from about 10 angstroms (Angstrom) to about 1000 angstroms. In one aspect of the present disclosure, the silica support has an average pore diameter of from about 50 angstroms to about 500 angstroms; alternatively, from about 75 angstroms to about 350 angstroms.

Silica supports suitable for use in the present disclosure may contain greater than about 50 wt% silica; alternatively, greater than about 80 wt% silica; or alternatively, greater than about 95 wt% silica. In one aspect, the silica support comprises silica in an amount in the range of from about 70 wt% to about 95 wt%, 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) with water₄) Or by contacting sodium silicate and a mineral acid. In a particular aspect, the silica support may be a hydrogel or a preformed silica support, wherein the preformed silica support has optionally been dried prior to contacting with any other catalyst components. The silica support may include 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 product from PQ Corporation having a particle size of 300m²Surface area per g and 1.6cm³A silica support material in a pore volume per gram; and V398400, a silica support material commercially available from Evonik.

In a particular aspect of the present disclosure, silica supports suitable for use in the present disclosure comprise chromium. Silica supports comprising chromium may be referred to as chromated silica supports or chromium-silica supports. In another aspect, the chromium-silica support comprises the features disclosed herein for the silica support while additionally containing chromium. A non-limiting example of a chromated silica support is HW30A, a chromium-silica support material commercially available from w.r.grace and Company.

The silica support may be present at about 50 wt% to about 99 wt%; or alternatively, in the range of from about 80 wt% to about 99 wt% is present in the olefin polymerization catalyst and its procatalyst. In this context, the percentage of silica support refers to the weight percentage (wt%) of silica support associated with the olefin polymerization catalyst after all processing steps are completed (i.e., after activation by calcination), based on the total weight of the olefin polymerization catalyst. Alternatively, the silica support percentage refers to the weight percent (wt%) of the silica support associated with the procatalyst after completion of all associated processing steps excluding activation by calcination, based on the total weight of the procatalyst.

In another aspect, the olefin polymerization catalysts and procatalysts thereof of the present disclosure comprise chromium. The source of chromium may be any chromium-containing compound capable of providing a sufficient amount of chromium to the olefin polymerization catalyst and procatalyst thereof. In one aspect, the chromium-containing compound can 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, dicyclopentadiene based 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 in the range of from about 0.01 wt% to about 10 wt%, based on the total weight of the olefin polymerization catalyst; alternatively, from about 0.5 wt% to about 5 wt%; alternatively, from about 1 wt% to about 4 wt%; or alternatively, from about 2 wt% to about 4 wt% chromium. In another aspect, the amount of chromium present in the olefin polymerization catalyst can range from about 1 wt% to about 5 wt% chromium based on the total weight of the olefin polymerization catalyst. Herein, the chromium percentage refers to the weight percentage (wt%) of chromium associated with the olefin polymerization catalyst after completion of all processing steps (i.e., after activation by calcination), based on the total weight of the olefin polymerization catalyst. In another aspect, the amount of chromium present in the procatalyst may be from about 0.01 wt% to about 10 wt%, based on the total weight of silica in the procatalyst; alternatively, from about 0.1 wt% to about 5 wt%; alternatively, from about 0.2 wt% to about 2 wt%; or alternatively, from about 0.5 wt% to about 1.5 wt% chromium. Herein, the chromium percentage refers to the weight percent (wt%) of chromium associated with the procatalyst after completion of all processing steps excluding activation by calcination, based on the total weight of silicon dioxide in the procatalyst.

In another aspect, the olefin polymerization catalysts and procatalysts thereof of the present disclosure comprise titanium. The source of titanium can 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 comprises 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 the 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 the ti (iii) species upon dissolution into solution.

In one aspect, titanium-containing compounds suitable for use in the present disclosure include compounds having at least one alkoxy group; or alternatively, a ti (iv) compound of at least two alkoxy groups. Ti (IV) Compound packages suitable for use in this disclosureIncluding but not limited to those having the formula TiO (OR)^K)₂、 Ti(OR^K)₂(acac)₂、Ti(OR^K)₂(oxal), Ti (IV) compounds of combinations thereof, wherein R is^KCan be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or combinations thereof; "acac" is an acetylacetonate ion; and "oxal" is oxalate. Alternatively, the titanium-containing compound comprises a titanium (IV) alkoxide. In one aspect, the titanium (IV) alkoxide can be titanium (IV) ethoxide, titanium (IV) isopropoxide, titanium (IV) n-propoxide, titanium (IV) n-butoxide, titanium (IV) 2-ethylhexanoate, or a combination thereof. In a particular aspect, the titanium-containing compound can be titanium (IV) isopropoxide.

In another aspect, titanium-containing compounds suitable for use in the present disclosure can include titanium dioxide hydrate, titanium hydroxide, titanic acid, titanyl sulfate, titanium acetylacetonate, titanyl acetylacetonate, or combinations thereof.

In another aspect, titanium-containing compounds suitable for use in the present disclosure can include titanium (IV) halides, non-limiting examples of which include titanium tetrachloride, titanium tetrabromide, titanium (IV) oxydichloride, and titanium (IV) dibromide. In another aspect, the titanium (IV) halide can comprise a compound having the general formula Ti (OR)^K)_nQ_4–nThe titanium alkoxy halide of (1); wherein R is^KCan be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or combinations thereof; wherein Q can be fluorine, chlorine, bromine, iodine, or combinations thereof; and wherein n may be an integer from 1 to 4.

The amount of titanium present in the olefin polymerization catalyst may be in the range of from about 0.01 wt% to about 10 wt%, based on the total weight of the olefin polymerization catalyst of the present disclosure; alternatively, from about 0.5 wt% to about 5 wt%; alternatively, from about 1 wt% to about 4 wt%; or alternatively, from about 2 wt% to about 4 wt% titanium. In another aspect, the amount of titanium present in the olefin polymerization catalyst can be in the range of from about 1 wt% to about 5 wt% titanium, based on the total weight of the olefin polymerization catalyst. In this context, the titanium percentage refers to the weight percentage (wt%) of titanium associated with the olefin polymerization catalyst after all processing steps are completed (i.e., after activation by calcination), based on the total weight of the olefin polymerization catalyst. In another aspect, the amount of titanium present in the procatalyst may be from about 0.01 wt% to about 25 wt%, based on the total weight of silica in the procatalyst of the present disclosure; alternatively, from about 0.1 wt% to about 20 wt%; alternatively, from about 0.5 wt% to about 10 wt%; alternatively, from about 1 wt% to about 6 wt%; or alternatively, from about 2 wt% to about 4 wt% titanium. In this context, titanium percentage refers to the weight percent (wt%) of titanium associated with the procatalyst after all processing steps are completed, excluding activation by calcination, based on the total weight of silica in the procatalyst.

In one aspect, the olefin polymerization catalysts and procatalysts thereof of the present disclosure comprise one or more carboxylic acids. The carboxylic acid can 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 can be C₁To C₁₅Monocarboxylic acids or C₁To C₅A monocarboxylic acid; alternatively, C₃To C₁₅Dicarboxylic acids or C₃To C₅A dicarboxylic acid; alternatively, C₁To C₁₅Tricarboxylic acids or C₁To C₅A tricarboxylic acid; alternatively, C₁To C₁₅Alpha-hydroxycarboxylic acids or C₁To C₅An alpha-hydroxycarboxylic acid; alternatively, C₁To C₁₅Beta-hydroxycarboxylic acids or C₁To C₅A beta-hydroxycarboxylic acid; or alternatively, C₁To C₁₅Alpha-ketocarboxylic acids or C₁To C₅An alpha-ketocarboxylic acid.

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, diglucosic acid, iminodiacetic acid, salicylic acid, catechol, 2- (hydroxymethyl) butyric acid, or a combination thereof. In another aspect, the carboxylic acid can be oxalic acid.

In another aspect, the olefin polymerization catalysts and procatalysts thereof of the present disclosure comprise at least two carboxylic acids. In such aspects, the at least two carboxylic acids can 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 can be oxalic acid and phenylmalonic acid.

In one aspect, the olefin polymerization catalysts and procatalysts thereof of the present disclosure comprise an acidic phenol. The acidic phenol can be any acidic phenol capable of providing an olefin polymerization catalyst and procatalyst of the type disclosed herein. In one aspect, the acidic phenol comprises catechol, salicyl alcohol, salicylic acid, phthalic acid, or a derivative thereof. In some aspects, the olefin polymerization catalysts and procatalysts thereof of the present disclosure comprise a carboxylic acid and an acidic phenol, both of the types disclosed herein.

The procatalyst of the present disclosure comprises a molar ratio of from about 1:1 to about 1: 10; alternatively, from 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 comprises a molar ratio of from about 1:1 to about 1: 10; alternatively, from about 1:1 to about 1: 5; or alternatively, an equivalent molar ratio of titanium to acidic phenol in a 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 and procatalysts thereof of the present disclosure comprise a nitrogen containing compound. The nitrogen-containing compound can be any nitrogen-containing compound suitable for providing effective titanation of olefin polymerization catalysts and procatalysts thereof. 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.

R in nitrogen-containing compounds utilized as described herein¹、R²、R³、R⁴、R⁵、R⁶、 R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²Are separate elements of the structure of the nitrogen-containing compound in which they are present and are described independently herein. R provided herein¹、R²、R³、R⁴、 R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And/or R¹²Can be utilized without limitation and in any combination to further describe the inclusion of R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、 R⁹、R¹⁰、R¹¹And/or R¹²Any nitrogen-containing compound structure of (a).

Typically, having R¹、R²、R³、R⁵、R⁶、R⁹、R¹⁰And/or R¹¹R of the corresponding nitrogen-containing compound of (2)¹、R²、R³、R⁵、R⁶、R⁹、R¹⁰And/or R¹¹Each may independently be hydrogen, an organic group, a hydrocarbyl group, or an aryl group. In one aspect, R¹、R²、R³、R⁵、R⁶、R⁹、R¹⁰And/or R¹¹May each independently be C₁To C₃₀An organic group; alternatively, C₁To C₁₂An organic group; or alternatively, C₁To C₆An organic group. In one aspect, R¹、R²、R³、R⁵、R⁶、R⁹、R¹⁰And/or R¹¹May each independently be C₁To C₃₀A hydrocarbyl group; alternatively, C₁To C₁₂A hydrocarbyl group; or alternatively, C₁To C₆A hydrocarbyl group. In other aspects, R¹、R²、R³、R⁵、R⁶、R⁹、R¹⁰And/or R¹¹May each independently be C₆To C₃₀An aryl group; or alternatively, C₆To C₁₂And (4) an aryl group. In another aspect, R can be used in the nitrogen-containing compounds of the present disclosure¹、R²、R³、R⁵、R⁶、R⁹、R¹⁰And/or R¹¹The organic group, hydrocarbyl group or aryl group of (a) may be substituted or unsubstituted. Those skilled in the art will understand that the terms "alkyl", "organo", "hydrocarbyl" and "aryl" are used herein according to the definitions from IUPAC Complex of Chemical technology, 2 nd edition (1997).

Having R⁴R of the corresponding nitrogen-containing compound of⁴Can be an organic group, a hydrocarbyl group or an aryl group. In one aspect, R⁴Can be C₁To C₃₀An organic group; alternatively, C₁To C₁₂An organic group; or alternatively, C₁To C₆An organic group. In one aspect, R⁴Can be C₁To C₃₀A hydrocarbyl group; alternatively, C₁To C₁₂A hydrocarbyl group; or alternatively, C₁To C₆A hydrocarbyl group. In other aspects, R⁴Can be C₆To C₃₀An aryl group; or alternatively, C₆To C₁₂And (4) an aryl group. In another aspect, R may be used in the nitrogen-containing compounds of the present disclosure⁴The organic group, hydrocarbyl group or aryl group of (a) may be substituted or unsubstituted.

In a particular aspect, can be used as R¹、R²、R³、R⁴、R⁵、R⁶、R⁹、R¹⁰And/or R¹¹Any substituted organic group, substituted hydrocarbyl group or substituted aryl group of (a) may contain one or more non-hydrogen substituents. Non-hydrogen substituents suitable for use herein may be halogen, C₁To C₁₂Hydrocarbyl radical, C₁To C₁₂A hydrocarbyloxy group, or a combination thereof. In one aspect, the halogen used as a non-hydrogen substituent can be fluorine, chlorine, bromine, or iodine. C as applicable herein₁To C₁₂Non-limiting examples of hydrocarbyloxy groupsIncluding methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, phenoxy, tolyloxy, xylenoxy, trimethylphenoxy and benzoyloxy.

Having R⁷And/or R⁸R of the corresponding nitrogen-containing compound of⁷And/or R⁸May each independently be hydrogen or methyl.

Having R¹²R of the corresponding nitrogen-containing compound of¹²May be branched alkyl or straight chain alkyl. In one aspect, R¹²Can be C₁To C₃₀A branched alkyl group; alternatively, C₁To C₁₂A branched alkyl group; or alternatively, C₁To C₆A branched alkyl group. In another aspect, R¹²Can be C₁To C₃₀Linear alkyl; alternatively, C₁To C₁₂A linear alkyl group; or alternatively, C₁To C₆A linear alkyl group.

In another aspect, the nitrogen-containing compounds of the present disclosure having structure 2 can have x, wherein x is an integer from 1 to 4. In one aspect, the nitrogen-containing compound having structure 3 can have y, wherein 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 can be alkanolamines, amides, amines, alkylamines, ammonium hydroxides, anilines, hydrazides, hydroxylamines, imines, ureas, or combinations thereof. In another aspect, the alkanolamines, amides, amines, ammonium hydroxides, hydrazides, hydroxylamines, imines, and/or ureas used as nitrogen-containing compounds may contain one or more substituent groups. In one aspect, any substituent group contained within any nitrogen-containing compound of the present disclosure can be halogen, C₁To C₁₂Organic group, C₁To C₁₂Hydrocarbyl radical, C₁To C₁₂A hydrocarbyloxy group, or a combination thereof. The halogen used as a substituent group in any aspect disclosed herein can be fluorine, chlorine, bromine, or iodine. C as used herein₁To C₁₂Non-limiting examples of hydrocarbyloxy groups include methoxy, ethoxy, propoxy, butyloxy, pentyloxy, hexyloxy, phenoxyoxyMesityloxy, xylyloxy, 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, glycol amine, hexylamine, hydroxylamine, imidazole, isopropanolamine, methacrylamide, methylamine, N-methylaniline, N-methyl-2-propanolamine, methyldiethanolamine, methylformamide, propylamine, 2-propanolamine, pyrazole, pyrrolidine, pyrrolidone, succinimide, tetraethylammonium hydroxide, pentahydrate, and the like, Tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, 1, 8-diazabicyclo [5.4.0] undec-7-ene, or a combination thereof.

The procatalyst of the present disclosure comprises a molar ratio of from about 2:1 to about 1: 10; alternatively, from about 1:1 to about 1: 5; or alternatively, an equivalent molar ratio of titanium to nitrogen-containing compound in a 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 comprises a titanium organic salt. In one aspect, the procatalyst composition comprising the organic salt of titanium further comprises a silica support and a chromium-containing compound, both of the types previously disclosed herein. In another aspect, the titanium organic salts useful herein comprise titanium, protonated nitrogen-containing compounds, and carboxylates.

In one aspect, the titanium organic salt comprises titanium. The source of titanium can be any titanium-containing compound capable of providing a sufficient amount of 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 can be any protonated nitrogen-containing compound that is capable of providing a sufficient amount of titanium to the procatalyst as disclosed herein. In another aspect, the protonated nitrogen-containing compounds may comprise protonated forms of any nitrogen-containing compound of the type previously disclosed herein.

In one aspect, the protonated nitrogen-containing compounds include protonated alkanolamines, protonated amides, protonated amines, protonated alkylamines, protonated ammonium hydroxides, protonated anilines, protonated hydroxylamines, protonated ureas, or combinations thereof.

In another aspect, the protonated nitrogen-containing compounds include protonated acetamides, protonated acrylamides, protonated allylamines, ammonium, protonated ammonium hydroxide, protonated butylamine, protonated tert-butylamine, protonated N, N '-dibutylurea, protonated creatine, protonated creatinine, protonated diethanolamine, protonated diethylhydroxylamine, protonated diisopropanolamine, protonated dimethylaminoethanol, protonated dimethylcarbamate, protonated dimethylformamide, protonated dimethylglycine, protonated dimethylisopropanolamine, protonated N, N' -dimethylurea, protonated ethanolamine, protonated ethylamine, protonated glycol amine, protonated hexylamine, protonated hydroxylamine, protonated imidazole, protonated isopropanolamine, protonated methacrylamide, protonated methylamine, protonated N-methylaniline, Protonated N-methyl-2-propanolamine, protonated methyldiethanolamine, protonated methylformamide, protonated propylamine, protonated 2-propanolamine, protonated pyrazole, protonated pyrrolidine, protonated pyrrolidone, protonated succinimide, protonated tetraethylammonium hydroxide, protonated tetramethylammonium hydroxide, protonated triethanolamine, protonated triisopropanolamine, protonated trimethylamine, protonated urea, protonated 1, 8-diazabicyclo [5.4.0] undec-7-ene, or a combination thereof.

In another aspect, the organic salt of titanium comprises a 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 may comprise the anionic form of any carboxylic acid of the type previously disclosed herein.

In another aspect, the carboxylate comprises C₁To C₁₅Monocarboxylate radical, C₂To C₁₅Dicarboxylate radical, C₃To C₁₅Tricarboxylic acid radical, C₁To C₁₅An alpha-hydroxycarboxylate, or a combination thereof.

In another aspect, the carboxylate comprises acetate, citrate, gluconate, glycolate, glyoxylate, lactate, malate, malonate, oxalate, phosphonoacetate, tartrate, or a combination thereof.

In another aspect, the amount of titanium present in the titanium organic salts of the present disclosure can be from about 0.01 wt% to about 20 wt%, based on the total weight of the silica of the procatalyst as disclosed herein; alternatively, from about 0.5 wt% to about 10 wt%; or alternatively, from about 1 wt% to about 6 wt% titanium. In another aspect, the organic salt of titanium comprises a molar ratio of about 1:1 to about 1: 10; alternatively, from 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 to about 1: 10; alternatively, from about 1:1 to about 1: 5; or alternatively, an equivalent molar ratio of titanium to nitrogen-containing compound in a 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 and procatalysts thereof of the present disclosure comprise a peroxy-containing compound. The peroxy-containing compound may be any peroxy-containing compound suitable to provide effective titanation of an olefin polymerization catalyst and procatalysts thereof. In another aspect, 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 any combination thereof. In one aspect, the peroxy-containing compound comprises 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 comprises hydrogen peroxide. In one aspect, the procatalyst of the present disclosure comprises an equivalent molar ratio of titanium to the peroxy-containing compound in the range of from about 1.0:0.5 to about 1:50, alternatively, from about 1:2 to about 1:20, or alternatively, from 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 the STM.

In one aspect of the disclosure, a method for preparing an olefin polymerization catalyst includes utilizing a dissolved titanium mixture (STM). In a particular aspect, the 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, the 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, the STM comprises a carboxylic acid of the type used as a component of the procatalyst as disclosed herein, alternatively at least two carboxylic acids of the type used as a component of the procatalyst as disclosed herein. In another aspect, the STM comprises a titanium-containing compound of the type used as a component of a procatalyst as disclosed herein. In another aspect, the STM comprises one or more nitrogen-containing compounds of the type used as a component of a procatalyst as disclosed herein. In another aspect, the STM comprises one or more peroxy-containing compounds of the type used as a component of a procatalyst as disclosed herein. In another aspect, the STM comprises one or more acidic phenols of the type used as components of a procatalyst as disclosed herein.

In another aspect, the 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, organic solvents suitable for use in the present disclosure can be esters, ketones, 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 a solvent include acetone, ethyl methyl ketone, methyl isobutyl ketone, or combinations thereof. In a particular aspect, the hydrocarbon suitable for use as a solvent can 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 a solvent include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, benzene, toluene, ethylbenzene, xylene, chlorobenzene, dichlorobenzene, or combinations thereof.

In a particular aspect, a dissolved 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, the 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 subsequently contacted with an acidic mixture to form an STM as disclosed herein. In another aspect, the nitrogen-containing compound used to form the basic mixture can be a component of an aqueous solution.

In another aspect, a dissolved 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, STMs are prepared by sequentially adding a titanium-containing compound and a nitrogen-containing compound to an acidic mixture as disclosed herein. In another aspect, STMs are 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 subsequently contacted with an acidic mixture to form an STM as disclosed herein. In another aspect, the nitrogen-containing compound used to form the basic mixture can 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 which are of the type disclosed herein. In one aspect, the STM of the present disclosure comprises a stmt having a molar mass of between about 1:1 to about 100: 1; alternatively, from about 1:1 to about 50: 1; or alternatively, an acidic mixture in a weight ratio of solvent to carboxylic acid in a range of about 1:1 to about 10: 1. In another aspect, the STM comprises a molar ratio of about 1:0.5 to about 1: 20; alternatively, from about 1:1 to about 1: 10; or alternatively, an equivalent molar ratio of titanium-containing compound to carboxylic acid in a 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 comprises a molar ratio of between about 0.1:1 to about 5: 1; alternatively, from about 0.5:1 to about 3: 1; alternatively, from about 1:1 to about 2: 1; or alternatively, an equivalent molar ratio of nitrogen-containing compound to carboxylic acid in a range of about 1:1 to about 2: 1. In another aspect, the STM comprises a molar ratio of about 1:0.5 to about 1: 50; alternatively, from about 1:1 to about 1: 20; alternatively, from 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 from about 1:3 to about 1: 8. In another aspect, the STM comprises a molar ratio of about 1:0.5 to about 1: 10; alternatively, from about 1:1 to about 1: 5; alternatively, from about 1:1 to about 1: 3; or alternatively, an equivalent molar ratio of titanium-containing compound to acidic phenol in a range of about 1:1 to about 1: 2.5.

In another aspect, the STM comprises a molar ratio of about 1:0.5 to about 1: 10; alternatively, from about 1:1 to about 1: 5; alternatively, from about 1:1 to about 1: 3; or alternatively, an equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in a range of from about 1:1 to about 1: 2.5. In other aspects, the equivalent molar ratio of the titanium-containing compound to the 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, the STM may be characterized as having a peak power of between about 2.5 to about 5.5; alternatively, from 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 benefit of this 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 the type disclosed herein, to form an acidic mixture. The method can further include contacting a titanium-containing compound of the type disclosed herein and 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 an 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 about 1:2 of the titanium-containing compound to the nitrogen-containing compound 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 is from about 3% to about 10% of the amount of the nitrogen-containing compound that constitutes an equivalent molar ratio of about 1:2 of the titanium-containing compound to the nitrogen-containing compound. The addition of the plurality of nitrogen-containing compounds can be stopped when the green end point of the bromocresol green indicator is reached. In some aspects, the green end point of the bromocresol green indicator correlates to a pH value within the STM of about 4.0. In another aspect, adding the nitrogen-containing compound to the acidic titanium mixture comprises partially neutralizing the acidic titanium mixture; or alternatively, completely neutralizing the acidic titanium mixture. The method for preparing an olefin polymerization catalyst may further comprise contacting a chromium-silica support of the type disclosed herein and the STM to form an addition product. In another aspect, the adduct can be prepared by heating the adduct to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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 can further include contacting a titanium-containing compound of the type disclosed herein and an 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 an 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 the titanium-containing compound to the 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 is from about 3% to about 10% of the amount of the nitrogen-containing compound that constitutes an equivalent molar ratio of about 1:2 titanium-containing compound to nitrogen-containing compound. The addition of the multiple nitrogen-containing compounds can be stopped when the green end point of the bromocresol green indicator is reached. In some aspects, the green end point of the bromocresol green indicator correlates to a pH value within the STM of about 4.0. In another aspect, adding the nitrogen-containing compound to the acidic titanium mixture comprises partially neutralizing the acidic titanium mixture; or alternatively, completely neutralizing the acidic titanium mixture.

The method for preparing an olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein and an STM to form a titanated support. In another aspect, the support may be prepared by heating a titanated support to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the titanated support at a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at a temperature of from 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of from about 75 ℃ to about 100 ℃ for a period of from 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 and a dried titanated support 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, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, the 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, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, which may be contacted with an STM to form an addition product, which may be formed by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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 which are of the type 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 the titanium-containing compound to the carboxylic acid of about 1:2. In a particular aspect, the amount of the 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 about 1:2 titanium-containing compound to carboxylic acid. The addition of multiple portions of the basic mixture can be stopped when the green end point of the bromocresol green indicator is reached. In some aspects, the green end point of the bromocresol green indicator correlates to a pH value within the STM of about 4.0. In another aspect, adding the basic mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or alternatively, completely neutralizing the acidic mixture. The method for preparing an olefin polymerization catalyst may further comprise contacting a chromium-silica support of the type disclosed herein and the STM to form an addition product. In another aspect, the adduct can be prepared by heating the adduct to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of about 75 ℃ to about 100 ℃ to dry the addition product. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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 which are of the type 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 the titanium-containing compound to the carboxylic acid of about 1:2. In a particular aspect, the amount of the 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 about 1:2 titanium-containing compound to carboxylic acid. The addition of multiple portions of the basic mixture can be stopped when the green end point of the bromocresol green indicator is reached. In some aspects, the green end point of the bromocresol green indicator correlates to a pH value within the STM of about 4.0. In another aspect, adding the basic mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or alternatively, completely neutralizing the acidic mixture. The method for preparing an olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein and an STM to form a titanated support. In another aspect, the support may be prepared by heating a titanated support to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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 and a dried titanated support 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, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, the 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, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, which may be contacted with an STM to form an addition product, which may be formed by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, one or more carboxylic acids, one or more nitrogen-containing compounds, and a peroxy-containing compound, each of the solvent, the carboxylic acids, the nitrogen-containing compounds, and the peroxy-containing compounds being of the type disclosed herein, to form an acidic mixture. Alternatively, a method for preparing an olefin polymerization catalyst comprises contacting a solvent, one or more acidic phenols, a nitrogen-containing compound, and a peroxy-containing compound, each of which is of the type disclosed herein, to form an acidic mixture. Alternatively, a method 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, the solvent, the carboxylic acid, the acidic phenol, the nitrogen-containing compound, and the peroxy-containing compound each being of the type disclosed herein. Alternatively, a method 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 the solvent, the carboxylic acid, the acidic phenol, and the peroxy-containing compound being of the type disclosed herein. Alternatively, a method 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, each of which is of the type disclosed herein, to form an acidic mixture. The method can further comprise contacting a titanium-containing compound of the type disclosed herein and an 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 dissolved titanium mixture (STM) as disclosed herein, for example the nitrogen-containing compound may be added to an 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 about 1:2 of the titanium-containing compound to the nitrogen-containing compound 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 the nitrogen-containing compound that constitutes an equivalent molar ratio of about 1:2 of the titanium-containing compound to the nitrogen-containing compound. The addition of the plurality of nitrogen-containing compounds can be stopped when the green end point of the bromocresol green indicator is reached. In some aspects, the green end point of the bromocresol green indicator correlates to a pH value within the STM of about 4.0. In another aspect, adding the nitrogen-containing compound to the acidic titanium mixture comprises partially neutralizing the acidic titanium mixture; or alternatively, completely neutralizing the acidic titanium mixture. The method for preparing an olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein and an STM to form a titanated support. In another aspect, the support may be prepared by heating a titanated support to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the titanated support at a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at a temperature of from 25 ℃ to about 300 ℃; alternatively, from 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 and a dried titanated support 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, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, the chromium-containing compound and titanated support may be contacted to form an addition product, which may be formed by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the addition product at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, which may be contacted with an STM to form an addition product, which may be formed by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, a carboxylic acid, and a peroxy-containing compound, each of which is of the type disclosed herein, to form an acidic mixture. Alternatively, a method 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 the solvent, the acidic phenol, and the peroxy-containing compound being of the type disclosed herein. Alternatively, a method 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 can further include contacting a titanium-containing compound of the type disclosed herein and 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 and an STM to form a titanated support. In another aspect, the support may be prepared by heating a titanated support to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the titanated support at a temperature in the range of from about 75 ℃ to about 100 ℃. The method further comprises maintaining the titanated support at a temperature of from 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, a temperature in the range of from about 75 ℃ to about 100 ℃ for a period of from 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 and a dried titanated support 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, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, the 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, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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, which may be contacted with an STM to form an addition product, which may be formed by heating the addition product to a temperature of from about 25 ℃ to about 300 ℃; alternatively, from about 50 ℃ to about 150 ℃; or alternatively, drying the addition product at a temperature in the range of about 75 ℃ to about 100 ℃. The method further comprises maintaining the adduct at a temperature of from about 25 ℃ to about 300 ℃; alternatively, from 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 the 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 the silica support to be contacted using a spray drying process. Spray drying as used herein refers to a process of producing a dry powder from a liquid or slurry by rapid drying with a 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 an STM comprising an aqueous solvent may allow the use of a hydrated silica support and eliminate the heat treatment required for the anhydrous catalyst preparation process (e.g., drying the hydrated silica support prior to contact with any other catalyst components).

As one of ordinary skill in the art will appreciate, calcining the procatalysts disclosed herein can result in the emission of Volatile Organic Compounds (VOCs). In various aspects of the present disclosure utilizing peroxide in the absence of nitrogen-containing compounds, the emission of VOCs is reduced when compared to an otherwise similar catalyst preparation conducted in the presence of nitrogen-containing compounds. In one aspect, the VOC emissions achieved by the disclosed catalysts can 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 conducted in the presence of a nitrogen-containing compound.

In some aspects of the present disclosure, the contacting of the components for preparing the olefin polymerization catalyst may be conducted in the presence of a reaction medium. In another aspect, the reaction medium may be formed during the contacting 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 1 wt% to about 99 wt%, based on the total weight of the reaction medium; alternatively, from about 1 wt% to about 50 wt%; alternatively, from about 1 wt% to about 20 wt%; or alternatively, in the range of from about 1 wt% to about 10 wt%. In another aspect, the reaction medium can contain greater than about 20 wt% water, based on the total weight of the reaction medium; alternatively, about 40 wt% water; alternatively, about 60 wt% water; alternatively, about 80 wt% water; or alternatively, about 90 wt% 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 a procatalyst prepared as disclosed herein by a calcination step. In some aspects, calcining the procatalyst includes heating the procatalyst in an oxidizing environment to produce the olefin polymerization catalyst. For example, the procatalyst may be heated to a temperature of from about 400 ℃ to about 1000 ℃ in the presence of air; alternatively, from about 500 ℃ to about 900 ℃; or alternatively, calcining the procatalyst at a temperature in the range of from about 500 ℃ to about 850 ℃. Calcining the procatalyst may further include maintaining the procatalyst in the presence of air at about 400 ℃ to about 1000 ℃; alternatively, from 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, from about 1 minute to about 12 hours; alternatively, from about 20 minutes to about 12 hours; alternatively, from about 1 hour to about 10 hours; alternatively, from about 3 hours to about 10 hours; or alternatively, for a period in the range of from 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 disclosure, the polymers of the present disclosure are produced by any olefin polymerization process using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and/or copolymers. The homopolymers and/or copolymers produced in the reactor may be referred to as resins and/or polymers. 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 multiple reactors. 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. 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 recycle 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, or multiple reactors of the same or different types, in the system 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 a first polymerization reactor into a second reactor. Alternatively, polymerization in multiple reactors may include manual or automated transfer of polymer from one reactor to a subsequent reactor or reactors for additional polymerization. Alternatively, a multistage or multistep polymerization can occur in a single reactor, with conditions being varied such that different polymerization reactions occur.

The desired polymerization conditions in one reactor may be the same or different from the operating conditions of any other reactor involved in the overall process to produce the polymer of the present disclosure. The multiple reactor system may include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, and a combination of high pressure reactors with loop reactors 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 present 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 comprise a vertical or horizontal loop. Generally, a continuous process may comprise continuously introducing monomer, olefin polymerization catalyst and/or diluent into a polymerization reactor and continuously removing a suspension comprising polymer particles and diluent from this reactor. 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 liquid comprising diluent from the solid polymer, monomer and/or comonomer. Various techniques may be used for this separation step, including but not limited to flashing which may include any combination of heating and pressure reduction; 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 in, for example, 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 these patents is incorporated by reference herein in their entirety.

Suitable diluents for use in slurry polymerization include, but are not limited to, the monomers being 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 can occur under bulk conditions where no diluent is used. One 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 recycled through a fluidized bed in the presence of an olefin polymerization catalyst under polymerization conditions. The recycle stream may be withdrawn from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product may be withdrawn from the reactor and fresh monomer may be added to replace polymerized monomer. Such gas phase reactors may comprise a process for multi-step gas phase polymerization of olefins, wherein olefins are polymerized in the gas phase in at least two separate gas phase polymerization zones, while feeding a polymer containing an olefin polymerization catalyst formed in a first polymerization zone to a 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 a high pressure kettle 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 a stream of inert gas and introduced into 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 optimum polymerization conditions.

According to another aspect of the present disclosure, the polymerization reactor may comprise a solution polymerization reactor wherein the monomers are contacted with the olefin polymerization catalyst composition by suitable agitation or other means. A carrier comprising an organic diluent or excess monomer may be employed. If desired, the monomers can be introduced into the vapor phase and contacted with the catalytic reaction products in the presence or absence of liquid material. The polymerization zone is maintained at a temperature and pressure that will result in the formation of a solution of polymer in the reaction medium. Agitation can be used to obtain better temperature control and to maintain a uniform polymerization mixture throughout the polymerization zone. The polymerization exotherm is dissipated by suitable means.

Polymerization reactors suitable for use in the present disclosure may further 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, recycle, storage, discharge, laboratory analysis, and process control.

The conditions 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 the various reactants. 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 the Gibbs Free Energy Equation. Typically, 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.

Suitable pressures 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 (1.4MPa) to 500psig (3.45 MPa). High pressure polymerizations in tubular or autoclave reactors are typically run in the range of about 20,000psig (138MPa) to 75,000psig (518 MPa). The polymerization reactor can also be operated in the supercritical region which 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 end use product proposed to be formed from the polymer and 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, tacticity, crack propagation, short chain branching, long chain branching, and rheological measurements.

The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifier and electron donor are generally important in producing particular polymer properties. Comonomers may be used to control product density. Hydrogen can be used to control product molecular weight. The co-catalyst can be used for alkylation, poison scavenging, and/or molecular weight control. The concentration of poisons may be minimized because poisons may affect the reaction and/or otherwise affect 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 olefin polymerization catalysts prepared as described herein. The polymers produced as disclosed herein can 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 a component of another product. Examples of other end use articles into which the polymer resin may be formed include pipes, films, and bottles.

One disclosed process 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 of between about 1g/10min to about 1000g/10 min; alternatively, from about 3g/10min to about 300g/10 min; alternatively, from about 6g/10min to about 100g/10 min; or alternatively, a High Load Melt Index (HLMI) in a range from 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 an HLMI of a polymer produced using an otherwise similar olefin polymerization catalyst that does not contain titanium.

In a particular aspect, polyethylene can be prepared with a de-titanated catalyst produced from a water-extracted procatalyst. In another aspect, the water-extracted procatalyst is a procatalyst extracted with water 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, a polyethylene prepared with a titanation catalyst may be characterized as having an HLMI in the range of about 1dg/min to about 7 dg/min. Such an HMLI value can indicate that the titanated catalyst has an amount of silica based of from about 0 wt% to about 1 wt%; or alternatively, an amount of titanium in a range of about 0.1 wt% 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 rate of a 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 is 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 manner.

Those skilled in the art will appreciate the inclusion of silicon dioxide (SiO)₂) And dioxygenTitanium (TiO)₂) The surface of the oxide(s) of (a) is generally terminated with a hydroxyl group which is a protic group which can participate in the acid-base reaction. Under strongly acidic conditions, hydroxyl groups can be protonated to generate a positive charge on the oxide surface. Under strongly basic conditions, hydroxyl groups can be deprotonated to create a negative charge on the oxide surface. Somewhere between the two limits there is a pH at which there is a 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 controlled by the chemical nature of the metallic or non-metallic elements 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. The curve of the Coulomb Si-Ti attraction (coulombic Si-Ti attraction) is also shown. The zeta potential is the difference in the electrical 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 between 3.0 and 5.0, titanium dioxide is positively charged and silicon dioxide is negatively charged. The figure also indicates that the 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, it can result in highly efficient titanation of the olefin polymerization catalyst from the aqueous Ti solution. To explore this theory, several series of experiments were conducted to establish conditions that result in the formation of aqueous Ti solutions having a pH of about 4.0.

All silica support materials, chemicals and solvents described herein were used as is and were not dried prior to use.

The catalysts used in the experiments described below include

It is a commercial Cr/silica-titania catalyst obtained from w.r.grace and Company and activated at various temperatures.

Prepared by ternary gelation of Si, Ti and Cr, containing 2.5 wt% Ti and 1 wt% Cr, having a thickness of about 500m²Surface area per gram, pore volume of 2.5mL/g and average particle size of about 130 microns. Another commercial Cr/silica-titania catalyst used is referred to as C-25305HM, available from Philadelphia Quartz (PQ) Corporation. It also contains 2.5 wt% Ti and 1 wt% Cr, having a thickness of about 500m²Surface area per gram, pore volume of 2.7mL/g and average particle size of about 100 microns. The main base catalyst for titanation described below is

HA30W, a commercial Cr/silica obtained from w.r.grace. This catalyst did not contain titanium, but did contain 1 wt% Cr. It has a thickness of about 500m²Surface 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 from w.r.grace

969 MPI. All three of these catalysts do not contain titanium, but do contain 1 wt% Cr. All three had a pore volume of about 1.6 mL/g. EP30X and 969MPI have a thickness of about 300m²Surface area in g and average particle size of about 100 microns. AGC D-70-150A (LV) has a value of about 400m²Surface area per gram and average particle size of about 80 microns.

The activity test was 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 the use of steam and water heat exchangers. These were connected in an electronic feedback loop so that the reactor temperature could be maintained at +/-0.5 ℃ during the reaction.

Unless otherwise stated, a small amount (typically 0.01 to 0.10 grams) of solid chromium catalyst is first charged to the dry reactor under nitrogen. Next, about 0.25g of sulfate treated alumina (600 deg.C) 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 (3.8MPa), which was maintained during the experiment. Stirring was continued for a specified 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 allotted time, the ethylene flow was stopped and the reactor was slowly depressurized and opened to recover granular polymer powder. In all cases, the reactor was clean without any indication of wall fouling, coating or other forms of fouling. The polymer powder was then removed and weighed. The activity is specified as grams of polymer produced per gram of solid catalyst charged per hour.

Example 1

Several control tests were performed and the results of the control tests 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 experiments. Runs 1.10-1.13 show the performance of two non-titanated catalysts, the latter of which HA30W provides a measure of the effectiveness of titanation of runs 1.16-1.18. Titanation shown in runs 1.16-1.18 Using Ti (OiPr)₄To titanate HA 30W. Titanation in run 1.15 the support was exposed to TiCl at 250 deg.C₄Vapors in an attempt to produce a titanation catalyst that is not contaminated with organic or alcohol by-products. 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, the titanium will react with the free adsorbed water and be ineffective. In trials 1.15-1.18, the catalyst was dried at 200 ℃ and subsequently titanated by gas phase or anhydrous solvent (usually heptane).

Example 2: acid titanation

A first series of experiments investigated the ability of carboxylic acids to form acidic Ti-containing solutions capable of providing effective titanation of olefin polymerization catalysts (i.e., catalysts) of the type disclosed herein. The results are listed in table 2. All of these experiments started with a hydrated silica support that was not heat treated prior to contact with any other catalyst components. The listed carboxylic acids were mixed with water or an alternative solvent system as listed to form a solution, but in all cases the solvent was not dried and no attempt was made to use anhydrous conditions. Addition of Ti (OiPr)₄And when dissolution HAs occurred, 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 before being used in polymerization experiments.

Table 2 summarizes the study of various carboxylic acids. The use of carboxylic acid alone (without addition of base) does not produce very effective titanation. Run 2.2 using acetic acid in propanol solvent provided the most effective titanation. Successful results were also observed when HA30W was impregnated with an acidic Ti-containing solution and dropped into a 300 ℃ activation tube ("hot drop", runs 2.12-2.16). This rapid drying process is moderately effective, as evidenced by the higher melt index obtained when producing the catalyst using this process as compared to oven drying. The "hot drop" drying process results in more efficient titanation when citric acid is used instead of oxalic acid. This result may 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 may result in a Ti-containing solution having a higher and closer pH to 4.0 when compared to Ti-containing solutions produced with oxalic acid.

Example 3: basic titanation

The next series of experiments investigated the ability of the base to form an alkaline Ti-containing solution capable of providing effective titanation of 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 hydroxides and alkali hydroxides are not. The quaternary ammonium hydroxide dissolves Ti, but uncharged primary, secondary or tertiary amines are less effective. The melt index potential resulting from the use of the basic solution was low, as was the non-titanated support, and therefore did not show evidence of effective titanation of the chromium-silica support.

Example 4: adjusting the pH with ammonium hydroxide

The results in tables 2 and 3 confirm that attaching titania to silica can be problematic at both high and low pH. 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. Mixing Ti (OiPr)₄Hydrolyzed to titanium dioxide dissolved in aqueous oxalic acid (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 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 an STM, is typically about two equivalents of base/Ti. The HA30W support was impregnated with STM and the product was dried and calcined at 650 ℃ in air for three hours before being used in the polymerization experiments.

The results listed in table 4 indicate that the method was successful. When compared with hydrogen hydroxideQuaternary ammonium hydroxides are more effective when ammonium. This result can be explained by the lower volatility of the tetraalkylammonium hydroxide. The results in table 4 also indicate that the amount of base used to make STM affects the melt index potential imparted by the resulting catalyst. The method also allows for efficient titanation on hydrogels rather than preformed silica supports (run 4.16). The catalyst of run 4.6 was prepared by reverse addition and showed excellent performance: dissolving Ti in NMe₄Aqueous OH to form an alkaline solution, which is added to aqueous oxalic acid to prepare the STM for impregnation of the HA30W support.

Example 5: adjusting pH with urea

The next series of experiments investigated the ability of urea to partially neutralize acidic Ti-containing solutions and produce STMs 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 the emission of volatile organic compounds and highly reactive volatile organic compounds produced during the calcination of the catalyst. The experimental procedure was essentially the same as described in example 4, except that the bromocresol green indicator was not used. The results are shown in table 5. The addition of urea to the acidic Ti-containing solution provides for increasingly effective titanation as the amount of urea increases. This effect was not observed in experiments investigating the use of urea in spray drying applications, probably because urea decomposes and/or evaporates during the spray drying operation. Effective titanation is also observed in the case of N, N' -dimethylurea, which is less volatile than urea.

Example 6: pH adjustment with alkanolamines

The next series of experiments investigated the ability of alkanolamines to partially neutralize acidic Ti-containing solutions and produce STMs capable of providing effective titanation to the catalyst. Ethanolamine and isopropanolamine are chosen because they generally exhibit low toxicity, are low cost, are readily available from a variety of sources, and have 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 were variable and the bulkier amines appeared to perform best. Without wishing to be bound by theory, this may be a result of the lower volatility of the bulkier compound and/or the lower dielectric constant of the Ti ions generated by the bulkier compound. Dimethylaminoethanol (DMAE) provides a relatively high melt index, is low cost, is available from a variety of suppliers, and has a low odor. The catalyst of run 6.11 was prepared by: titanium dioxide was dissolved into two equivalents of aqueous oxalic acid solution, 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 overnight at 100 ℃. The resulting dried titanated support was extracted with water, subsequently calcined at 650 ℃ and subjected to polymerization experiments. The melt index data indicates that the catalyst has experienced a substantial loss of Ti, presumably during the water extraction step. This observation indicates that after drying at 100 ℃, Ti may not have sufficiently attached to the silica and supports previous observations that attachment between Ti and silica occurs at least in part at temperatures greater than 150 ℃.

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 STMs 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 7. The general trend of higher performance with bulkier amines is observed, but sometimes impaired by a lack of solubility, for example in the case of 2-ethylhexylamine or DABCO. Bases capable of delocalizing the positive charges obtained after protonation show extremely good performance; examples include DBU, creatine and imidazole.

Example 8: adjusting the pH with an inorganic base

The next series of experiments investigated the ability of the inorganic base to partially neutralize the acidic Ti-containing solution and produce an STM 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 method is generally unsuccessful. Without wishing to be bound by theory, higher dielectric constants may have been affected, but the presence of divalent or trivalent metal cations may interfere with the delicate balance of surface charge between silicon dioxide and titanium dioxide. Trials 8.2 and 8.3 were partially successful and introduced equal amounts of Al ions together with Ti ions. Three equivalents of oxalic acid were added to dissolve two equivalents of metal (1Ti (OiPr))₄+1Al(OH)₃) This is a lower acid/metal ratio than in most of the other experiments described herein. Run 8.3 involved partial neutralization of the acid with tetraethylammonium hydroxide in an amount of 1.5 equivalents base/Ti. Phase (C)This is a lower alkali/metal ratio than in most of the other experiments described herein, but an increase in HLMI was observed. Without wishing to be bound by theory, it may be easier to coat titania onto alumina than to coat titania onto silica. Both Ti and Al are metals and the chemistries of both are more similar in many respects than those of Ti and Si.

Example 9: dissolution of Ti by other acids

The next series of experiments investigated the ability of carboxylic acids other than herbicidal acids to be partially neutralized and to produce STMs capable of providing 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 are generally less successful than experiments using oxalic acid. Several experiments added two equivalents of base/Ti, which exceeded the number of equivalents needed to obtain a pH of 4.0, since the acid tested was weaker than oxalic acid. In other experiments, base was added until the green end point of the bromocresol green indicator was reached, indicating a pH of 4.0. An example of this method is run 9.7, where the use of citric acid and tetramethylammonium hydroxide results in a highly effective titanation as evidenced by HLMI values of approximately 30. Run 9.14 indicates that in the absence of carboxylic acid, titanyl sulfate can be partially neutralized by DMAE to produce moderately effective titanation.

Example 10: dissolution of Ti with peroxide

The catalysts listed in Table 10 (invention runs 10.1-10.43) were prepared much as those previously described herein, except that a peroxide (usually H) was also used (usually H)₂O₂) Added to the formulation as a partial or complete replacement for the amine or acid. In this way, the amount of amine used, and in some tests the amount of acid used, can be reduced, which thereby reduces costs and emissions, and produces polymers with higher HLMI.

In these experiments, 30g of Cr/silica catalyst sold by w.r.grace under the name HA30W was weighed out into the bowl. It has a thickness of about 500m²Surface area per gram, pore volume of about 1.6mL/g, and it contains 1 wt% Cr. It is not pre-dried in any way. To a 100mL beaker was added 50mL of deionized water, into which the organic acid was dissolved. Peroxide is then also added to the solution in the invention test, usually H₂O₂. Then, 6.65mL of titanium tetraisopropoxide was added to the aqueous solution, which caused it to precipitate out immediately as hydrous titanium dioxide. The amount of titanium added was equal to 3.5 wt% Ti based on the weight of dry Cr/silica. The amounts of acid and peroxide used in each experiment were different, 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 to an orange or dark red solution (when H is present)₂O₂When present), typically after about 10 minutes. In the case when the titanium dioxide is not readily soluble, stirring is continued for several hours before finally 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 did form, the next step was to add a nitrogen compound to the solution in some experiments, while in others, no nitrogen compound was used. The nitrogen compound is always dissolved in the titanium solution. Likewise, the amount of nitrogen compound is set forth in Table 10 in terms of equivalent weight of nitrogen compound per equivalent 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 consistently moist (rather than wet) powder, that is, to reach incipient wetness. The bowl was then placed in a vacuum oven set at 100 ℃ overnight. The next day, the dry catalyst powder was poured through a 40 mesh screen to break up any small soft lumps. The resulting titanium-containing catalyst sample was calcined at 650 ℃ in dry air for 3 hours. It was then recovered under dry nitrogen and stored for later use.

Control run 10.2 shows that although two equivalents of oxalic acid can dissolve the titanium dioxide, the HLMI obtained is better than that obtained from a Cr/silica catalyst in the absence of titanium dioxide (table 1, run 1.12). In other words, titanation is ineffective with only oxalic acid. Control 10.2 served as 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 the dissolution of titanium dioxide in many acids that were not capable of dissolving Ti in the absence of peroxide. Some of these acids produce very high HLMI. It was also observed that even in the case where the titanium dioxide could be dissolved without peroxide, the addition of peroxide still greatly improved the HLMI due to the catalyst. Furthermore, when peroxide is added, in many experiments the amount of nitrogen compound used can be reduced or, in some cases, the nitrogen compound can be eliminated completely. This reduction is greatly improved because nitrogen compounds cause undesirable emissions during firing.

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 exploited₂O₂Dissolving the Ti and reducing the aforementioned ability of the nitrogen compound or even the acid ligand. In these experiments (inventions 11.44 to 11.60), the catalyst was prepared exactly as previously described herein. That is, 30g of Cr/silica was weighed into a bowl and 50mL of deionized water was measured into a 100mL beaker. Will be provided withAcids together with H when used₂O₂Dissolved together in water. 6.65mL of titanium tetraisopropoxide (3.5 wt% Ti based on Cr/silica weight) was then added and it immediately precipitated out as hydrous titanium dioxide. However, after a short stirring time of about 10 minutes, the Ti dissolved. Nitrogen compounds, when present, are then added and the solution is added to the dry catalyst to achieve incipient wetness. Drying and firing are accomplished as described above.

Only in inventive experiment 11.44 the protocol was slightly different. Here, 30g of silica was weighed into the bowl (instead of Cr/silica). Silica is EP30X from Philadelphia Quartz Corp, with 300m²Surface area in g. Similarly, 50mL of deionized water was measured into a beaker, to which was then added acid, H₂O₂And 6.65mL of titanium isopropoxide. After the 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 described previously. It should also be noted that acidic phenols can be substituted for organic acids to prepare effective ligands. Thus, several experiments with catechol and salicyl alcohol instead of carboxylic acid are shown.

In table 11, some of the large acids were found to be unable to dissolve the titanium dioxide until a small amount of smaller acid was also added. For example, in invention test 11.56, catechol was not effective until combined with a small amount of oxalic acid. Similarly, salicylic acid, which is ineffective alone, dissolves Ti when one equivalent of oxalic acid is also added and produces a high HLMI (invention test 11.54). Similar results occur with the invention in saligenin in runs 11.52 and 11.53, phenylpropionic acid in run 11.51, diglycolic acid in run 11.49, iminodiacetic acid in run 11.48, and methylmalonic acid in run 11.46.

The target titanium level was 3.5 wt% Ti. This is considered to be 1 equivalent of Ti. An attempt was made to dissolve 1 equivalent of titanium dioxide with the stated equivalents of carboxylic acid and with the stated equivalents of H2O2 and/or base,

after the Ti solution was impregnated onto the silica, the resulting mixture was dried in a vacuum oven at 100 ℃ overnight, followed by calcining a portion of the catalyst at 650 ℃ in dry air for 3 hours. DMAE-Dimethylaminoethanol, DMF-dimethylformamide

after the Ti solution was impregnated onto the silica, the resulting mixture was dried in a vacuum oven at 100 ℃ overnight, followed by calcining a portion of the catalyst at 650 ℃ in dry air 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.

The 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 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 dissolved titanium mixture, wherein an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the dissolved titanium mixture is from about 1:1 to about 1:4, and a pH of the dissolved titanium mixture is less than about 5.5; and d) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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 the catalyst by heating the procatalyst to a temperature in the range of from about 400 ℃ to about 1000 ℃ and maintaining the temperature of the procatalyst in the range of from about 400 ℃ to about 1000 ℃ for a period of from about 1 minute to about 24 hours.

A third aspect is the process of either 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 dissolved titanium mixture is about 1:2.

A fourth aspect is the method of any of the preceding three aspects, wherein the pH of the dissolved titanium mixture is in the range of about 3.5 to about 4.5.

A fifth aspect is the method of any of the preceding four aspects, wherein (c) comprises neutralizing the acidic titanium mixture, and wherein the neutralizing is partial or complete neutralization.

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 is¹、R²、R³、R⁹、R¹⁰And R¹¹Each independently is hydrogen, C₁To C₁₂Organic radicals or C₆To C₁₂An aryl group; r⁴Is C₁To C₁₂Organic radicals or C₆To C₁₂An aryl group; r⁵And R⁶Each independently is hydrogen, C₁To C₆Organic radicals or C₆To C₁₂An aryl group; r⁷And R⁸Each independently is hydrogen or CH₃；R¹²Is a branched chain C₁To C₆Alkyl, cyclic C₁To C₆Alkyl or straight-chain C₁To C₆An alkyl group; x is an integer from 1 to 4, y is an integer from 1 to 12, and Z is oxygen or sulfur.

A seventh aspect is the method of any of the preceding 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 one of the seven preceding aspects, wherein the nitrogen-containing compound comprises acetamide, ammonia, ammonium hydroxide, tert-butylamine, creatine, N '-dibutyl urea, diethanolamine, diisopropanolamine, dimethylaminoethanol, dimethyl carbamate, dimethyl formamide, dimethyl glycine, dimethyl isopropanolamine, N' -dimethyl urea, ethanolamine, ethylene glycol amine, hexylamine, hydroxylamine, imidazole, isopropanolamine, N-methylaniline, methyl diethanolamine, methyl formamide, pyrazole, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, or a combination thereof.

A ninth aspect is the method of any of the preceding eight aspects, wherein the carboxylic acid comprises C₁To C₁₅Monocarboxylic acid, C₂To C₁₅Dicarboxylic acid, C₃To C₁₅Tricarboxylic acid, C₁To C₁₅An alpha-hydroxycarboxylic acid, or a combination thereof.

A tenth aspect is the method of any one of the preceding nine aspects, wherein the carboxylic acid comprises acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid, or combinations thereof.

An eleventh aspect is the method of any of the preceding ten aspects, wherein the titanium-containing compound comprises titanium hydroxide, titanic acid, titanyl sulfate, titanium (IV) alkoxide, titanyl acetylacetonate, titanium (IV) halide, or a combination thereof.

A twelfth aspect is the method of any of the preceding eleventh aspects, wherein the titanium-containing compound comprises titanium (IV) isopropoxide.

A thirteenth aspect is the method of any of the preceding twelve aspects, wherein (d) further comprises spray drying the dissolved titanium mixture onto the chromium-silica support.

A fourteenth aspect is the method of any of the thirteen preceding aspects, wherein the chromium-silica support is characterized as having an average particle size of about 100m²G to about 1000m²Surface area per g and about 1.0cm³G to about 2.5cm³Pore volume per gram.

A fifteenth aspect is the method of any of the preceding fourteen aspects, wherein the amount of chromium present in the catalyst ranges from about 0.01 wt% to about 10 wt%, and the amount of titanium present in the catalyst ranges from about 0.01 wt% to about 10 wt%, based on the total weight of the catalyst.

A sixteenth aspect is the method of any one of the preceding fifteen aspects, wherein the solvent comprises an aqueous solvent, an alcohol, an organic solvent, or a combination thereof.

A seventeenth aspect is a method of forming an ethylene polymer, the method comprising contacting the catalyst formed by the method 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 process 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 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 dissolved titanium mixture, wherein an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the dissolved titanium mixture is from about 1:1 to about 1:4, and a pH of the dissolved titanium mixture is in a range from about 3.5 to about 4.5; d) contacting a silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved titanium mixture to form a titanated support, and drying the titanated support 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 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, further comprising: f) calcining the procatalyst to form the catalyst 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 time from about 1 minute to about 24 hours.

A twenty-first aspect is the method of the nineteenth aspect, wherein (c) comprises neutralizing the acidic titanium mixture, and wherein the neutralizing is partial neutralization or complete neutralization.

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 the titanium-containing compound to the 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 dissolved titanium mixture, wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid in the dissolved titanium mixture is from about 1:1 to about 1:4, and the pH of the dissolved titanium mixture is in a range from about 3.5 to about 4.5; and d) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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) Calcining the procatalyst to form the catalyst by heating the procatalyst to a temperature in the range of from about 400 ℃ to about 1000 ℃ and maintaining the temperature of the procatalyst in the range of from about 400 ℃ to about 1000 ℃ for a period of from 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 the titanium-containing compound to the 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 dissolved titanium mixture, wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid in the dissolved titanium mixture is from about 1:1 to about 1:4, and the pH of the dissolved titanium mixture is in a range from about 3.5 to about 4.5; d) contacting a silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved titanium mixture to form a titanated support, and drying the titanated support 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 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, further comprising: f) Calcining the procatalyst to form the catalyst by heating the procatalyst to a temperature in the range of from about 400 ℃ to about 1000 ℃ and maintaining the temperature of the procatalyst in the range of from about 400 ℃ to about 1000 ℃ for a period of from 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 ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silica; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.1 wt% to about 20 wt% based on the amount of silica; d) a carboxylic acid, wherein the molar equivalent 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 comprising at least one nitrogen atom, wherein the equivalent molar ratio of the titanium-containing compound to the 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 C₁To C₁₅Monocarboxylic acid, C₂To C₁₅Dicarboxylic acid, C₃To C₁₅Tricarboxylic acid, C₁To C₁₅An alpha-hydroxycarboxylic acid, or a combination thereof.

A twenty-eighth aspect is the procatalyst composition of any 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 of the twenty-sixth through twenty-eighteenth aspects, wherein the nitrogen-containing compound comprises an alkanolamine, an amide, an amine, an alkyl amine, an ammonium hydroxide, an aniline, a hydroxylamine, urea, or a combination thereof.

A thirtieth aspect is the procatalyst composition of any of the twenty-sixth through twenty-ninth aspects, wherein the nitrogen-containing compound comprises acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, t-butylamine, N '-dibutylurea, creatine, creatinine, monoethanolamine, diethylhydroxylamine, diisopropanolamine, dimethylaminoethanol, dimethylaminomethyl formate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N' -dimethylurea, ethanolamine, ethylamine, ethylene glycol amine, hexylamine, hydroxylamine, imidazole, isopropanolamine, methacrylamide, methylamine, N-methylaniline, N-methyl-2-propanolamine, methyldiethanolamine, methylformamide, propylamine, 2-propanolamine, pyrazole, pyrrolidine, and mixtures thereof, Pyrrolidone, succinimidyl amine, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, 1, 8-diazabicyclo [5.4.0] undec-7-ene, or combinations thereof.

A thirty-first aspect is the procatalyst composition of any of the twenty-sixth through thirty-first aspects, wherein the silica support further comprises alumina.

A thirty-second aspect is the procatalyst composition of any of the twenty-sixth through thirty-first aspects, wherein the silica support is characterized as having about 100m²G to about 1000m²Surface area per g and about 1.0cm³G to about 2.5cm³Pore volume per gram.

A thirty-third aspect is the procatalyst composition of any 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 of the twenty-sixth through thirty-third aspects, wherein the silica support comprises from about 1 wt% to about 20 wt% 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 ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% 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) an amount of titanium in a range of about 0.1 wt% to about 20 wt% 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 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 protonated acetamide, protonated acrylamide, protonated allylamine, ammonium, protonated ammonium hydroxide, protonated butylamine, protonated tertiary butylamine, protonated N, N '-dibutylurea, protonated creatine, protonated creatinine, protonated diethanolamine, protonated diethylhydroxylamine, protonated diisopropanolamine, protonated dimethylaminoethanol, protonated dimethylcarbamate, protonated dimethylformamide, protonated dimethylglycine, protonated dimethylisopropanolamine, protonated N, N' -dimethylurea, protonated ethanolamine, protonated ethylamine, protonated glycol amine, protonated hexylamine, protonated hydroxylamine, protonated imidazole, protonated isopropanolamine, protonated isopropanol amine, protonated acetamide, protonated ethanolamine, protonated imidazole, protonated isopropanol amine, protonated ethanolamine, protonated imidazole, protonated isopropanol amine, protonated ethanolamine, and/ethanol amine, Protonated methacrylamide, protonated methylamine, protonated N-methylaniline, protonated N-methyl-2-propanolamine, protonated methyldiethanolamine, protonated methylformamide, protonated propylamine, protonated 2-propanolamine, protonated pyrazole, protonated pyrrolidine, protonated pyrrolidone, protonated succinimide, protonated tetraethylammonium hydroxide, protonated tetramethylammonium hydroxide, protonated triethanolamine, protonated triisopropanolamine, protonated trimethylamine, protonated urea, protonated 1, 8-diazabicyclo [5.4.0] undec-7-ene, or combinations thereof.

A thirty-eighth aspect is the procatalyst composition of any of the thirty-fifth through thirty-seventh aspects, wherein the carboxylate comprises C₁To C₁₅Monocarboxylate radical, C₂To C₁₅Dicarboxylic acid radical, C₃To C₁₅Tricarboxylic acid radical, C₁To C₁₅An alpha-hydroxycarboxylate, or a combination thereof.

A thirty-ninth aspect is the procatalyst composition of any 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 of the thirty-fifth to thirty-ninth aspects, wherein the silica support further comprises alumina.

Fortieth itemOne aspect is the procatalyst composition of any of the thirty-fifth through forty-fourth aspects, wherein the silica support is characterized as having about 100m²G to about 1000m²Surface area per g and about 1.0cm³G to about 2.5cm³Pore volume per gram.

A forty-second aspect is the procatalyst composition of any of the thirty-fifth to forty-first aspects wherein the silica support comprises a hydrated silica support.

A forty-third aspect is the procatalyst composition of any of the thirty-fifth to forty-second aspects, wherein the silica support comprises from about 1 wt% to about 20 wt% 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 ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silica; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.01 wt% to about 0.1 wt% 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 comprising at least one nitrogen atom, wherein the equivalent molar ratio of the titanium-containing compound to the 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 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 dissolved titanium mixture, wherein an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the dissolved titanium mixture is from about 1:1 to about 1:4, and a pH of the dissolved titanium mixture is less than about 5.5; and d) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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 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 and the acidic mixture to form a solubilized titanium mixture, wherein an equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and an equivalent molar ratio of the titanium-containing compound to the 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 0.1 wt% to about 20 wt% 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, 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 comprisesC₁To C₁₅Monocarboxylic acid, C₂To C₁₅Dicarboxylic acid, C₃To C₁₅Tricarboxylic acid, C₁To C₁₅An alpha-hydroxycarboxylic acid, or a combination 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, α -hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, diglucosic 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 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 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 0.1 wt% to about 20 wt% water and the dissolved 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 process of the fifth aspect, wherein the carboxylic acid comprises C₁To C₁₅Monocarboxylic acid, C₁To C₁₅Dicarboxylic acid, C₂To C₁₅Tricarboxylic acid, C₁To C₁₅An alpha-hydroxycarboxylic acid, or a combination 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, α -hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, diglucosic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.

An eighth aspect is the method of any one 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, a urea, or a combination thereof.

A ninth aspect is the method of any 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 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 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 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 0.1 wt% to about 20 wt% water and the dissolved 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 C₁To C₁₅Monocarboxylic acid, C₂To C₁₅Dicarboxylic acid, C₃To C₁₅Tricarboxylic acid, C₁To C₁₅An alpha-hydroxycarboxylic acid, or a combination thereof.

A thirteenth aspect is the method of any 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, α -hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, diglucosic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof.

A fourteenth aspect is the method of any 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 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 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 and the acidic mixture to form a dissolved titanium mixture, wherein the dissolved titanium mixture has an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:1 to about 1: 4; and c) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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 and the acidic mixture to form a solubilized titanium mixture, wherein an 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 an 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 0.1 wt% to about 20 wt% water and the dissolved 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 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, 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 dissolved titanium mixture is from about 1:1 to about 1: 20; and c) contacting a chromium-silica support comprising from about 0.1 wt% to about 20 wt% water and the dissolved 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 alcohol, salicylic acid, phthalic acid, or any combination thereof.

A twentieth 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 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, 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 dissolved titanium mixture is from about 1:1 to about 1: 20; c) contacting the dissolved 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 in an amount in the range of from about 70 wt% to about 95 wt%, based on the total weight of the silica support, to form an addition product; 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 the procatalyst.

A twenty-first aspect 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) (ii) an equivalent molar ratio of titanium-containing compound to carboxylic acid when present in the acidic mixture of 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 of 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 of 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 said temperature in said range of about 50 ℃ to about 150 ℃ for a period of about 30 minutes to about 6 hours to form the procatalyst.

A twenty-second aspect is a composition comprising a) a silica support comprising silica, wherein the amount of silica ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.1 wt% to about 20 wt% 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 the titanium-containing compound to the 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 C₁To C₁₅Monocarboxylic acid, C₂To C₁₅Dicarboxylic acid, C₃To C₁₅Tricarboxylic acid, C₁To C₁₅An alpha-hydroxycarboxylic acid, or a combination 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, diglucosic 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-twelfth 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 thirtieth aspect is a composition comprising a) a silica support comprising silica, wherein the amount of silica ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; and c) an organic salt of titanium, wherein the organic salt of titanium comprises titanium, a carboxylate, and a peroxy-containing compound, and wherein the organic salt of titanium comprises i) an amount of titanium in a range of from about 0.1 wt% to about 20 wt%, 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 peroxy-containing compound is in the range of from about 1:0.5 to about 1: 20.

A thirty-first aspect is the composition of the thirty-second aspect, further comprising a nitrogen-containing compound, wherein the equivalent molar ratio of the titanium-containing compound to the 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-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof.

A thirty-third aspect is the composition of any one of the thirty-second to thirty-second 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 support comprising silica, wherein the amount of silica ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.01 wt% to about 0.1 wt% 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 a 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 the titanium-containing compound to the 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 support comprising silica, wherein the amount of silica ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; 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) an amount of titanium in a range of about 0.1 wt% to about 20 wt% 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 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 support comprising silica, wherein the amount of silica ranges from about 70 wt% to about 95 wt%, 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 0.1 wt% to about 5 wt% based on the amount of silicon dioxide; 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) an amount of titanium in a range from about 0.1 wt% to about 20 wt% 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 from about 1:0.5 to about 1: 10; and d) an acidic phenol, wherein the equivalent molar ratio of the titanium-containing compound to the 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 0.1 wt% to about 5 wt% based on the amount of silica; c) a titanium-containing compound, wherein the amount of titanium is in the range of about 0.01 wt% to about 0.1 wt% 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 the titanium-containing compound to the nitrogen-containing compound, when present, is in the range of about 1:0.5 to about 1: 5.

A forty-second aspect is a catalyst prepared according to the method of the first aspect, wherein the method further comprises heating the procatalyst in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ to form an olefin polymerization catalyst.

A forty-third aspect is a catalyst prepared according to the process of the fifth aspect, wherein the process further comprises heating the procatalyst in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ 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 in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ to form an 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 in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ to form an olefin polymerization catalyst.

A forty-sixth aspect is a catalyst made according to the method of the seventeenth aspect, wherein the method further comprises heating the procatalyst in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ to form an olefin polymerization catalyst.

A forty-seventh aspect is a catalyst made according to the process of the eighteenth aspect, wherein the process further comprises heating the procatalyst in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ to form an olefin polymerization catalyst.

A forty-eighth aspect is a catalyst made according to the method of the twentieth aspect, wherein the method further comprises heating the procatalyst in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ to form an olefin polymerization catalyst.

A forty-ninth aspect is a catalyst made according to the method of the twenty-first aspect, wherein the method further comprises heating the procatalyst in the presence of air to a temperature in the range of from about 400 ℃ to about 1000 ℃ to form an olefin polymerization catalyst.

The terms "a" and "an" and "the" are intended to include plural alternatives, such as at least one, unless specifically indicated otherwise. Herein, although methods and processes are described as "comprising" various components or steps, the methods and processes can also "consist essentially of" or "consist of" the various components or steps. Specific features of the disclosed subject matter may be disclosed as follows: the feature X may be A, B or C. It is also contemplated that for each feature, the statement may also recite a list of alternatives, such that the statement "feature X is a, alternatively, B, or alternatively, C" is also an aspect of the disclosure, whether or not the statement 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 exemplary only, and are not intended to be limiting. Many variations and modifications of the present disclosure are possible and are within the scope of the present 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.

Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an aspect of the present disclosure. Thus, the claims are a further description and are an addition to aspects of the present disclosure. The 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 noted upper and lower limits, even if the particular combination is not specifically listed.

Claims

1. A procatalyst composition comprising:

a chromium-containing compound; a titanium-containing compound comprising at least two carboxylic acids; and a silica support;

wherein the equivalent molar ratio of titanium-containing compound to the at least two carboxylic acids is from about 1:1 to about 1: 4.

2. The procatalyst composition of claim 1 wherein the silica support comprises from about 0.1 wt% to about 20 wt% water.

3. The procatalyst composition of claim 1 wherein the procatalyst further comprises a peroxy-containing compound.

4. The procatalyst composition of claim 3 wherein the equivalent molar ratio of titanium in the titanium-containing compound to the peroxy-containing compound is from about 1:1 to about 1: 20.

5. The procatalyst composition of claim 1 wherein the at least two carboxylic acids comprise C₁To C₁₅Monocarboxylic acid, C₁To C₁₅Dicarboxylic acid, C₃To C₁₅Tricarboxylic acid, C₁To C₁₅An alpha hydroxy carboxylic acid, or a combination thereof.

6. The procatalyst composition 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, gluconic acid, mandelic acid, 2, 4-hydroxybenzoic acid, 2, 6-pyridinedicarboxylic acid, nitrotriacetic acid, a-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, diglucosic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or combinations thereof.

7. The procatalyst composition of claim 1 wherein the at least two carboxylic acids comprise a first carboxylic acid selected from the group consisting of oxalate, lactate, and glycolate and a second carboxylic acid selected from the group consisting of methylmalonic acid, phenylmalonic acid, α -hydroxyisobutyric acid, salicylic acid, and citric acid.

8. The procatalyst composition of claim 1 wherein the silica support further comprises alumina.

9. The procatalyst composition of claim 1 wherein the silica support is characterized by about 100m²G to about 1000m²Surface area per g and about 1.0cm³G to about 2.5cm³Pore volume per gram.