RU2813293C2 - Methods of obtaining catalyst using hydrated reagents - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: methods of preparing olefin polymerization catalyst compositions and polymers prepared therefrom. A method of producing an olefin polymerization precatalyst is described, the method comprises contacting (i) a solvent, (ii) a carboxylic acid, (iii) a peroxide-containing compound, (iv) a titanium-containing compound, (v) a nitrogen-containing compound, (vi) a chromium-containing compound, and (vii ) a carrier of silicon dioxide to form a mixture; and spray drying the mixture to obtain a pre-catalyst powder; wherein: the weight ratio of solvent to carboxylic acid in the mixture is from about 1:1 to about 100:1; the equivalent molar ratio of titanium-containing compound to carboxylic acid in the mixture is from 1:1 to 1:4; the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the mixture is from 1:1 to 1:4; pH of the mixture ranges from 3.5 to 4.5; and the silica carrier includes from 0.1 wt.% to 20 wt.% of water.

EFFECT: obtaining a catalyst using hydrated reagents.

11 cl, 1 dwg, 11 tbl, 10 ex

Description

TECHNICAL FIELD

[0001] This disclosure relates to catalyst compositions. More specifically, this invention relates to methods for preparing olefin polymerization catalyst compositions and polymers prepared therefrom.

BACKGROUND OF THE ART

[0002] An economically important class of olefin polymerization catalysts includes chromium-silicon-titanium (Cr/Si-Ti) catalysts derived from silica catalyst supports. Careful 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 onto a silica catalyst support will reduce the cost of producing olefin polymerization catalysts. Thus, there is a continuing need to develop new methods for producing olefin polymerization catalysts.

SUMMARY OF THE INVENTION

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

[0004] Also disclosed herein is a pre-catalyst composition comprising a) a silica support containing silica, in which the amount of silica ranges from about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a protonated nitrogen-containing compound and a carboxylate, and 1) the amount of titanium is in the range of about 0.1% wt. up to about 20% wt. of the amount of silica, 2) the equivalent molar ratio of titanium to carboxylate ranges from about 1:1 to about 1:10, and 3) the equivalent molar ratio of titanium to protonated nitrogen-containing compound ranges from about 1:0.5 to about 1:10.

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

[0006] Also disclosed herein is a precatalyst composition prepared by a process comprising: a) contacting a solvent and a carboxylic acid to form an acid mixture, wherein the weight ratio of solvent to carboxylic acid in the acid mixture is from about 1:1 to about 100 :1, b) contacting the titanium-containing compound and the acidic mixture to form an acidic titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) bringing into contact a nitrogen-containing compound and an acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5.5, and d) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form an adduct; and drying the adduct by heating the adduct to a temperature in the range of about 50°C to about 150°C and maintaining the temperature of the adduct in the range of about 50°C to about 150°C. over 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) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form an acidic titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting the nitrogen-containing compound and the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5.5, and d) bringing to contact carrier of chromium-silica containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form an adduct; and drying the adduct by heating the adduct to a temperature in the range of about 50°C to about 150°C and maintaining the temperature of the adduct in the range of about 50°C to about 150°C. over a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

[0008] Also disclosed herein is a method comprising: a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form an acidic titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting the nitrogen-containing compound and the acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is from about 3.5 to about 4.5, and d) bringing into contact a silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form a titanium carrier; and drying the titanium carrier by heating the titanium carrier to a temperature in the range of about 50°C to about 150°C and maintaining the temperature of the titanium carrier 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 dried titanium support, and e) contacting to form a precatalyst a chromium-containing compound and at least one material selected from the group consisting of a silica support, a titanium support, and dried titanium carrier.

[0009] Also disclosed herein is a method comprising a) contacting a titanium-containing compound and a nitrogen-containing compound to form a base mixture, wherein the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in the base mixture is from about 1:1 to about 1:4 b) contacting a solvent and a carboxylic acid to form an acidic mixture in which the weight ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, c) contacting the base mixture and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of about 3.5 to about 4.5, and d) bringing into contact a chromium-silicon dioxide carrier containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form an adduct; and drying the adduct by heating the adduct to a temperature in the range of about 50°C to about 150°C and maintaining the temperature of the adduct 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.

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

[0011] Also disclosed herein is a method comprising a) contacting a solvent, a carboxylic acid, and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1 b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of the titanium-containing compound and peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20, c) bringing into contact a chromium-silica carrier containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[0012] Also disclosed herein is a method comprising a) contacting a solvent, at least two carboxylic acids and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, and wherein the at least two carboxylic acids include at least one simple carboxylic acid and at least one complex carboxylic acid; b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of the titanium-containing compound to the peroxide-containing compounds in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[0013] Also disclosed herein is a method comprising a) contacting a solvent, at least two carboxylic acids and a nitrogen-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4; and c) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[0014] Also disclosed herein is a method comprising a) contacting a solvent, at least two carboxylic acids, a nitrogen-containing compound and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1 :1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the 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) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[0015] Also disclosed herein is a method comprising a) contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio the titanium-containing compound to the acidic phenol in the solubilized titanium mixture is from about 1:1 to about 1:5, and wherein the equivalent molar ratio of the titanium-containing compound to the peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[0016] Also disclosed herein is a method comprising a) contacting a solvent, a carboxylic acid, an acidic phenol, and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and in which the equivalent the molar ratio of the titanium-containing compound to the acidic phenol in the solubilized titanium mixture is from about 1:1 to about 1:5, and wherein the equivalent molar ratio of the titanium-containing compound to the peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; c) bringing the solubilized titanium mixture into contact with a chromium-containing compound to form a chromium-titanium mixture; d) contacting the chromium-titanium mixture with a silica support containing silica, in which the amount of silica is in the range of about 70% wt. up to about 95% wt. from the total mass of the silica support, with the formation of the adduct; and e) drying the adduct 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. formation of a pre-catalyst.

[0017] Also disclosed herein is a method comprising a) preparing an acidic mixture containing 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 the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) contacting the acidic mixture with the chromium-containing compound, the titanium-containing compound and the silica support to form an adduct wherein: (1) the equivalent molar ratio of the titanium-containing compound to the carboxylic acid, if present in the acidic mixture, is from about 1: 1 to about 1:4, (2) the equivalent molar ratio of titanium-containing compound to acidic phenol, if present in the acid mixture, is from about 1: to about 1:5, and (3) the equivalent molar ratio of titanium-containing compound to peroxide-containing compound, if present in an acidic mixture, it is from about 1:1 to about 1:20; and c) drying the adduct 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 formation of a pre-catalyst.

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

[0019] Also disclosed herein is a composition comprising a) a silica carrier containing silica, in which the amount of silica ranges from about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a carboxylate and a peroxide-containing compound, and wherein the organotitanium salt contains 1) an amount of titanium in the range of about 0.1% wt. up to about 20% wt. based on the amount of silica, 2) an equivalent molar ratio of titanium to carboxylate ranging from about 1:1 to about 1:10, and 3) an equivalent molar ratio of titanium to peroxide-containing compound ranging from about 1:0.5 to about 1:20 .

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

[0021] Also disclosed herein is a composition comprising a) a silica carrier containing silica, in which the amount of silica ranges from about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the organotitanium salt contains 1) an amount of titanium in the range of about 0.1% wt. up to about 20% wt. based on the amount of silica, 2) an equivalent molar ratio of titanium to carboxylate ranging from about 1:1 to about 1:10, and 3) an equivalent molar ratio of titanium to protonated nitrogen-containing compound ranging from about 1:0.5 to about 1: 10; and d) a peroxide-containing compound, wherein the 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 carrier containing silica, in which the amount of silica ranges from about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the organotitanium salt contains 1) an amount of titanium in the range of about 0.1% wt. up to about 20% wt. based on the amount of silica, 2) an equivalent molar ratio of titanium to carboxylate ranging from about 1:1 to about 1:10, and 3) an equivalent molar ratio of titanium to protonated nitrogen-containing compound ranging from about 1:0.5 to about 1: 10; and d) an acidic phenol, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol 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 the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. on the amount of silicon dioxide; c) a titanium-containing compound, in which the amount of titanium is in the range from about 0.01% wt. up to about 0.1% wt. on the amount of silicon dioxide; and (1) wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid, if present, is in the range of about 1:1 to about 1:10; (2) wherein the equivalent molar ratio of titanium-containing compound to peroxide-containing compound, if present, is in the range of about 1:1 to about 1:10; (3) wherein the equivalent molar ratio of titanium-containing compound to acidic phenol, if present, in the acidic titanium mixture is from about 1:1 to about 1:5; and (4) wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound, if present, is in the range of about 1:0.5 to about 1:5.

BRIEF DESCRIPTION OF GRAPHIC MATERIALS

[0024] The following graphics are part of this description and are included to further demonstrate certain aspects of this disclosure. The subject matter of this disclosure may be better understood by reference to drawings in combination with detailed descriptions of specific aspects presented herein.

[0025] The graphic illustrates the relationship between zeta potential and pH value for silica and titanium dioxide.

[0026] Although the subject matter disclosed herein is susceptible to various modifications and alternative forms, only a few specific embodiments have been shown by way of example in the drawings and are described in detail below. The graphics and detailed descriptions of these specific embodiments are in no way intended to limit the breadth or scope of the subject matter of the invention or the appended claims. Rather, graphics and detailed written descriptions are provided to illustrate this disclosure to one skilled in the art and to enable such skilled person to make and use the concepts disclosed herein.

DETAILED DESCRIPTION OF THE INVENTION

[0027] This invention covers olefin polymerization catalysts and precatalysts therefor, methods for preparing olefin polymerization catalysts and precatalysts therefor, and methods for using olefin polymerization catalysts. In one aspect, the method of this invention includes contacting a silica support or a chromium-silica support (ie, the support) with titanium to form a Cr/Si-Ti catalyst. The techniques disclosed herein involve the use of a solubilized titanium mixture (STC) to facilitate the combination of titanium with a support in the presence of water. As used herein, a procedure for preparing an olefin polymerization catalyst involves contacting a chromium silica support with CTS under conditions suitable to form the catalyst composition. An alternative technique for preparing an olefin polymerization catalyst involves contacting a silica support with HTC and chromium under conditions suitable to form the catalyst composition. Although these aspects may be disclosed under a particular heading, that heading does not limit the disclosure contained therein. Moreover, the various aspects and embodiments disclosed herein may be combined in any manner.

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

[0029] Precatalyst compositions are disclosed herein. In one aspect, the precatalyst composition contains a silica support, a chromium-containing compound, a titanium-containing compound, a carboxylic acid, and a nitrogen-containing compound. Alternatively, the precatalyst composition contains a silica support, a chromium-containing compound, and an organotitanium salt. Alternatively, the precatalyst composition contains 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 peroxide-containing compounds, or any combination thereof.

[0030] In one aspect, the olefin polymerization catalyst and its precatalyst of the present invention comprise a silica support. The silica support may be any silica support suitable for the preparation of an olefin polymerization catalyst and its precatalyst as disclosed herein. In an additional aspect, the preparation of the olefin polymerization catalyst and its precatalyst eliminates heat treatment of the silica support before contacting any other catalyst component. Therefore, a silica support suitable for use in the present invention may be referred to as a hydrated silica support. Without wishing to be limited by theory, a hydrated silica support includes a silica support that releases water when the silica support is heated in the range of about 180°C to about 200°C under vacuum conditions for a period of time in the range of about 8 o'clock to about 20 o'clock. In yet another aspect, the silica support thus treated can release from about 0.1% wt. up to about 20% wt. water; alternatively, from about 1% wt. up to about 20% wt. water; alternatively, from about 1% wt. up to about 10% wt. water; or, alternatively, from about 0.1% wt. up to about 10% wt. water from the total mass of the silica carrier.

[0031] A silica support suitable for use in this invention may have a specific surface area and pore volume effective to provide an active olefin polymerization catalyst. In an aspect of the present invention, the silica support has a specific surface area ranging from about 100 m ² /g to about 1000 m ² /g; alternatively, from about 250 m ² /g to about 1000 m ² /g; alternatively, from about 250 m ² /g to about 700 m ² /g; alternatively, from about 250 m ² /g to about 600 m ² /g; or, alternatively, more than about 250 m ² /g. The silica support may further be characterized by a pore volume greater than about 0.9 cm ³ /g; alternatively, more than about 1.0 cm ³ /g; or, alternatively, more than about 1.5 cm ³ /g. In one aspect of the present invention, the silica support has a pore volume ranging from about 1.0 cm ³ /g to about 2.5 cm ³ /g. The silica support may further have an average particle size ranging from about 10 microns to about 500 microns; alternatively, from about 25 microns to about 300 microns; or, alternatively, from about 40 microns to about 150 microns. Typically, the average pore size of the silica support may range from about 10 Angstroms to about 1000 Angstroms. In one aspect of the present invention, the average pore size of the silica support is in the range of about 50 Angstroms to about 500 Angstroms; alternatively, from about 75 Angstroms to about 350 Angstroms.

[0032] The silica carrier suitable for use in this invention may contain more than about 50% wt. silicon dioxide; alternatively, more than about 80% wt. silicon dioxide; or, alternatively, more than about 95% wt. silica based on the total weight of the silica support. In one aspect, the silica support contains silica in an amount ranging from about 70% wt. up to about 95% wt. of the total mass of the silica support. The silica support can be prepared using any suitable method, for example, the silica support can be prepared by hydrolyzing tetrachlorosilane (SiCl ₄ ) with water or 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 may optionally be dried before contacting any other catalyst component. The silica support may include additional components that do not adversely affect the catalyst, such as zirconia, alumina, thorium dioxide, magnesium oxide, fluoride, sulfate, phosphate, or a combination thereof. In a specific aspect, the silica support of this invention comprises alumina. Non-limiting examples of silica supports suitable for use in this disclosure include ES70, which is a silica support material with a specific surface area of 300 m ² /g and a pore volume of 1.6 cm ³ /g, which is commercially available from PQ Corporation , and V398400, which is a silica carrier material commercially available from Evonik.

[0033] In a specific aspect of this disclosure, a silica support suitable for use in this invention contains chromium. The chromium-containing silica carrier may be referred to as a chromated silica carrier or a chromium-silica carrier. In another aspect, the chromium silica support has the characteristics disclosed herein for a silica support and further comprises chromium. A non-limiting example of a chromium-silica support material is HW30A, which is a chromium-silica support material commercially available from W.R. Grace and Company.

[0034] The silica support may be present in the olefin polymerization catalyst and its precatalyst in an amount ranging from about 50% by weight. up to about 99% wt.; or alternatively, from about 80% wt. up to about 99% wt. As used herein, the percentage of silica support refers to the weight percentage (% wt) of the silica support combined with the olefin polymerization catalyst of the total weight of the olefin polymerization catalyst after completion of all processing steps (i.e., after calcination activation). . Alternatively, the percentage of silica support refers to the percentage by weight (% wt) of the silica support combined with the pre-catalyst of the total weight of the pre-catalyst after completion of all relevant processing steps excluding calcination activation.

[0035] In yet another aspect, the olefin polymerization catalyst and its precatalyst of the present invention contain chromium. The chromium source may be any chromium-containing compound capable of providing sufficient chromium for 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 invention, 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 their combination. 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 thereof.

[0036] The amount of chromium present in the olefin polymerization catalyst can range from about 0.01 wt.%. up to about 10% wt.; alternatively, from about 0.5% wt. up to about 5% wt.; alternatively, from about 1% wt. up to about 4% wt.; or, alternatively, from about 2% wt. up to about 4% wt. chromium from the total mass of the olefin polymerization catalyst. In another aspect, the amount of chromium present in the olefin polymerization catalyst may range from about 1% wt. up to about 5% wt. chromium from the total mass of the olefin polymerization catalyst. As used herein, percentage chromium refers to the weight percentage (% wt) of chromium combined with the olefin polymerization catalyst of the total weight of the olefin polymerization catalyst after completion of all processing steps (ie, after activation by calcination). In yet another aspect, the amount of chromium present in the precatalyst may range from about 0.01 wt.%. up to about 10% wt.; alternatively, from about 0.1% wt. up to about 5% wt.; alternatively, from about 0.2% wt. up to about 2% wt.; or, alternatively, from about 0.5% wt. up to about 1.5% wt. chromium from the total mass of silicon dioxide in the pre-catalyst. As used herein, chromium percentage refers to the weight percentage (% wt) of chromium combined with the precatalyst of the total weight of silica in the precatalyst after completion of all processing steps excluding calcination activation.

[0037] In yet another aspect, the olefin polymerization catalyst and its precatalyst of the present invention contain titanium. The titanium source may be any titanium-containing compound capable of providing sufficient titanium for the olefin polymerization catalyst and its precatalyst. In yet another aspect, the titanium-containing compound includes a tetravalent titanium compound (Ti(IV)) or a trivalent titanium compound (Ti(III)). The Ti(IV) compound may be any compound that includes Ti(IV); alternatively, the Ti(IV) compound may be any compound that is capable of releasing Ti(IV) moieties when dissolved in solution. The Ti(III) compound may be any compound that includes Ti(III); alternatively, the Ti(III) compound may be any compound that is capable of releasing Ti(III) moieties when dissolved in solution.

[0038] In one aspect, a titanium-containing compound suitable for use in this invention includes a Ti(IV) compound having at least one alkoxide group; or, alternatively, at least two alkoxide groups. Ti(IV) compounds suitable for use in this invention include, but are not limited to, Ti(IV) compounds that have the general formula TiO( ^ORK ) ₂ , Ti( ^ORK ) ₂ (acac) ₂ , Ti( OR ^K ) ₂ (oxal), a combination thereof, where R ^K may be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or a combination thereof; "atsac" is acetylacetonate; and "oxal" means oxalate. Alternatively, the titanium-containing compound includes titanium (IV) alkoxide. In one aspect, the titanium (IV) alkoxide may be titanium (IV) ethoxide, titanium (IV) isopropoxide, titanium (IV) n-propoxide, titanium (IV) n-butoxide, titanium (IV) 2-ethyl hexoxide, or a combination thereof. In a particular aspect, the titanium-containing compound may be titanium (IV) isopropoxide.

[0039] In yet another aspect, a titanium-containing compound suitable for use in this invention may include titanium hydroxide, titanium hydroxide, titanic acid, titanyl sulfate, titanium acetylacetonate, titanium oxyacetylacetonate, or a combination thereof.

[0040] In yet another aspect, a titanium-containing compound suitable for use in this invention may include titanium (IV) halide, non-limiting examples of which include titanium tetrachloride, titanium tetrabromide, titanium (IV) oxychloride and titanium (IV) oxybromide. In a further aspect, the titanium (IV) halide may include a titanium alkoxy halide having the general formula Ti(OR ^K ) _n Q _4-n ; where R ^K may be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or a combination thereof; wherein Q may be fluoride, chloride, bromide, iodide, or a combination thereof; and where n can be an integer from 1 to 4.

[0041] The amount of titanium present in the olefin polymerization catalyst of this invention may range from about 0.01% wt. up to about 10% wt.; alternatively, from about 0.5% wt. up to about 5% wt.; alternatively, from about 1% wt. up to about 4% wt.; or, alternatively, from about 2% wt. up to about 4% wt. titanium from the total mass of the olefin polymerization catalyst. In another aspect, the amount of titanium present in the olefin polymerization catalyst may range from about 1% wt. up to about 5% wt. titanium from the total mass of the olefin polymerization catalyst. As used herein, percentage titanium refers to the percentage by weight (% wt) of titanium associated with the olefin polymerization catalyst based on the total weight of the olefin polymerization catalyst after completion of all processing steps (ie, after activation by calcination). In yet another aspect, the amount of titanium present in the precatalyst of this invention can range from about 0.01 wt. % to about 25 wt. %; alternatively, from about 0.1 wt. % to about 20 wt. %; alternatively, from about 0.5 wt. % to about 10 wt. %; alternatively, from about 1 wt. % to about 6 wt. %; or, alternatively, from about 2 wt. % to about 4 wt. % titanium based on the total mass of silica in the precatalyst. As used herein, percentage titanium refers to the weight percentage (%wt) of titanium combined with the precatalyst of the total weight of silica in the precatalyst after completion of all processing steps excluding calcination activation.

[0042] In one aspect, the olefin polymerization catalyst and its precatalyst of this invention contain one or more carboxylic acids. The carboxylic acid may be a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, an α-hydroxycarboxylic acid, a β-hydroxycarboxylic acid, an α-ketocarboxylic acid, or a combination thereof. In one aspect, the carboxylic acid may be a C ₁ -C ₁₅ monocarboxylic acid or a C ₁ -C ₅ monocarboxylic acid; alternatively, a C ₃ -C ₁₅ dicarboxylic acid or a C ₃ -C ₅ dicarboxylic acid; alternatively, a C ₁ -C ₁₅ -tricarboxylic acid or a C ₁ -C ₅ -tricarboxylic acid; alternatively, C ₁ -C ₁₅ -α-hydroxycarboxylic acid or C ₁ -C ₅ -α-hydroxycarboxylic acid; alternatively, C ₁ -C ₁₅ -β-hydroxycarboxylic acid or C ₁ -C ₅ -β-hydroxycarboxylic acid; or, alternatively, a C ₁ -C ₁₅ -α-ketocarboxylic acid or a C ₁ -C ₅ -α-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-pyridinedicarboxylic acid, nitrotriacetic acid, α-hydroxyisobutyric 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 its precatalyst of this invention contain at least two carboxylic acids. In such aspects, the at least two carboxylic acids may include at least one simple carboxylic acid and at least one complex carboxylic acid, wherein the complex carboxylic acid includes at least one ring structure. For example, the at least two carboxylic acids may be oxalic acid and phenylmalonic acid.

[0045] In one aspect, the olefin polymerization catalyst and its precatalyst of the present invention comprise an acidic phenol support. The acidic phenol may be any acidic phenol capable of providing an olefin polymerization catalyst and precatalyst of the type described herein. In one aspect, the acidic phenol includes catechols, salicylic alcohol, salicylic acid, phthalic acid, or derivatives thereof. In some aspects, the olefin polymerization catalyst and its precatalyst of this invention contain a carboxylic acid and an acidic phenol, both of the types disclosed herein.

[0046] The precatalyst of this disclosure has an equivalent molar ratio of titanium to carboxylic acid ranging 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 carboxylic acid is in the range of about 1:1 to about 1:2. Alternatively, the precatalyst of this invention comprises an equivalent molar ratio of titanium to phenol acid ranging 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 phenol acid is in the range of about 1:1 to about 1:2.

[0047] In one aspect, the olefin polymerization catalyst and its precatalyst of this invention contain a nitrogen-containing compound. The nitrogen-containing compound may be any nitrogen-containing compound suitable for providing effective titanation of the olefin polymerization catalyst and its precatalyst. 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.

NR ¹ R ² R ³ N(R ⁴ ) _x H _(4-x) OH NR ⁵ R ⁶ (CR ⁷ R ⁸ ) _yOH Structure 1 Structure 2 Structure 3 NR ⁹ R ¹⁰ OH Z=C(N(R ¹¹ ) ₂ ) ₂ N(R ¹² OH) ₃ Structure 4 Structure 5 Structure 6

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² in the nitrogen-containing compound used as described herein are independent elements structures of the nitrogen-containing compound in which they are present and are described independently of each other herein. Independent descriptions of R ¹ , R ^{2 ,} R ³ , R 4 , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and/or R ¹² presented in this document may be used without restriction and in any combination to further describe any structure of a nitrogen-containing compound that includes R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and/or ^R12 .

[0048] Typically, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and/or R ¹¹ of the corresponding nitrogen-containing compound, in which each R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and/or R ¹¹ may independently represent hydrogen, an organic group, a hydrocarbon group or an aryl group. In one aspect, each of R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and/or R ¹¹ may independently represent an organyl C ₁ -C ₃₀ group, alternatively an organic C ₁ group -C ₁₂ group, or, alternatively, an organic C ₁ -C ₆ group. In one aspect, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and/or R ¹¹ may each independently represent a C ₁ -C ₃₀ hydrocarbon group, alternatively a C ₁ hydrocarbon group -C ₁₂ group, or, alternatively, a hydrocarbon C ₁ -C ₆ group. In yet other aspects, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and/or R ¹¹ may each independently represent a C ₆ -C ₃₀ aryl group, or, alternatively, aryl C ₆ -C ₁₂ group. In a further aspect, any organyl group, hydrocarbon group or aryl group that can be used as ^R1 , ^R2 , ^R3 , ^R5 , ^R6 , ^R9 , ^R10 and/or ^R11 in the nitrogen-containing compound of this invention may be substituted or unsubstituted. One skilled in the art will appreciate that the terms “alkyl,” “organyl,” “hydrocarbyl,” and “aryl” are used herein as defined in the IUPAC Compendium of Chemical Terminology, ^2nd ed. (1997).

[0049] R ⁴ of the corresponding nitrogen-containing compound, which has R ⁴ may be an organic group, a hydrocarbon group or an aryl group. In one aspect, R ⁴ may be an organic C ₁ -C ₃₀ group, alternatively an organic C ₁ -C ₁₂ group, or alternatively an organic C ₁ -C ₆ group. In one aspect, R ⁴ may be a C ₁ -C ₃₀ hydrocarbon group, alternatively a C ₁ -C ₁₂ hydrocarbon group, or alternatively a C ₁ -C ₆ hydrocarbon group. In yet other aspects, R ⁴ may be an aryl C ₆ -C ₃₀ group or, alternatively, an aryl C ₆ -C ₁₂ group. In a further aspect, any organyl group, hydrocarbon group or aryl group that can be used as R ⁴ in the nitrogen-containing compound of this invention may be substituted or unsubstituted.

[0050] In a particular aspect, any substituted organic group, substituted hydrocarbon group, or substituted aryl group that can be used as R1 ^{, R2} , ^R3 , R4, ^R5 , ^{R6 , R9} , ^R10 and/ or R ¹¹ may contain one or more non-hydrogen substituents. Non-hydrogen substituents suitable for use herein may be halogen, a C ₁ -C ₁₂ hydrocarbon group, a C ₁ -C ₁₂ 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 C ₁ -C ₁₂ hydrocarboxy group suitable for use herein include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, phenoxy group, toloxy group, xyloxy group, trimethylphenoxy group and benzoxy group.

[0051] Each R ⁷ and/or R ⁸ of the corresponding nitrogen-containing compound that has R ⁷ and/or R ⁸ may independently represent hydrogen or a methyl group.

[0052] R ¹² of the corresponding nitrogen-containing compound, which has R ¹² may be a branched alkyl group or a linear alkyl group. In one aspect, R ¹² may be a branched C ₁ -C ₃₀ alkyl group, alternatively a branched C ₁ -C ₁₂ alkyl group, or alternatively a branched C ₁ -C ₆ alkyl group. In yet another aspect, R ¹² may be a linear C ₁ -C ₃₀ alkyl group, alternatively a linear C ₁ -C ₁₂ alkyl group, or alternatively a linear C ₁ -C ₆ alkyl group.

[0053] In yet another aspect, the nitrogen-containing compound of this disclosure having structure 2 may have x, where x is an integer from 1 to 4. In one aspect, the nitrogen-containing compound having structure 3 may have y, 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 represents oxygen or sulfur.

[0054] In one aspect, a nitrogen-containing compound suitable for use in this invention may be an alkanolamine, amide, amine, alkylamine, ammonium hydroxide, aniline, hydrazide, hydroxylamine, imine, 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 this invention may be a halogen, an organyl C ₁ -C ₁₂ group, a hydrocarbon C ₁ -C ₁₂ group, a C ₁ -C ₁₂ hydrocarboxy group, or a combination thereof. The halogen used as a substituent group in any aspect disclosed herein may be fluorine, chlorine, bromine or iodine. Non-limiting examples of C ₁ -C ₁₂ hydrocarboxy group suitable for use herein include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, phenoxy group, toloxy group, xyloxy group, trimethylphenoxy group and benzoxy group.

[0055] In yet another aspect, non-limiting examples of specific nitrogen-containing compounds suitable for use in this invention include acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, tert -butylamine, N,N'-dibutylurea, creatine, creatinine, diethanolamine , diethylhydroxyamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N,N'-dimethylurea, ethanolamine, ethylamine, glycolamine, hexylamine, hydroxyaamine, imidazole, isopropanolamine, methacrylamide, methylamine, N-methylaniline, N-methyl-2- propanolamine, methyldiethanolamine, methylformamide, propylamine, 2-propanolamine, pyrazole, pyrrolidine, pyrrolidinone, succinimide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, 1,8-diazabicyclo[5.4.0]undec-7-ene or their combination.

[0056] The precatalyst of this invention has an equivalent molar ratio of titanium to nitrogen compound ranging 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 one aspect, the equivalent molar ratio of titanium to nitrogen-containing compound is in the range of about 1:1 to about 1:2.

[0057] In a specific aspect, the pre-catalyst composition of this invention contains an organotitanium salt. In one aspect, the precatalyst composition containing the organotitanium salt further comprises a silica support and a chromium-containing compound, both of the types previously disclosed herein. In yet another aspect, an organotitanium salt suitable for use herein includes titanium, a protonated nitrogen-containing compound, and a carboxylate.

[0058] In one aspect, the organotitanium salt contains titanium. The titanium source may be any titanium-containing compound capable of providing sufficient titanium for the pre-catalyst as disclosed herein. In yet another aspect, the titanium source is a titanium-containing compound of the type described earlier herein.

[0059] In one aspect, the organotitanium salt contains a protonated nitrogen-containing compound. The protonated nitrogen-containing compound can be any protonated nitrogen-containing compound capable of providing sufficient titanium for the pre-catalyst as disclosed herein. In yet another aspect, the protonated nitrogen-containing compound may include the protonated form of any nitrogen-containing compound of the type disclosed previously herein.

[0060] In one aspect, the protonated nitrogen-containing compound includes a protonated alkanolamine, a protonated amide, a protonated amine, a protonated alkylamine, a protonated ammonium hydroxide, a protonated aniline, a protonated hydroxylamine, a protonated urea, or a combination thereof.

[0061] In yet another aspect, the protonated nitrogen-containing compound includes protonated acetamide, protonated acrylamide, protonated allylamine, ammonium, protonated ammonium hydroxide, protonated butylamine, protonated tert -butylamine, protonated N,N'-dibutylurea, protonated creatine, protonated creatinine, protonated diethanolamine , protonated diethylhydroxyamine, protonated diisopropanolamine, protonated dimethylaminoethanol, protonated dimethylcarbamate, protonated dimethylformamide, protonated dimethylglycine, protonated dimethylisopropanolamine, protonated N,N'-dimethylurea, protonated ethanolamine, protonated ethylamine, protonated glycolamine, protonated hexylamine, protonated hydroxylamine, protonated toned imidazole, protonated isopropanolamine , protonated methacrylamide, protonated methylamine, protonated N-methylaniline, protonated N-methyl-2-propanolamine, protonated methyldiethanolamine, protonated methylformamide, protonated propylamine, protonated 2-propanolamine, protonated pyrazole, protonated pyrrolidine, protonated pyrrolidinone, protonated succinimide, protonated tetraethylammonium hydroxy d , protonated tetramethylammonium hydroxide, protonated triethanolamine, protonated triisopropanolamine, protonated trimethylamine, protonated urea, protonated 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination thereof.

[0062] In yet another aspect, the organotitanium salt contains a carboxylate. The carboxylate may be any carboxylate capable of providing a sufficient amount of titanium for the pre-catalyst as disclosed herein. In one aspect, the carboxylate may comprise the anionic form of any carboxylic acid of the type disclosed previously herein.

[0063] In another aspect, the carboxylate includes C ₁ -C ₁₅ -monocarboxylate, C ₂ -C ₁₅ -dicarboxylate, C ₃ -C ₁₅ -tricarboxylate, C ₁ -C ₁₅ -alpha-hydroxycarboxylate, or a combination thereof.

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

[0065] In yet another aspect, the amount of titanium present in the organotitanium salt of this invention can range from about 0.01% wt. to about 20% wt., alternatively, from about 0.5% wt. to about 10% wt., or, alternatively, from about 1% wt. up to about 6% wt. titanium based on the total weight of silica pre-catalyst described herein. In another aspect, the organotitanium salt has an equivalent titanium to carboxylate molar ratio ranging 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 some aspects, the equivalent molar ratio of titanium to carboxylate may be about 1:2. In yet another aspect, the organotitanium salt has an equivalent molar ratio of titanium to nitrogen compound ranging 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, the olefin polymerization catalyst and its precatalyst of the present invention 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 its precatalyst. In yet another aspect, the peroxide-containing compound includes organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyethers, dialkyl peroxides, hydroperoxides, or any combination thereof. In one aspect, the peroxide-containing compound includes 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 includes hydrogen peroxide. In one aspect, the precatalyst of this invention has an equivalent molar ratio of titanium to peroxide-containing compound ranging from about 1.0:0.5 to about 1:50, alternatively, from about 1:2 to about 1:20, or, in alternatively, from about 1:5 to about 1:10. In some aspects, the use of a peroxide-containing compound in an olefin polymerization catalyst and its precatalyst results in increased solubility of the carboxylic acid-Ti component of the HTC.

[0067] In an aspect of this disclosure, a method for producing an olefin polymerization catalyst includes using a solubilized titanium mixture (STC). In a specific aspect, the STS of this invention includes a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, and a solvent. In another aspect, the CTS of this invention includes a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, optionally a peroxide-containing compound, and a solvent. In another aspect, the STS of this invention contains a carboxylic acid, a titanium-containing compound, a nitrogen-containing compound, a peroxide-containing compound, and a solvent. In yet another aspect, the STS of this invention contains a carboxylic acid, a titanium-containing compound, a peroxide-containing compound, and a solvent. In another aspect, the STS of this invention contains an acidic phenol, a titanium-containing compound, a nitrogen-containing compound, a peroxide-containing compound and a solvent. In another aspect, the STS of this invention contains an acidic phenol, a titanium-containing compound, a nitrogen-containing compound, and a solvent. In another aspect, the STS of this invention contains an acidic phenol, a titanium-containing compound, a peroxide-containing compound, and a solvent. In another aspect, the CTC of this invention contains a carboxylic acid, an acidic phenol, a titanium-containing compound, a peroxide-containing compound, and a solvent. In another aspect, the STS of this invention contains 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 CTC comprises a carboxylic acid of the type used as a component of a precatalyst disclosed herein, or alternatively at least two carboxylic acids of the type used as a component of a precatalyst disclosed herein. In yet another aspect, the CTC comprises a titanium-containing compound of the type used as a component of the precatalyst disclosed herein. In yet another aspect, the CTC contains one or more nitrogen-containing compounds of the type used as a component of the precatalyst disclosed herein. In yet another aspect, the CTC contains one or more peroxide-containing compounds of the type used as a component of the precatalyst disclosed herein. In yet another aspect, the CTC contains one or more acidic phenols of the type used as a component of the precatalyst disclosed herein.

[0068] In yet another aspect, the STS of this invention contains 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 this disclosure includes 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 yet another aspect, an organic solvent suitable for use in this 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, a 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 a 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 specific aspect, a solubilized titanium mixture (STC) disclosed herein includes an acid 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 CTC is prepared by sequentially adding a titanium-containing compound and then a nitrogen-containing compound to an acid mixture 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 then contacted with an acidic mixture to form the CTC disclosed herein. In yet another aspect, the nitrogen-containing compound used to form the base mixture may be a component of the aqueous solution.

[0070] In another aspect, the solubilized titanium mixture (STS) disclosed herein includes 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 the carboxylic acid with a peroxide-containing compound and a solvent. Alternatively, the acidic mixture can be prepared by contacting the acidic phenol with a peroxide-containing compound and a solvent. Alternatively, the acidic mixture can be prepared by contacting the acidic phenol with one or more carboxylic acids and optionally a peroxide-containing compound and a solvent.

[0071] In one aspect, the CTS is prepared by sequentially adding a titanium-containing compound and then a nitrogen-containing compound to an acid mixture disclosed herein. In another aspect, CTC is prepared by adding a titanium-containing compound to an acidic mixture disclosed herein. In some aspects, the order of addition is any order consistent with the materials disclosed herein. For example, any CTC may contain any of the components disclosed herein (eg, an acidic phenol, a nitrogen-containing compound, a peroxide-containing compound, a carboxylic acid), a titanium-containing compound, and a chromium-containing compound.

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

[0073] In one aspect, the CTC 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 types disclosed herein. In one aspect, the STS of this invention comprises an acid mixture having a solvent to carboxylic acid weight ratio ranging from about 1:1 to about 100:1, alternatively from about 1:1 to about 50:1, or in the alternative option, from about 1:1 to about 10:1. In yet another aspect, the CTC has an equivalent molar ratio of titanium-containing compound to carboxylic acid ranging 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 CTC has an equivalent molar ratio of nitrogen-containing compound to carboxylic acid ranging from 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 CTC has an equivalent molar ratio of titanium-containing compound to peroxide-containing compound ranging from 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 CTC has an equivalent molar ratio of titanium-containing compound to acidic phenol ranging from 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 CTC has an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound ranging from about 1:0.5 to about 1:10, in an alternative embodiment, from about 1:1 to about 1:5, in an alternative embodiment , from about 1:1 to about 1:3, or, alternatively, from about 1:1 to about 1:2.5. In other aspects, the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound may be about 1:2.

[0075] In a particular aspect, a CTC suitable for use in this disclosure may have a pH of less than about 5.5. Alternatively, the CTC may have a pH ranging from 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 this disclosure, the catalyst components disclosed herein may be contacted in any order or manner deemed appropriate by one of ordinary skill in the art using this disclosure to produce an olefin polymerization catalyst having the characteristics disclosed in this document.

[0077] In a specific aspect, a method for producing an olefin polymerization catalyst includes contacting a solvent and one or more carboxylic acids of the type disclosed herein to form an acidic mixture. The method may further include contacting a titanium-containing compound of the type disclosed herein and an acidic mixture to form an acidic titanium mixture. In one aspect, a nitrogen-containing compound of the type disclosed herein and an acidic titanium mixture can be contacted to form the HTS disclosed herein, for example, a nitrogen-containing compound can be added to the acidic titanium mixture to form an HTS. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture in a single portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the CTC of about 1:2. In a specific aspect, the amount of a nitrogen-containing compound added to the acidic titanium mixture is determined using an acid-base indicator (eg, bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in a plurality of portions, wherein one portion contains from about 3 % to about 10% of the amount of nitrogen-containing compound, which has an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. The addition of multiple portions of the nitrogen-containing compound can be stopped when the greenish tint of the bromocresol green indicator is reached. In some aspects, the green endpoint of the bromocresol green indicator correlates with a CTC pH value of about 4.0. In yet another aspect, adding a nitrogen-containing compound to the acidic titanium mixture involves partially neutralizing the acidic titanium mixture, or, alternatively, completely neutralizing the acidic titanium mixture. The method for preparing an olefin polymerization catalyst may further comprise contacting a chromium silica support of the type described herein and an HTS to form an adduct. In yet another aspect, the adduct can be dried by heating the adduct 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

[0078] In a specific aspect, a method for producing an olefin polymerization catalyst includes contacting a solvent and one or more carboxylic acids, both of the type disclosed herein, to form an acidic mixture. The method may further include contacting a titanium-containing compound of the type disclosed herein and an acidic mixture to form an acidic titanium mixture. In one aspect, a nitrogen-containing compound of the type disclosed herein and an acidic titanium mixture can be contacted to form the HTS disclosed herein, for example, a nitrogen-containing compound can be added to the acidic titanium mixture to form an HTS. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture in a unit portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the CTC of about 1:2. In a specific aspect, the amount of a nitrogen-containing compound added to the acidic titanium mixture is determined using an acid-base indicator (eg, bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in a plurality of portions, and wherein a single portion contains from about 3 % to about 10% of the amount of nitrogen-containing compound, which has an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. The addition of multiple portions of the nitrogen-containing compound can be stopped when the equivalence point for the greenish hue of the bromocresol green indicator is reached. In some aspects, the green hue equivalence point of the bromocresol green indicator correlates with a CTC pH value of about 4.0. In yet another aspect, adding a nitrogen-containing compound to the acidic titanium mixture involves partially neutralizing the acidic titanium mixture, or, alternatively, completely neutralizing the acidic titanium mixture.

[0079] A method for producing an olefin polymerization catalyst may further include contacting a silica support of the type described herein and HTC to form a titanium support. In yet another aspect, the titanium support can be dried by heating the titanium 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 includes maintaining the temperature of the titanium support in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the titanium carrier. The method may further include contacting a chromium-containing compound of the type described herein and a dried titanium support to form an adduct, which can be dried by heating the adduct to a temperature ranging 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In an alternative aspect, prior to drying the titanium support disclosed herein, the chromium-containing compound and the titanium support may be contacted to form an adduct, which can be dried by heating the adduct to a temperature in the range of about 25° C. to about 300° C., in the alternative alternatively, from about 50°C to about 150°C, or, alternatively, from about 75°C to about 100°C. The method further includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In yet another alternative aspect, the chromium-containing compound and the silica support can be contacted to form a chromium-silica support, which can be contacted with the CTS to form an adduct, which can be dried by heating the adduct 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

[0080] In yet another aspect, a method for producing an olefin polymerization catalyst includes contacting a titanium-containing compound and a nitrogen-containing compound, both of the types disclosed herein, to form a base mixture. The method may further include contacting a solvent and a carboxylic acid, both types disclosed herein, to form an acidic mixture. The base mixture and the acid mixture can be contacted to form a solubilized titanium titanium mixture (STC) disclosed herein, for example, the base mixture can be added to the acid mixture to form the STC. In some aspects, the base mixture is added to the acid mixture in a unit portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a particular aspect, the amount of the base mixture added to the acid mixture is determined using an acid-base indicator (eg, bromocresol green), wherein the base mixture is added to the acid mixture in a plurality of portions and wherein a single portion comprises from about 3% to about 10% of the amount of the main mixture, which has 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 the equivalence point for the greenish tint of the bromocresol green indicator is reached. In some aspects, the green hue equivalence point of the bromocresol green indicator correlates with a CTC pH value of about 4.0. In yet another aspect, adding a base mixture to an acid mixture involves partially neutralizing the acid mixture or, alternatively, completely neutralizing the acid mixture. The method for preparing an olefin polymerization catalyst may further comprise contacting a chromium silica support of the type described herein and an HTS to form an adduct. In yet another aspect, the adduct can be dried by heating the adduct 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

[0081] In yet another aspect, a method for producing an olefin polymerization catalyst includes contacting a titanium-containing compound and a nitrogen-containing compound, both of the type disclosed herein, to form a base mixture. The method may further include contacting a solvent and a carboxylic acid, both types disclosed herein, to form an acidic mixture. The base mixture and the acid mixture can be contacted to form a solubilized titanium mixture (STS) disclosed herein, for example, the base mixture can be added to the acid mixture to form the STS. In some aspects, the base mixture is added to the acidic mixture in a unit portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a particular aspect, the amount of the base mixture added to the acid mixture is determined using an acid-base indicator (for example, bromocresol green), wherein the base mixture is added to the acid mixture in a plurality of portions, and wherein a single portion contains from about 3% to about 10% of the amount of the base mixture, which has 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 the equivalence point for the greenish tint of the bromocresol green indicator is reached. In some aspects, the green hue equivalence point of the bromocresol green indicator correlates with a CTC pH value of about 4.0. In yet another aspect, adding a base mixture to an acid mixture involves partially neutralizing the acid mixture or, alternatively, completely neutralizing the acid mixture. The method of producing an olefin polymerization catalyst may further include contacting a silica support of the type disclosed herein and HTS to form a titanium support. In yet another aspect, the titanium support can be dried by heating the titanium 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 includes maintaining the temperature of the titanium support in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the titanium carrier. The method may further include contacting a chromium-containing compound of the type disclosed herein and a dried titanium support to form an adduct, which can be dried by heating the adduct to a temperature ranging 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In an alternative aspect, prior to drying the titanium support disclosed herein, the chromium-containing compound and the titanium support may be contacted to form an adduct, which can be dried by heating the adduct to a temperature in the range of about 25° C. to about 300° C., in the alternative alternatively, from about 50°C to about 150°C, or, alternatively, from about 75°C to about 100°C. The method further includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In yet another alternative aspect, the chromium-containing compound and the silica support can be contacted to form a chromium-silica support, which can be contacted with the CTS to form an adduct, which can be dried by heating the adduct 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

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

[0083] In one aspect, a nitrogen-containing compound of the type disclosed herein and an acidic titanium mixture can be contacted to form a solubilized titanium mixture (STC) disclosed herein, for example, a nitrogen-containing compound can be added to an acidic titanium mixture to form a STC. In some aspects, the nitrogen-containing compound is added to the acidic titanium mixture in a unit portion in an amount sufficient to form an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the CTC of about 1:2. In a specific aspect, the amount of a nitrogen-containing compound added to the acidic titanium mixture is determined using an acid-base indicator (eg, bromocresol green), wherein the nitrogen-containing compound is added to the acidic titanium mixture in a plurality of portions, and wherein a single portion contains from about 3 % to about 10% of the amount of nitrogen-containing compound, which has an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. The addition of multiple portions of the nitrogen-containing compound can be stopped when the equivalence point for the greenish hue of the bromocresol green indicator is reached. In some aspects, the green hue equivalence point of the bromocresol green indicator correlates with a CTC pH value of about 4.0. In yet another aspect, adding a nitrogen-containing compound to the acidic titanium mixture involves partially neutralizing the acidic titanium mixture, or, alternatively, completely neutralizing the acidic titanium mixture. The method of producing an olefin polymerization catalyst may further include contacting a silica support of the type disclosed herein and HTS to form a titanium support. In yet another aspect, the titanium support can be dried by heating the titanium 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 includes maintaining the temperature of the titanium support in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the titanium carrier. The method may further include contacting a chromium-containing compound of the type disclosed herein and a dried titanium support to form an adduct, which can be dried by heating the adduct to a temperature ranging 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In an alternative aspect, prior to drying the titanium support disclosed herein, the chromium-containing compound and the titanium support may be contacted to form an adduct, which can be dried by heating the adduct to a temperature in the range of about 25° C. to about 300° C., in the alternative alternatively, from about 50°C to about 150°C, or, alternatively, from about 75°C to about 100°C. The method further includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In yet another alternative aspect, the chromium-containing compound and the silica support can be contacted to form a chromium-silica support, which can be contacted with the CTS to form an adduct, which can be dried by heating the adduct 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

[0084] In yet another aspect, a method for producing an olefin polymerization catalyst includes contacting a solvent, a carboxylic acid, and a peroxide-containing compound, each of the type disclosed herein, to form an acid mixture. Alternatively, a method for preparing an olefin polymerization catalyst includes 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 producing an olefin polymerization catalyst includes 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 include contacting a titanium-containing compound of the type disclosed herein and an acidic mixture to form an acidic titanium mixture. The method of producing an olefin polymerization catalyst may further include contacting a silica support of the type disclosed herein and HTS to form a titanium support. In yet another aspect, the titanium support can be dried by heating the titanium 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 includes maintaining the temperature of the titanium support in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the titanium carrier. The method may further include contacting a chromium-containing compound of the type disclosed herein and a dried titanium support to form an adduct, which can be dried by heating the adduct to a temperature ranging 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In an alternative aspect, prior to drying the titanium support disclosed herein, the chromium-containing compound and the titanium support may be contacted to form an adduct, which can be dried by heating the adduct to a temperature in the range of about 25° C. to about 300° C., in the alternative alternatively, from about 50°C to about 150°C, or, alternatively, from about 75°C to about 100°C. The method further includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst. In yet another alternative aspect, the chromium-containing compound and the silica support can be contacted to form a chromium-silica support, which can be contacted with the CTS to form an adduct, which can be dried by heating the adduct 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 includes maintaining the temperature of the adduct in the range of about 25°C to about 300°C, alternatively, from about 50°C to about 150°C, or, in the alternative, from about 75°C to about 100°C C for a period of time from about 30 minutes to about 6 hours to form the pre-catalyst.

[0086] The use of a solubilized titanium mixture (STS) in the preparation of the olefin polymerization catalyst of this invention may be advantageous because the STS can promote the combination of titanium with a silica support in the presence of an aqueous solvent (eg, water). Additional advantages may occur when the STS used to prepare the olefin polymerization catalyst contains an aqueous solvent (eg, water). The solubility of titanium in an aqueous solvent may be sufficient to allow the use of spray drying techniques to bring the HTS and the silica support into contact. Spray drying, as used herein, refers to a method of producing dry powder from a liquid or slurry by rapid drying with hot gas. Spray drying techniques can be used to produce olefin polymerization catalysts in a continuous production process with the ability to produce large volumes of olefin polymerization catalysts. Spray drying techniques can also be used to produce olefin polymerization catalysts having a constant particle size distribution. The use of an aqueous solvent-containing CTS may allow the use of a hydrated silica support and eliminate the heat treatment required for anhydrous catalyst preparation processes (eg, drying the hydrated silica support before contacting any other catalyst component).

[0087] As one of ordinary skill in the art will appreciate, calcination of the precatalysts disclosed herein may result in the emission of volatile organic compounds (VOCs). In various aspects of this invention that use peroxide in the absence of a nitrogen-containing compound, VOC emissions are reduced compared to producing the same catalyst in the presence of a nitrogen-containing compound. In one aspect, VOC emissions of the catalyst of this invention can be reduced by about 10% or more, alternatively by about 20% or more, or alternatively by about 30% or more, compared to an otherwise similar catalyst production. carried out in the presence of a nitrogen-containing compound.

[0088] In some aspects of the present invention, contacting the components used in the preparation of the olefin polymerization catalyst may be carried out in the presence of a reaction medium. In yet another aspect, a reaction medium may be formed during contacting of components used in the preparation of an olefin polymerization catalyst. The reaction medium may contain a solvent (eg, water) as disclosed herein, and one or more liquids associated with components used in the preparation of the olefin polymerization catalyst (eg, water associated with a silica support). In one aspect, the reaction medium excludes any solid component used in the preparation of the olefin polymerization catalyst disclosed herein (eg, the silica support and any associated solids). In some aspects, the amount of water present in the reaction medium may range from about 1% by weight. up to about 99% wt., alternatively, from about 1% wt. up to about 50% wt., alternatively, from about 1% wt. to about 20% wt., or, alternatively, from about 1% wt. up to about 10% wt. from the total mass of the reaction medium. In yet another aspect, the reaction medium may contain more than about 20% wt. water, alternatively, about 40% wt. water, alternatively, about 60% wt. water, alternatively, about 80% wt. water, or, alternatively, about 90% wt. water based on the total weight of the reaction medium, wherein water may be the source of one or more components used in the preparation of the olefin polymerization catalyst.

[0089] In any aspect of the present invention, a method for producing an olefin polymerization catalyst further comprises activating a precatalyst prepared as disclosed herein through a calcination step. In some aspects, calcining the precatalyst includes heating the precatalyst in an oxidizing environment to produce an olefin polymerization catalyst. For example, the precatalyst may be calcined by heating the precatalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C, alternatively, from about 500°C to about 900°C, or, alternatively, from about 500°C to about 850°C. Calcining the pre-catalyst may further include maintaining the temperature of the pre-catalyst in the presence of air in the range of about 400° C. to about 1000° C., alternatively, from about 500° C. to about 900° C., or, alternatively, from about 500° C. °C to about 850°C for a period of time ranging from about 1 minute to about 24 hours, in an alternative embodiment, from about 1 minute to about 12 hours, in an alternative embodiment, from about 20 minutes to about 12 hours, in an alternative 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 an olefin polymerization catalyst.

[0090] The olefin polymerization catalysts of this invention are suitable for use in any olefin polymerization process using various types of polymerization reactors. In an aspect of the present invention, the polymer of the present invention is produced by any process for polymerizing olefins using various types of polymerization reactors. As used herein, the term “polymerization reactor” includes any reactor capable of polymerizing olefin monomers to produce homopolymers and/or copolymers. The homopolymers and/or copolymers produced in the reactor may be referred to as resins and/or polymers. Various types of reactors include, but are not limited to, those which may be referred to as batch, slurry, gas phase, solution, high pressure, tubular, autoclave or other reactor and/or reactors. Gas-phase reactors may include fluidized bed reactors or staged horizontal reactors. Slurry reactors may contain vertical or horizontal loops. High pressure reactors may include autoclave or tube reactors. Reactor types may include batch or continuous processes. Continuous processes may use batch or continuous discharge or transfer of product. The processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, olefin polymerization catalyst and/or cocatalysts, diluents and/or other polymerization process materials.

[0091] The polymerization reactor systems of this invention may include a single type of reactor in a system or a plurality of reactors of the same or different types operating in any suitable configuration. The production of polymers in a plurality of reactors may include multiple steps in at least two separate polymerization reactors interconnected by a transfer system allowing the polymers produced in the first polymerization reactor to be transferred to the second reactor. Alternatively, multi-reactor polymerization may involve transferring polymer, either manually or automatically, from one reactor to a subsequent reactor or reactors for additional polymerization. Alternatively, multistage or multistage polymerization may occur in a single reactor in which conditions are changed such that a different polymerization reaction occurs.

[0092] The desired polymerization conditions in one of the reactors may be the same as or different from the operating conditions of any other reactors involved in the overall polymer production process of this invention. 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 loop and/or gas phase reactors. Multiple reactors can be operated in series or in parallel. In an aspect of this disclosure, any arrangement and/or any combination of reactors can be used to produce the polymer of this invention.

[0093] In accordance with one aspect of this disclosure, a polymerization reactor system may include at least one loop slurry reactor. Such reactors are conventional and may include vertical or horizontal loops. Typically, continuous processes may involve continuously introducing monomer, olefin polymerization catalyst, and/or diluent into a polymerization reactor and continuously removing a slurry containing polymer particles and diluent from the reactor. The monomer, diluent, olefin polymerization catalyst, and optionally any comonomer may be continuously fed to the loop slurry reactor in which the polymerization occurs. The reactor effluent may be flashed to remove liquids that contain diluent from the solid polymer, monomer and/or comonomer. Various technologies may be used for this separation step, including, but not limited to, flashing, which may involve any combination of heat application and pressure reduction, separation by cyclone action in either a cyclone or hydrocyclone, separation by centrifugation, or other suitable separation method.

[0094] A typical suspension polymerization process (also known as a particle molding process) is described, for example, in US Pat. Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415, each of which is incorporated herein by reference in its entirety.

[0095] Diluents suitable for use in slurry polymerization include, but are not limited to, the polymerizable monomer and hydrocarbons, which are liquids under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons, for example, propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some loop polymerization reactions can occur under bulk conditions when no diluent is used. An example is the polymerization of propylene monomer as described in US Pat. No. 5,455,314, which is incorporated herein by reference in its entirety.

[0096] In accordance with another aspect of this disclosure, the polymerization reactor may comprise at least one gas phase reactor. Such systems may utilize a continuous recycle stream containing one or more monomers continuously circulated through a fluidized bed in the presence of an olefin polymerization catalyst under polymerization conditions. The recycle stream may be withdrawn from the fluidized bed and returned back to the reactor. At the same time, the polymer product can be withdrawn from the reactor and new or fresh monomer can be added to replace the polymerized monomer. In such gas phase reactors, a multi-stage gas phase olefin polymerization process may occur in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones by feeding the olefin polymerization catalyst-containing polymer formed in the first polymerization zone to the second polymerization zone. One type of gas phase reactor suitable for use is disclosed in US Pat. Nos. 4,588,790, 5,352,749, and 5,436,304, each of which is incorporated herein by reference in its entirety.

[0097] In accordance with another aspect of this disclosure, the high pressure polymerization reactor may include a tubular reactor or an autoclave reactor. Tubular reactors may have multiple zones into which fresh monomer, initiators or olefin polymerization catalysts are introduced. The monomer can be carried away by the inert gas stream and introduced into one zone of the reactor. Initiators, olefin polymerization catalysts, and/or catalyst components may be entrained in the gas stream and introduced into another zone of the reactor. Gas streams can be mixed for polymerization. Heat and pressure can be used appropriately to obtain optimal conditions for the polymerization reaction.

[0098] In accordance with another aspect of this disclosure, the polymerization reactor may include a solution polymerization reactor in which the monomer is contacted with the olefin polymerization catalyst composition under suitable stirring or other means. A carrier containing an organic diluent or excess monomer may be used. If desired, the monomer may be brought into contact in the vapor phase with the product of the catalytic reaction in the presence or absence of liquid material. The polymerization zone may be maintained at temperatures and pressures that will result in the formation of a polymer solution in the reaction medium. Stirring may be used to obtain better temperature control and to maintain homogeneity of the polymerization mixtures throughout the polymerization zone. Suitable means are used to remove the exothermic heat of polymerization.

[0099] Polymerization reactors suitable for use in this disclosure may further comprise any combination of at least one feedstock supply system, at least one olefin polymerization catalyst or catalyst component supply system, and/or at least one recovery system polymer. Suitable reactor systems of this disclosure may further comprise systems for feed purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recirculation, storage, discharge, laboratory analysis, and process control.

[00100] Conditions that control polymerization efficiency and polymer properties include, but are not limited to, temperature, pressure, type and amount of olefin polymerization catalyst or cocatalyst, and concentrations of various reactants. Polymerization temperature can affect catalyst performance, polymer molecular weight, and molecular weight distribution. A suitable polymerization temperature may be any temperature below the depolymerization temperature according to the Gibbs free energy equation. Typically, it 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 pressure will also vary depending on the reactor and polymerization process. The liquid phase polymerization pressure in the loop reactor is typically less than 1000 psig. (6.9 MPa). Pressures for gas phase polymerization are typically in the range of about 200 psi. inch g. (1.4 MPa) up to 500 psi. inch g. (3.45 MPa). High pressure polymerization in tubular or autoclave reactors typically occurs at pressures ranging from about 20,000 psig. (138 MPa) up to 75,000 psi. inch g. (518 MPa). Polymerization reactors can also operate in the supercritical region, which generally occurs at higher temperatures and pressures. Operating at conditions above the critical point indicated on the pressure/temperature diagram (in the supercritical phase) may provide benefits.

[00102] The concentration of various reagents can be adjusted to produce polymers with specific physical and mechanical properties. The proposed final product to be produced from the polymer and the method of obtaining that product may be varied to determine the desired properties of the final product. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, toughness, creep, stress relaxation, and hardness test results. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting point, glass transition temperature, melt crystallization temperature, density, stereoregularity, crack growth, short chain branching, long chain branching, and rheological measurements.

[00103] The concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers, and electron donors are generally important to obtain specific polymer properties. The comonomer can be used to control the density of the product. Hydrogen can be used to control the molecular weight of a product. Cocatalysts can be used for alkylation, depoisoning, and/or molecular weight control. The concentration of poisons can be kept to a minimum because poisons can interfere with reactions and/or otherwise affect the properties of the polymer product. Modifiers can be used to control product properties, and electron donors can influence stereoregularity.

[00104] Polymers, such as polyethylene homopolymers and copolymers of ethylene with other monoolefins, can be prepared in the manner described above using olefin polymerization catalysts prepared as described herein. The polymers produced as disclosed herein can be formed into manufactured 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 polymer resin may be extruded into a sheet, which is then thermoformed into an end-use article such as a container, cup, tray, tray, toy, or other product component. Examples of other end-use products into which polymer resins can be molded include pipes, films and bottles.

[00105] The method of this disclosure includes contacting an olefin polymerization catalyst of the type described with an olefin monomer under conditions suitable for forming a polyolefin, and isolating the polyolefin. In one aspect, the olefin monomer is an ethylene monomer and the polyolefin is an ethylene polymer (polyethylene).

[00106] The polyethylene produced as described herein may have a high stress melt flow index (HSMF) in the range of about 1 g/10 min to about 1000 g/10 min, alternatively, from about 3 g/10 min. 10 minutes to about 300 g/10 minutes, alternatively, from about 6 g/10 minutes to about 100 g/10 minutes, or, alternatively, from about 15 g/10 minutes to about 40 g/10 minutes. In a further aspect, polyethylene produced as described herein can have a HLTST that is about 1.5 to about 15 times higher than the HLTST of a polymer produced using an otherwise similar olefin polymerization catalyst that does not contain titanium.

[00107] In a particular aspect, polyethylene can be produced using a detanized catalyst obtained from a water-extracted pre-catalyst. In yet another aspect, the water-extracted pre-catalyst is a pre-catalyst that has been extracted with water before calcination. For example, the precatalyst prepared as described herein can be extracted with water and then calcined to produce a detanatized catalyst (ie, an olefin polymerization catalyst obtained from the water-extracted precatalyst). In a further aspect, polyethylene produced using a detitanized catalyst may have a VLTR in the range of about 1 dg/min to about 7 dg/min. This VNLTR value may indicate that the detanized catalyst has the amount of titanium relative to the amount of silica in the range of 0% wt. up to 1% wt. or, alternatively, from about 0.1% wt. up to 0.5% wt.

[00108] Melt index (MRI) is the rate of flow of molten polymer through a 0.0825 inch diameter orifice under a force of 2160 grams at 190°C, as determined in accordance with ASTM D1238-82 Condition E. I10 represents the flow rate of molten polymer through a 0.0825 inch diameter hole under a force of 10,000 grams at 190°C, as determined according to ASTM D1238-82 Condition N. HSLFT (High Load Melt Flow Index) is the rate of flow of molten polymer through a 0.0825 inch diameter orifice under a force of 21600 g at 190°C, as determined according to ASTM D1238-82 Condition F.

EXAMPLES

[00109] The following examples are provided as specific aspects of this disclosure and to demonstrate the practical implementation and its advantages. It is understood that the examples are given by way of illustration and are in no way intended to limit the description or the following claims.

[00110] One skilled in the art will appreciate that the surfaces of oxides, including silicon dioxide (SiO ₂ ) and titanium dioxide (TiO ₂ ), are typically terminated with hydroxyl groups, which are protic groups that can participate in acid-base reactions. Under strongly acidic conditions, hydroxyl groups can be protonated to create a positive charge on the oxide surface. Under highly alkaline conditions, hydroxyl groups can be deprotonated to establish a negative charge on the oxide surface. There is a pH value somewhere between two limits at which there is zero net charge on the surface of the oxide. The pH value corresponding to zero net charge is the isoelectric point. Each oxide has a characteristic acidity and a specific isoelectric point determined by the chemical properties of the metallic or nonmetallic element of the oxide.

[00111] The Figure depicts the zeta potential as a function of solution pH for silica and titanium dioxide, as well as the isoelectric point of both oxides. The Si-Ti Coulomb attraction curve is also depicted. Zeta potential is the difference in electrical charge potential that exists between the surface of a solid particle immersed in a conducting liquid (such as water) and the bulk of the liquid. The Figure shows that titanium dioxide is positively charged and silicon dioxide is negatively charged within the pH range from 3.0 to 5.0. The Figure also shows that the Si-Ti Coulomb attraction is maximum at a pH value of about 4.0. Without wishing to be bound by theory, highly efficient titanation of an olefin polymerization catalyst from an aqueous Ti solution can occur when the Si-Ti Coulombic attraction is maximized by maintaining the pH of the solution at about 4.0. To test this theory, several series of experiments were carried out to establish the conditions leading to the formation of an aqueous solution of Ti with a pH value of about 4.0.

[00112] All silica support materials, chemicals and solvents described herein were used as prepared and were not dried prior to use.

[00113] Catalysts used in the experiments described below include Magnapore ^® , a commercial Cr/silica-titania catalyst obtained from WR Grace and Company and activated at various temperatures. Magnapore ^® is prepared by gelling Si, Ti and Cr containing 2.5% wt. Ti and 1% wt. Cr, with a surface area of about 500 m ² /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 was called C-25305HM and was obtained from Philadelphia Quartz (PQ) Corporation. It also contains 2.5% wt. Ti and 1% wt. Cr, has a surface area of about 500 m ² /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 titanation described below was ^Sylopol® HA30W, a commercial Cr/silica obtained from WR Grace. This catalyst did not contain titanium, but contained 1% wt. Cr. It had a specific surface area of about 500 m ² /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 WR Grace. All three of these catalysts did not contain titanium, but contained 1% wt. Cr. All three had a pore volume of about 1.6 ml/g. EP30X and 969MPI had a specific surface area of about 300 m ² /g and an average particle size of about 100 microns. AGC D-70-150A(LV) had a specific surface area of about 400 m ² /g and an average particle size of about 80 microns.

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

[00115] Unless otherwise specified, a small amount (typically 0.01 to 0.10 g) of solid chromium catalyst was first charged under a nitrogen atmosphere into a dry reactor. About 0.25 g of sulfate-treated alumina (600°C) was then added as a poison scavenger. 1.2 liters of liquid isobutane was then charged and the reactor was heated to a set temperature, typically 105 degrees C. Finally, ethylene was added to the reactor until a fixed pressure was reached, typically 550 psi. inch (3.8 MPa), which was maintained during the experiment. Stirring was allowed to continue for a specified time, usually about one hour, and activity was recorded by recording the flow of ethylene into the reactor to maintain a set pressure.

[00116] After the allotted time, the ethylene flow was stopped, the reactor was slowly depressurized and opened to recover the granular polymer powder. In all cases, the reactor was clean, with no signs of scale, coating or other forms of contamination on the walls. The polymer powder was then removed and weighed. The activity was expressed in grams of polymer produced per gram of solid catalyst charged per hour.

Example 1

[00117] Several control experiments were conducted, and the results of the control experiments are shown in Table 1. The performance of the experimental catalysts shown in the following examples, in terms of productivity, activity and melt flow potential, can be compared with these control experiments. Runs 1.10-1.13 represent the efficiency of two non-titanium catalysts, the latter of which, HA30W, provides the titanation efficiency of runs 1.16-1.18. The titanation shown in runs 1.16-1.18 used Ti(OiPr) ₄ to titanate HA30W. In the titanation run 1.15, the support was exposed to TiCl ₄ vapor at 250°C in an attempt to obtain a titanated catalyst uncontaminated by organic or alcohol by-products. In both of these methods, the carrier had to be dried to remove free water from the surface, usually by heat treatment from about 150°C to about 800°C. Otherwise, titanium will react with free adsorbed water and will be ineffective. In runs 1.15-1.18, the catalyst was dried at 200°C before titanation, either in the gas phase or in an anhydrous solvent (usually heptane).

Table 1: Performance characteristics of reference catalysts Run no. Catalytic base Treatment Ti% wt. Pace. Act. Indicator Time, min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 1.1 Magnapor® No 2.5 871°С 8 5362 7149 2.27 29.2 121 1.2 Magnapore® No 2.5 871°С 8 1921 4117 1.58 22.7 108 1.3 Magnapore® No 2.5 871°С 7 2822 3938 0.73 13.7 66.2 1.4 Magnapore® No 2.5 650°C 6 2071 2825 0.45 30.0 1.5 Magnapore® No 2.5 650°C 6 1653 3672 0.58 36.3 1.6 Magnapore® No 2.5 650°С 7 3411 5831 0.50 29.7 1.7 Magnapore® No 2.5 650°С 7 2150 2283 0.47 26.9 1.8 PQ C-25305HM No 2.5 650°C 5 1535 1674 0.91 52.7 1.9 PQ C-25305HM No 2.5 650°C 5 1596 4352 0.86 53.9 1.10 969MPI No 0 780°C 20 2830 2326 1.5 8.7 1.11 969MPI No 0 650°С 18 1835 1835 0.16 12.8 1.12 HA30W No 0 650°C eleven 2973 2973 0.87 5.5 1.13 " " " 650°С 18 3117 2309 0.24 4.22 19.6 1.14 D-70-150A(LV) PPC C1 Act. 3.0 650°C 12 3221 2577 0.35 6.3 30.5 1.15 D-70-150A(LV) TiCl ₄ pairs 3.0 650°C 6 3092 2728 0.46 8.20 36.3 1.16 HA30W Ti(OiPr) ₄ /C7 3.5 650°C 8 2534 2715 0.40 7.70 36.7 1.17 HA30W Ti(OiPr) ₄ /C7 4.8 650°С eleven 2455 1259 0.23 4.69 21.5 1.18 " " " " 5 2271 2349 0.29 5.91 28.0 Run at 105°C, 550 psi. inch g.

Example 2: Acid titanation

[00118] The first series of experiments examined the ability of carboxylic acids to form an acidic Ti-containing solution capable of effectively titanating an olefin polymerization catalyst of the type described herein (ie, the catalyst). The results are shown in Table 2. All of these experiments started with hydrated silica supports that were not heat treated before contact with any other catalyst component. The listed carboxylic acids were mixed with water or an alternative solvent system as indicated 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 resulting acidic Ti-containing solution was impregnated with a chromium silica support (HA30W). The product was then dried and air calcined for three hours at 650°C before being used in polymerization experiments.

[00119] Table 2 shows the results of a study of various carboxylic acids. Using carboxylic acids alone (without adding a base) did not result in very effective titanation. Run 2.2, which used acetic acid in propanol solvent, provided the most efficient titanation. Successful results were also observed when HA30W was soaked in an acidic Ti-containing 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 flow rate obtained when preparing the catalyst using this method compared to oven drying. The "hot drop" drying method resulted in more efficient titanation when citric acid was used instead of oxalic acid. This result could be obtained due to the fact that the first pK _a of citric acid (3.13) is higher than the first pK _a 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 compared to a Ti-containing solution prepared using oxalic acid.

Table 2: Titanation with simple acids Run no. Acid/Solvent Acid/Ti Indicator Time, min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 2.1 Acetic acid solvent Large XS 7 1453 1478 0.09 2.39 11.0 2.2 Acetic acid/n-propanol Large XS 5 3178 3467 0.49 8.69 39.1 2.3 Glycolic acid 4:1 17 3098 3320 0.97 5.7 2.4 Glycolic acid 2:1 9 2186 2851 0.37 2.9 2.5 _HNO3 1.7% 15 2846 2339 0.08 1.1 2.6 HNO ₃ /H ₂ O+n-propanol 1.7% 16 3111 3010 0.002 0.15 1.8 2.7 Phosphonoacetic acid 4:1 7,867 627 1.14 6.0 2.8 Oxalic acid, hot drop** 3:1 13 2933 3088 1.03 6.4 2.9 " " 9 2848 3224 1.59 9.0 2.10 Citric acid, hot drop** 3:1 9 3737 3114 0.11 3.41 17.3 2.11 " " 14 2986 5599 0 1.53 9.0 2.12 " " 9 3238 1833 0 3.02 16.0 The catalysts used the original HA30W base containing 3.5% wt. Ti, water was used as a solvent, and they were activated at 650°C.
Runs were typically conducted at 105°C and 550 psi. inch g.
*Run was carried out at 100°C with 5 ml 1-hexene and 550 psi. inch g.
** These catalysts were dried by immersing them in a hot activator tube set at 300°C.

Example 3: Alkali titanation

[00120] The next series of experiments examined the ability of the base to form an alkaline Ti-containing solution capable of effectively titanating the catalyst. The results are shown in Table 3. The experimental approach was essentially identical to the method described in Example 2. Ti dissolved in some strong bases, such as organic bases, was effective, but ammonium hydroxide and alkali metal hydroxides were not effective. Quaternary ammonium hydroxides dissolved Ti, but uncharged primary, secondary, or tertiary amines were less effective. All melt flow potentials obtained from alkaline solutions were low, similar to the non-titanium support, and thus did not show evidence of effective titanation of the chromium-silica support.

Table 3: Titanation with simple bases Run no. Base/Solvent Base/Ti Indicator Time min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 3.1 NEt ₄ OH 4:1 34 0 0 3.2 " 4:1 0 0 0 3.3 NEt ₄ OH 1:1 24 2314 1876 0 0.28 2.6 3.4 NTA+NET _4OH 1.2:2:1 Insoluble 3.5 AcAc+NEt ₄ OH 1:1:1 18 2474 2699 0.20 2.6 3.6 Dimethylglycine 4.5:1 n/a 2749 n/a 0.018 1.3 7.0 3.7 " 16 3060 3165 0.013 1.0 5.9 3.8 Triethanolamine 2:1 Insoluble 3.9 Dimethylaminoethanol 1:1 19 1186 1581 2.6 3.10 NMe ₄ OH+Et-diamine 2:2:1 0 67 59 3.11 NMe ₄ OH+Et-diamine 0.6:4:1 37 3035.97 1023 0 0.0 1.6 3.12 Ethylenediamine 4:1 Insoluble 3.13 arginine 4:1 Insoluble The catalysts used the original HA30W base containing 3.5% wt. Ti, and they were activated at 650°C.
Runs were typically conducted at 105°C and 550 psi. inch g.
*Run at 100°C with 5 ml 1-hexene and 550 psi. inch g.
NTA=nitrilotetetraacetic acid

Example 4: Adjusting pH with Ammonium Hydroxides

[00121] The results in Table 2 and Table 3 confirmed that the addition of titanium dioxide to silica can be problematic at both high and low pH. The following series of experiments were carried out to test the theory that the maximum Si-Ti Coulomb attraction occurs at a pH value of about 4.0. Ti(OiPr) ₄ was hydrolyzed to titanium dioxide, which was dissolved in an aqueous solution of oxalic acid (2 equivalents of oxalic acid per Ti), producing an acidic Ti-containing solution with a pH value of about 1. Ammonium hydroxide or quaternary derivative as listed in Table 4 , was added until the green hue equivalence point of the bromocresol green indicator was reached, indicating a pH value of about 4.0, to produce a solubilized Ti mixture (STC) of the type disclosed herein. The stoichiometry required to partially neutralize the acidic Ti-containing solution and thus obtain HTS was usually about two equivalents of base per Ti. The HA30W support was impregnated with STS, and the product was dried and calcined in air for three hours at 650°C before being used in polymerization experiments.

[00122] The results shown in Table 4 indicate that the approach was successful. Quaternary ammonium hydroxides have proven to be more effective than ammonium hydroxide. This result can be explained by the lower volatility of tetraalkylammonium hydroxides. The results in Table 4 also show that the amount of base used to prepare the CTC influenced the melt flow potential imparted by the resulting catalyst. This method also allowed efficient titanation to be performed on a hydrogel rather than on a preformed silica support (Run 4.16). The catalyst from Run 4.6 was produced by back addition and showed remarkable performance: Ti was dissolved in aqueous NMe ₄ OH to form an alkaline solution, which was added to an aqueous oxalic acid solution to produce the CTC used to impregnate the HA30W support.

Table 4: Partial neutralization with ammonium hydroxides Run no. Base Base/Ti Indicator Time (min) Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 4.1 _NH4OH 2.0 eleven 2570 3281 0.10 3.16 16.8 4.2 _NH4OH 2.4 13 3144 3092 0.12 3.26 16.8 4.3 _NH4OH 2.7 eleven 2978 2414 0.14 3.62 17.6 4.4 _NMe4OH 2.0 12 3181 3976 0.51 9.1 44.4 4.5 _NMe4OH 2.1 eleven 3402 3581 0.32 6.4 31.8 4.6 _NMe4OH 2.0 R 13 1508 542 1.63 28.8 143 4.7 _NMe4OH 1R 1ШК Precipitation has fallen 4.8 NEt ₄ OH 1.0 18 2943 4772 0.14 3.39 16.9 4.9 NEt ₄ OH 1.5 16 3062 5104 0.20 4.22 21.0 4.10 NEt ₄ OH '' eleven 2182 3193 0.13 3.45 18.0 4.11 NEt ₄ OH 1.5 13 2415 3916 0.24 5.32 26.8 4.12 NEt ₄ OH 2.0 13 3165 6126 0.27 5.34 26.8 4.13 NEt ₄ OH 2.5 12 3226 6244 0.18 3.95 21.2 4.14 NEt ₄ OH 3.0 22 2865 2605 0.00 1.20 6.8 4.15 NEt ₄ OH 4.0 Precipitation has fallen 4.16 NEt ₄ OH 2.0H 18 2769 1678 0.25 5.48 27.8 4.17 NEt ₄ OH 2.0w Cr 9 3157 2282 0.28 5.70 28.4 Ti(OiPr) ₄ was dissolved in 2 equiv. oxalic acid solution, then a base was added to partially neutralize the acid. The solution was then added to primary HA30W and dried. Each catalyst contained 3.5% wt. Ti and was activated at 650°C. Runs were carried out at 105°C and 550 psi. inch g.
R: Ti was dissolved in the base, then acid was added.
H: A hydrogel was used instead of a preformed silica carrier.
Cr: Cr was added to the oxalic acid rather than being on the catalyst in the first place.

Example 5: Adjusting pH with Urea

[00123] In the next series of experiments, the ability of urea to partially neutralize an acidic Ti-containing solution and create a HTS capable of providing effective titanation of the catalyst was studied. Urea easily decomposes when heated into volatile products. Replacing carbon-containing catalyst components with urea compounds can reduce emissions of VOCs and highly reactive VOCs produced during catalyst calcination. The experimental approach was essentially identical to the method described in Example 4, but without the use of bromocresol green indicator. The results are shown in Table 5. The addition of urea to the acidic Ti-containing solution provides increasingly effective titanation as the amount of urea increases. This effect was not observed in experiments that examined the use of urea in spray drying, possibly because the urea decomposed and/or evaporated during the spray drying operation. Effective titanation was also observed with N,N'-dimethylurea, which is less volatile than urea.

Table 5: Oxalic acid with urea Run no. Base Urea/Ti Indicator Time, min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 5.1 Urea 1:1 15 3804 4389 0.11 3.04 15.3 5.2 Urea 2:1 eleven 4519 3819 0.49 6.00 27.8 5.3 Urea 3:1 10 2553 4140 0.26 5.86 29.4 5.4 Urea 3:1 8 2370 3231 0.28 6.14 30.0 5.5 Urea 4:1 16 3423 4668 0.44 8.07 40.0 5.6 N,N'-dimethylurea 2:1 14 3712 5179 0.36 6.87 34.3 Ti(OiPr) ₄ was dissolved in 2 equiv. oxalic acid solution, then a base was added to partially neutralize the acid. The solution was then added to primary HA30W and dried.
Each catalyst contained 3.5% wt. Ti and was activated at 650°C.
Runs were carried out at 105°C and 550 psi. inch g.

Example 6: pH Adjustment with Alkanolamines

[00124] In the next series of experiments, the ability of alkanolamines to partially neutralize an acidic Ti-containing solution and create a HTS capable of providing effective titanation of the catalyst was studied. Ethanolamines and isopropanolamines were chosen because they generally have low toxicity, low cost, are readily available from a variety of sources, and have less odor than 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 varied, and it appeared that the bulkier amines performed better. Without wishing to be bound by theory, this may be a result of the lower volatility of the bulkier compounds and/or the lower dielectric constant of the Ti ions as a result of the bulkier compounds. Dimethylaminoethanol (DMAE) provides a relatively high melt flow rate, is low cost, is available from a variety of suppliers, and has a low odor. The catalyst from Run 6.11 was prepared by dissolving titanium dioxide in two equivalents of aqueous oxalic acid followed by adding two equivalents of DMAE to form a solubilized Ti solution (STS) of the type described herein. The HA30W support was impregnated with CTS to form a titanium support, which was dried in vacuum overnight at 100°C. The resulting dried titanium support was extracted with water before calcination at 650°C and subjected to polymerization experiments. The melt flow data suggest that the catalyst lost a large amount of Ti, presumably during the aqueous extraction step. This observation indicates that Ti may not have been fully attached to the silica after drying at 100°C and confirms previous observations that adhesion between Ti and silica occurs at least partially at temperatures above 150°C .

Table 6: Oxalic acid with alkanolamines Run no. Catalyst base ShchK/Ti Base Base/Ti Indicator Time, min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 6.1 HA30W 2.0 Ethanolamine 2.0 10 3627 5062 0.29 5.9 30.7 6.2 HA30W 2.0 Ethanolamine 2.0 12 3621 3394 0.46 8.4 40.4 6.3 HA30W 1.5 Ethanolamine 1.35 10 3157 3105 0.21 4.6 22.7 6.4 HA30W 2.0 Diethanolamine 2.0 10 2977 3370 0.42 7.9 39.9 6.5 HA30W 2.0 Triethanolamine 2.0 12 3142 3928 0.30 6.2 31.0 6.6 HA30W 2.0 DMAE 2.0 13 4179 4179 0.64 10.7 52.1 6.7 HA30W 2.0 DMAE 2.0 13 3329 3504 0.45 8.4 41.2 6.8 HA30W 3.0 DMAE 3.0 8 3403 3646 0.33 6.8 34.1 6.9 HA30W 2.0 DMAE 3.0 8 3170 2291 0.26 5.7 28.9 6.10 HA30W 2.0 DMAE 3.0 6 2984 3197 0.19 4.9 25.6 6.11 HA30W 2.0 DMAE* 2.0 15 2467 1495 0.09 1.3 7.0 6.12 969MS 2.0 DMAE† 2.0 10 3510 4213 0.73 13.2 66.2 6.13 969MS 2.0 DMAE‡ 2.0 9 3192 3547 1.12 18.1 84.1 6.14 Evonik 2.0 DMAE 2.0 10 2784 6425 0.66 12.4 61.1 6.15 Evonik 2.0 DMAE 2.0 14 2784 3212 0.97 16.4 79.6 6.16 HA30W 2.0 Diglycolamine 2.0 12 3015 3769 0.54 9.6 47.3 6.17 HA30W 2.0 Methyl diethanolamine 2.0 12 3255 3551 0.43 7.4 35.5 6.18 HA30W 2.0 Isopropanol amine 2.5 13 3418 4102 0.31 6.1 30.5 6.19 HA30W 2.0 Diisopropanol amine 2.0 13 3282 4102 0.38 7.0 34.7 6.20 HA30W 2.0 Triisopropanol
amine 2.0 12 3091 3198 0.36 6.9 32.3 6.21 HA30W " " " 10 2774 2484 0.46 8.1 38.2 6.22 HA30W 2.0 Dimethyl isopropanolamine 2.0 16 3080 3187 0.56 9.8 46.0 Ti(OiPr) ₄ was dissolved in 2 equiv. oxalic acid solution, then a base was added to partially neutralize the acid.
The solution was then added to primary HA30W and dried. Each catalyst contained 3.5% wt. Ti and was activated at 650°C.
Runs were carried out at 105°C and 550 psi. inch g.
* Dried at 100°C, then rinsed with water before drying again.
† Dried at temperatures up to and including 650°C in N ₂ .
‡ Dried at temperatures up to and including 650°C in air.
SA: oxalic acid, DMAE: dimethylaminoethanol

Example 7: pH Adjustment with Other Amines

[00125] In the next series of experiments, the ability of a number of other amines to partially neutralize an acidic Ti-containing solution and create a HTS capable of providing effective titanation of the catalyst was studied. The experimental approach was essentially identical to the method described in Example 5, and the results are shown in Table 7. There was a general trend toward increased productivity when using bulkier amines, but was sometimes compromised by insufficient solubility of, for example, 2-ethylhexylamine or DABCO . Bases capable of delocalizing the positive charge resulting from protonation have shown very good results; examples include DBU, creatine, and imidazole.

Table 7: Oxalic acid with other amines Run no. Base Base/Ti Indicator Time, min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 7.1 Hydrazine 2.00 12 3304 2643 0.00 2.3 12.4 7.2 Hydroxylamine 2.50 4 1638 1694 0.23 5.4 27.1 7.3 Trimethylamine 2.00 15 3143 4013 0.38 7.2 35.5 7.4 Hexylamine 2.00 9 3312 3896 0.54 8.2 45.1 7.5 tert-butylamine+ethanolamine 1.0+1.0 10 3257 3832 0.45 5.0 38.0 7.6 2-ethylhexylamine 2.00 Besieged 7.7 2-ethylhexylamine* 2.00 Besieged 7.8 Ethylenediamine 0.40 Besieged 7.9 Diethylenetriamine 2.00 Besieged 7.10 Diethylenetriamine 0.50 Besieged 7.11 Formamide 2.00 13 2642 2366 0.15 3.7 18.8 7.12 Methylformamide 2.00 eleven 3294 4034 0.31 6.0 30.0 7.13 Dimethylformamide 2.00 eleven 3839 2992 0.59 11.4 43.6 7.14 Acetamide 2.00 14 3129 4941 0.39 6.7 32.8 7.15 DBU 2.00 7 3390 3632 0.56 10.0 48.1 7.16 DABCO 2.00 Besieged 7.17 DABCO 2.00 Besieged 7.18 N-methylaniline 2.40 12 3044 3728 0.66 11.6 55.8 7.19 " " 17 1711 567 0.38 7.8 41.2 7.20 Imidazole 2.00 6 2785 2457 0.32 6.6 32.2 7.21 Pyrazole 2.00 9 3062 3467 0.21 4.6 22.5 7.22 Glycine 2.00 15 3150 3098 0.09 2.7 13.6 7.23 Dimethylglycine 2.00 10 3297 3243 0.18 4.2 21.5 7.24 Arginine 1.85 17 3244 3089 0.08 2.6 14.4 7.25 " " 13 3142 2945 2.3 7.26 creatine 2.00 6 2733 4316 0.47 8.5 42.2 7.27 " " 5 3422 3366 0.34 6.9 35.0 7.28 Melamine 2.00 Besieged 7.29 Uricil 2.00 Besieged 7.30 Cyanuric acid 2.00 Besieged 7.31 Methyl carbamate 2.00 14 2930 2980 0.14 3.5 18.2 7.32 Dimethyl carbamate 2.00 14 3380 3219 0.26 5.3 25.7 Ti(OiPr) ₄ was dissolved in 2 equiv. oxalic acid solution, then a base was added to partially neutralize the acid. The solution was then added to primary HA30W and dried. Each catalyst contained 3.5% wt. Ti and was activated at 650°C. Runs were carried out at 105°C and 550 psi. inch g.
* Ethylhexylamine was added directly to the oxalic acid solution.

Example 8: pH Adjustment Using Inorganic Bases

[00126] In the next series of experiments, the ability of inorganic bases to partially neutralize an acidic Ti-containing solution and create a HTS capable of providing effective titanation of the catalyst was studied. 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. Without wishing to be limited by theory, higher dielectric constant could have an effect, but the presence of divalent or trivalent metal cations could interfere with the delicate balance of surface charge between silica and titanium dioxide. Runs 8.2 and 8.3 were partially successful and introduced equal amounts of Al ions with Ti ions simultaneously. Three equivalents of oxalic acid were added to dissolve two equivalents of metal (1 Ti(OiPr) ₄ +1 Al(OH) ₃ ), which represents a lower acid/metal ratio than most other experiments reported herein. Run 8.3 involved partial neutralization of the acid with tetraethylammonium hydroxide at 1.5 base equivalents per Ti. This is a lower base/metal ratio than most of the other experiments reported here, but an increase in HNLST was observed. Without wishing to be bound by theory, coating titanium dioxide on alumina may be simpler than coating titanium dioxide on silica. Both Ti and Al are metals, and their chemical properties are in many ways more similar than the chemical properties of Ti and Si.

Table 8. Oxalic acid with inorganic bases Run no. Description Indicator Time, min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR, dg/min 8.1 Ti+2 SC+1.2 Al(OH) ₃ 10 3333 2273 0.0 0.65 4.7 8.2 Ti+3 AS+Al(OH) ₃ 17 3286 2987 0.0 1.43 8.0 8.3 Ti+3 AK+Al(OH) ₃ +1.5 NEt ₄ OH 12 3205 4274 0.0 2.04 11.2 8.4 Ti+2 SC+1.4 Mg(OH) ₂ 12 3199 3047 0.0 0.80 5.1 8.5 Ti+2 SC+1 Mg(OH) ₂ 12 3220 3645 0.0 1.04 6.1 8.6 Ti+2 OA+0.4 ZnO Insoluble Ti(OiPr) ₄ was dissolved in an alkali solution to which other metals were added. The solution was then added to primary HA30W and dried. Each catalyst contained 3.5% wt. Ti and was activated at 650°C.
Runs were carried out at 105°C and 550 psi. inch g.
OA=oxalic acid

Example 9: Solvation of Ti with other acids

[00127] The next series of experiments examined the ability of carboxylic acids other than oxalic acid to partially neutralize and create a HTS capable of effectively titanating the 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 those using oxalic acid. In some experiments, two equivalents of base per Ti were added, which was more than needed to obtain a pH of 4.0 because the acids tested were weaker than oxalic acid. In other experiments, base was added until the bromocresol green indicator green equivalence point was reached, indicating a pH value of 4.0. An example of this method is Run 9.7, in which the use of citric acid and tetramethylammonium hydroxide resulted in a highly efficient titanation, as evidenced by a HNLTR value of almost 30. Run 9.14 showed that titanyl sulfate, in the absence of a carboxylic acid, could be partially neutralized by DMAE to produce a moderately effective titanation.

Table 9: Solvation of Ti with other acids and partial neutralization Run no. Description Indicator Time, min Prod., y/y Activity, g/g-h MTR, dg/min I10, dg/min VNPTR,
dg/min 9.1 Ti+2 maleic acid+2 NEt ₄ OH Undissolved 9.2 Ti+2 lactic acid+2 NEt ₄ OH 9 3348 3720 0.05 2.2 12.1 9.3 Ti+2 lactic acid+0.3 ethanolamine, green equivalence point 12 3803 3406 0.02 1.8 10.1 9.4 Ti+1.5 NMe ₄ OH+1.5 DMAE
then 1 malonic acid Gel-like 9.5 Ti+4 Malic acid+1,6 ethanolamine, green equivalence point 13 3112 2964 0.10 3.1 16.1 9.6 Ti+2 citric acid+2 NEt ₄ OH 14 3218 3510 0.10 3.0 15.4 9.7 Ti+2.5 citric acid+1.66 NMe ₄ OH 17 3280 4278 0.29 6.0 29.5 9.8 Ti+5 glycolic acid+1,6 ethanolamine, green equivalence point eleven 2930 2790 0.16 3.9 19.9 9.9 Ti+5 glycolic acid+1,6 ethanolamine, green equivalence point 8 3270 2582 0.10 3.3 17.4 9.10 0.5 NMe ₄ OH + 1.5 DMAE, then Ti, then 4.6 glycolic acid 9 4568 3754 0.21 4.9 24.1 9.11 Ti+3 glyoxylic acid+3 NEt ₄ OH 22 3284 2855 0.00 1.1 6.5 9.12 Ti+HNO ₃ +NH ₄ OH up to ppt* 15 3174 3662 0.01 0.7 4.9 9.13 Ti+dihydroxyfumaric acid Undissolved 9.14 TiOSO ₄ +DMAE 10 3197 2863 0.022 1.7 9.8 An attempt was made to dissolve Ti(OiPr) ₄ in various acidic solutions followed by partial neutralization with a base. This solution was then added to primary HA30W and dried to obtain 3.5% wt. Ti followed by activation at 650°C.
*969MS
DMAE=dimethylaminoethanol

Example 10: Solvation of Ti with peroxides

[00128] The catalysts listed in Table 10 (invention runs 10.1-10.43) were prepared in much the same way as those described previously herein, except that peroxide (usually H ₂ O ₂ ) was also added to the formulation instead of part or all of the amine or acid. Thus, the amount of amine used and, in some runs, the amount of acid used could be reduced, thereby reducing costs and emissions and resulting in a polymer with a higher HNLST.

[00129] In these experiments, 30 g of a Cr/silica catalyst sold as HA30W by WR Grace was weighed into a bowl. It had a specific surface area of about 500 m ² /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, typically H ₂ O ₂ , is then also added to the solution in the runs of the invention. Thereafter, 6.65 ml of titanium tetraisopropoxide was added to the aqueous solution, causing it to immediately precipitate as aqueous titanium dioxide. The amount of added titanium was equivalent to 3.5% wt. Ti based on dry weight of Cr/silica. The amount of acid and peroxide used varied in each experiment, but both amounts are given in Table 10 as acid or peroxide equivalents added per titanium equivalent. The precipitated slurry was stirred until the titanium dioxide dissolved in an orange or dark red solution (when H ₂ O ₂ was present), usually after about 10 minutes. In cases where the titanium dioxide did not dissolve quickly, stirring was continued for several hours before it was finally concluded that no soluble complex had formed and the experiment was stopped. Table 10 shows some control runs.

[00130] However, when a soluble complex did form, the next step in some experiments was to add a nitrogen compound to the solution, while in other experiments no nitrogen compound was used. The nitrogen compound was always dissolved in the titanium solution. Again, the amount of nitrogen compound is given in Table 10 as nitrogen compound equivalents per titanium equivalent. Finally, the titanium solution was added to the Cr/silica mixture in the bowl and mixed by hand for several minutes to obtain a constantly moist (but not wet) powder, i.e. to the initial moisture content. 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 sieve to break up any small soft lumps. A sample of the resulting titanium-containing catalyst was calcined for 3 hours in dry air at 650°C. It was then recovered under a dry nitrogen atmosphere and stored for later use.

[00131] Control Run 10.2 shows that although two equivalents of oxalic acid can dissolve titanium dioxide, the resulting VNPTP is better than that obtained using a Cr/silica catalyst in the absence of titanium dioxide (Table 1, Run 1.12). In other words, titanation was ineffective only with oxalic acid. Control 10.2 serves as a baseline for other later experiments. Any VNPTR above 5-7 indicates an improvement in the effectiveness of the titanation procedure.

[00132] Referring to Table 10, it was observed that the addition of peroxide causes titanium dioxide to dissolve in many acids that cannot dissolve Ti in the absence of peroxide. Some of these acids gave very high VNLTR. But it can also be seen that even in those cases where titanium dioxide was soluble without peroxide, the addition of peroxide significantly improved the HLTR from the catalyst. Additionally, in many experiments the amount of nitrogen compound used could be reduced, and in some cases the nitrogen compound could be eliminated entirely by adding peroxide. Since the nitrogen compound causes unwanted emissions during calcination, this reduction is a great improvement.

[00133] In Table 11, various combinations of organic acids (and/or nitrogen compounds) were used to further reduce emissions and maximize HNLTR. Many of these experiments further exploited the aforementioned ability of H ₂ O ₂ to dissolve Ti and reduce nitrogen compounds or even acidic ligands. In these experiments (11.44-11.60 according to the invention), the catalysts were prepared exactly as described earlier in this document. That is, 30 g of Cr/silica was weighed into a bowl, and 50 ml of deionized water was weighed into a 100 ml beaker. Acids were dissolved in water along with H ₂ O ₂ when used. 6.65 ml of titanium tetraisopropoxide (3.5 wt% Ti by weight of Cr/silica) was then added and it immediately precipitated as aqueous titanium dioxide. However, after briefly stirring for about 10 min, the Ti dissolved. The nitrogen compound was then added, if added at all, and the solution was added to the dry catalyst until the initial moisture content was reached. Drying and calcination were carried out as described above.

[00134] Only in experiment 11.44 according to the invention, the protocol was slightly different. In it, 30 g of silica (not Cr/silica) was weighed into a bowl. The silica was EP30X from Philadelphia Quartz Corp., having a specific surface area of 300 m ² /g. Again, 50 ml of deionized water was measured into the beaker, followed by acids, H ₂ O ₂ and 6.65 ml of titanium isopropoxide. After dissolving the Ti, 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. It should also be noted that acidic phenols can replace organic acid to create effective ligands. Thus, several runs are shown with catechol and salicylic alcohol instead of carboxylic acid.

[00135] Table 11 lists some large acids that were unable to dissolve titanium dioxide until a small amount of a smaller acid was also added. For example, in Run 11.56 of the invention, catechol was ineffective until combined with a small amount of oxalic acid. Likewise, salicylic acid, ineffective on its own, dissolved Ti and gave a high HLST when one equivalent of oxalic acid was also added (run 11.54 of the invention). A similar result was obtained with salicylic alcohol in runs 11.52 and 11.53 of the invention, 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.

Table 10: Solvation of titanium with carboxylic acid, peroxide and partial neutralization Run no. Comments Catalyst Polymer Time, Performance, Activity, VNPTR, I10, PTR, Shift, emissions, G G min y/y y/y/h dg/min dg/min dg/min VNPTR/PTR Potential Control 1 1 oxalic acid, insoluble -2.0 Example 1 according to the invention 1 oxalic acid+7 H2O2 0.0499 151 66 3026 2751 14.1 2.79 0.085 166 -2.0 Control 2 2 oxalic acid 0.0582 163 0 2800 2560 6.9 1.20 0.010 722 -4.0 2 according to the invention 2 oxalic acid+22 H2O2 0.0671 212 109 3159 1739 12.3 2.36 0.059 208 -4.0 3 according to the invention 2 oxalic acid+7 H2O2+2 DMF 0.0876 244 81 2785 2063 39.9 7.39 0.487 82 8.0 4 according to the invention 2 oxalic acid+2 tert-butyl hydroperoxide 0.0576 170 40 2951 4427 14.1 2.71 0.067 212 10.0 5 according to the invention 2 oxalic acid+7 H2O2+2 DMF 0.0473 146 50 3087 3704 43.2 8.88 - 0.505 86 8.0 6 according to the invention 2 oxalic acid+7 H2O2+2 DMF+1 NH4OH 0.0651 214 100 3287 1972 34.1 7.05 0.422 81 8.0 Control 3 2 glycolic acid, insoluble 0.0 7 according to the invention 2 glycolic acid+7 H2O2 0.0611 171 0 2800 2950 14.5 3.00 0.121 120 0.0 8 according to the invention 2 glycolic acid+15 H2O2+1 MeNH2 0.0814 226 49 2776 3400 23.2 4.77 0.196 118 4.0 9 according to the invention 2 glycolic acid+7 H2O2+3 DMF 0.0292 82 71 2808 2373 24.7 4.27 0.230 107 18.0 Control 4 3 glycolic acid, insoluble 0.0 10 according to the invention 3 glycolic acid+14 H2O2 0.0558 157 63 2814 2680 7.7 1.31 0.007 1097 0.0 11 according to the invention 3 glycolic acid+7 H2O2+1.3 DMAE 0.0486 185 47 3807 4859 32.0 6.65 0.247 130 10.8 Control 5 4 Glycolic acid, insoluble after 1 day 0.0 Control 6 4 glycolic acid after 4 days 0.0723 224 56 3098 3320 5.7 0.97 0.006 946 0.0 12 according to the invention 4 glycolic acid+7 H2O2 +1.6 ethanolamine 0.0669 196 63 2930 2790 19.9 3.90 0.161 124 8.0 13 according to the invention 4 glycolic acid+7 H2O2 + +1.6 DMF 0.0948 310 76 3270 2582 17.4 3.31 0.105 166 8.0 Control 7 2 Lactic acid, insoluble for 2 days 4.0 14 according to the invention 2 lactic acid+7 H2O2 0.0547 150 0 2744 1953 14.3 1.15 0.110 130 4.0 15 according to the invention 2 lactic acid+7 H2O2+2 H2NOH 0.0470 123 86 2617 1826 21.7 4.17 0.155 140 6.0 16 according to the invention 2 lactic acid+7 H2O2+2 MeNH2 0.0430 141 52 3279 3784 30.7 8.27 0.384 80 12.0 17 according to the invention 2 lactic acid+7 H2O2+2 H2NOH 0.0470 123 86 2617 1826 21.7 4.17 0.155 140 6.0 18 according to the invention 2 lactic acid+7 H2O2+3 DMF 0.1086 221 71 2035 1720 86.2 17.19 1,293 67 22.0 Control 8 3 lactic acid 0.0803 180 Reference 2242 1933 6.7 1.10 0.009 741 6.0 19 according to the invention 3 lactic acid+7 H2O2 0.0506 176 49 3478 4259 28.5 5.96 0.300 95 6.0 20 according to the invention 3 lactic acid+7 H2O2+1.5 NH4OH 0.0556 165 45 2968 3957 26.9 5.39 0.256 105 9.0 21 according to the invention 3 lactic acid+7 H2O2+1 DMAE 0.0537 170 42 3166 4522 40.7 9.08 0.531 77 15.0 22 according to the invention 3 lactic acid+7 H2O2+2 DMF 0.0576 192 99 3333 2020 68.5 13.89 0.983 70 18.0 Control 9 2 malic acid, insoluble in 2 days 2.0 23 according to the invention 2 malic acid+7 H2O2 0.0928 240 58 2586 2675 12.5 2.33 0.100 125 2.0 Control 10 2 malonic acid, insoluble in 1 day 0.0 24 according to the invention 2 malonic acid+7 H2O2 0.0347 96 39 2767 4256 9.3 1.76 0.018 520 0.0 Control 11 3 citric acid 0.0459 132 Reference 2877 3144 5.17 1.02 0.008 646 6.0 Control 12 3 citric acid 0.0521 120 53 2303 2607 4.30 0.48 0.008 538 6.0 25 according to the invention 3 citric acid+7 H2O2 0.0594 171 43 2879 4017 11.5 2.17 0.032 364 6.0 Control 13 3 glyceric acid, insoluble in 2 days 3.0 26 according to the invention 1.2 glyceric acid+7 H2O2 0.0608 24 10 395 2368 15.7 2.90 0.099 158 1.2 27 according to the invention 1.2 glyceric acid+7 H2O2 0.0622 234 76 3762 2970 10.5 1.98 0.019 550 1.2 Control 14 2 tartaric acid 0.0610 180 68 2950 2988 5.9 1.20 0.008 743 -1.0 28 according to the invention 2 tartaric acid+14 H2O2 0.0206 58 94 2816 1797 7.4 1.27 0.009 818 -1.0 Control 15 2 gluconic acid, insoluble 9.0 29 according to the invention 2 gluconic acid+7 H2O2 0.0482 137 41 2842 4159 10.9 2.02 0.029 379 9.0 30 according to the invention 2 gluconic acid+7 H2O2+5 NH3 0.0702 210 89 2991 2017 8.9 1.63 0.022 406 -1.0 Control 16 2 mandelic acid, insoluble in 2 days 16.0 31 according to the invention 2 mandelic acid+7 H2O2 0.0698 13 10 186 1117 10.3 2.10 0.027 381 16.0 32 according to the invention 2 mandelic acid+7 H2O2 0.0487 132 46 2710 3535 24.5 4.87 0.236 104 16.0 33 according to the invention 2 mandelic acid+7 H2O2+9 NH3 0.0664 205 54 3087 3430 16.9 3.16 0.099 170 34.0 Control 17 3 mandelic acid, insoluble in 2 days 24.0 34 according to the invention 3 mandelic acid+7 H2O2 0.0279 108 43 3871 5401 42.1 8.96 0.505 83 24.0 Control 18 2-(2,4-OH)benzoic acid, insoluble in 1 day 10.0 35 according to the invention 2 (2,4-OH)benzoic acid+7 H2O2 0.0496 136 52 2742 3164 17.7 3.38 0.110 161 10.0 Control 19 2 2,6-pyridine dicarboxylic acid, insoluble within 1 day 10.0 36 according to the invention 2 2,6-pyridinedicarboxylic acid+7 H2O2 0.0540 176 51 3259 3834 55.2 12.38 0.759 73 10.0 Control 20 2 nitrilotriacetic acid, insoluble in 1 day 8.0 37 according to the invention 2 nitrilotriacetic acid+7 H2O2+5 NH4OH 0.0683 230 80 3367 2526 9.9 1.74 0.022 452 18.0 Control 21 2 α-OH-isobutyric acid, insoluble 8.0 38 according to the invention 2 α-OH-isobutyric acid+7 H2O2 0.0375 119 57 3173 3340 10.9 2.15 0.064 170 8.0 39 according to the invention 2 α-OH-isobutyric acid+7 H2O2 0.0591 185 92 3130 2041 16.1 3.0 0.093 174 8.0 40 according to the invention 2 α-OH-isobutyric acid+14 H2O2 0.0692 128 34 1850 3264 21.5 4.32 0.185 116 8.0 Control 22 3 α-OH-isobutyric acid, insoluble within 2 days 12.0 41 according to the invention 3 α-OH-isobutyric acid+7 H2O2 0.0596 189 54 3171 3523 47.1 10.35 0.618 76 12.0 42 according to the invention 3 α-OH-isobutyric acid+7 H2O2 0.0459 103 40 2244 3366 65.6 14.17 0.855 77 12.0 43 according to the invention 3 α-OH-isobutyric acid+7 H2O2 0.0392 117 51 2985 3511 62.1 12.94 0.824 75 12.0 The target titanium content level was 3.5% wt. Ti. This is considered 1 Ti equivalent. An attempt was made to dissolve 1 equivalent of titanium dioxide with the indicated amount equivalents of carboxylic acid and the specified amount of equivalents of H2O2 and/or base. After impregnation of silica with Ti solution, the resulting mixture was dried in a vacuum oven at 100 ° C overnight, and then part of the catalyst calcined in dry air at 650 °C for 3 hours. DMAE=dimethylaminoethanol, DMF=dimethylformamide Table 11: Solvation of Ti with peroxide and acids Run no. Comments Catalyst Polymer Time, Performance, Activity, VNPTR, I10, PTR, Shift, emissions, G G min y/y y/y/h dg/min dg/min dg/min VNPTR/PTR Potential 44 according to the invention 1 oxalic acid+2 α-OH-isobutyric acid+7 H2O2 0.0328 107 78 3262 2509 16.2 3.11 0.105 154 6.0 45 according to the invention 2 lactic acid+1 oxalic acid+2 DMAE 0.0627 185 44 2951 4023 38.7 8.06 0.441 88 20.0 Control 23 2 methylmalonic acid + 7 H2O2, insoluble 4.0 46 according to the invention 2 methylmalonic acid+1 oxalic acid+7 H2O2 0.0847 207 62 2444 2365 14.8 2.88 0.081 184 2.0 47 according to the invention 1 or 2 iminodiacetic acid, insoluble 6.0 48 according to the invention 1 iminodiacetic acid+1 oxalic acid+7 H2O2 0.0473 128 47 2706 3455 16.4 3.23 0.106 155 1.0 Control 24 2 diglycolic acid + 14 H2O2, insoluble 2.0 49 according to the invention 2 diglycolic acid+14 H2O2+2 oxalic acid 0.0466 136 60 2918 2918 11.4 2.07 0.039 292 -2.0 50 according to invention 2 phenylmalonic acid + 14 H2O2, does not dissolve Ti 16.0 51 according to the invention 2 phenylmalonic acid + 1 oxalic acid 0.0617 185 58 2998 3102 17.0 3.35 0.114 149 14.0 Control 25 3 salicylic alcohol+7 H2O2 0.0597 160 99 2680 1624 3.5 0.52 24.0 52 according to the invention 1 oxalic acid+2 salicylic alcohol+7 H2O2 0.0586 188 43 3208 4477 10.6 1.81 0.021 511 14.0 53 according to the invention 2 lactic acid+7 H2O2+2 salicylic alcohol 0.052 148 53 2846 3222 12.4 2.37 0.058 213 20.0 54 according to the invention 1 salicylic acid + 2 oxalic acid 0.0488 198 78 4057 3121 19.2 3.77 0.145 133 2.0 55 according to the invention 3 catechol, insoluble 18.0 Control 26 2 catechol + 1 lactic acid, insoluble 14.0 Control 27 1 catechol + 2 lactic acid, insoluble 10.0 56 according to the invention 1 catechol + 1.4 oxalic acid 0.0595 185 66 3109 2827 10.0 1.81 0.029 348 3.2 58 according to the invention 2 (HO-Me)2-butyric acid+1 oxalic acid+7 H2O2 0.0340 107 39 3147 4842 22.4 4.47 0.245 91 12.0 59 according to the invention 2 (HO-Me)2-butyric acid+1 oxalic acid+7 H2O2+ 1.7 DMAE 0.0415 125 33 3012 5476 33.4 6.86 0.345 97 27.3 The target titanium content level was 3.5% wt. Ti. This is considered 1 Ti equivalent. An attempt was made to dissolve 1 equivalent of titanium dioxide with the indicated amount equivalents of carboxylic acid and the specified amount of equivalents of H2O2 and/or base. After impregnation of silica with Ti solution, the resulting mixture was dried in a vacuum oven at 100 ° C overnight, and then part of the catalyst calcined in dry air at 650 °C for 3 hours. DMAE=dimethylaminoethanol, DMF=dimethylformamide

ADDITIONAL DISCLOSURE - PART 1

[00136] The following listed aspects of this disclosure are presented as non-limiting examples.

[00137] The first aspect is a method comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) bringing contacting the titanium-containing compound and the acidic mixture to form an acidic titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting the nitrogen-containing compound and the acidic titanium mixture forming a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5.5, and d) bringing into contact a chromium-silica carrier containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form an adduct; and drying the adduct by heating the adduct 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 a time of about 30 minutes to about 6 hours to form the pre-catalyst.

[00138] The 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 the range of about 400°C to about 1000°C and maintaining the temperature of the pre-catalyst in the range of about 400°C C to about 1000°C for a period of time from about 1 minute to about 24 hours to form the catalyst.

[00139] The third aspect, which is a method according to any of the first two aspects, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the acidic titanium mixture is about 1:2, and the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is about 1:2.

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

[00141] The fifth aspect, which is a method according to any of the first four aspects, wherein (c) involves neutralizing the acidic titanium mixture, and wherein the neutralization is partial neutralization or complete neutralization.

[00142] The sixth aspect, which is a method according to 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: where each of R ¹ , R ² , R ³ , R ⁹ , R ¹⁰ and R ¹¹ independently represent hydrogen, an organic C ₁ -C ₁₂ group or an aryl C ₆ -C ₁₂ group; R ⁴ represents an organic C ₁ -C ₁₂ group or an aryl C ₆ -C ₁₂ group; each of R ⁵ and R ⁶ independently represents hydrogen, an organic C ₁ -C ₆ group or an aryl C ₆ -C ₁₂ group; R ⁷ and R ⁸ are each independently hydrogen or CH ₃ ; R ¹² represents a branched alkyl C ₁ -C ₆ group, a cyclic alkyl C ₁ -C ₆ group or a linear alkyl C ₁ -C ₆ group; x is an integer from 1 to 4, y is an integer from 1 to 12, and Z is oxygen or sulfur.

NR ¹ R ² R ³ N(R ⁴ ) _x H _(4-x) OH NR ⁵ R ⁶ (CR ⁷ R ⁸ ) _yOH Structure 1 Structure 2 Structure 3 NR ⁹ R ¹⁰ OH Z=C(N(R ¹¹ ) ₂ ) ₂ N(R ¹² OH) ₃ Structure 4 Structure 5 Structure 6

[00143] The seventh aspect, which is a method according to any of the first six aspects, wherein the nitrogen-containing compound includes an alkanolamine, an amine, ammonium hydroxide, hydroxylamine, urea, or a combination thereof.

[00144] The eighth aspect, which is a method according to any of the first seven aspects, in which the nitrogen-containing compound includes acetamide, ammonia, ammonium hydroxide, tert -butylamine, creatine, N,N'-dibutylurea, diethanolamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N,N'-dimethylurea, ethanolamine, glycolamine, hexylamine, hydroxylamine, imidazole, isopropanolamine, N-methylaniline, methyldiethanolamine, methylformamide, pyrazole, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea or their combination.

[00145] The ninth aspect, which is a method according to any of the first eight aspects, in which the carboxylic acid includes a C ₁ -C ₁₅ monocarboxylic acid, a C ₂ -C ₁₅ dicarboxylic acid, a C ₃ -C ₁₅ tricarboxylic acid, C ₁ -C ₁₅ α-hydroxycarboxylic acid or a combination thereof.

[00146] The tenth aspect, which is a method according to any of the first nine aspects, wherein the carboxylic acid includes acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid, or a combination thereof.

[00147] The eleventh aspect, which is a method according to any of the first ten aspects, wherein the titanium-containing compound includes titanium hydroxide, titanic acid, titanyl sulfate, titanium (IV) alkoxide, titanylacetylacetonate, titanium (IV) halide, or a combination thereof.

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

[00149] The thirteenth aspect, which is a method according to any of the first twelve aspects, wherein (d) further comprising spray drying the solubilized titanium mixture on a chromium silica support.

[00150] A fourteenth aspect, which is a method according to any of the first thirteen aspects, wherein the chromium silica support has a specific surface area of about 100 m ² /g to about 1000 m ² /g and a pore volume of about 1.0 cm ³ /g to about 2.5 cm ³ /g.

[00151] The fifteenth aspect, which is a method according to any of the first fourteen aspects, in which the amount of chromium present in the catalyst is from about 0.01% by weight. up to about 10% wt. of the total weight of the catalyst, and the amount of titanium present in the catalyst ranges from about 0.01% wt. up to about 10% wt. of the total mass of the catalyst.

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

[00153] The seventeenth aspect, which is a method for forming an ethylene polymer, comprising contacting a catalyst obtained by the method of the second aspect with an ethylene monomer under conditions suitable for the formation of an ethylene polymer, and isolating the ethylene polymer.

[00154] The eighteenth aspect, which is the method of the seventeenth aspect, wherein the ethylene polymer has a high-stress melt flow index (HSMLF) that is from about 1.5 to about 15 times higher than the HSLFR of an ethylene polymer produced at the same time. all other catalysts obtained in the absence of a nitrogen-containing compound.

[00155] A nineteenth aspect, which is a method comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the mass ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b ) contacting the titanium-containing compound and the acidic mixture to form an acidic titanium mixture in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting the nitrogen-containing compound and the acidic mixture titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4 ,5, and d) bringing into contact a silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form a titanium support; and drying the titanium support by heating to a temperature ranging from about 50° C. to about 150° C. and maintaining the temperature in a 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 dried titanium support, and e) contacting to form a precatalyst a chromium-containing compound and at least one material selected from the group consisting of a silica support, a titanium support, and a dried titanium support.

[00156] The twentieth aspect, which is the method of the nineteenth aspect, further comprising e) calcining the pre-catalyst by heating to a temperature in the range of about 400°C to about 1000°C and maintaining the temperature in the range of about 400°C to about 1000 °C for a period of time from about 1 minute to about 24 hours to form the catalyst.

[00157] The twenty-first aspect, which is the method of the nineteenth aspect, wherein (c) involves neutralizing the acidic titanium mixture, and wherein the neutralization is partial neutralization or complete neutralization.

[00158] A twenty-second aspect, which is a method comprising a) contacting a titanium-containing compound and a nitrogen-containing compound to form a base mixture, in which the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in the base mixture is from about 1:1 to about 1 :4, b) contacting a solvent and a carboxylic acid to form an acidic mixture in which the mass ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, c) contacting the base mixture and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4.5 , and d) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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.

[00159] The twenty-third aspect, which is the method of the twenty-second aspect, further comprising e) calcining the pre-catalyst by heating the pre-catalyst to a temperature in the range of about 400°C to about 1000°C and maintaining the temperature of the pre-catalyst in the range of about 400°C to about 1000°C for a period of time from about 1 minute to about 24 hours to form the catalyst.

[00160] Twenty-fourth aspect, which is a method comprising a) contacting a titanium-containing compound and a nitrogen-containing compound to form a base mixture, in which the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in the base mixture is from about 1:1 to about 1 :4, b) contacting a solvent and a carboxylic acid to form an acidic mixture in which the mass ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, c) contacting the base mixture and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is in the range of from about 3.5 to about 4.5 , d) bringing into contact a silica carrier containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form a titanium support; and drying the titanium support 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 dried titanium support, and e) contacting, to form a pre-catalyst, a chromium-containing compound and at least one material selected from the group consisting of a silica support, a titanium support and a dried titanium carrier.

[00161] The twenty-fifth aspect, which is the method of the twenty-fourth aspect, further comprising e) calcining the pre-catalyst by heating the pre-catalyst to a temperature in the range of about 400°C to about 1000°C and maintaining the temperature of the pre-catalyst in the range of about 400°C to about 1000°C for a period of time from about 1 minute to about 24 hours to form the catalyst.

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

[00163] The twenty-seventh aspect, which is the precatalyst composition of the twenty-sixth aspect, in which the carboxylic acid includes a C ₁ -C ₁₅ monocarboxylic acid, a C ₂ -C ₁₅ dicarboxylic acid, a C ₃ -C ₁₅ tricarboxylic acid, C ₁ -C ₁₅ α-hydroxycarboxylic acid or a combination thereof.

[00164] The twenty-eighth aspect, which is the precatalyst composition of any of the twenty-sixth or twenty-seventh aspects, wherein the carboxylic acid includes acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid, or a combination thereof.

[00165] The twenty-ninth aspect, which is a precatalyst composition according to any one of the twenty-sixth to twenty-eighth aspects, wherein the nitrogen-containing compound includes an alkanolamine, amide, amine, alkylamine, ammonium hydroxide, aniline, hydroxylamine, urea, or a combination thereof.

[00166] The thirtieth aspect, which is a precatalyst composition according to any one of the twenty-sixth to twenty-ninth aspects, wherein the nitrogen-containing compound includes acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, tert -butylamine, N,N'- dibutylurea, creatine, creatinine, diethanolamine, diethylhydroxyamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N,N'-dimethylurea, ethanolamine, ethylamine, glycolamine, hexylamine, hydroxylamine, imidazole, isopropanolamine, methacrylamide, methylamine, N-methylaniline , N-methyl-2-propanolamine, methyldiethanolamine, methylformamide, propylamine, 2-propanolamine, pyrazole, pyrrolidine, pyrrolidinone, succinimide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, 1,8-diazabicyclo[5.4.0 ]undec-7-ene or a combination thereof.

[00167] The thirty-first aspect, which is the precatalyst composition of any one of the twenty-sixth to thirtyth aspects, wherein the silica support further comprises alumina.

[00168] Thirty-second aspect, which is a precatalyst composition according to any one of the twenty-sixth to thirty-first aspects, wherein the silica support has a specific surface area of about 100 m ² /g to about 1000 m ² /g and a pore volume from about 1.0 cm ³ /g to about 2.5 cm ³ /g.

[00169] The thirty-third aspect, which is the precatalyst composition of any one of the twenty-sixth to thirty-second aspects, wherein the silica support comprises a hydrated silica support.

[00170] The thirty-fourth aspect, which is the precatalyst composition of any one of the twenty-sixth to thirty-third aspects, wherein the silica support contains from about 1% by weight. up to about 20% wt. water from the total mass of the silica carrier.

[00171] The thirty-fifth aspect is a pre-catalyst composition comprising a) a silica support containing silica, in which the amount of silica ranges from about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a protonated nitrogen-containing compound and a carboxylate, and 1) the amount of titanium is in the range of about 0.1% wt. up to about 20% wt. of the amount of silica, 2) the equivalent molar ratio of titanium to carboxylate ranges from about 1:1 to about 1:10, and 3) the equivalent molar ratio of titanium to protonated nitrogen-containing compound ranges from about 1:0.5 to about 1:10.

[00172] The thirty-sixth aspect, which is the precatalyst composition of the thirty-fifth aspect, wherein the protonated nitrogen-containing compound comprises a protonated alkanolamine, a protonated amide, a protonated amine, a protonated alkylamine, a protonated ammonium hydroxide, a protonated aniline, a protonated hydroxylamine, a protonated urea, or combination.

[00173] The thirty-seventh aspect is the precatalyst composition of the thirty-fifth aspect, wherein the protonated nitrogen-containing compound includes protonated acetamide, protonated acrylamide, protonated allylamine, ammonium, protonated ammonium hydroxide, protonated butylamine, protonated tert -butylamine, protonated N,N' -dibutylurea, protonated creatine, protonated creatinine, protonated diethanolamine, protonated diethylhydroxyamine, protonated diisopropanolamine, protonated dimethylaminoethanol, protonated dimethylcarbamate, protonated dimethylformamide, protonated dimethylglycine, protonated dimethylisopropanolamine, protonated N,N'-dimethylurea, protonated ethanolamine, protonated ethylamine, protonated glycolamine, protonated hexylamine, protonated hydroxylamine, protonated imidazole, protonated isopropanolamine, protonated methacrylamide, protonated methylamine, protonated N-methylaniline, protonated N-methyl-2-propanolamine, protonated methyldiethanolamine, protonated methylformamide, protonated propylamine, protonated 2-propanolamine, protonated pyrazole, protonated pyrrolidine, protonated pyrrolidinone, protonated succinimide, protonated tetraethylammonium hydroxide, protonated tetramethylammonium hydroxide, protonated triethanolamine, protonated triisopropanolamine, protonated trimethylamine, protonated urea, protonated 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination thereof.

[00174] The thirty-eighth aspect, which is a precatalyst composition according to any one of the thirty-fifth to thirty-seventh aspects, wherein the carboxylate comprises a C ₁ -C ₁₅ -monocarboxylate, a C ₂ -C ₁₅ -dicarboxylate, a C ₃ -C ₁₅ - tricarboxylate, C ₁ -C ₁₅ -α-hydroxycarboxylate, or a combination thereof.

[00175] The thirty-ninth aspect, which is the precatalyst composition of any one of the thirty-fifth to thirty-eighth aspects, wherein the carboxylate includes acetate, citrate, glycolate, oxalate, phosphonoacetate, or a combination thereof.

[00176] A fortieth aspect, which is a precatalyst composition according to any one of the thirty-fifth to thirty-ninth aspects, wherein the silica support further comprises alumina.

[00177] The forty-first aspect, which is a precatalyst composition according to any one of the thirty-fifth to fortieth aspects, wherein the silica support has a specific surface area of about 100 m ² /g to about 1000 m ² /g and a pore volume of about 1.0 cm ³ /g to about 2.5 cm ³ /g.

[00178] A forty-second aspect, which is a precatalyst composition according to any one of the thirty-fifth to forty-first aspects, wherein the silica support comprises a hydrated silica support.

[00179] The forty-third aspect, which is the precatalyst composition of any one of the thirty-fifth to forty-second aspects, wherein the silica support contains from about 1% by weight. up to about 20% wt. water from the total mass of the silica carrier.

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

[00181] The forty-first aspect, which is a precatalyst composition prepared by a process comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form an acidic titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the acidic titanium mixture is from about 1:1 to about 1:4, c) contacting a nitrogen-containing compound and an acidic titanium mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is less than about 5 ,5, and d) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

ADDITIONAL DISCLOSURE - PART 2

[00182] The following listed aspects of this disclosure are presented as non-limiting examples.

[00183] The first aspect, which is a method comprising a) contacting a solvent, a carboxylic acid and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100: 1b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of the titanium-containing compound and peroxide-containing compounds in the solubilized titanium mixture is from about 1:1 to about 1:20, c) bringing into contact a chromium-silica carrier containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[00184] The second aspect, which is the method of the first aspect, wherein the peroxide-containing compound includes hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide, or any combination thereof.

[00185] The third aspect, which is a method according to any of the first to second aspects, wherein the carboxylic acid includes a C ₁ -C ₁₅ monocarboxylic acid, a C ₂ -C ₁₅ dicarboxylic acid, a C ₃ -C ₁₅ tricarboxylic acid , C ₁ -C ₁₅ -α-hydroxycarboxylic acid or a combination thereof.

[00186] The fourth aspect, which is a method according to any of the first to third aspects, wherein the carboxylic acid includes 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, α-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid or a combination thereof.

[00187] The fifth aspect, which is a method comprising a) contacting a solvent, a carboxylic acid, a nitrogen-containing compound and a peroxide-containing compound to form an acidic mixture, in which the mass ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar the ratio of titanium-containing compound and peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20, c) bringing into contact a chromium-silica carrier containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[00188] The sixth aspect, which is the method of the fifth, in which the carboxylic acid includes a C ₁ -C ₁₅ monocarboxylic acid, a C ₁ -C ₁₅ dicarboxylic acid, a C ₂ -C ₁₅ tricarboxylic acid, a C ₁ -C ₁₅ α-hydroxycarboxylic acid or a combination thereof.

[00189] The seventh aspect, which is a method according to any of the fifth to sixth aspects, wherein the carboxylic acid includes 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, α-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid or a combination thereof.

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

[00191] The ninth aspect, which is a method according to any one of aspects five to eight, wherein the peroxide-containing compound includes organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyethers, dialkyl peroxides, hydroperoxides, or a combination thereof.

[00192] The tenth aspect, which is a method according to any one of aspects five to nine, wherein the peroxide-containing compound includes hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide, or any combination thereof.

[00193] An eleventh aspect, which is a method comprising a) contacting a solvent, at least two carboxylic acids and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 up to about 100:1, and wherein the at least two carboxylic acids include at least one simple carboxylic acid and at least one complex carboxylic acid; b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar ratio of the titanium-containing compound to the peroxide-containing compounds in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[00194] The twelfth aspect, which is the method of the eleventh aspect, wherein the at least two carboxylic acids include a C ₁ -C ₁₅ monocarboxylic acid, a C ₂ -C ₁₅ dicarboxylic acid, a C ₃ -C ₁₅ tricarboxylic acid, C ₁ -C ₁₅ α-hydroxycarboxylic acid or a combination thereof.

[00195] The thirteenth aspect, which is a method according to any of the eleventh to twelfth aspects, wherein the at least two carboxylic acids include citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid acid, phosphonoacetic acid, tartaric acid, glyceric acid, gluconic acid, mandelic acid, 2,4-hydroxybenzoic acid, 2,6-pyridinedicarboxylic acid, nitrotriacetic acid, α-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid , hydroxymethyl-2-butyric acid, or a combination thereof.

[00196] The fourteenth aspect, which is the method of any of the eleventh to thirteenth aspects, wherein the peroxide-containing compound includes organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyethers, dialkyl peroxides, hydroperoxides, or a combination thereof.

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

[00198] A sixteenth aspect, which is a method comprising a) contacting a solvent, at least two carboxylic acids and a nitrogen-containing compound to form an acidic mixture, in which the mass ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4; and c) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[00199] A seventeenth aspect, which is a method comprising a) contacting a solvent, at least two carboxylic acids, a nitrogen-containing compound and a peroxide-containing compound to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4 , and the equivalent molar ratio of titanium-containing compound and peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20, c) contacting a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

[00200] The eighteenth aspect, which is a method comprising a) contacting a solvent, a carboxylic acid, an acidic phenol and a peroxide-containing compound to form an acidic mixture, in which the mass ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and the equivalent molar the ratio of the titanium-containing compound to the acidic phenol in the solubilized titanium mixture is from about 1:1 to about 1:5, and wherein the equivalent molar ratio of the titanium-containing compound to the peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) bringing into contact a chromium-silica support containing from about 0.1% wt. up to about 20% wt. water, and a solubilized titanium mixture to form the adduct, and drying the adduct 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 for the pre-catalyst to form.

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

[00202] The twentieth aspect, which is a method comprising a) contacting a solvent, a carboxylic acid, an acidic phenol and a peroxide-containing compound to form an acidic mixture, in which the mass ratio of the solvent to the carboxylic acid in the acidic mixture is from about 1:1 to about 100:1, b) contacting the titanium-containing compound and the acidic mixture to form a solubilized titanium mixture, in which the equivalent molar ratio of the titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4, and in which the equivalent molar ratio of titanium-containing compound to acidic phenol in the solubilized titanium mixture is from about 1:1 to about 1:5, and wherein the 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 into contact with a chromium-containing compound to form a chromium-titanium mixture; d) contacting the chromium-titanium mixture with a silica support containing silica, in which the amount of silica is in the range of about 70% wt. up to about 95% wt. from the total mass of the silica support, with the formation of the adduct; and e) drying the adduct 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. formation of a pre-catalyst.

[00203] The twenty-first aspect, which is a method comprising a) producing an acidic mixture containing 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 the weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) reacting the acidic mixture with the chromium-containing compound, the titanium-containing compound and the silica support to form an adduct, wherein: (1) the equivalent molar ratio of the titanium-containing compound to the carboxylic acid, if present in the acidic mixture, is from about 1:1 to about 1:4, (2) the equivalent molar ratio of titanium-containing compound to acidic phenol when present in the acid mixture is from about 1: to about 1:5, and (3) the equivalent molar ratio of titanium-containing compound to peroxide-containing compound when present in an acidic mixture, ranges from about 1:1 to about 1:20; and c) drying the adduct 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 formation of a pre-catalyst.

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

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

[00206] The twenty-fourth aspect, which is a composition according to any of the twenty-second to twenty-third aspects, wherein the carboxylic acid includes a C ₁ -C ₁₅ monocarboxylic acid, a C ₂ -C ₁₅ dicarboxylic acid, a C ₃ -C tricarboxylic acid ₁₅ -acid, C ₁ -C ₁₅ -α-hydroxycarboxylic acid, or a combination thereof.

[00207] A twenty-fifth aspect, which is a composition according to any one of aspects twenty-two to twenty-four, wherein the carboxylic acid includes 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, α-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid or a combination thereof.

[00208] The twenty-sixth aspect, which is a composition according to any of the twenty-third to twenty-fifth aspects, wherein the nitrogen-containing compound includes an alkanolamine, amide, amine, alkylamine, ammonium hydroxide, aniline, hydroxylamine, urea, or a combination thereof.

[00209] A twenty-seventh aspect, which is a composition according to any one of aspects twenty-two to twenty-six, wherein the peroxide-containing compound includes organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyethers, dialkyl peroxides, hydroperoxides, or a combination thereof.

[00210] A twenty-eighth aspect, which is a composition according to any one of aspects twenty-two to twenty-seven, wherein the peroxide-containing compound includes hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide, or any of these combination.

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

[00212] The thirtieth aspect, which is a composition containing a) a silica carrier containing silica, in which the amount of silica is in the range of about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a carboxylate and a peroxide-containing compound, and wherein the organotitanium salt contains 1) an amount of titanium in the range of about 0.1% wt. up to about 20% wt. based on the amount of silica, 2) an equivalent molar ratio of titanium to carboxylate ranging from about 1:1 to about 1:10, and 3) an equivalent molar ratio of titanium to peroxide-containing compound ranging from about 1:0.5 to about 1:20 .

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

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

[00215] The thirty-third aspect, which is a composition according to any one of aspects thirty to thirty-two, wherein the carboxylate includes acetate, citrate, gluconate, glycolate, glyoxylate, lactate, malate, malonate, oxalate, phosphonoacetate, tartrate, or a combination thereof.

[00216] The thirty-fourth aspect, which is a composition containing a) a silica carrier containing silica, in which the amount of silica is in the range of about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, c) a titanium-containing compound, in which the amount of titanium is in the range from about 0.01% wt. up to about 0.1% wt. based on the amount of silica, d) at least two carboxylic acids, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is in the range from about 1:1 to about 1:10, and e) a peroxide-containing compound, wherein the equivalent molar ratio of titanium-containing compound to the peroxide-containing compound is in the range of about 1:1 to about 1:10.

[00217] The thirty-fifth aspect, which is the composition of the thirty-fourth aspect, wherein the at least two carboxylic acids include at least one simple carboxylic acid and at least one complex carboxylic acid.

[00218] A thirty-sixth aspect, which is a composition of aspects thirty-four to thirty-five, wherein the peroxide-containing compound includes hydrogen peroxide, tert-butyl peroxide, or a combination thereof.

[00219] The thirty-seventh aspect, which is a composition of aspects thirty-four to thirty-six, further comprising an acidic phenol.

[00220] The twenty-eighth aspect, which is the composition of any of the thirty-four to thirty-seven aspects, further comprising a nitrogen-containing compound, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is in the range of about 1:0.5 to about 1: 10.

[00221] The thirty-ninth aspect, which is a composition containing a) a silica carrier containing silica, in which the amount of silica is in the range of about 70% by weight. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the organotitanium salt contains 1) an amount of titanium in the range of about 0.1% wt. up to about 20% wt. based on the amount of silica, 2) an equivalent molar ratio of titanium to carboxylate ranging from about 1:1 to about 1:10, and 3) an equivalent molar ratio of titanium to protonated nitrogen-containing compound ranging from about 1:0.5 to about 1: 10; and d) a peroxide-containing compound, wherein the equivalent molar ratio of titanium-containing compound to peroxide-containing compound is from about 1:1 to about 1:20.

[00222] The fortieth aspect, which is a composition containing a) a silica carrier containing silica, in which the amount of silica is in the range of about 70% wt. up to about 95% wt. based on the total weight of the silica support, b) a chromium-containing compound in which the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. from the amount of silicon dioxide, and c) an organotitanium salt, wherein the organotitanium salt contains titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein the organotitanium salt contains 1) an amount of titanium in the range of about 0.1% wt. up to about 20% wt. based on the amount of silica, 2) an equivalent molar ratio of titanium to carboxylate ranging from about 1:1 to about 1:10, and 3) an equivalent molar ratio of titanium to protonated nitrogen-containing compound ranging from about 1:0.5 to about 1: 10; and d) an acidic phenol, wherein the equivalent molar ratio of titanium-containing compound to acidic phenol in the acidic titanium mixture is from about 1:1 to about 1:5.

[00223] The forty-first aspect, which is a composition containing 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 the amount of chromium is in the range of about 0.1% wt. up to about 5% wt. on the amount of silicon dioxide; c) a titanium-containing compound, in which the amount of titanium is in the range from about 0.01% wt. up to about 0.1% wt. on the amount of silicon dioxide; and (1) wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid, if present, is in the range of about 1:1 to about 1:10; (2) wherein the equivalent molar ratio of titanium-containing compound to peroxide-containing compound, if present, is in the range of about 1:1 to about 1:10; (3) wherein the equivalent molar ratio of titanium-containing compound to acidic phenol, if present, in the acidic titanium mixture is from about 1:1 to about 1:5; and (4) wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound, if present, is in the 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 includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C to form a polymerization catalyst olefins

[00225] The forty-third aspect, which is a catalyst produced by the method of the fifth aspect, wherein the method further includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C to form an olefin polymerization catalyst.

[00226] The forty-fourth aspect, which is a catalyst produced by the method of the eleventh aspect, wherein the method further includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C to form an olefin polymerization catalyst.

[00227] A forty-fifth aspect, which is a catalyst produced by the method of the sixteenth aspect, wherein the method further includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C to form an olefin polymerization catalyst.

[00228] A forty-sixth aspect, which is a catalyst produced by the method of the seventeenth aspect, wherein the method further includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C to form an olefin polymerization catalyst.

[00229] The forty-seventh aspect, which is a catalyst produced by the method of the eighteenth aspect, wherein the method further includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C to form an olefin polymerization catalyst.

[00230] The forty-eighth aspect, which is a catalyst produced by the method of the twentieth aspect, wherein the method further includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400°C to about 1000°C to form an olefin polymerization catalyst.

[00231] A forty-ninth aspect, which is a catalyst prepared by the method of the twenty-first aspect, wherein the method further includes heating the pre-catalyst in the presence of air to a temperature in the range of about 400° C. to about 1000° C. to form an olefin polymerization catalyst .

[00232] The singular terms are intended, unless specifically stated otherwise, to include multiple alternatives, such as at least one. Although the compositions and methods are described herein as “comprising” various components or steps, the compositions and methods may also “substantially consist of” or “consist of” various components or steps. A particular attribute of a disclosed object may be disclosed as follows: attribute X may be A, B, or C. It is also contemplated that for each attribute the statement may be formulated as a list of alternatives such that the statement “attribute X is A, alternatively B or alternatively C" is also an aspect of this disclosure, whether or not this statement is expressly stated.

[00233] Although various aspects of the present invention have been shown and described, modifications thereto may be made by one skilled in the art without departing from the spirit and teachings of the present invention. The aspects of this disclosure described herein are illustrative only and are not intended to be limiting. Many variations and modifications of this disclosure are possible and are within the scope of this invention. In cases in which numerical ranges or limits are expressly stated, such express ranges or limits should be understood to include repeating areas or limits of similar magnitude falling within the expressly stated ranges or limits (e.g., from about 1 to about 10 includes 2, 3, 4, etc.; more than 0.10 includes 0.11, 0.12, 0.13, etc.). The use of the term “optional” in relation to any element of a claim means that the object element is required or, alternatively, not required. Both alternatives are intended to be within the scope of the claims. It should be understood that the use of broader terms such as “comprises”, “includes”, “having”, etc. provides support for narrower terms such as “consisting of”, “consisting essentially of”, “consisting of” mostly from."

[00234] Accordingly, the scope of protection is not limited to the description set forth above, but is limited only by the following claims, which scope includes all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as aspects of this disclosure. Thus, the claims provide further description and are in addition to the preferred aspects of this disclosure. Discussion of a reference in this disclosure is not an admission that it is prior art to the disclosure, especially any reference that may have a publication date after the priority date of this application. The disclosure of all patents, patent applications and publications set forth herein are hereby incorporated by reference to the extent that they provide illustrative, procedural or other details in addition to those set forth herein.

[00235] All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. In the event of any conflict, this application, including definitions, shall control. For all ranges disclosed herein, such ranges are intended to include any combination of the upper and lower limits mentioned, even if a particular combination is not specifically stated.

Claims (26)

1. A method for producing a pre-catalyst for the polymerization of olefins, including: contacting (i) a solvent, (ii) a carboxylic acid, (iii) a peroxide-containing compound, (iv) a titanium-containing compound, (v) a nitrogen-containing compound, (vi) a chromium-containing compound, and (vii) a silica support to form a mixture; And spray drying the mixture to obtain a pre-catalyst powder; wherein: the weight ratio of solvent to carboxylic acid in the mixture is from about 1:1 to about 100:1; the equivalent molar ratio of titanium-containing compound to carboxylic acid in the mixture is from 1:1 to 1:4; the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in the mixture is from 1:1 to 1:4; The pH of the mixture ranges from 3.5 to 4.5; And the silica carrier includes from 0.1 wt.% to 20 wt.% water. 2. The method of claim 1, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in the mixture is 1:2, and the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in the mixture is 1:2. 3. The method according to claim 1, in which the nitrogen-containing compound has structure 1, structure 2, structure 3, structure 4, structure 5 or structure 6: NR ¹ R ² R ³ N(R ⁴ ) _x H _{(4 - x)} OH NR ⁵ R ⁶ (CR ⁷ R ⁸ ) _yOH Structure 1 Structure 2 Structure 3 NR ⁹ R ¹⁰ OH Z=C(N(R ¹¹ ) ₂ ) ₂ N(R ¹² OH) ₃ Structure 4 Structure 5 Structure 6 Where each R ¹ , R ² , R ³ , R ⁹ , R ¹⁰ and R ¹¹ independently represents hydrogen, an organyl C ₁ -C ₁₂ group or an aryl C ₆ -C ₁₂ group; R ⁴ represents an organic C ₁ -C ₁₂ group or an aryl C ₆ -C ₁₂ group; each R ⁵ and R ⁶ independently represents hydrogen, an organic C ₁ -C ₆ group or an aryl C ₆ -C ₁₂ group; R ⁷ and R ⁸ are each independently hydrogen or CH ₃ ; R ¹² represents a branched alkyl C ₁ -C ₆ group, a cyclic alkyl C ₁ -C ₆ group or a linear alkyl C ₁ -C ₆ group; x is an integer from 1 to 4, y is an integer from 1 to 12, and Z is oxygen or sulfur. 4. The method of claim 1, wherein the nitrogen-containing compound comprises an alkanolamine, an amide, an amine, ammonium hydroxide, hydroxylamine, urea, or a combination thereof. 5. The method according to claim 1, in which the nitrogen-containing compound includes acetamide, ammonia, ammonium hydroxide, tert-butylamine, creatine, N,N'-dibutylurea, diethanolamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, acetamide, methylacetamide, dimethylacetamide, dimethylglycine , dimethylisopropanolamine, N,N'-dimethylurea, ethanolamine, glycolamine, hexylamine, hydroxylamine, imidazole, isopropanolamine, N-methylaniline, methyldiethanolamine, methylformamide, pyrazole, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethanolamine, triisopropanolamine, trimethylamine, urea, or a combination thereof. 6. The method according to claim 1, in which the carboxylic acid includes a monocarboxylic C ₁ -C ₁₅ acid, a dicarboxylic C ₂ -C ₁₅ acid, a tricarboxylic C ₃ -C ₁₅ acid, a C ₁ -C ₁₅ -α-hydroxycarboxylic acid or a combination thereof. 7. The method according to claim 1, in which the carboxylic acid includes acetic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, glyceric acid, mandelic acid acid, 2,4-hydroxybenzoic acid, 2,6-pyridinedicarboxylic acid, nitrotriacetic acid, α-hydroxyisobutyric acid, methylmalonic acid, phenylmalonic acid, digluconic acid, iminodiacetic acid, hydroxymethyl-2-butyric acid, or a combination thereof. 8. The method according to claim 1, wherein the equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the mixture is from 1:1 to 1:20. 9. The method of claim 1, wherein the peroxide-containing compound includes organic peroxides, diacyl peroxides, peroxydicarbonates, monoperoxycarbonates, peroxyketals, peroxyethers, dialkyl peroxides, hydroperoxides, or a combination thereof. 10. The method of claim 1, wherein the peroxide-containing compound includes hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide, or a combination thereof. 11. The method of claim 1, wherein the solvent includes an aqueous solvent, an alcohol, an organic solvent, or a combination thereof.