BR122022026872B1 - PRE-CATALYST COMPOSITION - Google Patents

Abstract

a method comprising a) bringing a solvent, a carboxylic acid and a peroxide-containing compound into contact to form an acid mixture wherein a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about 100 :1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a pre-catalyst.

Description

(Divided from BR 11 2022 013017 1, filed on 01/26/2021) TECHNICAL FIELD

[0001] The present disclosure relates to catalyst compositions. More specifically, the present disclosure relates to methods of preparing olefin polymerization catalyst compositions and polymers prepared therefrom.

FUNDAMENTALS

[0002] An economically important class of olefin polymerization catalysts includes chromium-silica-titanium (Cr/Si-Ti) catalysts prepared from silica-based catalyst supports. Rigorous drying of water-sensitive catalyst components used to produce Cr/Si-Ti catalysts increases production time and cost. The development of an aqueous solution suitable for depositing titanium on a silica-based catalyst support would reduce the production costs of olefin polymerization catalysts. Therefore, there is a continuous need to develop new methods of producing olefin polymerization catalysts.

SUMMARY

[0003] Disclosed herein is a precatalyst composition comprising a) a silica support comprising silica in which an amount of silica is in a range of about 70% by weight to about 95% by weight based on a total weight of the silica support, b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica, c) a compound containing titanium wherein an amount of titanium is in a range of about 0.1% by weight to about 20% by weight based on the amount of silica, d) a carboxylic acid wherein an equivalent molar ratio of titanium-containing compound for carboxylic acid is in a range of about 1:1 to about 1:10, and e) a nitrogen-containing compound with a molecular formula containing at least one nitrogen atom in which an equivalent molar ratio of titanium-containing compound to titanium-containing compound Nitrogen is in a range of about 1:0.5 to about 1:10.

[0004] Also disclosed herein is a precatalyst composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on a total weight of the silica support, b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1 wt% to about 5 wt% based on the amount of silica, and c) a titane-organic salt, wherein the titane-organic salt comprises titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein i) an amount of titanium is in a range from about 0.1% by weight to about 20 % by weight based on the amount of silica, ii) an equivalent molar ratio of titanium to carboxylate is in a range of about 1:1 to about 1:10, and iii) an equivalent molar ratio of titanium to nitrogen-containing compound protonated is in a range of about 1:0.5 to about 1:10.

[0005] Also disclosed herein is a precatalyst composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on a total weight of the silica support, b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica, c) a titanium-containing compound in which an amount of titanium is in a range of about 0.01% by weight to about 0.1% by weight based on the amount of silica, d) a carboxylic acid in which an equivalent molar ratio of titanium-containing compound to carboxylic acid is in a range of about 1:1 to about 1:10, and e) a nitrogen-containing compound with a molecular formula containing at least one nitrogen atom in which an equivalent molar ratio of titanium-containing compound for nitrogen-containing compound it is in a range of about 1:0.5 to about 1:10.

[0006] Also disclosed herein is a precatalyst composition prepared by a method comprising a) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about 100:1, b) placing a titanium-containing compound and the acidic mixture in contact to form an acidic titanium mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic mixture of titanium is about 1:1 to about 1:4, c) placing a nitrogen-containing compound and the acid titanium mixture in contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to titanium-containing compound nitrogen in the solubilized titanium mixture is from about 1:1 to about 1:4 and a pH of the solubilized titanium mixture is less than about 5.5, and d) placing a chromium-silica support comprising of about 0 .1 wt% to about 20 wt% water and the solubilized titanium mixture in contact to form an addition product and dry the addition product by heating the addition product to a temperature in a range of about 50° C to about 150°C and maintaining the temperature of the addition product in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form the pre- catalyst.

[0007] Further disclosed herein is a method comprising a) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about of 100:1, b) placing a titanium-containing compound and the acid mixture in contact to form a titanium acid mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the titanium acid mixture is about 1:1 to about 1:4, c) placing a nitrogen-containing compound and the acidic titanium mixture in contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is about 1:1 to about 1:4 and a pH of the solubilized titanium mixture is less than about 5.5, and d) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and dry the addition product by heating the addition product to a temperature in a range of about 50°C to about 150°C and maintaining the temperature of the addition product in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[0008] Also disclosed herein is a method comprising a) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about of 100:1, b) placing a titanium-containing compound and the acid mixture in contact to form a titanium acid mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the titanium acid mixture is about 1:1 to about 1:4, c) placing a nitrogen-containing compound and the acidic titanium mixture in contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is about 1:1 to about 1:4 and a pH of the solubilized titanium mixture is in a range of about 3.5 to about 4.5, d) placing a silica support comprising of about 0.1 % by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form a titanized support and dry the titanized support by heating the titanized support to a temperature in a range of about 50°C to about 150°C. °C and maintain the temperature of the titanized support in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a dry titanized support and e) place, to form a precatalyst, a chromium-containing compound and at least one material selected from the group consisting of the silica support, in contact with the titanized support and the dry titanized support.

[0009] Also disclosed herein is a method comprising a) placing a titanium-containing compound and a nitrogen-containing compound in contact to form a base mixture in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the base mixture is about from 1:1 to about 1:4, b) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is about 1:1 to about of 100:1, c) bringing the basic mixture and the acidic mixture into contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is about 1:1 to about 1:4 and a pH of the solubilized titanium mixture is in a range of about 3.5 to about 4.5 and d) placing a chromium-silica support comprising from about 0.1% by weight to about of 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and dry the addition product by heating the addition product to a temperature in a range of about 50°C to about 150°C and maintaining the temperature of the addition product in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[0010] Also disclosed herein is a method comprising a) placing a titanium-containing compound and a nitrogen-containing compound in contact to form a base mixture in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the base mixture is about from 1:1 to about 1:4, b) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is about 1:1 to about of 100:1, c) bringing the basic mixture and the acidic mixture into contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is about 1:1 to about 1:4 and a pH of the solubilized titanium mixture is in a range of about 3.5 to about 4.5, d) placing a silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form a titanized support and dry the titanized support by heating the titanized support to a temperature in a range of about 50°C to about 150°C and maintaining the temperature of the titanized support in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a dry titanized support, and e) placing, to form a pre-catalyst, a chromium-containing compound and at least one material selected from the group consisting of the silica support, in contact with the titanized support and the dry titanized support.

[0011] Also disclosed herein is a method comprising a) placing a solvent, a carboxylic acid and a peroxide-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acidic mixture is about 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[0012] Also disclosed herein is a method comprising a) placing a solvent, at least two carboxylic acids and a peroxide-containing compound in contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is 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) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a time period of about 30 minutes to about 6 hours to form a pre-catalyst.

[0013] Also disclosed herein is a method comprising a) placing a solvent, at least two carboxylic acids and a nitrogen-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acidic mixture is about 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 c) placing a chromium-silica support comprising about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating to a temperature in the range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a pre-catalyst.

[0014] Also disclosed herein is a method comprising a) placing a solvent, at least two carboxylic acids, a nitrogen-containing compound and a peroxide-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acidic mixture it is from about 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[0015] Also disclosed herein is a method comprising a) placing a solvent, a carboxylic acid, an acidic phenol and a peroxide-containing compound in contact to form an acidic mixture in which 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 a solubilized titanium mixture in which 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, wherein an 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 an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating to a temperature in the range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a pre-catalyst.

[0016] Also disclosed herein is a method comprising a) placing a solvent, a carboxylic acid, an acidic phenol and a peroxide-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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, wherein an 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 an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; c) bringing the solubilized titanium mixture with a chromium-containing compound into contact to form a chromium titanium mixture; d) placing the chromium titanium mixture with a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the silica support in contact to form an addition product; and e) drying the addition product by heating to a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[0017] Also disclosed herein is a method comprising a) preparing an acidic mixture comprising a solvent and at least two components selected from the group consisting of one or more carboxylic acids, one or more acidic phenols, one or more peroxide-containing compounds and one or more nitrogen-containing compounds, wherein a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about 100:1; b) contacting the acid mixture with a chromium-containing compound, a titanium-containing compound and a silica support to form an addition product in which: (i) an equivalent molar ratio of titanium-containing compound to carboxylic acid, when present in the acid mixture, is about 1:1 to about 1:4, (ii) an equivalent molar ratio of titanium-containing compound to acid phenol, when present in the acid mixture, is about 1: to about 1:5 , and (iii) an equivalent molar ratio of titanium-containing compound to peroxide-containing compound, when present in the acid mixture, is from about 1:1 to about 1:20; and c) drying the addition product by heating to a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time of about 30 minutes to about 6 hours to form a pre-catalyst.

[0018] Also disclosed herein is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on a total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in a range of about 0.1% by weight to about 20% by weight based on the amount of silica; d) a carboxylic acid in which an equivalent molar ratio of titanium-containing compound to carboxylic acid is in a range of about 1:1 to about 1:10; and e) a peroxide-containing compound in which an equivalent molar ratio of titanium-containing compound to peroxide-containing compound is in a range of about 1:1 to about 1:20.

[0019] Also disclosed herein is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on a total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica; and c) a titano-organic salt, wherein the titano-organic salt comprises titanium, a carboxylate and a peroxide-containing compound and wherein the titano-organic salt comprises i) an amount of titanium is in a range of about 0.1 % by weight to about 20% by weight based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate is in a range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to peroxide-containing compound is in a range of about 1:0.5 to about 1:20.

[0020] Also disclosed herein is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the support silica; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in the range of about 0.01% by weight to about 0.1% by weight based on the amount of silica; d) at least two carboxylic acids in which an equivalent molar ratio of titanium-containing compound to carboxylic acids is in the range of about 1:1 to about 1:10; and e) a peroxide-containing compound in which an equivalent molar ratio of titanium-containing compound to peroxide-containing compounds is in the range of about 1:1 to about 1:10.

[0021] Also disclosed herein is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the support silica; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titano-organic salt, wherein the titano-organic salt comprises titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the titano-organic salt comprises: i) an amount of titanium is in a range of about 0.1 wt% to about 20 wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate is in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound is in the range of about 1:0.5 to about 1:10; and d) a peroxide-containing compound wherein an equivalent molar ratio of titanium-containing compound to peroxide-containing compound is from about 1:1 to about 1:20.

[0022] Also disclosed herein is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the support silica; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; and c) a titano-organic salt, wherein the titano-organic salt comprises titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the titano-organic salt comprises i) an amount of titanium is in a range of about 0 .1 wt% to about 20 wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate is in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound is in the range of about 1:0.5 to about 1:10; and d) an acidic phenol in which an equivalent molar ratio of titanium-containing compound to acidic phenol in the acidic titanium mixture is from about 1:1 to about 1:5.

[0023] 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 peroxide-containing compounds and one or more nitrogen-containing compounds; b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in a range of about 0.01% by weight to about 0.1% by weight based on the amount of silica; and (i) wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid, when present, is in a range of about 1:1 to about 1:10; (ii) wherein an equivalent molar ratio of titanium-containing compound to peroxide-containing compound, when present, is in a range of about 1:1 to about 1:10; (iii) wherein an equivalent molar ratio of titanium-containing compound to acidic phenol, when present, in the acidic titanium mixture is in a range of about 1:1 to about 1:5; and (iv) wherein an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound, when present, is in a range of about 1:0.5 to about 1:5.

BRIEF DESCRIPTION OF THE FIGURE

[0024] The following figure is part of the present specification and is included to further demonstrate certain aspects of the present disclosure. The subject matter of the present disclosure can be better understood by reference to the figure in combination with the detailed description of specific aspects presented herein.

[0025] The Figure illustrates the relationships between zeta potential and pH value for silica and titania.

[0026] Although the subject matter disclosed in this document is susceptible to various modifications and alternative forms, only some specific aspects have been shown by way of example in the figure and are described in detail below. The figure and detailed descriptions of these specific aspects are not intended to limit the breadth or scope of the subject matter disclosed or the appended claims in any way. Instead, the figure and detailed written descriptions are provided to illustrate the present disclosure to one of ordinary skill in the art and to enable such a person to make and use the concepts disclosed herein.

DETAILED DESCRIPTION

[0027] The present disclosure covers olefin polymerization catalysts and pre-catalysts thereof, methods of preparing olefin polymerization catalysts and pre-catalysts thereof, and methods of using olefin polymerization catalysts. In one aspect, a method of the present disclosure comprises contacting a silica support or a chromium-silica support (i.e., support) with titanium to produce a Cr/Si-Ti catalyst. The methodologies disclosed in this document include the use of a solubilized titanium mixture (STM) to facilitate the association of titanium with the support in the presence of water. Here, a methodology for preparing the olefin polymerization catalyst comprises contacting the chromium-silica support with the STM under suitable conditions to form the catalyst composition. An alternative methodology for preparing the olefin polymerization catalyst comprises contacting the silica support with the STM and chromium under suitable conditions to form a catalyst composition. Although these aspects may be disclosed under a specific title, the title does not limit the disclosure found therein. Furthermore, the various aspects and embodiments disclosed herein may be combined in any manner.

[0028] Aspects of the present disclosure are directed to catalyst compositions and pre-catalyst compositions. In one aspect, a catalyst composition comprises an olefin polymerization catalyst. In a further aspect, the olefin polymerization catalyst comprises a treated precatalyst composition. In yet another aspect, the treated precatalyst composition comprises a precatalyst that has been subjected to an activation treatment (e.g., calcination) as disclosed herein.

[0029] Pre-catalyst compositions are disclosed in this document. In one aspect, a precatalyst composition comprises a silica support, a chromium-containing compound, a titanium-containing compound, a carboxylic acid, and a nitrogen-containing compound. Alternatively, the pre-catalyst composition comprises the silica support, the chromium-containing compound and a titane-organic salt. Alternatively, the precatalyst composition comprises a silica support, a chromium-containing compound, a titanium-containing compound, a carboxylic acid, a nitrogen-containing compound and a peroxide-containing compound. Alternatively, the precatalyst composition comprises a silica support, a chromium-containing compound, a titanium-containing compound, a carboxylic acid and a peroxide-containing compound. Alternatively, the precatalyst composition comprises a silica support, a chromium-containing compound, a titanium-containing compound, an acidic phenol and a peroxide-containing compound. In some aspects, the precatalyst compositions comprise 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 compounds containing peroxide or any combination thereof.

[0030] In one aspect, an olefin polymerization catalyst and a pre-catalyst thereof of the present disclosure comprise a silica support. The silica support may be any silica support suitable for preparing the olefin polymerization catalyst and the precatalyst thereof as disclosed herein. In a further aspect, the preparation of the olefin polymerization catalyst and the precatalyst thereof excludes heat treatment of the silica support prior to contact with any other catalyst component. Accordingly, the silica support suitable for use in the present disclosure may be a hydrated silica support. Without wishing to be limited by theory, the hydrated silica support comprises a silica support in which water evolution occurs when the silica support is heated within a range of about 180°C to about 200°C under conditions of vacuum for a period of time ranging from about 8 hours to about 20 hours. In a further aspect, the silica support thus treated can evolve from about 0.1% by weight to about 20% by weight water; alternatively, about 1% by weight to about 20% by weight water; alternatively, about 1% by weight to about 10% by weight water; or alternatively, about 0.1 wt% to about 10 wt% water based on the total weight of the silica support.

[0031] The silica support suitable for use in the present disclosure may have an effective surface area and pore volume to provide for the production of an active olefin polymerization catalyst. In one aspect of the present disclosure, the silica support has a surface area in the range of about 100 m2/gram to about 1,000 m2/gram; alternatively, from about 250 m2/gram to about 1,000 m2/gram; alternatively, from about 250 m2/gram to about 700 m2/gram; alternatively, from about 250 m2/gram to about 600 m2/gram; or alternatively, greater than approximately 250 m2/gram. The silica support may further be characterized by a pore volume greater than about 0.9 cm3/gram, alternatively greater than about 1.0 cm3/gram, or alternatively greater than about 1.5 cm3/gram. In one aspect of the present disclosure, the silica support is characterized by a pore volume in a range of about 1.0 cm3/gram to about 2.5 cm3/gram. The silica support may further be characterized by an average particle size in a range of about 10 microns to about 500 microns, alternatively about 25 microns to about 300 microns or alternatively about 40 microns to about 150 microns. Generally, an average pore size of the silica support can be in a range of about 10 Angstroms to about 1,000 Angstroms. In one aspect of the present disclosure, the average pore size of the silica support is in a range of about 50 Angstroms to about 500 Angstroms; alternatively, from about 75 Angstroms to about 350 Angstroms.

[0032] The silica support suitable for use in the present disclosure may contain more than about 50% by weight silica; alternatively, more than about 80% by weight silica; or alternatively, more than about 95% by weight silica based on the total weight of the silica support. In one aspect, the silica support comprises an amount of silica in a range of about 70% by weight to about 95% by weight based on the total weight of the silica support. The silica support can be prepared using any suitable method, for example, the silica support can be prepared by hydrolysis of tetrachlorosilane (SiCl4) with water 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 contact with any other catalyst component. The silica support may include additional components that do not adversely affect the catalyst, such as zirconia, alumina, thorium, magnesia, fluoride, sulfate, phosphate, or a combination thereof. In a particular aspect, the silica support of the present disclosure comprises alumina. Non-limiting examples of silica supports suitable for use in this disclosure include ES70, which is a silica support material with a surface area of 300 m2/gram and a pore volume of 1.6 cm3/gram, which is commercially available. from PQ Corporation and V398400, which is a silica support material that is commercially available from Evonik.

[0033] In a particular aspect of the present disclosure, a silica support suitable for use in the present disclosure comprises chromium. The silica support comprising chromium may be called a chrome-plated silica support or a chromium-silica support. In another aspect, the chromium-silica support comprises the features disclosed herein for the silica support while additionally containing chromium. A non-limiting example of chromium-silica support is HW30A, which is a chromium-silica support material that is commercially available from W. R. Grace and Company.

[0034] The silica support may be present in the olefin polymerization catalyst and a pre-catalyst thereof in an amount ranging from about 50% by weight to about 99% by weight; or alternatively, from about 80% by weight to about 99% by weight. %. In this document, a percentage of silica support refers to a weight percentage (wt%) of the silica support associated with the olefin polymerization catalyst based on the total weight of the olefin polymerization catalyst after completion of all processing steps (i.e. after activation through calcination). Alternatively, the percentage of silica support refers to a weight percentage (wt%) of the silica support associated with the precatalyst based on the total weight of the precatalyst after completion of all relevant processing steps, excluding activation by calcination.

[0035] In yet another aspect, an olefin polymerization catalyst and a precatalyst thereof of the present disclosure comprise chromium. The chromium source can be any chromium-containing compound capable of supplying a sufficient amount of chromium to the olefin polymerization catalyst and its precatalyst. In one aspect, the chromium-containing compound may be a water-soluble chromium compound or a hydrocarbon-soluble chromium compound. Examples of water-soluble chromium compounds include chromium trioxide, chromium acetate, chromium nitrate, or a combination thereof. Examples of hydrocarbon-soluble chromium compounds include tertiary butyl chromate, biscyclopentadienyl chromium(II), chromium(III) acetylacetonate, or a combination 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) dionates or a combination 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 a combination of them.

[0036] An amount of chromium present in the olefin polymerization catalyst can be in a range of about 0.01% by weight to about 10% by weight; alternatively, from about 0.5% by weight to about 5% by weight; alternatively, from about 1% by weight to about 4% by weight; or alternatively, from about 2 wt% to about 4 wt% chromium based on the total weight of the olefin polymerization catalyst. In another aspect, the amount of chromium present in the olefin polymerization catalyst may be in a range of about 1 wt% to about 5 wt% chromium based on the total weight of the olefin polymerization catalyst. In this document, a chromium percentage refers to a weight percentage (wt%) of the chromium associated with the olefin polymerization catalyst based on the total weight of the olefin polymerization catalyst after completion of all processing steps ( i.e. after activation through calcination). In a further aspect, an amount of chromium present in a precatalyst can be in a range of about 0.01% by weight to about 10% by weight; alternatively, from about 0.1% by weight to about 5% by weight; alternatively, from about 0.2% by weight to about 2% by weight; or alternatively, from about 0.5 wt% to about 1.5 wt% chromium based on the total weight of silica within the precatalyst. In this document, a chromium percentage refers to a weight percentage (wt%) of chromium associated with the precatalyst based on the total weight of silica within the precatalyst after completion of all processing steps excluding the activation by calcination.

[0037] In a further aspect, an olefin polymerization catalyst and a precatalyst thereof of the present disclosure comprise titanium. The source of titanium can be any titanium-containing compound capable of supplying a sufficient amount of titanium to the olefin polymerization catalyst and its precatalyst. In a further aspect, the titanium-containing compound comprises a tetravalent titanium compound (Ti(IV)) or a trivalent titanium compound (Ti(III)). The compound Ti(IV) can be any compound comprising Ti(IV); alternatively, the Ti(IV) compound may be any compound that is capable of releasing a Ti(IV) species upon dissolution in solution. The Ti(III) compound may be any compound comprising Ti(III); alternatively, the Ti(III) compound may be any compound that is capable of releasing a Ti(III) species upon dissolution in solution.

[0038] In one aspect, the titanium-containing compound suitable for use in the present disclosure comprises a Ti(IV) compound with at least one alkoxide group; or alternatively, at least two alkoxide groups. Ti(IV) compounds suitable for use in the present disclosure include, but are not limited to, Ti(IV) compounds having the general formula TiO(ORK)2, Ti(ORK)2(acac)2, Ti(ORK) 2(oxal), a combination thereof in which RK can be ethyl, isopropyl, n-propyl, isobutyl, n-butyl or a combination thereof; “acac” is acetylacetonate; and “oxal” is oxalate. Alternatively, the titanium-containing compound comprises a titanium(IV) alkoxide. In one aspect, the titanium(IV) alkoxide may be titanium(IV) ethoxide, titanium(IV) isopropoxide, titanium(IV) n-propoxide, titanium(IV) n-butoxide, 2-ethylhexoxide titanium(IV) or a combination thereof. In a particular aspect, the titanium-containing compound may be titanium(IV) isopropoxide.

[0039] In yet another aspect, the titanium-containing compound suitable for use in the present disclosure may comprise hydrated titania, titanium hydroxide, titanic acid, titanyl sulfate, titanium acetylacetonate, titanium oxyacetylacetonate or a combination thereof.

[0040] In yet another aspect, the titanium-containing compound suitable for use in the present disclosure may comprise a titanium(IV) halide, non-limiting examples of which include titanium tetrachloride, titanium tetrabromide, titanium(IV) oxychloride and titanium(IV) oxybromide. titanium(IV). In a further aspect the titanium(IV) halide may comprise a titanium alkoxyhalide with the general formula Ti(ORK)nQ4-n; wherein RK may be ethyl, isopropyl, n-propyl, isobutyl, n-butyl or a combination thereof; wherein Q may be a fluoride, a chloride, a bromide, an iodide or a combination thereof; and where n can be an integer from 1 to 4.

[0041] An amount of titanium present in an olefin polymerization catalyst of the present disclosure can range from about 0.01% by weight to about 10% by weight; alternatively, from about 0.5% by weight to about 5% by weight; alternatively, from about 1% by weight to about 4% by weight; or alternatively, from about 2 wt% to about 4 wt% titanium based on the total weight of the olefin polymerization catalyst. In another aspect, the amount of titanium present in the olefin polymerization catalyst can vary from about 1% by weight to about 5% by weight titanium based on the total weight of the olefin polymerization catalyst. In this document, a titanium percentage refers to a weight percentage (wt%) of the titanium associated with the olefin polymerization catalyst based on the total weight of the olefin polymerization catalyst after completion of all processing steps ( i.e. after activation through calcination). In a further aspect, an amount of titanium present in a precatalyst of the present disclosure can range from about 0.01% by weight to about 25% by weight; alternatively, from about 0.1% by weight to about 20% by weight; alternatively, from about 0.5% by weight to about 10% by weight; alternatively, from about 1% by weight to about 6% by weight; or alternatively, from about 2 wt% to about 4 wt% titanium based on the total weight of silica within the precatalyst. In this document, titanium percentage refers to a weight percentage (wt%) of titanium associated with the precatalyst based on a total weight of silica within the precatalyst after completion of all processing steps excluding activation via calcination.

[0042] In one aspect, an olefin polymerization catalyst and a precatalyst 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 a-hydroxycarboxylic acid, a β-hydroxycarboxylic acid, an a-ketocarboxylic acid or a combination thereof. In one aspect, the carboxylic acid can be a C1 to C15 monocarboxylic acid or a C1 to C5 monocarboxylic acid; alternatively, a C3 to C15 dicarboxylic acid or a C3 to C5 dicarboxylic acid; alternatively, a C1 to C15 tricarboxylic acid or a C1 to C5 tricarboxylic acid; alternatively, a C1 to C15 α-hydroxycarboxylic acid or a CI to C5 α-hydroxycarboxylic acid; alternatively, a CI to C15 β-hydroxycarboxylic acid or a CI to C5 β-hydroxycarboxylic acid; or alternatively, a C1 to C15 a-ketocarboxylic acid or a C1 to C5 a-ketocarboxylic acid.

[0043] In a particular aspect, one or more carboxylic acids may 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-pyridine dicarboxylic acid, nitrotriacetic acid, a-hydroxyisobutric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, salicylic acid, catechol, 2-(hydroxymethyl)butyric acid or a combination thereof. In yet another aspect, the carboxylic acid may be oxalic acid.

[0044] In yet another aspect, the olefin polymerization catalyst and a precatalyst thereof of the present disclosure comprises at least two carboxylic acids. In such aspects, the at least two carboxylic acids may comprise at least one simple carboxylic acid and at least one complex carboxylic acid wherein the complex carboxylic acid comprises at least one ring structure. For example, the at least two carboxylic acids can be oxalic acid and phenyl malonic acid.

[0045] In one aspect, an olefin polymerization catalyst and a pre-catalyst thereof of the present disclosure comprise an acidic phenol. The acidic phenol may be any acidic phenol capable of providing an olefin polymerization catalyst and precatalyst of the type disclosed herein. In one aspect, the acidic phenol comprises catechols, salicylic alcohol, salicylic acid, phthalic acid or derivatives thereof. In some aspects, an olefin polymerization catalyst and a precatalyst thereof of the present disclosure comprise a carboxylic acid and an acidic phenol, both of the type disclosed herein.

[0046] A precatalyst of the present disclosure comprises an equivalent molar ratio of titanium to carboxylic acid in a range of about 1:1 to about 1:10; alternatively, from about 1:1 to about 1:5 or alternatively, from about 1:1.5 to about 1:4. In one aspect, the equivalent molar ratio of titanium to carboxylic acid is in a range of about 1:1 to about 1:2. Alternatively, a precatalyst of the present disclosure comprises an equivalent molar ratio of titanium to acidic phenol in a range of from about 1:1 to about 1:10; alternatively, from about 1:1 to about 1:5 or alternatively, from about 1:1.5 to about 1:4. In one aspect, the equivalent molar ratio of titanium to acid phenol is in a range of about 1:1 to about 1:2.

[0047] In one aspect, an olefin polymerization catalyst and a pre-catalyst thereof of the present disclosure comprise a nitrogen-containing compound. The nitrogen-containing compound may be any nitrogen-containing compound suitable for providing effective titanation of the olefin polymerization catalyst and the precatalyst thereof. In a further aspect, the nitrogen-containing compound may have Structure 1, Structure 2, Structure 3, Structure 4, Structure 5, Structure 6 or a combination thereof. R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 within the nitrogen-containing compound used as described herein are elements independent of the structure of the nitrogen-containing compound in which they are present and are independently described in this document. The independent descriptions of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and/or R12 provided herein may be used without limitation, and in any combination, to further describe any 123456 structure of nitrogen-containing compound comprising an R, R, R, R, R, R, 7 8 9 10 11 12 R, R, R, R, R, and/or R. 1 2 3 5 6 9 10 11

[0048] Generally, R, R, R, R, R, R, R, and/or R of a respective 1 2 3 5 6 9 10 11 nitrogen-containing compound that has a R, R, R, R, R, R, R, and/or R may independently be hydrogen, an organyl group, a hydrocarbyl group or an aryl group. 1 2 3 5 6 9 10 11 In one aspect, R, R, R, R, R, R, R, and/or R may independently be a C1 to C30 organyl group; alternatively, a C1 to C12 organyl group; or alternatively, 1 2 3 5 6 9 10 11 a C1 to C6 organyl group. In one aspect, R, R, R, R, R, R, R, and/or R may each independently be a C1 to C30 hydrocarbyl group; alternatively, a C1 to C12 hydrocarbyl group; or alternatively, a C1 to C6 hydrocarbyl group. In still other aspects, R, R, R, R, R, R, R, and/or R may each independently be a C6 to C30 aryl group; or alternatively, a C6 to C12 aryl group. In a further aspect, any organyl group, hydrocarbyl group, or aryl group that can be used as R1, R2, R3, R5, R6, R9, R10, and/or R11 within the nitrogen-containing compound of the present disclosure may be substituted or unsubstituted. substituted. It will be understood by one skilled in the art that the terms "alkyl", "organyl", "hydrocarbyl" and "aryl" are used in this document in accordance with the definitions of the IUPAC Compendium of Chemical Terminology, 2 Ed (1997).

[0049] R4 of a respective nitrogen-containing compound that has an R4 may be an organyl group, a hydrocarbyl group or an aryl group. In one aspect, R4 may be a C1 to C30 organyl group; alternatively, a C1 to C12 organyl group; or alternatively, a C1 to C6 organyl group. In one aspect, R4 may be a C1 to C30 hydrocarbyl group; alternatively, a C1 to C12 hydrocarbyl group; or alternatively, a C1 to C6 hydrocarbyl group. In still other aspects, R4 may be a C6 to C30 aryl group; or alternatively, a C6 to C12 aryl group. In a further aspect, any organyl group, hydrocarbyl group or aryl group that can be used as R4 within the nitrogen-containing compound of the present disclosure can be substituted or unsubstituted.

[0050] In a particular aspect, any substituted organyl group, substituted hydrocarbyl group or substituted aryl group that can be used as R1, R2, R3, R4, R5, R6, R9, R10, and/or R11 can contain one or more non-hydrogen substituents. Suitable non-hydrogen substituents for use herein may be a halogen, a C1 to C12 hydrocarbyl group, a C1 to C12 hydrocarboxy group, or a combination thereof. In one aspect, the halogen used as the non-hydrogen substituent may be fluorine, chlorine, bromine or iodine. Non-limiting examples of the C1 to C12 hydrocarboxy group suitable for use herein include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a phenoxy group, a toloxy group, a xyloxy group , a trimethylphenoxy group and a benzoxy group.

[0051] R7 and/or R8 of a respective nitrogen-containing compound that has an R7 and/or R8 can each independently be hydrogen or a methyl group.

[0052] R12 of a respective nitrogen-containing compound that has an R12 may be a branched alkyl group or a linear alkyl group. In one aspect, R12 may be a branched C1 to C30 alkyl group; alternatively, a branched C1 to C12 alkyl group; or alternatively, a branched C1 to C6 alkyl group. In a further aspect, R12 may be a C1 to C30 linear alkyl group; alternatively, a linear C1 to C12 alkyl group; or alternatively, a linear C1 to C6 alkyl group.

[0053] In yet another aspect, a nitrogen-containing compound of the present disclosure that has Structure 2 can have x where x is an integer from 1 to 4. In one aspect, the nitrogen-containing compound that has Structure 3 can have y in where y is an integer from 1 to 12. In yet another aspect, the nitrogen-containing compound having Structure 5 may have Z where Z is oxygen or sulfur.

[0054] In one aspect, a nitrogen-containing compound suitable for use in the present disclosure may be an alkanolamine, an amide, an amine, an alkylamine, an ammonium hydroxide, an aniline, a hydrazide, a hydroxylamine, an imine, a urea or a combination thereof. In a further aspect, the alkanolamine, amide, amine, ammonium hydroxide, hydrazide, hydroxylamine, imine and/or urea used as the nitrogen-containing compound may contain one or more substituent groups. In one aspect, any substituent group contained in any nitrogen-containing compound of the present disclosure may be a halogen, a C1 to C12 organyl group, a C1 to C12 hydrocarbyl group, a C1 to C12 hydrocarboxy group, or a combination thereof. The halogen used as the substituent group of any aspect disclosed herein may be fluorine, chlorine, bromine or iodine. Non-limiting examples of the C1 to C12 hydrocarboxy group suitable for use herein include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a phenoxy group, a toloxy group, a xyloxy group , a trimethylphenoxy group and a benzoxy group.

[0055] In yet 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, tert-butylamine, N,N'-dibutyl urea, creatine, creatinine, diethanol amine, diethylhydroxy amine, diisopropanol amine, dimethylaminoethanol, dimethyl carbamate, dimethyl formamide, dimethyl glycine, dimethylisopropanol amine, N,N'-dimethyl urea, ethanol amine, ethyl amine, glycol amine, hexyl amine, hydroxyamine, imidazole , isopropanol amine, methacryl amide, methyl amine, N-methyl aniline, N-methyl-2-propanol amine, methyldiethanol amine, methyl formamide, propyl amine, 2-propanol amine, pyrazole, pyrrolidine, pyrrolidinone, succinimide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanol amine, triisopropanol amine, trimethyl amine, urea, 1,8-diazabicyclo[5.4.0]undec-7-ene or a combination thereof.

[0056] A precatalyst of the present disclosure comprises an equivalent molar ratio of titanium to nitrogen-containing compound in a range of about 2:1 to about 1:10; alternatively, from about 1:1 to about 1:5; or alternatively, from about 1:1.5 to about 1:4. In one aspect, the equivalent molar ratio of titanium to nitrogen-containing compound is in a range of about 1:1 to about 1:2.

[0057] In a particular aspect, a pre-catalyst composition of the present disclosure comprises a titano-organic salt. In one aspect, the pre-catalyst composition comprising the titane-organic salt further comprises a silica support and a chromium-containing compound, both of the type disclosed hereinbefore. In a further aspect, the titano-organic salt suitable for use herein comprises titanium, a protonated nitrogen-containing compound and a carboxylate.

[0058] In one aspect, the titano-organic salt comprises titanium. The source of titanium can be any titanium-containing compound capable of supplying a sufficient amount of titanium to a precatalyst as disclosed herein. In a further aspect, the source of titanium is a titanium-containing compound of the type disclosed hereinbefore.

[0059] In one aspect, the titano-organic salt comprises a protonated nitrogen-containing compound. The protonated nitrogen-containing compound can be any protonated nitrogen-containing compound capable of supplying a sufficient amount of titanium to a precatalyst as disclosed herein. In a further aspect, the protonated nitrogen-containing compound may comprise a protonated form of any nitrogen-containing compound of the type previously disclosed herein.

[0060] In one aspect, 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. same.

[0061] In yet another aspect, the protonated nitrogen-containing compound comprises protonated acetamide, protonated acrylamide, protonated allyl amine, ammonium, protonated ammonium hydroxide, protonated butylamine, protonated tert-butyl amine, N,N'-protonated dibutyl urea, creatine, protonated creatinine, protonated diethanolamine, protonated diethylhydroxyamine, protonated diisopropanol amine, protonated dimethylaminoethanol, protonated dimethylcarbamate, protonated dimethylformamide, protonated dimethylglycine, protonated dimethylisopropanol amine, protonated N,N'-dimethylurea, protonated ethanolamine, protonated ethylamine, glycol protonated amine, protonated hexyl amine, protonated hydroxyamine, protonated imidazole, protonated isopropanol amine, protonated methacrylamide, protonated methyl amine, protonated N-methyl aniline, protonated N-methyl-2-propanol amine, protonated methyldiethanol amine, protonated methyl formamide, protonated propylamine , 2-protonated propanol amine, protonated pyrazole, protonated pyrrolidine, protonated pyrrolidinone, protonated succinimide, protonated tetraethylammonium hydroxide, protonated tetramethylammonium hydroxide, protonated triethanolamine, protonated triisopropanol amine, protonated trimethylamine, protonated urea, 1,8-diazabicyclo[5.4. Protonated 0]undec-7-ene, or a combination thereof.

[0062] In yet another aspect, the titano-organic salt comprises a carboxylate. The carboxylate can be any carboxylate capable of supplying a sufficient amount of titanium to a precatalyst as disclosed herein. In one aspect, the carboxylate may comprise an anionic form of any carboxylic acid of the type disclosed hereinbefore.

[0063] In a further aspect, the carboxylate comprises a C1 to C15 monocarboxylate, a C2 to C15 dicarboxylate, a C3 to C15 tricarboxylate, a C1 to C15 α-hydroxycarboxylate or a combination thereof.

[0064] In yet another aspect, the carboxylate comprises acetate, citrate, gluconate, glycolate, glyoxylate, lactate, malate, malonate, oxalate, phosphonoacetate, tartrate or a combination thereof.

[0065] In a further aspect, an amount of titanium present in the titano-organic salt of the present disclosure can vary from about 0.01% by weight to about 20% by weight; alternatively, from about 0.5% by weight to about 10% by weight; or alternatively, from about 1 wt% to about 6 wt% titanium based on the total weight of silica of a precatalyst as disclosed herein. In another aspect, the titano-organic salt comprises an equivalent molar ratio of titanium to carboxylate in a range of about 1:1 to about 1:10; alternatively, from about 1:1 to about 1:5 or alternatively, from 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 yet another aspect, the titano-organic salt comprises an equivalent molar ratio of titanium to nitrogen-containing compound in a range of from about 2:1 to about 1:10; alternatively, from about 1:1 to about 1:5; or alternatively, from about 1:1.5 to about 1:4. In yet another aspect, the equivalent molar ratio of titanium to nitrogen-containing compound may be about 1:2.

[0066] In one aspect, an olefin polymerization catalyst and a pre-catalyst thereof of the present disclosure comprise a peroxide-containing compound. The peroxide-containing compound may be any peroxide-containing compound suitable for providing effective titanation of the olefin polymerization catalyst and the precatalyst thereof. In a further aspect, the peroxide-containing compound comprises organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyesters, dialkyl peroxides, hydroperoxides or any combination thereof. In one aspect, the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or any combination thereof. In one aspect, the peroxide-containing compound comprises hydrogen peroxide. In one aspect, a precatalyst of the present disclosure comprises an equivalent molar ratio of titanium to peroxide-containing compound in a range of about 1.0:0.5 to about 1:50, alternatively, of about 1:2. to about 1:20 or alternatively, from about 1:5 to about 1:10. In some aspects, the use of a peroxide-containing compound in the olefin polymerization catalyst and a precatalyst thereof results in an increased solubility of the carboxylic acid-Ti component of the STM.

[0067] In one aspect of the present disclosure, a method for preparing an olefin polymerization catalyst comprises the use of a solubilized 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, the STM of the present disclosure comprises a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, optionally a peroxide-containing compound, and a solvent. In another aspect, the STM of the present disclosure comprises a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, a peroxide-containing compound, and a solvent. In yet another aspect, the STM of the present disclosure comprises a carboxylic acid, a titanium-containing compound, a peroxide-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, a peroxide-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, the STM of the present disclosure comprises an acidic phenol, a titanium-containing compound, a peroxide-containing compound, and a solvent. In another aspect, the STM of the present disclosure comprises a carboxylic acid, an acidic phenol, a titanium-containing compound, a peroxide-containing compound, and a solvent. In another aspect, the STM of the present disclosure comprises a carboxylic acid, an acidic phenol, a nitrogen-containing compound, a titanium-containing compound, a peroxide-containing compound, and a solvent. In one aspect, the STM comprises a carboxylic acid of the type used as a component of a precatalyst as disclosed herein, alternatively at least two carboxylic acids of the type used as a component of the precatalyst disclosed herein. In a further aspect, the STM comprises a titanium-containing compound of the type used as a component of the precatalyst as disclosed herein. In a further aspect, the STM comprises one or more nitrogen-containing compounds of the type used as a component of the precatalyst as disclosed herein. In a further aspect, the STM comprises one or more peroxide-containing compounds of the type used as a component of the precatalyst as disclosed herein. In yet another aspect, the STM comprises one or more acidic phenols of the type used as a component of the precatalyst as disclosed herein.

[0068] In a further 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. A non-limiting example of an aqueous solvent suitable for use in the present disclosure comprises deionized water, distilled water, filtered water, or a combination thereof. Non-limiting examples of alcohols suitable for use as a solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, benzyl alcohol, phenol or a combination thereof. In a further aspect, the organic solvent suitable for use in the present disclosure may be an ester, a ketone or a combination thereof. Non-limiting examples of esters suitable for use as a solvent include ethyl acetate, propyl acetate, butyl acetate, isobutyl isobutyrate, methyl lactate, ethyl lactate or a combination thereof. Non-limiting examples of ketones suitable for use as a solvent include acetone, ethyl methyl ketone, methyl isobutyl ketone or a combination thereof. In a particular aspect, the hydrocarbon suitable for use as a solvent may be a halogenated aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated aromatic hydrocarbon or a combination thereof. Non-limiting examples of the hydrocarbon suitable for use as a solvent include methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, benzene, toluene, ethylbenzene, xylenes, chlorobenzene, dichlorobenzene or a combination thereof.

[0069] In a particular aspect, a solubilized titanium mixture (STM), as disclosed herein, comprises an acidic mixture that can be prepared by contacting one or more carboxylic acids and a solvent or, alternatively, one or more acidic phenols and a solvent. In one aspect, the STM is prepared by sequentially adding a titanium-containing compound followed by a nitrogen-containing compound to the acid mixture, as disclosed herein. In an alternative aspect, the titanium-containing compound and the nitrogen-containing compound may be contacted to form a basic mixture which is subsequently contacted with the acidic mixture to form the STM as disclosed herein. In a further aspect, the nitrogen-containing compound used to form the basic mixture can be a component of an aqueous solution.

[0070] In another aspect, a solubilized titanium mixture (STM), as disclosed herein, comprises an acid mixture. The acidic mixture can be prepared by contacting a carboxylic acid with a peroxide-containing compound and a solvent. Alternatively, the acidic mixture can be prepared by contacting at least two carboxylic acids with a peroxide-containing compound and a solvent. Alternatively, the acidic mixture can be prepared by contacting an acidic phenol with a peroxide-containing compound and a solvent. Alternatively, the acidic mixture can be prepared by contacting an acidic phenol with one or more carboxylic acids and, optionally, with a peroxide-containing compound and a solvent.

[0071] In one aspect, the STM is prepared by sequentially adding a titanium-containing compound followed by a nitrogen-containing compound to the acid mixture, as disclosed herein. In another aspect, the STM is prepared by adding a titanium-containing compound to the acid mixture, as disclosed herein. In some respects, the order of addition is any order consistent with the materials disclosed herein. For example, any STM may comprise any of the components disclosed herein (e.g., acidic phenol, nitrogen-containing compound, peroxide-containing compound, carboxylic acid), the titanium-containing compound, and a chromium-containing compound.

[0072] In an alternative aspect, the titanium-containing compound and the nitrogen-containing compound may be contacted to form a basic mixture which is subsequently contacted with the acidic mixture to form the STM as disclosed herein. In a further aspect, the nitrogen-containing compound used to form the basic mixture can be a component of an aqueous solution.

[0073] In one aspect, the STM comprises one or more carboxylic acids, alternatively one or more acidic phenols, alternatively a combination of one or more acidic phenols and one or more carboxylic acids, all of the type disclosed herein. In one aspect, an STM of the present disclosure comprises an acid mixture with a weight ratio of solvent to carboxylic acid in a range of from about 1:1 to about 100:1; alternatively, from about 1:1 to about 50:1; or alternatively, from about 1:1 to about 10:1. In a further aspect, the STM comprises an equivalent molar ratio of titanium-containing compound to carboxylic acid in a range of from about 1:0.5 to about 1:20; alternatively, from about 1:1 to about 1:10; or alternatively, from about 1:1 to about 1:5. In some aspects, the equivalent molar ratio of titanium-containing compound to carboxylic acid may be about 1:2.5. In another aspect, the STM comprises an equivalent molar ratio of nitrogen-containing compound to carboxylic acid in a range of 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, from about 1:1 to about 2:1. In another aspect, the STM comprises an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in a range 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, from about 1:3 to about 1:8. In another aspect, the STM comprises an equivalent molar ratio of titanium-containing compound to acidic phenol in a range 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, from about 1:1 to about 1:2.5.

[0074] In yet another aspect, the STM comprises an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in a range 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, from about 1:1 to about 1:2.5. In still other aspects, the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound may be about 1:2.

[0075] In a particular aspect, the STM suitable for use in the present disclosure can be characterized by a pH of less than about 5.5. Alternatively, the STM may be characterized by a pH in a range of about 2.5 to about 5.5; alternatively, from about 3.0 to about 5.0; or alternatively, from about 3.5 to about 4.5.

[0076] In one aspect of the present disclosure, the catalyst components disclosed herein may be brought into contact in any order or manner deemed suitable by one skilled in the art with the aid of the present disclosure to produce an olefin polymerization catalyst with the characteristics disclosed in this document.

[0077] In a particular aspect, a method for preparing an olefin polymerization catalyst comprises contacting a solvent and one or more carboxylic acids, both of the type disclosed in this document, to form an acidic mixture. The method may further comprise contacting a titanium-containing compound of the type disclosed herein and the acid mixture to form an acid titanium mixture. In one aspect, a nitrogen-containing compound of the type disclosed herein, and the acidic titanium mixture can be brought into contact to form an STM as disclosed herein, for example, the nitrogen-containing compound can be added to the acidic titanium mixture to form the STM. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture as a single portion of an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2 within the STM. In a particular aspect, an amount of nitrogen-containing compound to be added to the acidic titanium mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in multiple portions and wherein a single portion comprises from about 3% to about 10% of the amount of nitrogen-containing compound comprising an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. Addition of the multiple portions of the nitrogen-containing compound can be stopped when a green end point of a green bromocresol indicator is reached. In some aspects, the green hue endpoint of the bromocresol green indicator correlates with a pH value within the STM of about 4.0. In a further aspect, adding the nitrogen-containing compound to the titanium acid mixture comprises partially neutralizing the titanium acid mixture; or alternatively, completely neutralize the acidic titanium mixture. The method for preparing the 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 a further aspect, the addition product can be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[0078] In a further aspect, a method for preparing an olefin polymerization catalyst comprises contacting a solvent and one or more carboxylic acids, both of the type disclosed in this document, to form an acidic mixture. The method may further comprise contacting a titanium-containing compound of the type disclosed herein and the acid mixture to form an acid titanium mixture. In one aspect, a nitrogen-containing compound of the type disclosed herein, and the acidic titanium mixture can be brought into contact to form an STM as disclosed herein, for example, the nitrogen-containing compound can be added to the acidic titanium mixture to form the STM. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture as a single portion of an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2 within the STM. In a particular aspect, an amount of nitrogen-containing compound to be added to the acidic titanium mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in multiple portions and wherein a single portion comprises from about 3% to about 10% of the amount of nitrogen-containing compound comprising an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. Addition of the multiple portions of the nitrogen-containing compound can be stopped when a green end point of a green bromocresol indicator is reached. In some aspects, the green hue endpoint of the bromocresol green indicator correlates with a pH value within the STM of about 4.0. In a further aspect, adding the nitrogen-containing compound to the titanium acid mixture comprises partially neutralizing the titanium acid mixture; or alternatively, completely neutralize the acidic titanium mixture.

[0079] The method for preparing the olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed in this document and the STM to form a titanized support. In a further aspect, the titanized support can be dried by heating the titanized support to a temperature in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the titanized support in the range of 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of about 30 minutes to about 6 hours to form a dry titanized support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein and the dried titanized support to form an addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst. In an alternative aspect, prior to drying the titanized support as disclosed herein, the chromium-containing compound and the titanized support may be contacted to form the addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst. In yet another alternative aspect, the chromium-containing compound and the silica support may be contacted to form a chromium-silica support which may be contacted with the STM to form the addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst.

[0080] In yet another aspect, a method for preparing an olefin polymerization catalyst comprises contacting a titanium-containing compound and a nitrogen-containing compound, both of the type disclosed in this document, to form a basic mixture. The method may further comprise contacting a solvent and a carboxylic acid, both of the type disclosed in this document, to form an acidic mixture. The base mixture and the acid mixture can be contacted to form a solubilized titanium mixture (STM) as disclosed herein, for example, the base mixture can be added to the acid mixture to form the STM. In some aspects, the basic mixture is added to the acidic mixture as a single portion of an amount sufficient to form an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a particular aspect, an amount of base mixture to be added to the acid mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the base mixture is added to the acid mixture in multiple portions and wherein a A single portion comprises from about 3% to about 10% of the amount of basic mixture comprising an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. The addition of multiple portions of the base mixture can be stopped when a green endpoint of a green bromocresol indicator is reached. In some aspects, the green hue endpoint of the bromocresol green indicator correlates with a pH value within the STM of about 4.0. In a further aspect, adding the basic mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or, alternatively, neutralize the acidic mixture completely. The method for preparing the olefin polymerization catalyst may further comprise contacting a chromo-silica support of the type disclosed herein and the STM to form an addition product. In a further aspect, the addition product can be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst.

[0081] In a still further aspect, a method for preparing an olefin polymerization catalyst comprises contacting a titanium-containing compound and a nitrogen-containing compound, both of the type disclosed in this document, to form a basic mixture. The method may further comprise contacting a solvent and a carboxylic acid, both of the type disclosed in this document, to form an acidic mixture. The base mixture and the acid mixture can be contacted to form a solubilized titanium mixture (STM) as disclosed herein, for example, the base mixture can be added to the acid mixture to form the STM. In some aspects, the basic mixture is added to the acidic mixture as a single portion of an amount sufficient to form an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a particular aspect, an amount of base mixture to be added to the acid mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the base mixture is added to the acid mixture in multiple portions and wherein a A single portion comprises from about 3% to about 10% of the amount of basic mixture comprising an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. The addition of multiple portions of the base mixture can be stopped when a green endpoint of a green bromocresol indicator is reached. In some aspects, the green hue endpoint of the bromocresol green indicator correlates with a pH value within the STM of about 4.0. In a further aspect, adding the basic mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or, alternatively, neutralize the acidic mixture completely. The method for preparing the olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein and the STM to form a titanized support. In a further aspect, the titanized support can be dried by heating the titanized support to a temperature in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the titanized support in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of about 30 minutes to about 6 hours to form a dry titanized support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein and the dried titanized support to form an addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst. In an alternative aspect, prior to drying the titanized support as disclosed herein, the chromium-containing compound and the titanized support may be brought into contact to form the addition product which may be dried by heating the addition product to a temperature at a range from about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst. In yet another alternative aspect, the chromium-containing compound and the silica support may be contacted to form a chromium-silica support which may be contacted with the STM to form the addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst.

[0082] In a further aspect, a method for preparing an olefin polymerization catalyst comprises contacting a solvent, one or more carboxylic acids, one or more nitrogen-containing compounds and a peroxide-containing compound, each of the disclosed type 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 peroxide-containing compound, each 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 peroxide-containing compound, each of the types herein. disclosed, to form an acidic mixture. Alternatively, a method for preparing an olefin polymerization catalyst comprises bringing a solvent, one or more carboxylic acids, one or more acidic phenols and a peroxide-containing compound, each of the type disclosed herein, into contact to form an acidic mixture. . 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 peroxide-containing compound, each of the type disclosed herein, to form a acid mixture. The method may further comprise contacting a titanium-containing compound of the type disclosed herein and the acid mixture to form an acid titanium mixture.

[0083] In one aspect, a nitrogen-containing compound of the type disclosed herein and the acidic titanium mixture can be contacted to form a solubilized titanium mixture (STM) as disclosed herein, for example, the nitrogen-containing compound can be added to the acidic titanium mixture to form the STM. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture as a single portion of an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2 within the STM. In a particular aspect, an amount of nitrogen-containing compound to be added to the acidic titanium mixture is determined with an acid-base indicator (e.g., bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in multiple portions and wherein a single portion comprises from about 3% to about 10% of the amount of nitrogen-containing compound comprising an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. Addition of the multiple portions of the nitrogen-containing compound can be stopped when a green end point of a green bromocresol indicator is reached. In some aspects, the green hue endpoint of the bromocresol green indicator correlates with a pH value within the STM of about 4.0. In a further aspect, adding the nitrogen-containing compound to the titanium acid mixture comprises partially neutralizing the titanium acid mixture; or alternatively, completely neutralize the acidic titanium mixture. The method for preparing the olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein and the STM to form a titanized support. In a further aspect, the titanized support can be dried by heating the titanized support to a temperature in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the titanized support in the range of 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of about 30 minutes to about 6 hours to form a dry titanized support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein and the dried titanized support to form an addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst. In an alternative aspect, prior to drying the titanized support as disclosed herein, the chromium-containing compound and the titanized support may be brought into contact to form the addition product which may be dried by heating the addition product to a temperature at a range from about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst. In yet another alternative aspect, the chromium-containing compound and the silica support may be contacted to form a chromium-silica support which may be contacted with the STM to form the addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst.

[0084] In another aspect, a method for preparing an olefin polymerization catalyst comprises contacting a solvent, a carboxylic acid and a peroxide-containing compound, each 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 peroxide-containing compound, each of the type disclosed herein, to form an acidic mixture. Alternatively, a method for preparing an olefin polymerization catalyst comprises contacting a solvent, a carboxylic acid, an acidic phenol and a peroxide-containing compound, each of the type disclosed herein, to form an acidic mixture.

[0085] The method may further comprise contacting a titanium-containing compound of the type disclosed in this document and the acid mixture to form an acid titanium mixture. The method for preparing the olefin polymerization catalyst may further comprise contacting a silica support of the type disclosed herein and the STM to form a titanized support. In a further aspect, the titanized support can be dried by heating the titanized support to a temperature in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the titanized support in the range of 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of about 30 minutes to about 6 hours to form a dry titanized support. The method may further comprise contacting a chromium-containing compound of the type disclosed herein and the dried titanized support to form an addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst. In an alternative aspect, prior to drying the titanized support as disclosed herein, the chromium-containing compound and the titanized support may be contacted to form the addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst. In yet another alternative aspect, the chromium-containing compound and the silica support may be contacted to form a chromium-silica support which may be contacted with the STM to form the addition product which may be dried by heating the addition product to a temperature in a range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C. The method further comprises maintaining the temperature of the addition product in the range of about 25°C to about 300°C; alternatively, from about 50°C to about 150°C; or alternatively, from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to form the precatalyst.

[0086] The use of a solubilized titanium mixture (STM) in the preparation of an olefin polymerization catalyst of the present disclosure can be advantageous because the STM can facilitate the association of titanium with a silica support in the presence of an aqueous solvent ( e.g. water). Other advantages may occur 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 use of spray drying methodologies to contact the STM and the silica support. Spray drying, as used herein, refers to a method of producing a dry powder from a liquid or paste by rapid drying with a hot gas. Spray drying methodologies can be used in the preparation of olefin polymerization catalysts in a continuous production method with the potential to produce large volumes of olefin polymerization catalysts. Spray drying methodologies can also be used in the preparation of olefin polymerization catalysts with a consistent particle size distribution. The use of the STM comprising the aqueous solvent may allow the use of a hydrated silica support and avoid the heat treatment required for anhydrous methods of catalyst preparation (e.g., drying the hydrated silica support before contact with any other catalyst components ).

[0087] As will be understood by one skilled in the art, calcination of the pre-catalysts disclosed in this document can result in the emission of volatile organic compounds (VOC). In various aspects of the present disclosure using peroxide in the absence of a nitrogen-containing compound, emissions of VOCs are reduced when compared to an otherwise similar catalyst preparation carried out in the presence of a nitrogen-containing compound. In one aspect, emissions of VOCs by a catalyst of the present disclosure 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 a otherwise similar catalyst preparation carried out in the presence of a nitrogen-containing compound.

[0088] In some aspects of the present disclosure, the contact of the components used in the preparation of the olefin polymerization catalyst can be carried out in the presence of a reaction medium. In a further aspect, the reaction medium can be formed during contact of the components used in preparing 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 in preparing the olefin polymerization catalyst (e.g., water associated with the silica support). In one aspect, the reaction medium excludes any solid component used in preparing the olefin polymerization catalyst disclosed herein (e.g., silica support and any solids associated therewith). In some aspects, a sum of an amount of water present in the reaction medium may be in a range of about 1% by weight to about 99% by weight; alternatively, from about 1% by weight to about 50% by weight; alternatively, from about 1% by weight to about 20% by weight; or alternatively, from about 1 wt% to about 10 wt% based on the total weight of the reaction medium. In yet another aspect, the reaction medium may contain more than about 20% by weight water; alternatively, about 40% by weight water; alternatively, about 60% by weight water; alternatively, about 80% by weight water; or alternatively, about 90% by weight of water based on the total weight of the reaction medium, wherein the water may originate from one or more components used in preparing the olefin polymerization catalyst.

[0089] In any aspect of the present disclosure, a method for preparing an olefin polymerization catalyst further comprises activating a precatalyst prepared as disclosed herein through a calcination step. In some aspects, calcining the precatalyst comprises heating the precatalyst in an oxidizing environment to produce the olefin polymerization catalyst. For example, the precatalyst can be calcined by heating the precatalyst in the presence of air to a temperature in a range of about 400°C to about 1,000°C; alternatively, from about 500°C to about 900°C; or alternatively, from about 500°C to about 850°C. Calcining the precatalyst may further comprise maintaining the temperature of the precatalyst in the presence of air in the range of about 400°C to about 1,000°C; alternatively, from about 500°C to about 900°C; or alternatively, from about 500°C to about 850°C for a period of time in a range of 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, from about 3 hours to about 5 hours to produce the olefin polymerization catalyst.

[0090] The olefin polymerization catalysts of the present disclosure are suitable for use in any olefin polymerization method, using various types of polymerization reactors. In one aspect of the present disclosure, a polymer of the present disclosure is produced by any olefin polymerization method, 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. Homopolymers and/or copolymers produced in the reactor can be referred to as resin and/or polymers. The various types of reactors include, but are not limited to, those that may be referred to as batch, slurry, gas phase solution, high pressure, tubular, autoclave or other reactor and/or reactors. Gas phase reactors may comprise fluidized bed reactors or horizontal stack reactors. Slurry reactors may comprise vertical and/or horizontal loops. High pressure reactors may comprise autoclave and/or tubular reactors. Reactor types may include batch and/or continuous processes. Continuous processes may use intermittent and/or continuous product discharge or transfer. The processes may also include partial or total direct recycling of unreacted monomer, unreacted comonomer, olefin polymerization catalyst and/or cocatalysts, diluents and/or other materials from the polymerization process.

[0091] The polymerization reactor systems of the present disclosure may comprise one type of reactor in a system or multiple reactors of the same or different type, operated in any suitable configuration. Polymer production in multiple reactors may include several phases in at least two separate polymerization reactors interconnected by a transfer system, making it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. Alternatively, polymerization in multiple reactors may include transferring, manually or automatically, the polymer from one reactor to the subsequent reactor or reactors for further polymerization. Alternatively, multistep or multistage polymerization can occur in a single reactor, where conditions are changed such that a different polymerization reaction occurs.

[0092] The desired polymerization conditions in one of the reactors may be the same or different from the operating conditions of any other reactors involved in the overall polymer production process of the present disclosure. Multiple reactor systems 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 circuit and/or gas. Multiple reactors can be operated in series or in parallel. In one aspect of the present disclosure, any arrangement and/or any combination of reactors can be employed to produce the polymer of the present disclosure.

[0093] According to one aspect of the present disclosure, the polymerization reactor system may comprise at least one loop slurry reactor. Such reactors are common and may include vertical or horizontal circuits. Generally, continuous processes may comprise the continuous introduction of a monomer, an olefin polymerization catalyst and/or a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent. Monomer, diluent, olefin polymerization catalyst, and optionally any comonomer can be continuously fed to a closed-loop slurry reactor where polymerization occurs. The reactor effluent may be washed to remove liquids comprising the solid polymer diluent, monomer and/or comonomer. Various technologies may be used for this separation step including, but not limited to, washing which may include any combination of adding heat and reducing pressure; separation by cyclonic action in a cyclone or hydrocyclone; centrifugal separation; or other appropriate method of separation.

[0094] Typical slurry polymerization processes (also known as particulate processes) are described in US Patents 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833 .415, for example; each of which is incorporated herein by reference in its entirety.

[0095] Diluents suitable for use in paste polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under 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. An example is the polymerization of propylene monomer as disclosed in US Patent 5,455,314, which is incorporated herein by reference in its entirety.

[0096] According to yet another aspect of the present disclosure, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recycling stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the olefin polymerization catalyst under polymerization conditions. A recycle stream can be withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, the polymeric product can be removed from the reactor and new or freshly prepared monomer can be added to replace the polymerized monomer. Such gas-phase reactors may comprise a process for multi-step gas-phase polymerization of olefins, wherein the olefins are polymerized in the gas phase in at least two independent gas-phase polymerization zones while feeding a polymer containing olefin polymerization catalyst. formed in a first polymerization zone to a second polymerization zone. A type of gas phase reactor suitable for use is disclosed in US Patents 4,588,790, 5,352,749 and 5,436,304, each of which is incorporated herein by reference in its entirety.

[0097] According to yet another aspect of the present disclosure, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones where fresh monomers, initiators or olefin polymerization catalysts are added. The monomer can be entrained in an inert gas stream and introduced into a zone of the reactor. Initiators, olefin polymerization catalysts and/or catalyst components can be entrained in a gas stream and introduced into another zone of the reactor. The gas streams can be mixed by polymerization. Heat and pressure can be used appropriately to obtain ideal polymerization reaction conditions.

[0098] According to yet another aspect of the present disclosure, the polymerization reactor may comprise a solution polymerization reactor in which the monomer is brought into contact with the olefin polymerization catalyst composition by suitable stirring or other means. . A carrier comprising an organic diluent or excess monomer may be employed. If desired, the monomer can be placed in the vapor phase and in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Agitation can be employed to achieve better temperature control and maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.

[0099] Polymerization reactors suitable for use in the present disclosure may further comprise any combination of at least one feedstock feed system, at least one feed system for an olefin polymerization catalyst or catalyst components and/or at least one polymer recovery system. Reactor systems suitable for the present disclosure may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, charging, laboratory analysis and process control.

[00100] Conditions that are controlled for 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 the concentrations of various reagents. Polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature in accordance with the Gibbs Free Energy Equation. Typically, this includes from about 60°C to about 280°C, for example, and/or from about 70°C to about 110°C, depending on the type of polymerization reactor and/or polymerization process.

[00101] Suitable pressures will also vary depending on the reactor and polymerization process. The pressure for liquid phase polymerization in a loop reactor is typically less than 1,000 psig (6.9 MPa). The pressure for gas phase polymerization is generally in the range of about 200 psig (1.4 MPa) to 500 psig (3.45 MPa). High-pressure polymerization in tubular or autoclave reactors is generally performed in a range of about 20,000 psig (138 MPa) to 75,000 psig (518 MPa). Polymerization reactors can also be operated in a supercritical region that occurs at generally higher temperatures and pressures. Operation under conditions above the critical point indicated by a pressure/temperature diagram (supercritical phase) can offer advantages.

[00102] The concentration of various reagents can be controlled to produce polymers with certain physical and mechanical properties. The proposed end-use product that will be formed by the polymer and the method of forming that product may vary to determine the desired properties of the final product. Mechanical properties include, but are not limited to, test values of tensile strength, flexural modulus, impact strength, creep, stress relaxation, and hardness. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack growth, short chain branching, branching long chain and rheological measurements.

[00103] The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers and electron donors are generally important in producing specific properties of the polymer. Comonomer can be used to control product density. Hydrogen can be used to control the molecular weight of the product. Cocatalysts can be used to alkylate, eliminate poisons and/or control molecular weight. The concentration of poisons can be minimized, as poisons can affect reactions and/or affect the properties of the polymeric product. Modifiers can be used to control product properties and electron donors can affect stereoregularity.

[00104] Polymers, such as polyethylene homopolymers and copolymers of ethylene with other mono-olefins can be produced in the manner described above using the olefin polymerization catalysts prepared as described herein. Polymers produced as disclosed herein can be formed into articles of manufacture or end-use articles using techniques known in the art, such as extrusion, blow molding, injection molding, fiber spinning, thermoforming and casting. For example, a polymeric resin may be extruded into a sheet, which is then thermoformed into an end-use article, such as a container, a cup, a tray, a pallet, a toy, or a component of another product. Examples of other end-use articles into which polymer resins can be formed include tubes, films and bottles.

[00105] A method of the present disclosure comprises contacting an olefin polymerization catalyst of the type described with an olefin monomer under conditions suitable for the formation of a polyolefin and recovery of the polyolefin. In one aspect, the olefin monomer is an ethylene monomer and the polyolefin is a polymer of ethylene (polyethylene).

[00106] Polyethylene prepared as described here can be characterized by a high load melt index (HLMI), in a range of about 1 g/10 min. at approximately 1,000 g/10 min.; alternatively, about 3 g/10 min. at about 300 g/10 min.; alternatively, about 6 g/10 min. at approximately 100 g/10 min.; or alternatively, about 15 g/10 min. at about 40 g/10 min. In a further aspect, polyethylene prepared as described herein can be characterized by an HLMI that is from about 1.5 to about 15 times greater than the HLMI of a polymer produced using an olefin polymerization catalyst that does not contain otherwise similar titanium.

[00107] In a particular aspect, polyethylene can be prepared with a denitanized catalyst that was produced from a water-extracted pre-catalyst. In a further aspect, the water extracted precatalyst is a precatalyst that has been extracted with water before being calcined. For example, a precatalyst prepared as described herein can be extracted with water and subsequently calcined to provide the denitanized catalyst (i.e., olefin polymerization catalyst derived from the water extracted precatalyst). In a further aspect, polyethylene prepared with a denitanized catalyst can be characterized by an HLMI in the range of about 1 dg/min to about 7 dg/min. Such an HMLI value may indicate that the detitanized catalyst has an amount of titanium based on an amount of silica in a range of about 0% by weight to about 1% by weight; or alternatively, about 0.1% by weight to about 0.5% by weight. %.

[00108] The melt index (MI) represents the flow rate of a molten polymer through a 0.0825 inch diameter orifice when subjected to a force of 2,160 grams at 190°C, as determined in accordance with condition E of ASTM D123882. I10 represents the flow rate of a polymer melt through a 0.0825 inch diameter orifice when subjected to a force of 10,000 grams at 190°C, as determined in accordance with condition N of ASTM D1238-82. The HLMI (High Load Melt Index) represents the flow rate of a polymer melt through a 0.0825 inch diameter orifice when subjected to a force of 21,600 grams at 190°C, as determined in accordance with condition F of ASTM D1238-82.

EXAMPLES

[00109] The following examples are given as particular aspects of the present disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the following claims in any way.

[00110] It will be understood by one skilled in the art that the surfaces of oxides, including silica (SiO2) and titania (TiO2), generally end with hydroxyl groups which are protic groups that can participate in acid-base reactions. Under strongly acidic conditions, hydroxyl groups can be protonated to establish a positive charge on the oxide surface. Under strongly alkaline conditions, hydroxyl groups can be deprotonated to establish a negative charge on the oxide surface. There is a pH value somewhere between the two limits at which zero net charge exists on the oxide surface. The pH value that correlates with zero net charge is the isoelectric point. Each oxide has a characteristic acidity and a specific isoelectric point controlled by the chemical properties of the metallic or non-metallic element of the oxide.

[00111] The Figure displays the zeta potential as a function of the pH value of the solution for silica and titania, together with the value of the isoelectric point of both oxides. A Si-Ti Columbian attraction curve is also shown. Zeta potential is the difference in electrical charge potential existing 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 titania is positively charged and silica is negatively charged within a zone of pH values between 3.0 and 5.0. The Figure also indicates that the attraction for Columbian Si-Ti is greatest around a pH value of about 4.0. Not wishing to be limited by theory, highly effective titanation of an olefin polymerization catalyst from an aqueous Ti solution can result when columbic Si-Ti attraction is maximized by maintaining a pH value of the solution at about 4. ,0. To explore this theory, several series of experiments were conducted to establish conditions that lead to the formation of an aqueous Ti solution with a pH value of about 4.0.

[00112] All silica support materials, chemical reagents and solvents described in this document were used as received and were not dried before use.

[00113] The catalysts used in the experiments described below include Magnapore® a commercial Cr/silica-titania catalyst obtained from W. R. Grace and Company and activated at various temperatures. Magnapore® is prepared by tergelation of Si, Ti and Cr, containing 2.5 wt% Ti and 1 wt% Cr, having a surface area of about 500 m2/g, a pore volume of 2.5 mL /g and an average particle size of about 130 microns. Another commercial Cr/silica-titania catalyst that was used, called C-25305HM, was obtained from Philadelphia Quartz (PQ) Corporation. It also contains 2.5 wt% Ti and 1 wt% Cr, having a surface area of about 500 m2/g, a pore volume of 2.7 mL/g, and an average particle size of about 100 microns. The main base catalyst used for the titrations described below was Sylopol® HA30W, a commercial Cr/silica obtained from W.R. Grace. This catalyst did not contain titanium, but contained 1 wt% Cr. It had a surface area of about 500 m2/g, a pore volume of about 1.6 mL/g, and an average particle size of about 100 microns. Three other commercial Cr/silica catalysts were also used; one called EP30X from PQ Corporation, another under the trade name D-70-150A (LV) from Asahi Glass Corporation (AGC) and the third was Sylopol® 969MPI from W.R. Grace. All three of these catalysts did not contain titanium, but did contain 1 wt% Cr. All three had a pore volume of about 1.6 mL/g. EP30X and 969MPI had a surface area of about 300 m2/g and an average particle size of about 100 microns. AGC D-70-150A(LV) had a surface area of about 400 m2/g and an average particle size of about 80 microns.

[00114] Activity tests were conducted in a 2.2 liter steel reactor equipped with a marine agitator running at 400 rpm. The reactor was surrounded by a steel jacket circulating water, the temperature of which was controlled by the use of steam and water heat exchangers. These were connected to an electronic feedback circuit so that the reactor temperature could be maintained at +/- 0.5°C during the reaction.

[00115] Unless otherwise indicated, a small amount (0.01 to 0.10 grams typically) of the solid chromium catalyst was first charged under nitrogen into the dry reactor. Then, about 0.25 g of sulfate-treated alumina (600°C) was added as a poison remover. Next, 1.2 liters of isobutane liquid was charged and the reactor heated to the specified temperature, typically 105 degrees C. Finally, ethylene was added to the reactor to equal a fixed pressure, typically 550 psig (3.8 MPa), which was maintained during the experiment. Agitation was maintained for the specified time, typically around an hour, and activity was recorded by recording the flow of ethylene into the reactor to maintain the set pressure.

[00116] After the expected time, the ethylene flow was stopped and the reactor was slowly depressurized and opened to recover a granular polymer powder. In all cases, the reactor was clean, with no indication of any wall scale, coating, or other forms of fouling. The polymer powder was then removed and weighed. Activity was specified as gram of polymer produced per gram of solid catalyst loaded per hour.

Example 1

[00117] Several control runs were conducted and the results of the control runs are listed in Table 1. The performance of the experimental catalysts shown in the additional examples in terms of productivity, activity and melt index potential can be compared to these control runs. control. Runs 1.10 - 1.13 display the performance of two non-titanized catalysts, the latter of which, HA30W, provides a metric of the effectiveness of the titanations of runs 1.16 - 1.18. The titrations shown in runs 1.16 - 1.18 used Ti(OiPr)4 to titanate HA30W. Titanation in Run 1.15 exposed the support to TiCl4 vapor at 250°C in an attempt to produce a titanized catalyst uncontaminated by organic or alcohol byproducts. In both methods, the support must be dried to remove free water from the surface, usually by a heat treatment of about 150°C to about 800°C. Otherwise, titanium will react with free adsorbed water and be ineffective. In runs 1.15 - 1.18, the catalyst was dried at 200°C before being titanized by gas phase or anhydrous solvent (usually heptane).

Example 2: Acid Titanation

[00118] The first series of experiments studied the ability of carboxylic acids to form a Ti-containing acidic solution capable of providing effective titanation to an olefin polymerization catalyst of the type disclosed in this document (i.e., catalyst). The results are listed in Table 2. All of these experiments began with hydrated silica supports that were not subjected to heat treatment before contact with any other catalyst component. The carboxylic acids listed were mixed with water, or an alternative solvent system as listed, to form a solution, but in all cases the solvents were not dried, and no attempt was made to use anhydrous conditions. Ti(OiPr)4 was added and when dissolution occurred, the Ti-containing acid solution thus formed was impregnated onto a chromium-silica support (HA30W). The product was then dried and calcined in air for three hours at 650°C before use in polymerization experiments.

[00119] Table 2 summarizes the study of a variety of carboxylic acids. The use of carboxylic acids alone (without added base) did not produce very effective titanation. Run 2.2, which used acetic acid in propanol solvent, provided the most effective titanation. Successful results were also observed when HA30W was impregnated with the Ti-containing acid solution and dropped into an activator tube at 300°C (“hot-drop”, runs 2.12 - 2.16). This rapid drying method was moderately effective, as evidenced by the higher melt index obtained when the catalyst was produced using this method compared to oven drying. The “hot-drop” method of drying resulted in more effective titanation when citric acid was used in place of oxalic acid. This result may have occurred because the first pKa of citric acid (3.13) is greater than the first pKa of oxalic acid (1.23). The lower acidity of citric acid can produce a Ti-containing solution with a pH value that is higher and closer to 4.0 when compared to the Ti-containing solution produced with oxalic acid.

Example 3: Alkaline Titanation

[00120] The next series of experiments studied the ability of a base to form an alkaline Ti-containing solution capable of providing effective titanation for a catalyst. The results are listed in Table 3. The experimental approach was essentially identical to the method described in Example 2. Ti dissolved in some strong bases, for example organic bases, were effective, but ammonium hydroxide and alkali hydroxides were not effective. Quaternary ammonium hydroxides dissolved Ti, but uncharged primary, secondary, or tertiary amines were less effective. The melt index potentials resulting from the use of alkaline solutions were all low, like the non-titanized support, and therefore showed no evidence of effective titanation of the chromium-silica support.

Example 4: pH Adjustment with Ammonium Hydroxides

[00121] The results in Table 2 and Table 3 confirmed that the bonding of titania to silica can be problematic at high pH and low pH. The next series of experiments was conducted to probe the theory that the maximum attraction of Columbian Si-Ti occurs at a pH value of about 4.0. Ti(OiPr)4 was hydrolyzed into titania which was dissolved in an aqueous solution of oxalic acid (2 equivalents of oxalic acid per Ti), to produce an acidic solution containing Ti- with a pH value of about 1. Ammonium hydroxide , or a quaternary derivative as listed in Table 4, was added until a green color endpoint of a bromocresol green indicator was reached, indicating a pH value of about 4.0, to produce a solubilized Ti mixture (STM) of the type disclosed in this document. The stoichiometry required to partially neutralize the Ti-containing acid solution, and thereby produce the STM, was generally about two equivalents of base per Ti. An HA30W support was impregnated with the STM and the product was dried and calcined in air for three hours at 650°C before use in polymerization experiments.

[00122] The results listed in Table 4 indicate that the approach was successful. Quaternary ammonium hydroxides were more effective when compared to ammonium hydroxide. This result can be explained by the lower volatility of tetraalkylammonium hydroxides. The results in Table 4 also indicate that the amount of base used to prepare the STM impacted the potential melt index imparted by the resulting catalyst. The method also allowed for effective titanation on a hydrogel rather than a preformed silica support (Run 4.16). The catalyst from Run 4.6 was prepared by inverse addition and exhibited remarkable performance: Ti was dissolved in aqueous NMe4OH to form an alkaline solution which was added to an aqueous oxalic acid solution to prepare the STM used for impregnation of the HA30W support.

Example 5: pH adjustment with Urea

[00123] The next series of experiments studied the ability of urea to partially neutralize an acidic solution containing Ti- and create an STM capable of providing effective titanation to a catalyst. Urea is easily decomposed after heating into volatile products. Replacing carbon-containing catalyst components with urea compounds has the potential to reduce emissions of volatile organic compounds and highly reactive volatile organic compounds created during the calcination of catalysts. The experimental approach was essentially identical to the method described in Example 4, but without the use of the bromocresol green indicator. The results are shown in Table 5. Addition of urea to the Ti-containing acid solution provided increasingly effective titanation as the amount of urea increased. This effect was not observed in experiments investigating the use of urea in spray drying applications, possibly because the urea decomposed and/or evaporated during the spray drying operation. Effective titanation has also been observed with N,N'-dimethyl urea, which is less volatile than urea.

Example 6: pH adjustment with alkanolamines

[00124] The next series of experiments studied the ability of alkanolamines to partially neutralize an acidic solution containing Ti- and create an STM capable of providing effective titanation to a catalyst. Ethanol amines and isopropanol amines were chosen because they generally exhibit low toxicity, are low in cost, are readily available from multiple sources, and have less odor in contrast to most amines. The experimental approach was essentially identical to the method described in Example 5 and the results are shown in Table 6. The results were varied and the bulkier amines appeared to perform better. Not wishing to be limited by theory, this may be a result of the lower volatility of the bulkier compounds and/or the lower permittivity of Ti ions resulting from the bulkier compounds. Dimethylaminoethanol (DMAE) provided a relatively high melt index, is low cost, available from several suppliers, and has a low odor. The catalyst of Run 6.11 was prepared by dissolving titania in two equivalents of aqueous oxalic acid, followed by the addition of two equivalents of DMAE to form a solubilized Ti solution (STM) of the type disclosed herein. An HA30W support was impregnated with the STM to form a titanized support that was dried under vacuum conditions overnight at 100°C. The resulting dry titanized support was extracted with water before being calcined at 650°C and subjected to polymerization experiments. The melt index data suggests that the catalyst experienced extensive Ti loss, presumably during the water extraction step. This observation indicates that Ti may not have been completely bonded to silica after drying at 100°C and supports previous observations that bonding between Ti and silica occurs at least partially at temperatures above 150°C.

Example 7: pH adjustment with other amines

[00125] The next series of experiments studied the ability of a variety of other amines to partially neutralize a Ti-containing acidic solution and create an STM capable of providing effective titration to a catalyst. The experimental approach was essentially identical to the method described in Example 5 and the results are shown in Table 7. A general trend toward higher performance of bulkier amines was observed, but was sometimes compromised by a lack of solubility, e.g., 2- ethylhexylamine or DABCO. Bases capable of delocalizing a positive charge obtained after protonation showed very good performance; examples include DBU, creatine and imidazole.

Example 8: pH adjustment with inorganic bases

[00126] The next series of experiments studied the ability of inorganic bases to partially neutralize an acidic solution containing Ti- and create an STM capable of providing effective titanation to a catalyst. The experimental approach was essentially identical to the method described in Example 5 and the results are shown in Table 8. This approach was generally unsuccessful. Not wishing to be limited by theory, higher permittivity may have been an influence, but the presence of divalent or trivalent metal cations could have interfered with the delicate balance of surface charge between silica and titania. Runs 8.2 and 8.3 were partially successful and co-introduced equal amounts of Al ions with Ti ions. Three equivalents of oxalic acid were added to dissolve two equivalents of metal (1 Ti(OiPr)4 + 1 Al(OH)3 ) which is a lower acid/metal ratio than in most other experiments described in this paper. Run 8.3 included partial neutralization of the acid with tetraethylammonium hydroxide in an amount of 1.5 base equivalents per Ti. This is a lower base/metal ratio than in most other experiments described in this document, but an increase in HLMI was observed. Not wishing to be limited by theory, titania coating on alumina may be easier than titania coating on silica. Ti and Al are both metals and the chemical properties of the two are in many ways more similar than the chemical properties of Ti and Si.

Example 9: Solvation of Ti by other acids

[00127] The next series of experiments studied the ability of carboxylic acids other than oxalic acid to be partially neutralized and create an STM capable of providing effective titanation to a catalyst. The experimental approach was essentially identical to the method described in Example 4 and the results are shown in Table 9. The experiments were generally less successful than experiments using oxalic acid. Several of the experiments added two equivalents of base per Ti, which was more than necessary to obtain a pH value of 4.0 because the acids tested were weaker than oxalic acid. In other experiments, base was added until a green-hued endpoint of bromocresol green indicator was reached, indicating a pH value of 4.0. An example of this method is Run 9.7, where the use of citric acid and tetramethylammonium hydroxide produced highly effective titanation, as evidenced by an HLMI value of nearly 30. Run 9.14 indicated that titanyl sulfate, in the absence of an acid carboxylic acid, could be partially neutralized by DMAE to produce moderately effective titanation.

Example 10: Solvation of Ti with peroxides

[00128] The catalysts listed in Table 10 (inventive embodiments 10.1-10.43) were prepared very similar to those described previously in this document, except that a peroxide (generally H2O2) was also added to the recipe, as a substitute for part or all of the amine or acid. In this way, the amount of amine used, and in some runs the amount of acid used, could be reduced, which reduced expense and emissions and resulted in a polymer with a higher HLMI.

[00129] In these experiments, 30 g of a Cr/silica catalyst sold under the name HA30W by W.R. Grace were weighed in a bowl. It had a surface area of about 500 m2/g, a pore volume of about 1.6 mL/g, and contained 1 wt% Cr. It has not been pre-dried in any way. In a 100 mL beaker, 50 mL of deionized water was added, in which the organic acid was dissolved. A peroxide was then also added to the solution in the inventive embodiments, generally H2O2. Subsequently, 6.65 mL of titanium tetraisopropoxide was added to the water solution, which caused it to immediately precipitate as hydrated titania. The amount of titanium added was equivalent to 3.5% by weight of Ti based on the weight of dry Cr/silica. The amount of acid and peroxide used varied in each experiment, but these amounts are listed in Table 10 as acid or peroxide equivalents added per titanium equivalent. The precipitated slurry was stirred until the titanium dissolved into an orange or dark red solution (when H2O2 was present), generally after about 10 minutes. In cases where titania did not dissolve readily, stirring was allowed to continue for several hours before it was finally concluded that no soluble complex had formed and the experiment was terminated. These are some of the control runs in Table 10.

[00130] However, when a soluble complex formed, the next step was to add a nitrogen compound to the solution in some experiments, while in other experiments, no nitrogen compound was used. The nitrogen compound always dissolved in the titanium solution. Again, the amount of nitrogen compound is listed in Table 10 as nitrogen compound equivalents per titanium equivalent. Finally, the titanium solution was added to the Cr/silica in the bowl and was manually stirred for several minutes to make a consistent wet (but not wet) powder, that is, at incipient moisture. The bowl was then placed overnight in a vacuum oven set at 100°C. The next day, the dry catalyst powder was poured through a 40 mesh screen to break up any small soft clumps. A sample of the resulting titanium-containing catalyst was calcined for 3 hours in dry air at 650°C. It was then recovered under dry nitrogen and stored for later use.

[00131] Control run 10.2 shows that although two equivalents of oxalic acid can dissolve titania, the HLMI obtained is better than that obtained from the Cr/silica catalyst in the absence of titania (Table 1, Run 1.12). In other words, titanation was ineffective with oxalic acid alone. Control 10.2 serves as a baseline for other subsequent experiments. Any HLMI greater than 57 represented an improvement in the efficiency of the titanation procedure.

[00132] Referring to Table 10, it was observed that the addition of peroxide caused titania to dissolve in many acids that could not dissolve Ti in the absence of peroxide. Some of these acids produced very high HLMI. But it can also be seen that even in cases where titania was soluble without peroxide, the addition of peroxide still greatly improved the HLMI of the catalyst. Furthermore, in many experiments, the amount of nitrogen compound used could be reduced, or in some cases, the nitrogen compound could be eliminated entirely, when peroxide was added. As the nitrogenous compound causes undesirable emissions during calcination, this reduction is a great improvement.

[00133] In Table 11, various combinations of organic acids (and/or nitrogen compounds) were used in an effort to further reduce emission and maximize HLMI. In many of these experiments, the aforementioned ability of H2O2 to dissolve Ti and reduce nitrogen compound or even acidic ligands, was further explored. In these experiments (inventives 11.44 to 11.60) the catalysts were prepared exactly as described previously in this document. That is, 30 g of Cr/silica was weighed in a bowl and 50 mL of deionized water was measured in a 100 mL beaker. The acids were dissolved in water along with H2O2 when used. Then, 6.65 mL of titanium tetraisopropoxide (3.5 wt% Ti based on the weight of Cr/silica) was added and immediately precipitated as hydrated titania. However, after brief stirring for about 10 min, the Ti dissolved. The nitrogen compound was then added, if any, and the solution added to the dry catalyst at incipient moisture. Drying and calcination were carried out as described above.

[00134] Only in inventive experiment 11.44 was the protocol slightly different. In this paper, 30 g of a silica was weighed into the bowl (Cr/silica instead). The silica was EP30X from Philadelphia Quartz Corp., having a surface area of 300 m2/g. Again, 50 mL of deionized water was measured in a beaker, followed by acids, H2O2 and 6.65 mL of titanium isopropoxide. After the Ti dissolved, 1.25 g of basic chromium acetate was also added to the solution. The silica was then impregnated with the solution as described above. It was dried and calcined as before. Also note that acidic phenols can replace organic acid to make effective binders. Thus, several runs are shown with catechol and salicylic alcohol in place of the carboxylic acid.

[00135] In Table 11, there were some large acids that were found to be unable to dissolve titania until a smaller amount of a smaller acid was also added. In inventive embodiment 11.56, for example, catechol was ineffective until combined with a small amount of oxalic acid. Likewise, salicylic acid, ineffective on its own, dissolved Ti and produced a high HLMI when an equivalent of oxalic acid was also added (inventive embodiment 11.54). A similar result occurred with salicylic alcohol in inventive runs 11.52 and 11.53, phenylmalonic acid in run 11.51, diglycolic acid in run 11.49, iminodiacetic acid in run 11.48 and methylmalonic acid in run 11.46.

ADDITIONAL DISCLOSURE - PART I

[00136] The following enumerated aspects of the present disclosure are provided as non-limiting examples.

[00137] A first aspect, which is a method comprising a) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is about 1:1 at about 100:1; b) placing a titanium-containing compound and the acid mixture in contact to form a titanium acid mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the titanium acid mixture is from about 1:1 to about 1: 4; c) placing a nitrogen-containing compound and the acidic titanium mixture in contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is about 1:1 to about of 1:4 and a pH of the solubilized titanium mixture is less than about 5.5; and d) placing a chromium-silica support comprising about 0.1 wt% to about 20 wt% water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating to a temperature in the range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a pre-catalyst.

[00138] A second aspect which is the method of the first aspect further comprising e) calcining the pre-catalyst by heating the pre-catalyst to a temperature in a range of about 400°C to about 1,000°C and maintaining the temperature of the precatalyst in the range of about 400°C to about 1,000°C for a period of time from about 1 minute to about 24 hours to form a catalyst.

[00139] A third aspect which is the method of either of the first two aspects in which the equivalent molar ratio of titanium-containing compound to carboxylic acid in the titanium acid mixture is about 1:2 and the equivalent molar ratio of titanium-containing compound titanium to nitrogen-containing compound in the solubilized titanium mixture is about 1:2.

[00140] A fourth aspect which is the method of any of the first three aspects in which the pH of the solubilized titanium mixture is in a range of about 3.5 to about 4.5.

[00141] A fifth aspect which is the method of any of the first four aspects in which (c) comprises neutralizing the titanium acid mixture and in which the neutralization is a partial neutralization or a complete neutralization.

[00142] A sixth aspect which is the method of any of the first five aspects in which the nitrogen-containing compound has Structure 1, Structure 2, Structure 3, Structure 4, Structure 5 or Structure 6: wherein R1, R2, R3, R9, R10 and R11 are each independently hydrogen, a C1 to C12 organyl group, or a C6 to C12 aryl group; R4 is a C1 to C12 organyl group or a C6 to C12 aryl group; R5 and R6 are each independently hydrogen, a C1 to C6 organyl group, or a C6 to C12 aryl group; R7 and R8 are each independently hydrogen or CH3; R12 is a C1 to C6 branched alkyl group, a C1 to C6 cyclic alkyl group, or a C1 to C6 straight alkyl group; x is an integer from 1 to 4, y is an integer from 1 to 12, and Z is oxygen or sulfur.

[00143] A seventh aspect which is the method of any of the first six aspects in which the nitrogen-containing compound comprises an alkanolamine, an amine, an ammonium hydroxide, a hydroxylamine, a urea or a combination thereof.

[00144] An eighth aspect which is the method of any of the first seven aspects in which the nitrogen-containing compound comprises acetamide, ammonia, ammonium hydroxide, tert-butylamine, creatine, N,N'-dibutyl urea, diethanol amine, diisopropanol amine, dimethylaminoethanol, dimethyl carbamate, dimethyl formamide, dimethyl glycine, dimethylisopropanol amine, N,N'-dimethyl urea, ethanol amine, glycol amine, hexyl amine, hydroxyl amine, imidazole, isopropanol amine, N-methyl aniline, methyldiethanol amine, methyl formamide, pyrazole, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanol amine, triisopropanol amine, trimethyl amine, urea or a combination thereof.

[00145] A ninth aspect which is the method of any of the first eight aspects wherein the carboxylic acid comprises a C1 to C15 monocarboxylic acid, a C2 to C15 dicarboxylic acid, a C3 to C15 tricarboxylic acid, a C1 to C15 α acid - hydroxycarboxylic, or a combination thereof.

[00146] A tenth aspect which is the method of any of the first nine aspects in which the carboxylic acid comprises acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid or a combination thereof.

[00147] An eleventh aspect which is the method of any of the first ten aspects in which the titanium-containing compound comprises a titanium hydroxide, a titanic acid, a titanyl sulfate, a titanium(IV) alkoxide, a titanium acetylacetonate titanil, a titanium(IV) halide or a combination thereof.

[00148] A twelfth aspect which is the method of any of the first eleven aspects in which the titanium-containing compound comprises titanium(IV) isopropoxide.

[00149] A thirteenth aspect which is the method of any of the first twelve aspects in which (d) further comprises spray drying the titanium mixture solubilized on the chromium-silica support.

[00150] A fourteenth aspect which is the method of any of the first thirteen aspects in which the chromium-silica support is characterized by a surface area of about 100 m2/gram to about 1,000 m2/gram and a volume pore size of about 1.0 cm3/gram to about 2.5 cm3/gram.

[00151] A fifteenth aspect which is the method of any of the first fourteen aspects in which an amount of chromium present in the catalyst varies from about 0.01% by weight to about 10% by weight of the catalyst and a The amount of titanium present in the catalyst varies from about 0.01 wt% to about 10 wt% by weight of the catalyst.

[00152] A sixteenth aspect which is the method of any of the first fifteen aspects in which the solvent comprises an aqueous solvent, an alcohol, an organic solvent or a combination thereof.

[00153] A seventeenth aspect which is a method of forming an ethylene polymer comprising contacting the catalyst formed by the method of the second aspect with an ethylene monomer under conditions suitable for forming the ethylene polymer and recovering the ethylene polymer .

[00154] An eighteenth aspect which is the method of the seventeenth aspect in which the ethylene polymer has a high charge 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 a nitrogen-containing compound.

[00155] A nineteenth aspect which is a method of a) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is about 1:1 to about 100:1, b) placing a titanium-containing compound and the acidic mixture in contact to form an acidic titanium mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is about 1 :1 to about 1:4, c) placing a nitrogen-containing compound and the acidic titanium mixture in contact to form a solubilized titanium mixture in which 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 a pH of the solubilized titanium mixture is in a range of about 3.5 to about 4.5, d) placing a silica support comprising of about 0 .1 wt% to about 20 wt% water and the solubilized titanium mixture in contact to form a titanized support and dry the titanized support by heating to a temperature in a range of about 50°C to about 150° C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a dry titanized support and e) place, to form a precatalyst , a chromium-containing compound and at least one material selected from the group consisting of the silica support, in contact with the titanized support and the dry titanized support.

[00156] A twentieth aspect which is the method of the nineteenth aspect further comprising: f) calcining the pre-catalyst by heating to a temperature in the range of about 400°C to about 1,000°C and maintaining the temperature in the range of about 400°C to about 1,000°C for a period of time from about 1 minute to about 24 hours to form a catalyst.

[00157] A twenty-first aspect which is the method of the nineteenth aspect in which (c) comprises neutralizing the titanium acid mixture and in which the neutralization is a partial neutralization or a complete neutralization.

[00158] A twenty-second aspect which is a method comprising a) placing a titanium-containing compound and a nitrogen-containing compound in contact to form a basic mixture in which an 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) bringing a solvent and a carboxylic acid into contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acidic mixture is about 1:1 to about 100:1, c) bringing the base mixture and the acidic mixture into contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is about 1: 1 to about 1:4 and a pH of the solubilized titanium mixture is in a range of about 3.5 to about 4.5 and d) placing a chromium-silica support comprising of about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and dry the addition product by heating to a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[00159] A twenty-third aspect which is the method of the twenty-third aspect further comprising e) calcining the pre-catalyst by heating the pre-catalyst to a temperature in a range of about 400°C to about 1,000°C and maintaining the temperature of the precatalyst in the range of about 400°C to about 1,000°C for a period of time from about 1 minute to about 24 hours to form a catalyst.

[00160] A twenty-fourth aspect which is a method comprising a) placing a titanium-containing compound and a nitrogen-containing compound in contact to form a base mixture in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the base mixture is from about 1:1 to about 1:4, b) bringing a solvent and a carboxylic acid into contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acidic mixture is about 1:1 to about 100:1, c) bringing the base mixture and the acidic mixture into contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is about 1: 1 to about 1:4 and a pH of the solubilized titanium mixture is in a range of about 3.5 to about 4.5, d) placing a silica support comprising from about 0.1 wt.% to about 20% by weight of water and the solubilized titanium mixture in contact to form a titanized support and dry the titanized support by heating to a temperature in a range of about 50°C to about 150°C and maintaining the temperature at range from about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a dry titanized support, and e) placing, to form a precatalyst, a chromium-containing compound and at least one material selected from the group consisting of the silica support, in contact with the titanized support and the dry titanized support.

[00161] A twenty-fifth aspect which is the method of the twenty-fifth aspect further comprising f) calcining the pre-catalyst by heating the pre-catalyst to a temperature in a range of about 400°C to about 1,000°C and maintaining the temperature of the precatalyst in the range of about 400°C to about 1,000°C for a period of time from about 1 minute to about 24 hours to form a catalyst.

[00162] A twenty-sixth aspect which is a pre-catalyst composition comprising: a) a silica support comprising silica in which an amount of silica is in a range of about 70% by weight to about 95% by weight based in the total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in the range of about 0.1% by weight to about 20% by weight based on the amount of silica; d) a carboxylic acid in which an 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 with a molecular formula containing at least one nitrogen atom in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.

[00163] A twenty-seventh aspect which is the pre-catalyst composition of the twenty-sixth aspect in which the carboxylic acid comprises a C1 to C15 monocarboxylic acid, a C2 to C15 dicarboxylic acid, a C3 to C15 tricarboxylic acid, a C1 to C15 acid α-hydroxycarboxylic acid or a combination thereof.

[00164] A twenty-eighth aspect which is the pre-catalyst composition of any of the twenty-sixth or twenty-seventh aspects in which the carboxylic acid comprises acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid or a combination thereof.

[00165] A twenty-ninth aspect which is the pre-catalyst composition of any one of the twenty-sixth to twenty-eighth aspects in which 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.

[00166] A thirtieth aspect which is the pre-catalyst composition of any one of the twenty-sixth to twenty-ninth aspects in which the nitrogen-containing compound comprises acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, tert-butylamine, N, N'-dibutyl urea, creatine, creatinine, diethanol amine, diethylhydroxy amine, diisopropanol amine, dimethylaminoethanol, dimethyl carbamate, dimethyl formamide, dimethyl glycine, dimethylisopropanol amine, N,N'-dimethyl urea, ethanol amine, ethyl amine, glycol amine, hexyl amine, hydroxyamine, imidazole, isopropanol amine, methacryl amide, methyl amine, N-methyl aniline, N-methyl-2-propanol amine, methyldiethanol amine, methyl formamide, propyl amine, 2-propanol amine, pyrazole, pyrrolidine, pyrrolidinone, succinimide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanol amine, triisopropanol amine, trimethyl amine, urea, 1,8-diazabicyclo[5.4.0]undec-7-ene or a combination thereof.

[00167] A thirty-first aspect which is the pre-catalyst composition of any one of the twenty-sixth to the thirtieth aspects in which the silica support further comprises alumina.

[00168] A thirty-second aspect which is the pre-catalyst composition of any one of the twenty-sixth to thirty-first aspects, wherein the silica support is characterized by a surface area of about 100 m2/gram to about 1,000 m2 /gram and a pore volume of about 1.0 cm 3 /gram to about 2.5 cm 3 /gram.

[00169] A thirty-third aspect which is the pre-catalyst composition of any one of the twenty-sixth to thirty-second aspects in which the silica support comprises a hydrated silica support.

[00170] A thirty-fourth aspect which is the pre-catalyst composition of any one of the twenty-sixth to thirty-third aspects wherein the silica support comprises from about 1% by weight to about 20% by weight of water based on the total weight of the silica support.

[00171] A thirty-fifth aspect which is a pre-catalyst composition comprising: a) a silica support comprising silica in which an amount of silica is in a range of about 70% by weight to about 95% by weight based in the total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; and c) a titano-organic salt, wherein the titano-organic salt comprises titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein: i) an amount of titanium is in the range of about 0.1% by weight to about 20% by weight based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate is in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.

[00172] A thirty-sixth aspect which is the pre-catalyst composition of the thirty-fifth aspect in which the protonated nitrogen-containing compound comprises a protonated alkanolamine, a protonated amide, a protonated amine, a protonated alkylamine, a protonated ammonium hydroxide, an aniline protonated, a protonated hydroxylamine, a protonated urea or a combination thereof.

[00173] A thirty-seventh aspect which is the pre-catalyst composition of the thirty-fifth aspect in which the protonated nitrogen-containing compound comprises protonated acetamide, protonated acrylamide, protonated allyl amine, ammonium, protonated ammonium hydroxide, protonated butylamine, tert-butyl amine protonated, N,N'-protonated dibutyl urea, creatine, protonated creatinine, protonated diethanolamine, protonated diethylhydroxyamine, protonated diisopropanol amine, protonated dimethylaminoethanol, protonated dimethylcarbamate, protonated dimethylformamide, protonated dimethylglycine, protonated dimethylisopropanol amine, N,N' -protonated dimethylurea, protonated ethanolamine, protonated ethylamine, protonated glycol amine, protonated hexyl amine, protonated hydroxyamine, protonated imidazole, protonated isopropanol amine, protonated methacrylamide, protonated methyl amine, protonated N-methyl aniline, protonated N-methyl-2-propanol amine , protonated methyldiethanol amine, protonated methyl formamide, protonated propylamine, 2-protonated propanol amine, protonated pyrazole, protonated pyrrolidine, protonated pyrrolidinone, protonated succinimide, protonated tetraethylammonium hydroxide, protonated tetramethylammonium hydroxide, protonated triethanolamine, protonated triisopropanol amine, protonated trimethylamine, protonated urea, protonated 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination thereof.

[00174] A thirty-eighth aspect which is the pre-catalyst composition of any one of the thirty-fifth to thirty-seventh aspects in which the carboxylate comprises a C1 to C15 monocarboxylate, a C2 to C15 dicarboxylate, a C3 to C15 tricarboxylate, a C1 to C15 α-hydroxycarboxylate or a combination thereof.

[00175] A thirty-ninth aspect that is the pre-catalyst composition of any one of the thirty-fifth to thirty-eighth aspects in which the carboxylate comprises acetate, citrate, glycolate, oxalate, phosphonoacetate or a combination thereof.

[00176] A fortieth aspect which is the pre-catalyst composition of any one of the thirty-fifth to thirty-ninth aspects in which the silica support further comprises alumina.

[00177] A forty-first aspect which is the pre-catalyst composition of any one of the thirty-fifth to fortieth aspect wherein the silica support is characterized by a surface area of about 100 m2/gram to about 1,000 m2/gram and a pore volume of about 1.0 cm3/gram to about 2.5 cm3/gram.

[00178] A forty-second aspect which is the pre-catalyst composition of any one of the thirty-fifth to forty-first aspects in which the silica support comprises a hydrated silica support.

[00179] A forty-third aspect which is the pre-catalyst composition of any one of the thirty-fifth to forty-second aspects wherein the silica support comprises from about 1% by weight to about 20% by weight of water based on the total weight of the silica support.

[00180] A forty-fourth aspect which is a pre-catalyst composition comprising: a) a silica support comprising silica in which an amount of silica is in a range of about 70% by weight to about 95% by weight based in the total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in the range of about 0.01% by weight to about 0.1% by weight based on the amount of silica; d) a carboxylic acid in which an 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 with a molecular formula containing at least one nitrogen atom in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1:10.

[00181] A forty-fifth aspect which is a pre-catalyst composition prepared by a method comprising a) bringing a solvent and a carboxylic acid into contact to form an acid mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about 100:1; b) placing a titanium-containing compound and the acid mixture in contact to form a titanium acid mixture in which an equivalent molar ratio of titanium-containing compound to carboxylic acid in the titanium acid mixture is from about 1:1 to about 1: 4; c) placing a nitrogen-containing compound and the acidic titanium mixture in contact to form a solubilized titanium mixture in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is about 1:1 to about of 1:4 and a pH of the solubilized titanium mixture is less than about 5.5; and d) placing a chromium-silica support comprising about 0.1 wt% to about 20 wt% water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating to a temperature in the range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

ADDITIONAL DISCLOSURE - PART II

[00182] The following enumerated aspects of the present disclosure are provided as non-limiting examples.

[00183] A first aspect is a method comprising a) placing a solvent, a carboxylic acid and a peroxide-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acidic mixture is about from 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[00184] A second aspect which is the method of the first aspect in which the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.

[00185] A third aspect which is the method of any of the first to second aspects wherein the carboxylic acid comprises a C1 to C15 monocarboxylic acid, a C2 to C15 dicarboxylic acid, a C3 to C15 tricarboxylic acid, a C1 to C15 acid α-hydroxycarboxylic acid, or a combination thereof.

[00186] A fourth aspect which is the method of any of the first to third aspects in which 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-pyridine dicarboxylic acid, nitrotriacetic acid, a-hydroxyisobutyric acid, methylmalonic acid, phenyl malonic acid, digluconic acid , iminodiacetic acid, hydroxymethyl-2-butyric acid or a combination thereof.

[00187] A fifth aspect which is a method comprising a) placing a solvent, a carboxylic acid, a nitrogen-containing compound and a peroxide-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the mixture acidic is from about 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[00188] A sixth aspect which is the method of the fifth aspect in which the carboxylic acid comprises a C1 to C15 monocarboxylic acid, a C1 to C15 dicarboxylic acid, a C2 to C15 tricarboxylic acid, a C1 to C15 a-hydroxycarboxylic acid, or a combination of them.

[00189] A seventh aspect which is the method of any of the fifth to sixth aspects in which 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-pyridine dicarboxylic acid, nitrotriacetic acid, a-hydroxyisobutyric acid, methylmalonic acid, phenyl malonic acid, digluconic acid , iminodiacetic acid, hydroxymethyl-2-butyric acid or a combination thereof.

[00190] An eighth aspect which is the method of any of the fifth to seventh aspects, wherein the nitrogen-containing compound comprises an alkanolamine, an amide, an amine, an alkylamine, an ammonium hydroxide, an aniline, a hydroxylamine, a urea or a combination thereof.

[00191] A ninth aspect which is the method of any of the fifth to eighth aspects wherein the peroxide-containing compound comprises organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyesters, dialkyl peroxides, hydroperoxides or a combination thereof .

[00192] A tenth aspect which is the method of any of the fifth to ninth aspects wherein the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, hydroperoxide tert-butyl, phthaloyl peroxide or a combination thereof.

[00193] An eleventh aspect which is a method comprising a) bringing a solvent, at least two carboxylic acids and a peroxide-containing compound into contact 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 and wherein the at least two carboxylic acids comprise at least one simple carboxylic acid and at least one complex carboxylic acid; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a time period of about 30 minutes to about 6 hours to form a pre-catalyst.

[00194] A twelfth aspect which is the method of the eleventh aspect in which the at least two carboxylic acids comprise a C1 to C15 monocarboxylic acid, a C2 to C15 dicarboxylic acid, a C3 to C15 tricarboxylic acid, a C1 to C15 acid α-hydroxycarboxylic acid, or a combination thereof.

[00195] A thirteenth aspect which is the method of any one of the eleventh to twelfth aspects in which 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-pyridine dicarboxylic acid, nitrotriacetic acid, a-hydroxyisobutyric acid, methylmalonic acid, phenyl malonic acid , digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid or a combination thereof.

[00196] A fourteenth aspect which is the method of any one of the eleventh to thirteenth aspects in which the peroxide-containing compound comprises organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyesters, dialkyl peroxides, hydroperoxides or a combination thereof.

[00197] A fifteenth aspect which is the method of any of the eleventh to fourteenth aspects in which the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, dicumyl peroxide, cumene, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.

[00198] A sixteenth aspect which is a method comprising a) bringing a solvent, at least two carboxylic acids and a nitrogen-containing compound into contact 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) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 c) placing a chromium-silica support comprising about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating to a temperature in the range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a pre-catalyst.

[00199] A seventeenth aspect which is a method comprising a) bringing a solvent, at least two carboxylic acids, a nitrogen-containing compound and a peroxide-containing compound into contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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 peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromium-silica support comprising from about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating the a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[00200] An eighteenth aspect which is a method comprising a) placing a solvent, a carboxylic acid, an acidic phenol and a peroxide-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the acid 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 in which 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, wherein an 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 an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) placing a chromo-silica support comprising about 0.1% by weight to about 20% by weight of water and the solubilized titanium mixture in contact to form an addition product and drying the addition product by heating to a temperature in the range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a pre-catalyst.

[00201] A nineteenth aspect which is the method of the eighteenth aspect in which the acidic phenol comprises catechol, salicylic alcohol, salicylic acid, phthalic acid or any combination thereof.

[00202] A twentieth aspect which is a method comprising a) placing a solvent, a carboxylic acid, an acidic phenol and a peroxide-containing compound in contact to form an acidic mixture in which a weight ratio of solvent to carboxylic acid in the mixture acidic is from about 1:1 to about 100:1; b) bringing a titanium-containing compound and the acidic mixture into contact to form a solubilized titanium mixture in which 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, wherein an 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 an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; c) bringing the solubilized titanium mixture with a chromium-containing compound into contact to form a chromium titanium mixture; d) placing the chromium titanium mixture with a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the silica support in contact to form an addition product; and e) drying the addition product by heating to a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to form a precatalyst.

[00203] A twenty-first aspect which 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 compounds containing peroxide and one or more nitrogen-containing compounds, wherein a weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about 100:1; b) contacting the acid mixture with a chromium-containing compound, a titanium-containing compound and a silica support to form an addition product in which: (i) an equivalent molar ratio of titanium-containing compound to carboxylic acid, when present in the acid mixture, is about 1:1 to about 1:4, (ii) an equivalent molar ratio of titanium-containing compound to acid phenol, when present in the acid mixture, is about 1: to about 1:5 , and (iii) an equivalent molar ratio of titanium-containing compound to peroxide-containing compound, when present in the acid mixture, is from about 1:1 to about 1:20; and c) drying the addition product by heating to a temperature in a range of about 50°C to about 150°C and maintaining the temperature in the range of about 50°C to about 150°C for a period of time of about 30 minutes to about 6 hours to form a pre-catalyst.

[00204] A twenty-second aspect which is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on a total weight the silica support; b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in a range of about 0.1% by weight to about 20% by weight based on the amount of silica; d) a carboxylic acid in which an equivalent molar ratio of titanium-containing compound to carboxylic acid is in a range of about 1:1 to about 1:10; and e) a peroxide-containing compound in which an equivalent molar ratio of titanium-containing compound to peroxide-containing compound is in a range of about 1:1 to about 1:20.

[00205] A twenty-third aspect which is the composition of the twenty-second aspect further comprising a nitrogen-containing compound in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in a range of about 1:0.5 to about 1:10.

[00206] A twenty-fourth aspect which is the composition of any one of the twenty-second to twenty-third aspects in which the carboxylic acid comprises a C1 to C15 monocarboxylic acid, a C2 to C15 dicarboxylic acid, a C3 to C15 tricarboxylic acid, a Ci to C15 a-hydroxycarboxylic acid, or a combination thereof.

[00207] A twenty-fifth aspect which is the composition of any of the twenty-second to twenty-fourth aspects in which carboxylic acid comprises, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, acid oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, gluconic acid, mandelic acid, 2,4-hydroxybenzoic acid, 2,6-pyridine dicarboxylic acid, nitrotriacetic acid, a-hydroxyisobutyric acid, methylmalonic acid, phenyl malonic acid, acid digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid or a combination thereof.

[00208] A twenty-sixth aspect which is the composition of any one of the twenty-third to twenty-fifth aspects in which 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.

[00209] A twenty-seventh aspect which is the composition of any one of the twenty-second to twenty-sixth aspects in which the peroxide-containing compound comprises organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyesters, dialkyl peroxides, hydroperoxides or a combination thereof.

[00210] A twenty-eighth aspect which is the composition of any one of the twenty-second to twenty-seventh aspects in which the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide , tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.

[00211] A twenty-ninth aspect which is the composition of any one of the twenty-second to twenty-eighth aspects further comprising an acidic phenol.

[00212] A thirtieth aspect which is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on a total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica; and c) a titano-organic salt, wherein the titano-organic salt comprises titanium, a carboxylate and a peroxide-containing compound and wherein the titano-organic salt comprises i) an amount of titanium is in a range of about 0.1 % by weight to about 20% by weight based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate is in a range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to peroxide-containing compound is in a range of about 1:0.5 to about 1:20.

[00213] A thirty-first aspect which is the composition of the thirtyth aspect further comprising a nitrogen-containing compound wherein an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in a range of about 1:0.5 to about 1 :5.

[00214] A thirty-second aspect which is the composition of any one of the thirtyth to thirty-first aspects in which the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide , tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.

[00215] A thirty-third aspect which is the composition of any one of the thirtyth to thirty-second aspects in which the carboxylate comprises acetate, citrate, gluconate, glycolate, glyoxylate, lactate, malate, malonate, oxalate, phosphonoacetate, tartrate or a combination thereof same

[00216] A thirty-fourth aspect which is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in the range of about 0.01% by weight to about 0.1% by weight based on the amount of silica; d) at least two carboxylic acids in which an equivalent molar ratio of titanium-containing compound to carboxylic acids is in the range of about 1:1 to about 1:10; and e) a peroxide-containing compound in which an equivalent molar ratio of titanium-containing compound to peroxide-containing compounds is in the range of about 1:1 to about 1:10.

[00217] A thirty-fifth aspect which is the composition of the thirty-fourth aspect in which the at least two carboxylic acids comprise at least one simple carboxylic acid and at least one complex carboxylic acid.

[00218] A thirty-sixth aspect which is the composition of the thirty-fourth to thirty-fifth aspects in which the peroxide-containing compound comprises hydrogen peroxide, tert-butyl peroxide or a combination thereof.

[00219] A thirty-seventh aspect which is the composition of the thirty-fourth to thirty-sixth aspects further comprising an acidic phenol.

[00220] A thirty-eighth aspect which is the composition of any one of the thirty-fourth to thirty-seventh aspects further comprising a nitrogen-containing compound in which an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in a range of about 1: 0.5 to about 1:10.

[00221] A thirty-ninth aspect which is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the silica support; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titano-organic salt, wherein the titano-organic salt comprises titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the titano-organic salt comprises: i) an amount of titanium is in a range of about 0.1 wt% to about 20 wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate is in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound is in the range of about 1:0.5 to about 1:10; and d) a peroxide-containing compound wherein an equivalent molar ratio of titanium-containing compound to peroxide-containing compound is from about 1:1 to about 1:20.

[00222] A fortieth aspect which is a composition comprising a) a silica support comprising silica wherein an amount of silica is in a range of about 70% by weight to about 95% by weight based on the total weight of the support silica; b) a chromium-containing compound in which an amount of chromium is in the range of about 0.1% by weight to about 5% by weight based on the amount of silica; and c) a titano-organic salt, wherein the titano-organic salt comprises titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the titano-organic salt comprises i) an amount of titanium is in a range of about 0 .1 wt% to about 20 wt% based on the amount of silica; ii) an equivalent molar ratio of titanium to carboxylate is in the range of about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen-containing compound is in the range of about 1:0.5 to about 1:10; and d) an acidic phenol in which an equivalent molar ratio of titanium-containing compound to acidic phenol in the acidic titanium mixture is from about 1:1 to about 1:5.

[00223] A forty-first aspect which 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 peroxide-containing compounds and one or more nitrogen-containing compounds; b) a chromium-containing compound in which an amount of chromium is in a range of about 0.1% by weight to about 5% by weight based on the amount of silica; c) a titanium-containing compound in which an amount of titanium is in a range of about 0.01% by weight to about 0.1% by weight based on the amount of silica; and (i) wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid, when present, is in a range of about 1:1 to about 1:10; (ii) wherein an equivalent molar ratio of titanium-containing compound to peroxide-containing compound, when present, is in a range of about 1:1 to about 1:10; (iii) wherein an equivalent molar ratio of titanium-containing compound to acidic phenol, when present, in the acidic titanium mixture is in a range of about 1:1 to about 1:5; and (iv) wherein an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound, when present, is in a range of about 1:0.5 to about 1:5.

[00224] A forty-second aspect which is a catalyst prepared in accordance with the method of the first aspect wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range of from about 400°C to about 1,000°C. °C to form an olefin polymerization catalyst.

[00225] A forty-third aspect which is a catalyst prepared in accordance with the method of the fifth aspect, wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range from about 400°C to about of 1,000°C to form an olefin polymerization catalyst.

[00226] A forty-fourth aspect which is a catalyst prepared in accordance with the method of the eleventh aspect, wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range of about 400°C at about 1,000°C to form an olefin polymerization catalyst.

[00227] A forty-fifth aspect which is a catalyst prepared in accordance with the method of the seventh aspect, wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range from about 400°C to about of 1,000°C to form an olefin polymerization catalyst.

[00228] A forty-sixth aspect which is a catalyst prepared in accordance with the method of the seventeenth aspect, wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range of about 400°C at about 1,000°C to form an olefin polymerization catalyst.

[00229] A forty-seventh aspect which is a catalyst prepared in accordance with the method of the eighteenth aspect, wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range of about 400°C at about 1,000°C to form an olefin polymerization catalyst.

[00230] A forty-eighth aspect which is a catalyst prepared in accordance with the method of the twentieth aspect, wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range of about 400°C to about 1,000°C to form an olefin polymerization catalyst.

[00231] A forty-ninth aspect which is a catalyst prepared according to the method of the twenty-first aspect, wherein the method further comprises heating the pre-catalyst in the presence of air to a temperature in a range from about 400°C to about of 1,000°C to form an olefin polymerization catalyst.

[00232] The terms “a”, “an” and “the” are intended, unless specifically indicated otherwise, to include plural alternatives, for example, at least one. In this document, while methods and processes are described in terms of “comprising” multiple components or steps, the methods and processes may also “consist essentially of” or “consist of” multiple components or steps. A particular characteristic of the disclosed subject matter may be disclosed as follows: characteristic “Feature X is A, alternatively B, or alternatively C” is also an aspect of the present disclosure, regardless of whether or not the statement is explicitly recited.

[00233] Although various aspects of the present disclosure have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit and teachings of the present 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. When numerical ranges or limitations are expressly indicated, such express ranges or limitations shall be understood to include iterative ranges or limitations of similar magnitude that fall within the expressly indicated ranges or limitations (e.g., “from about 1 to about 10” includes, 2, 3, 4, etc.; “greater than 0.10” includes 0.11, 0.12, 0.13, etc.). The use of the term “optionally” with respect to any element of a claim is intended to mean that the element in question is necessary or, alternatively, not necessary. Both alternatives are intended to be within the scope of the claim. The use of broader terms, such as “comprises”, “includes”, “having”, etc. should be understood as providing support for narrower terms such as “consisting of”, “consisting essentially of”, “substantially comprised of”, etc.

[00234] Therefore, the scope of protection is not limited by the description set out above, but is limited only by the claims that follow, the scope of which includes all equivalents of the subject matter in question of the claims. Any and all claims are incorporated into the specification as an aspect of the present disclosure. Thus, the claims are a further description and are in addition to aspects of the present disclosure. Discussion of a reference in the present 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 patent application. The present disclosure of all patents, patent applications and publications cited herein are incorporated herein by reference to the extent they provide exemplary, procedural or other details supplementary to those set forth herein.

[00235] All publications, patent applications and patents mentioned in this document are incorporated by reference in their entirety. In case of conflict, this specification, including definitions, is intended to control. With respect to all ranges disclosed herein, such ranges are intended to include any combination of the upper and lower limits mentioned, even if the particular combination is not specifically listed.

Claims (12)

1. Pre-catalyst composition, characterized by comprising: a) a silica support comprising silica; wherein an amount of silica is in a range of 70% by weight to 95% by weight based on the total weight of the silica support; and wherein the silica support comprises from 0.1% by weight to 20% by weight water; b) a chromium-containing compound; wherein an amount of chromium is in the range of 0.1% by weight to 5% by weight based on the amount of silica; c) a titanium-containing compound comprising one or more carboxylic acids; wherein an amount of titanium is in the range of 0.1% by weight to 20% by weight based on the amount of silica; and wherein an equivalent molar ratio of titanium in the titanium-containing compound to the one or more carboxylic acids is in the range of 1:1 to 1:4; and d) one or more phenol acids, wherein an equivalent molar ratio of titanium-containing compound to one or more phenol acids is in the range of 1:1 to 1:5. 2. Pre-catalyst composition according to claim 1, characterized by the fact that one or more carboxylic acids comprise a C1 to C15 monocarboxylic acid, a C1 to C15 dicarboxylic acid, a C1 to C15 tricarboxylic acid, a CI to C15 a-hydroxycarboxylic acid, or a combination thereof. 3. Pre-catalyst composition according to claim 1, characterized by the fact that one or more carboxylic acids comprise acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, acid oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, mandelic acid, 2,4-hydroxybenzoic acid, 2,6-pyridine dicarboxylic acid, nitrotriacetic acid, a-hydroxyisobutyric acid, methylmalonic acid, phenyl malonic acid, digluconic acid, acid iminodiacetic acid, 2-(hydroxymethyl)butyric acid, citric acid or a combination thereof. 4. Pre-catalyst composition according to claim 1, characterized by the fact that one or more acidic phenols comprise catechol, salicylic alcohol, salicylic acid, phthalic acid, derivatives thereof or any combination thereof. 5. Pre-catalyst composition according to claim 2, characterized by the fact that one or more phenol acids comprise catechol, salicylic alcohol, salicylic acid, phthalic acid, derivatives thereof or any combination thereof. 6. Pre-catalyst composition according to claim 3, characterized by the fact that one or more acidic phenols comprise catechol, salicylic alcohol, salicylic acid, phthalic acid, derivatives thereof or any combination thereof. 7. Pre-catalyst composition according to claim 1, characterized by additionally comprising one or more peroxide-containing compounds, wherein the equivalent molar ratio of titanium in the titanium-containing compound to one or more peroxide-containing compounds is in a range of 1 :1 to 1:20. 8. Pre-catalyst composition according to claim 3, characterized by additionally comprising one or more peroxide-containing compounds, wherein the equivalent molar ratio of titanium in the titanium-containing compound to one or more peroxide-containing compounds is in a range of 1 :1 to 1:20. 9. Pre-catalyst composition according to claim 6, characterized by additionally comprising one or more peroxide-containing compounds, wherein the equivalent molar ratio of titanium in the titanium-containing compound to one or more peroxide-containing compounds is in a range of 1 :1 to 1:20. 10. Pre-catalyst composition according to claim 7, characterized by the fact that one or more peroxide-containing compounds comprise hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof. 11. Pre-catalyst composition according to claim 8, characterized by the fact that one or more peroxide-containing compounds comprise hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof. 12. Pre-catalyst composition according to claim 9, characterized by the fact that one or more peroxide-containing compounds comprise hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.