RU2774275C2 - Methods for producing a catalyst applying hydrated reagents - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to compositions of a catalyst precursor for olefin polymerisation. The composition of a catalyst precursor comprises : a) a silicon dioxide carrier containing silicon dioxide, wherein the amount of silicon dioxide is from approximately 70 wt.% to approximately 95 wt.% relative to the total mass of the silicon dioxide carrier; b) a chromium-containing compound, wherein the amount of chromium is from 0.1 wt.% to 5 wt.% relative to the amount of silicon dioxide; c) a titanium-containing compound, wherein the amount of titanium is from 0.1 wt.% to 20 wt.% relative to the amount of silicon dioxide; d) carboxylic acid, wherein the equivalent molar ratio of the titanium-containing compound to carboxylic acid is from 1:1 to 1:10; and e) a nitrogen-containing compound containing at least one nitrogen atom, wherein the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound is from 1:0.5 to 1:10. Also claimed is a composition of a catalyst precursor containing, instead of components c), d) and e), an organic salt of titanium, containing titanium, a protonated nitrogen-containing compound, and a carboxylate. The composition of the catalyst precursor is produced by a method including: a) bringing a solvent and a carboxylic acid into contact, resulting in an acidic mixture, wherein the mass ratio of the solvent to carboxylic acid in said acidic mixture is from 1:1 to 100:1; b) bringing a titanium-containing compound and an acidic mixture into contact, resulting in an acidic titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to carboxylic acid in said acidic titanium mixture is from 1:1 to 1:4; c ) bringing a nitrogen-containing compound and an acidic titanium mixture into contact, resulting in a solubilised titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in said solubilised titanium mixture is from 1:1 to 1:4, and the pH of the solubilised titanium mixture is less than 5.5; and d) bringing a chromium-silicon dioxide carrier containing from 0.1 wt.% to 20 wt.% water and solubilised titanium mixture into contact, resulting in an addition product, and drying said addition product by heating to a temperature in the range from 50°C to 150°C and maintaining the temperature in the range from 50°C to 150°C for a time from 30 minutes to 6 hours, resulting in a catalyst precursor.

EFFECT: development of an aqueous solution suitable for applying titanium to a catalyst carrier based on silicon dioxide, allowing for a reduction in the production cost of olefin polymerisation catalysts.

20 cl, 1 dwg, 11 tbl, 9 ex

Description

FIELD OF TECHNOLOGY

[0001] The present invention relates to catalyst compositions. More specifically, the present invention relates to methods for preparing compositions of catalysts for the polymerization of olefins and polymers obtained from these compositions.

BACKGROUND OF THE INVENTION

[0002] An economically important class of olefin polymerization catalysts includes chromium-silica-titanium (Cr/Si-Ti) catalysts derived from silica catalyst supports. Rigid drying of the components of water sensitive catalysts used to obtain Cr/Si-Ti catalysts increases the time and cost of production. The development of an aqueous solution suitable for supporting titanium on a silica-based catalyst support will reduce the cost of producing catalysts for the polymerization of olefins. Thus, there is a continuing need to develop new methods for the preparation of catalysts for the polymerization of olefins.

BRIEF DESCRIPTION OF THE INVENTION

[0003] Provided herein is a catalyst precursor composition comprising a) a silica carrier containing silica, wherein the amount of silica is from about 70% by weight. up to about 95% of the mass. based on the total weight of silicon dioxide carrier, b) chromium-containing compound, while the amount of chromium is from about 0.1% of the mass. up to about 5% of the mass. based on the amount of silicon dioxide, c) titanium-containing compound, while the amount of titanium is from about 0.1% of the mass. up to about 20% of the mass. based on the amount of silicon dioxide, d) a carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is from 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 from about 1:0.5 to about 1:10.

[0004] This document also describes the composition of the catalyst precursor, containing a) silicon dioxide media containing silicon dioxide, while the amount of silicon dioxide is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier, b) chromium-containing compound, while the amount of chromium is from about 0.1% of the mass. up to about 5% of the mass. based on the amount of silicon dioxide, and c) organotitanium salt, while the specified organotitanium salt contains titanium, protonated nitrogen-containing compound and carboxylate, and i) the amount of titanium is from about 0.1% of the mass. up to about 20% of the mass. based on the amount of silica, ii) the equivalent molar ratio of titanium to carboxylate is from about 1:1 to about 1:10, and iii) the equivalent molar ratio of titanium to protonated nitrogen-containing compound is from about 1:0.5 to about 1: ten.

[0005] Also provided herein is a catalyst precursor composition comprising a) a silica carrier containing silica, wherein the amount of silica is from about 70% by weight. up to about 95% of the mass. based on the total weight of silicon dioxide carrier, b) chromium-containing compound, while the amount of chromium is from about 0.1% of the mass. up to about 5% of the mass. based on the amount of silicon dioxide, c) titanium-containing compound, while the amount of titanium is from about 0.01% of the mass. up to about 0.1% of the mass. based on the amount of silicon dioxide, d) a carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is from 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 from about 1:0.5 to about 1:10.

[0006] Also described herein is a catalyst precursor composition obtained by 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 said acidic mixture is from about 1:1 to about 100:1, b) contacting a titanium-containing compound and an acidic mixture to obtain an acidic titanium mixture, while the equivalent molar ratio of a titanium-containing compound to carboxylic acid in said acidic titanium mixture is from about 1:1 to about 1:4, c ) contacting a nitrogen-containing compound and an acidic titanium mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in said 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 chromium-silica media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to form an adduct, and drying said 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 about 30 minutes to about 6 hours to form a catalyst precursor.

[0007] This document further provides a process comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said 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, wherein the equivalent molar ratio of the titanium-containing compound to the carboxylic acid in said acidic titanium mixture is from about 1:1 to about 1:4, c) contacting the nitrogen-containing compound, and an acidic titanium mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said 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 chromium-silicon dioxide media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to form an adduct, and drying said adduct by heating the adduct to a temperature in the range from about 50°C to about 150°C and maintaining the temperature of the adduct in the range from about 50°C to about 150°C over a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[0008] Also described herein is a process comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from about 1:1 to about 100:1 , b) contacting a titanium-containing compound and an acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said acidic titanium mixture is from about 1:1 to about 1:4, c) contacting a nitrogen-containing compound and an acidic titanium mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said 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, d) bringing into contact silicon dioxide media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to obtain a titanated carrier and drying said titanated carrier by heating the titanated carrier to a temperature in the range from about 50°C to about 150°C and maintaining the temperature of the titanated carrier in the range from about 50°C to about 150°C over a period of time from about 30 minutes to about 6 hours to obtain a dried titanized support, and e) bringing into contact, to obtain a catalyst precursor, a chromium-containing compound and at least one material selected from the group consisting of a silica support, a titanated support and dried titanized support.

[0009] Also described 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 titanium-containing compound to nitrogen-containing compound in said base mixture is from about 1:1 to about 1:4, b) contacting the solvent and carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from about 1:1 to about 100:1, c) contacting the base mixture, and an acidic mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said 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) contacting a chromium silica carrier containing total from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to form an adduct, and drying said adduct by heating the adduct to a temperature in the range from about 50°C to about 150°C and maintaining the temperature of the adduct in the range from about 50°C to about 150°C over a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[0010] Also provided 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 titanium-containing compound to nitrogen-containing compound in said base mixture is from about 1:1 to about 1: 4b) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from about 1:1 to about 100:1, c) contacting the base mixture and the acidic mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said 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, d) contacting a silica carrier containing from n approximately 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to obtain a titanated carrier and drying said titanated carrier by heating the titanated carrier to a temperature in the range from about 50°C to about 150°C and maintaining the temperature of the titanated carrier in the range from about 50°C to about 150°C over a period of time from about 30 minutes to about 6 hours to obtain a dried titanized support, and e) bringing into contact, to obtain a catalyst precursor, a chromium-containing compound and at least one material selected from the group consisting of a silica support, a titanated support and dried titanized support.

BRIEF DESCRIPTION OF GRAPHICS

[0011] The following figure is part of the present description of the invention and is included to further demonstrate some aspects of the present invention. The subject matter of the present invention may be better understood by reference to this figure in conjunction with a detailed description of the specific aspects presented herein.

[0012] The figure shows the relationship between the zeta potential and the pH value for silicon dioxide and titanium dioxide.

[0013] Although the subject matter described herein is susceptible to various modifications and alternative forms, only a few specific aspects have been shown in the graph as an example and are detailed below. The figure and the detailed description of such specific aspects are in no way intended to limit the scope or scope of the proposed subject matter or the appended claims. Rather, the figure and the detailed written description are provided to illustrate the present invention to a person skilled in the art and to enable such person to make and use the concepts provided herein.

DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention includes olefin polymerization catalysts and their precursors, methods for making olefin polymerization catalysts and their precursors, and methods for using olefin polymerization catalysts. In one aspect, the process of the present invention comprises contacting a silica support or a chromium silica support (ie support) with titanium to form a Cr/Si-Ti catalyst. The methodologies described herein involve the use of a solubilized titanium blend (STM) to facilitate the association of titanium with a carrier in the presence of water. As used herein, the methodology for preparing an olefin polymerization catalyst includes contacting a chromium silica support with an STM under conditions suitable for preparing the catalyst composition. An alternative methodology for preparing an olefin polymerization catalyst involves contacting a silica support with STM and chromium under conditions suitable for preparing the catalyst composition. Although such aspects may be described under a specific heading, said heading does not limit the disclosure contained therein. Moreover, the various aspects and implementations described herein may be combined in any manner.

[0015] Aspects of the present invention relate to catalyst compositions and catalyst precursor compositions. In one aspect, the catalyst composition comprises an olefin polymerization catalyst. In a further aspect, the olefin polymerization catalyst comprises a treated catalyst precursor composition. In yet another aspect, the treated catalyst precursor composition comprises a catalyst precursor that has been subjected to an activation treatment (eg, calcination) as described herein.

[0016] Catalyst precursor compositions are described herein. In one aspect, the catalyst precursor composition comprises a silica support, a chromium compound, a titanium compound, a carboxylic acid, and a nitrogen compound. Alternatively, the catalyst precursor composition contains a silica support, a chromium-containing compound, and an organotitanium salt.

[0017] In one aspect, the olefin polymerization catalyst and precursor of the present invention comprise a silica support. The silica support may be any silica support suitable for the preparation of the olefin polymerization catalyst and its precursor as described herein. In a further aspect, the preparation of the olefin polymerization catalyst and its precursor eliminates heat treatment of the silica support prior to contact with any other catalyst component. Therefore, a silica carrier suitable for use in the present invention may be referred to as a hydrated silica carrier. Without wishing to be limited by theory, a hydrated silica carrier includes a silica carrier in which water is released when said silica carrier is heated at a temperature of from about 180°C to about 200°C under vacuum for a period of time from about 8 hours to about 20 hours. According to an additional aspect, the silica carrier may contain from about 0.1% of the mass. up to about 20% of the mass. water; alternatively about 1% of the mass. up to about 20% of the mass. water; alternatively from about 1% of the mass. up to about 10% of the mass. water; or alternatively from about 0.1% of the mass. up to about 10% of the mass. water based on the total weight of silicon dioxide carrier.

[0018] A silica support suitable for use in the present invention may have a surface area and pore volume effective to provide an active olefin polymerization catalyst. According to one aspect of the present invention, the surface area of the silica carrier is 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 silicon dioxide carrier may further have a pore volume greater than about 0.9 ^cc /g; alternatively, more than about 1.0 ^cc /g; or alternatively, more than about 1.5 ^cc /g. According to one aspect of the present invention, the silica support provided has a pore volume in the range of about 1.0 cm ³ /g to about 2.5 cm ³ /g. The silicon dioxide carrier 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. In general, the average pore size of the silica support may be from about 10 angstroms to about 1000 angstroms. According to one aspect of the present invention, the average pore size of the silica carrier is from about 50 angstroms to about 500 angstroms; alternatively from about 75 angstroms to about 350 angstroms.

[0019] Silica carrier suitable for use in the present invention may contain more than about 50% of the mass. silicon dioxide; alternatively, more than about 80% of the mass. silicon dioxide; or alternatively more than about 95% of the mass. silicon dioxide based on the total weight of silicon dioxide carrier. According to one aspect, the amount of silicon dioxide in the silicon dioxide carrier is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier. 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 by contacting sodium silicate and a mineral acid. In a specific aspect, the silica support may be a hydrogel or a finished silica support, wherein said finished silica support has optionally been dried prior to being contacted with any other catalyst component. The silica support may contain additional components that do not adversely affect the catalyst, such as zirconia, alumina, thorium oxide, magnesium oxide, fluoride, sulfate, phosphate, or a combination thereof. In a specific aspect, the silica carrier of the present invention contains alumina. Non-limiting examples of silica carriers suitable for use in the present invention include ES70, which is a silica carrier material with a surface area of 300 m ² /g and a pore volume of 1.6 cm ³ /g, which is available from PQ Corporation, and V398400, which is a silicon dioxide carrier material available from Evonik.

[0020] According to a specific aspect of the present invention, a silica carrier suitable for use in the present invention contains chromium. The silica carrier containing chromium may be referred to as a chromium silica carrier or a chromium silica carrier. According to another aspect, the chromium-silica carrier has the characteristics described herein for the silica carrier, and additionally contains chromium. A non-limiting example of a chromium silica carrier is HW30A, which is a chromium silica carrier material available from W. R. Grace and Company.

[0021] The silicon dioxide carrier may be present in the olefin polymerization catalyst and its precursor in an amount of from about 50% by weight. up to about 99% of the mass.; or alternatively from about 80% of the mass. up to about 99% of the mass. As used herein, the percentage of silica carrier refers to the weight percent (% wt.) of silica carrier bound to the olefin polymerization catalyst, based on the total weight of the olefin polymerization catalyst after all processing steps have been completed (i.e., after activation by calcination). Alternatively, the percentage of silica support refers to the percentage by weight (wt %) of the silica support associated with the catalyst precursor, based on the total weight of the catalyst precursor after all relevant processing steps have been completed except activation by calcination.

[0022] According to a further aspect, the olefin polymerization catalyst and its precursor of the present invention contain chromium. The chromium source can be any chromium-containing compound capable of providing sufficient chromium to the olefin polymerization catalyst and its precursor. 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 chromium compounds soluble in hydrocarbons include tert-butyl chromate, bis(cyclopentadienyl)chromium(II), chromium(III) acetylacetonate, or a combination thereof. According to 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.

[0023] The amount of chromium present in the olefin polymerization catalyst can be from about 0.01 wt. up to about 10% wt.; alternatively from about 0.5% of the mass. up to about 5% wt.; alternatively from about 1% of the mass. up to about 4% wt.; or alternatively from about 2% of the mass. up to about 4% of the mass. based on the total weight of the olefin polymerization catalyst. In another aspect, the amount of chromium present in the olefin polymerization catalyst may be from about 1 wt. up to about 5% of the mass. based on the total weight of the olefin polymerization catalyst. As used herein, the percentage of chromium refers to the weight percent (wt %) of chromium bound to the olefin polymerization catalyst, based on the total weight of the olefin polymerization catalyst after all processing steps have been completed (i.e., after activation by calcination). In a further aspect, the amount of chromium present in the catalyst precursor may be from about 0.01 wt. up to about 10% wt.; alternatively from about 0.1% of the mass. up to about 5% wt.; alternatively from about 0.2% of the mass. up to about 2% wt.; or alternatively from about 0.5% of the mass. up to about 1.5% of the mass. based on the total weight of silica in the catalyst precursor. As used herein, percent chromium refers to the percent by weight (wt %) of chromium bound to the catalyst precursor, based on the total weight of silica in the catalyst precursor after all processing steps except activation by calcination have been completed.

[0024] According to a further aspect, the olefin polymerization catalyst and its precursor of the present invention contain titanium. The source of titanium can be any titanium-containing compound capable of providing sufficient titanium to the olefin polymerization catalyst and its precursor. According to a further aspect, the titanium-containing compound comprises a tetravalent titanium compound (Ti(IV)) or a trivalent titanium compound (Ti(III)). The Ti(IV) compound may be any compound containing Ti(IV); alternatively, the Ti(IV) compound may be any compound capable of releasing Ti(IV) forms when dissolved in solution. The Ti(III) compound may be any compound containing Ti(III); alternatively, the Ti(III) compound may be any compound capable of releasing Ti(III) forms when dissolved in solution.

[0025] According to one aspect, a titanium-containing compound suitable for use in the present invention includes a Ti(IV) compound containing at least one alkoxide group; or alternatively at least two alkoxide groups. Ti(IV) compounds suitable for use in the present invention include, but are not limited to, Ti(IV) compounds having the general formula TiO(OR ^K ) ₂ , Ti(OR ^K ) 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; "acac" is acetylacetonate; and "oxal" is 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-ethylhexoxide, or a combination thereof. . According to a specific aspect, the titanium-containing compound may be titanium (IV) isopropoxide.

[0026] In a further aspect, a titanium-containing compound suitable for use in the present invention may include hydrated titanium dioxide, titanium hydroxide, titanic acid, titanyl sulfate, titanium acetylacetonate, titanium hydroxyacetylacetonate, or a combination thereof.

[0027] According to another aspect, a titanium-containing compound suitable for use in the present invention may include titanium (IV) halide, non-limiting examples of which include titanium tetrachloride, titanium tetrabromide, titanium (IV) oxychloride, and titanium (IV) oxybromide. According to an additional aspect, the titanium (IV) halide may include a titanium alkoxyhalide with the general formula Ti(OR ^K ) _n Q _4-n ; where R ^K can be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or a combination thereof; where Q may be fluoride, chloride, bromide, iodide, or a combination thereof; and n may be an integer from 1 to 4.

[0028] The amount of titanium present in the olefin polymerization catalyst of the present invention may vary from about 0.01 wt. up to about 10% wt.; alternatively from about 0.5% of the mass. up to about 5% wt.; alternatively from about 1% of the mass. up to about 4% wt.; or alternatively from about 2% of the mass. up to about 4% of the mass. based on the total weight of the olefin polymerization catalyst. According to another aspect, the amount of titanium present in the olefin polymerization catalyst may vary from about 1 wt. up to about 5% of the mass. based on the total weight of the olefin polymerization catalyst. As used herein, the percentage of 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 all processing steps have been completed (i.e., after activation by calcination). According to an additional aspect, the amount of titanium present in the catalyst precursor proposed in the present invention may vary from about 0.01% of the mass. up to about 25% wt.; alternatively from about 0.1% of the mass. up to about 20% wt.; alternatively from about 0.5% of the mass. up to about 10% wt.; alternatively from about 1% of the mass. up to about 6% wt.; or alternatively from about 2% of the mass. up to about 4% of the mass. based on the total weight of silica in the catalyst precursor. As used herein, the percentage of titanium refers to the percentage by weight (% wt.) of titanium bound to the catalyst precursor, based on the total weight of silica in the catalyst precursor after all processing steps except activation by calcination have been completed.

[0029] According to one aspect, the olefin polymerization catalyst and its precursor of the present invention contain a carboxylic acid. The carboxylic acid may be a monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, α-hydroxycarboxylic acid, β-hydroxycarboxylic acid, 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 C ₁ -C ₁₅ dicarboxylic acid or C ₁ -C ₅ dicarboxylic acid; alternatively C ₁ -C ₁₅ tricarboxylic acid or C ₁ -C ₅ tricarboxylic acid; alternatively C ₁ -C ₁₅ α-hydroxycarboxylic acid or C ₁ -C ₅ β-hydroxycarboxylic acid; alternatively C ₁ -C ₁₅ β-hydroxycarboxylic acid or C ₁ -C ₅ α-hydroxycarboxylic acid; or alternatively C ₁ -C ₁₅ α-ketocarboxylic acid or C ₁ -C ₅ α-ketocarboxylic acid.

[0030] In a specific aspect, the carboxylic acid may be acetic acid, citric acid, gluconic acid, glycolic acid, glyoxalic acid, lactic acid, malic acid, malonic acid, oxalic acid, phosphonoacetic acid, tartaric acid, or a combination thereof. In yet another aspect, the carboxylic acid may be oxalic acid.

[0031] The equivalent molar ratio of titanium to carboxylic acid in the catalyst precursor of the present invention is 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 from about 1:1 to about 1:2.

[0032] According to one aspect, the catalyst for the polymerization of olefins and its precursor proposed in the present invention contain a nitrogen-containing compound. The nitrogen-containing compound may be any nitrogen-containing compound suitable for efficient titanation of the olefin polymerization catalyst and its precursor. According to an additional 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 ) _y OH Structure 1 Structure 2 Structure 3 NR ⁹ R ^10OH Z=C(N(R ¹¹ ) ₂ ) ₂ N(R ¹² OH) ₃ Structure 4 Structure 5 Structure 6

R^one, R², R³, R^four, R⁵, R⁶, R⁷, R^eight, R⁹, R^ten, R^eleven and R¹² in the applied nitrogen-containing compound described herein are independent structural elements of the nitrogen-containing compound in which they are present and are independently described herein. Independent descriptions of R^one, R², R³, R^four, R⁵, R⁶, R⁷, R^eight, R⁹, R^ten, R^elevenand/or R¹², given herein, can be used without limitation and in any combination to further describe any structure of nitrogen-containing compounds, including R^one, R², R³, R^four, R⁵, R⁶, R⁷, R^eight, R⁹, R^ten, R^elevenand/or R¹².

[0033] In general, each R^one, R², R³, R⁵, R⁶, R⁹, R^tenand/or R^elevenin the corresponding nitrogen-containing compound that contains R^one, R², R³, R⁵, R⁶, R⁹, R^tenR^elevenand/or R^eleven, may independently represent hydrogen, an organyl group, a hydrocarbyl group, or an aryl group. According to one aspect, each R^one, R², R³, R⁵, R⁶, R⁹, R^tenand/or R^eleven can independently represent C_one-C_thirtyan organo group; alternatively C_one-C₁₂ an organo group; or alternatively C_one-C₆organ group. According to one aspect, each R^one, R², R³, R⁵, R⁶, R⁹, R^tenand/or R^eleven can independently represent C_one-C_thirtya hydrocarbyl group; alternatively C_one-C₁₂a hydrocarbyl group; or alternatively C_one-C₆hydrocarbyl group. According to yet other aspects, each R^one, R², R³, R⁵, R⁶, R⁹, R^tenand/or R^eleven can independently represent C₆-C_thirtyan aryl group; or alternatively C₆-C₁₂aryl group. According to a further aspect, any organo group, hydrocarbyl group, or aryl group that can be used as R^one, R², R³, R⁵, R⁶, R⁹, R^tenand/or R^eleven in the nitrogen-containing compound of the present invention may or may not contain substituents. One skilled in the art will appreciate that the terms "alkyl", "organyl", "hydrocarbyl", and "aryl" are used herein in accordance with the definitions given in the IUPAC Compendium of Chemical Terminology, 2nd edition (1997).

[0034] R ⁴ in the corresponding nitrogen-containing compound that contains R ⁴ may be an organyl group, a hydrocarbyl group, or an aryl group. According to one aspect, R ⁴ may be a C ₁ -C ₃₀ organyl group; alternatively a C ₁ -C ₁₂ organyl group; or alternatively a C ₁ -C ₆ organyl group. According to one aspect, R ⁴ may be a C ₁ -C ₃₀ hydrocarbyl group; alternatively a C ₁ -C ₁₂ hydrocarbyl group; or alternatively a C ₁ -C ₆ hydrocarbyl group. In yet other aspects, R ⁴ may be a C ₆ -C ₃₀ aryl group; or alternatively a C ₆ -C ₁₂ aryl group. According to a further aspect, any organyl group, hydrocarbyl group, or aryl group that can be used as R ⁴ in the nitrogen-containing compound of the present invention may or may not contain substituents.

[0035] In a specific aspect, any substituted organyl group, substituted hydrocarbyl group, or substituted aryl group that can be used as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and/or R ¹¹ may contain one or more non-hydrogen substituents. Suitable non-hydrogen substituents for use in the present invention may be a halogen, a C ₁ -C ₁₂ hydrocarbyl 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 groups suitable for use in the present invention include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, phenoxy, toloxy, xyloxy, trimethylphenoxy, and benzoxy.

[0036] Each R ⁷ and/or R ⁸ in the corresponding nitrogen-containing compound that contains R ⁷ and/or R ⁸ may independently represent hydrogen or a methyl group.

[0037] R ¹² in the corresponding nitrogen-containing compound that contains R ¹² may be a branched alkyl group or a linear alkyl group. According to one aspect, R ¹² may be a branched C ₁ -C ₃₀ alkyl group; alternatively branched C ₁ -C ₁₂ alkyl group; or alternatively a branched C ₁ -C ₆ alkyl group. According to an additional 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.

[0038] In a further aspect, the structure 2 nitrogen compound of the present invention may have x, where x is an integer from 1 to 4. In one aspect, the structure 3 nitrogen compound may have y, where y is an integer a number from 1 to 12. According to a further aspect, the nitrogen-containing compound with structure 5 may have Z, where Z is oxygen or sulfur.

[0039] According to one aspect, a nitrogen-containing compound suitable for use in the present 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 compound may contain one or more substituent groups. In one aspect, any substituent group contained in any nitrogen-containing compound of the present invention may be a halogen, a C ₁ -C ₁₂ organyl group, a C ₁ -C ₁₂ hydrocarbyl group, a C ₁ -C ₁₂ hydrocarboxy group, or a combination thereof. The halogen used as a substituent group according to any aspect described herein may be fluorine, chlorine, bromine, or iodine. Non-limiting examples of C ₁ -C ₁₂ hydrocarboxy groups suitable for use in the present invention include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, phenoxy, toloxy, xyloxy, trimethylphenoxy, and benzoxy.

[0040] In a further aspect, non-limiting examples of specific nitrogen compounds suitable for use in the present invention include acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, t-butylamine, N,N'-dibutylurea, creatine, creatinine, diethanolamine , diethylhydroxyamine, diisopropanolamine, dimethylaminoethanol, dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N, N'-dimethylurea, ethanolamine, ethylamine, glycolamine, hexylamine, hydroxyamine, 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.

[0041] The equivalent molar ratio of titanium to nitrogen-containing compound in the catalyst precursor of the present invention is 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 from about 1:1 to about 1:2.

[0042] In a specific aspect, the catalyst precursor composition of the present invention comprises an organotitanium salt. In one aspect, the organotitanium salt-containing catalyst precursor composition further comprises a silica carrier and a chromium-containing compound, both of which are of the type previously described herein. In a further aspect, an organotitanium salt suitable for use in the present invention includes titanium, a protonated nitrogen compound, and a carboxylate.

[0043] According to one aspect, the organotitanium salt contains titanium. The titanium source can be any titanium-containing compound capable of providing sufficient titanium to the catalyst precursor as described herein. In a further aspect, the titanium source is a titanium-containing compound of the type previously described herein.

[0044] According to one aspect, the organotitanium salt includes a protonated nitrogen-containing titanium compound. The protonated nitrogen compound can be any protonated nitrogen compound capable of providing sufficient titanium to the catalyst precursor as described herein. In a further aspect, the protonated nitrogen compound may include the protonated form of any nitrogen compound of the type previously described herein.

[0045] In one aspect, the protonated nitrogen 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.

[0046] According to a further aspect, the protonated nitrogen 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 hydroxyamine, protonated isoprotonated imidazole , protonated methacrylamide, protonated methylamine, protonated N-methylaniline, protonated N-methyl-2-prop anolamine, 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 urea, protonated urea ,8-diazabicyclo[5.4.0]undec-7-ene or a combination thereof.

[0047] In yet another aspect, the organotitanium salt comprises a carboxylate. The carboxylate may be any carboxylate capable of providing sufficient titanium to the catalyst precursor as described herein. In one aspect, the carboxylate may include the anionic form of any carboxylic acid of the type previously described herein.

[0048] In a further aspect, the carboxylate includes C ₁ -C ₁₅ monocarboxylate, C ₁ -C ₁₅ dicarboxylate, C ₁ -C ₁₅ tricarboxylate, C ₁ -C ₁₅ α-hydroxycarboxylate, or a combination thereof.

[0049] In yet another aspect, the carboxylate includes acetate, citrate, gluconate, glycolate, glyoxylate, lactate, malate, malonate, oxalate, phosphonoacetate, tartrate, or a combination thereof.

[0050] According to an additional aspect, the amount of titanium present in the organotitanium salt proposed in the present invention can be from about 0.01% of the mass. up to about 20% wt.; alternatively from about 0.5% of the mass. up to about 10% wt.; or alternatively from about 1% of the mass. up to about 6% of the mass. based on the total weight of silica in the catalyst precursor described herein. In another aspect, the equivalent molar ratio of titanium to carboxylate in the organotitanium salt is 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. According to yet another aspect, the equivalent molar ratio of titanium to nitrogen-containing compound in the organotitanium salt is 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. According to a further aspect, the equivalent molar ratio of titanium to nitrogen-containing compound may be about 1:2.

[0051] According to one aspect of the present invention, a method for producing an olefin polymerization catalyst comprises the use of a solubilized titanium blend (STM). In a specific aspect, the STM of the present invention contains a carboxylic acid, a titanium compound, a nitrogen compound, and a solvent. In one aspect, the STM contains a carboxylic acid of the type used as a component of the catalyst precursor described herein. In a further aspect, the STM contains a titanium-containing compound of the type used as a component of the catalyst precursor described herein. In a further aspect, the STM contains a nitrogen-containing compound of the type used as a component of the catalyst precursor described herein.

[0052] According to an additional aspect, the STM proposed in the present 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 the present invention 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 a further aspect, an organic solvent suitable for use in the present invention 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 specific 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.

[0053] According to a specific aspect, the solubilized titanium mixture (STM) described herein includes an acidic mixture that can be obtained by bringing into contact a carboxylic acid and a solvent. According to one aspect, the STM is obtained by sequentially adding a titanium-containing compound, followed by adding a nitrogen-containing compound to the acidic mixture described herein. According to an alternative aspect, the titanium-containing compound and the nitrogen-containing compound can be contacted to form a base mixture, which is then contacted with an acidic mixture to form STM, as described herein. In a further aspect, the nitrogen compound used to form the base mixture may be a component of the aqueous solution.

[0054] In one aspect, the solubilized titanium blend (STM) of the present invention comprises an acidic blend in which the weight ratio of solvent to carboxylic acid is from about 1:1 to about 100:1; alternatively from about 1:1 to about 50:1; or alternatively from about 1:1 to about 10:1. According to a further aspect, the equivalent molar ratio of titanium-containing compound to carboxylic acid in STM is from about 1:1 to about 1:20; alternatively from about 1:1 to about 1:10; or alternatively from about 1:1 to about 1:4. In some aspects, the equivalent molar ratio of titanium-containing compound to carboxylic acid may be about 1:2. According to another aspect, the equivalent molar ratio of nitrogen-containing compound to carboxylic acid in STM is from about 1:5 to about 5:1; alternatively from about 0.5:1 to about 3:1; alternatively from about 0.5:1 to about 1.5:1; or alternatively from about 1.5:1 to about 2.5:1.

[0055] According to another additional aspect, the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in STM is from about 1:5 to about 5:1; alternatively from about 1:4 to about 2:1; alternatively from about 1:3 to about 1:1; or alternatively from about 0.4:1 to about 0.67:1. In other aspects, the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound may be about 1:2.

[0056] According to a specific aspect, an STM suitable for use in the present invention may have a pH of less than about 5.5. Alternatively, the STM 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.

[0057] According to one aspect of the present invention, the catalyst components described herein can be brought into contact in any order or in any manner that one of ordinary skill in the art deems appropriate, using the present invention to obtain an olefin polymerization catalyst having those described in this document specifications.

[0058] In a specific aspect, a process for preparing an olefin polymerization catalyst comprises contacting a solvent and a carboxylic acid, both of the type described herein, to form an acidic mixture. Such a method may further include bringing into contact a titanium-containing compound of the type described herein and an acidic mixture to form an acidic titanium mixture. In one aspect, a nitrogen compound of the type described herein and an acidic titanium mixture can be contacted to form a solubilized titanium mixture (STM) as described herein, for example, to form an STM, a nitrogen compound can be added to an acidic titanium mixture. In some aspects, the nitrogen compound is added to the acidic titanium mixture in a single portion in an amount sufficient to provide an equivalent molar ratio of titanium compound to nitrogen compound of about 1:2 in the STM. In a specific aspect, the amount of nitrogen compound to be added to the titanium acid mixture is determined using an acid-base indicator (e.g., bromocresol green), wherein the nitrogen compound is added to the titanium acid mixture in multiple portions, with one portion ranging from about 3% to about 10% of the amount of nitrogen-containing compound, which corresponds to an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. The addition of several portions of the nitrogen-containing compound can be stopped when the green color corresponding to the end point of the indicator bromcresol green is reached. In some aspects, the green endpoint of the bromcresol green indicator correlates in STM with a pH value of about 4.0. According to a further aspect, adding the nitrogen-containing compound to the acidic titanium mixture comprises partially neutralizing the acidic titanium mixture; or alternatively complete neutralization of the acidic titanium mixture. The proposed process for preparing an olefin polymerization catalyst may further include contacting a chromium silica support of the type described herein and an STM to form an adduct. In a further aspect, the adduct may be dried by heating said 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 proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[0059] In a further aspect, a process for preparing an olefin polymerization catalyst comprises contacting a solvent and a carboxylic acid, both of the type described herein, to form an acidic mixture. The proposed method may further include bringing into contact a titanium-containing compound of the type described herein and an acidic mixture to obtain an acidic titanium mixture. In one aspect, a nitrogen compound of the type described herein and an acidic titanium mixture can be contacted to form a solubilized titanium mixture (STM) as described herein, for example, to form an STM, a nitrogen compound can be added to an acidic titanium mixture. In some aspects, the nitrogen compound is added to the acidic titanium mixture in a single portion in an amount sufficient to provide an equivalent molar ratio of titanium compound to nitrogen compound of about 1:2 in the STM. In a specific aspect, the amount of nitrogen compound to be added to the titanium acid mixture is determined using an acid-base indicator (e.g., bromocresol green), wherein the nitrogen compound is added to the titanium acid mixture in multiple portions, with one portion ranging from about 3% to about 10% of the amount of nitrogen-containing compound, which corresponds to an equivalent molar ratio of titanium-containing compound to nitrogen-containing compound of about 1:2. The addition of several portions of the nitrogen-containing compound can be stopped when the green color corresponding to the endpoint of the indicator bromcresol green is reached. In some aspects, the green endpoint of the bromcresol green indicator correlates in STM with a pH value of about 4.0. According to a further aspect, adding the nitrogen-containing compound to the acidic titanium mixture comprises partially neutralizing the acidic titanium mixture; or alternatively complete neutralization of the acidic titanium mixture. The proposed method for producing an olefin polymerization catalyst may further include contacting a silica support of the type described herein and an STM to form a titanated support. According to a further aspect, the titanized support can be dried by heating the titanated 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 proposed method further includes maintaining the temperature of the titanized support in the range from 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a dried titanized carrier. The proposed method may further include bringing into contact a chromium-containing compound of the type described herein and a dried titanized support to obtain an addition product that can be dried by heating said addition product to a temperature in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C. The proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor. In an alternative aspect, prior to drying the titanated support as described herein, the chromium-containing compound and the titanated support may be contacted to form an adduct that can be dried by heating said 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 proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor. According to another alternative aspect, the chromium-containing compound and the silica carrier can be contacted to form a chromium-silica carrier, which can be contacted with STM to form an adduct that can be dried by heating said adduct to a temperature in the range of about 25°C. up to about 300 °C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C. The proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[0060] According to a further aspect, a method for preparing an olefin polymerization catalyst comprises contacting a titanium-containing compound and a nitrogen-containing compound, both of which are of the type described herein, to form a base mixture. The proposed method may further include contacting a solvent and a carboxylic acid, both of which are of the type described herein, to form an acidic mixture. The base mixture and the acid mixture can be contacted to form the solubilized titanium mixture (STM) described herein, for example, the base mixture can be added to the acid mixture to form the STM. In some aspects, the base mixture is added to the acidic mixture in a single portion in an amount sufficient to provide an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a specific aspect, the amount of base mix to be added to the acid mix is determined using an acid-base indicator (e.g., bromcresol green), where the base mix is added to the acid mix in multiple portions, with one serving being from about 3% up to about 10% of the base mixture, which corresponds to an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. Addition of several portions of the main mixture can be stopped when the green color corresponding to the end point of the indicator bromcresol green is reached. In some aspects, the green endpoint of the bromcresol green indicator correlates in STM with a pH value of about 4.0. According to a further aspect, adding the base mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or alternatively complete neutralization of the acidic mixture. The proposed process for preparing an olefin polymerization catalyst may further include contacting a chromium silica support of the type described herein and an STM to form an adduct. In a further aspect, the adduct may be dried by heating said 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 proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[0061] According to another additional aspect, a method for producing an olefin polymerization catalyst comprises contacting a titanium-containing compound and a nitrogen-containing compound, both of which are of the type described herein, to form a master mixture. The proposed method may further include contacting a solvent and a carboxylic acid, both of which are of the type described herein, to form an acidic mixture. The base mixture and the acid mixture can be contacted to form the solubilized titanium mixture (STM) described herein, for example, the base mixture can be added to the acid mixture to form the STM. In some aspects, the base mixture is added to the acidic mixture in a single portion in an amount sufficient to provide an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. In a specific aspect, the amount of base mix to be added to the acid mix is determined using an acid-base indicator (e.g., bromcresol green), where the base mix is added to the acid mix in multiple portions, with one serving being from about 3% up to about 10% of the base mixture, which corresponds to an equivalent molar ratio of titanium-containing compound to carboxylic acid of about 1:2. Addition of several portions of the main mixture can be stopped when the green color corresponding to the end point of the indicator bromcresol green is reached. In some aspects, the green endpoint of the bromcresol green indicator correlates in STM with a pH value of about 4.0. According to a further aspect, adding the base mixture to the acidic mixture comprises partially neutralizing the acidic mixture; or alternatively complete neutralization of the acidic mixture. The proposed method for producing an olefin polymerization catalyst may further include contacting a silica support of the type described herein and an STM to form a titanated support. According to a further aspect, the titanized support can be dried by heating the titanated 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 proposed method further includes maintaining the temperature of the titanized support in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a dried titanized carrier. The proposed method may further include bringing into contact a chromium-containing compound of the type described herein and a dried titanized support to obtain an addition product that can be dried by heating said addition product to a temperature in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C. The proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor. In an alternative aspect, prior to drying the titanated support as described herein, the chromium-containing compound and the titanated support may be contacted to form an adduct that can be dried by heating said 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 proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor. According to another alternative aspect, the chromium-containing compound and the silica carrier can be contacted to form a chromium-silica carrier, which can be contacted with STM to form an adduct that can be dried by heating said adduct to a temperature in the range of about 25°C. up to about 300 °C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C. The proposed method further includes maintaining the temperature of the adduct in the range from about 25°C to about 300°C; alternatively from about 50°C to about 150°C; or alternatively from about 75°C to about 100°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[0062] The use of a solubilized titanium blend (STM) in the preparation of the olefin polymerization catalyst of the present invention can be beneficial because STM can promote the association of titanium with a silica support in the presence of an aqueous solvent (eg, water). Additional advantages may occur when the STM used to prepare the olefin polymerization catalyst contains an aqueous solvent (eg water). The solubility of titanium in the aqueous solvent may be sufficient to allow spray drying techniques to contact the STM and the silica carrier. Spray drying as used in the present invention refers to a method for obtaining a dry powder from a liquid or suspension by rapid drying with hot gas. Spray drying techniques can be used in the production of 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 in the preparation of olefin polymerization catalysts having a suitable particle size distribution. The use of an STM containing an aqueous solvent allows the use of a hydrated silica support and avoids the heat treatment required when using anhydrous catalyst preparation methods (eg, drying the hydrated silica support before contacting any other catalyst component).

[0063] According to some aspects of the present invention, the contacting of the components used in the preparation of the olefin polymerization catalyst may be carried out in the presence of a reaction medium. According to a further aspect, the reaction medium can be obtained during bringing into contact of the components used in the preparation of the catalyst for the polymerization of olefins. The reaction medium may contain a solvent (eg water) as described 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 does not contain any solid component used in the preparation of the olefin polymerization catalyst described herein (eg, the silica support and any solids associated therewith). According to some aspects, the total amount of water present in the reaction medium may be from about 1% of the mass. up to about 99% wt.; alternatively from about 1% of the mass. up to about 50% wt.; alternatively from about 1% of the mass. up to about 20% wt.; or alternatively from about 1% of the mass. up to about 10% of the mass. based on the total weight of the reaction medium. According to an additional aspect, the reaction medium may contain more than about 20% of the mass. water; alternatively about 40% of the mass. water; alternatively about 60% of the mass. water; alternatively about 80% of the mass. water; or alternatively about 90% of the mass. water based on the total weight of the reaction medium, while the water may come from one or more components used in the preparation of the catalyst for the polymerization of olefins.

[0064] According to any aspect of the present invention, the process for producing an olefin polymerization catalyst further comprises activating the catalyst precursor obtained as described herein through a calcination step. In some aspects, calcining the catalyst precursor comprises heating the catalyst precursor in an oxidizing environment to form an olefin polymerization catalyst. For example, the catalyst precursor can be calcined by heating the catalyst precursor 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 catalyst precursor may further include maintaining the temperature of the catalyst precursor 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 to about 850°C for a period of time from about 1 minute to about 24 hours; alternatively from about 1 minute to about 12 hours; alternatively from about 20 minutes to about 12 hours; alternatively from about 1 hour to about 10 hours; alternatively from about 3 hours to about 10 hours; or alternatively from about 3 hours to about 5 hours to form an olefin polymerization catalyst.

[0065] The olefin polymerization catalysts of the present invention are suitable for use in any olefin polymerization process using various types of polymerization reactors. According to one aspect of the present invention, the polymer proposed in the present invention is obtained by any method of polymerization of olefins using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and/or copolymers. The homopolymers and/or copolymers produced in said reactor may be referred to as resin and/or polymers. Various types of reactors include, but are not limited to, reactors which may be referred to as batch, slurry, gas phase, solution, high pressure, tubular, autoclave or other reactors and/or reactors. Gas phase reactors may include fluidized bed reactors or stepped horizontal reactors. Slurry reactors may include vertical and/or horizontal loops. High pressure reactors may include autoclave and/or tubular reactors. Reactor types may include batch and/or continuous processes. In continuous processes, intermittent and/or continuous discharge or conveyance of the product may be used. The processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, olefin polymerization catalyst and/or co-catalysts, diluents and/or other materials involved in the polymerization process.

[0066] The polymerization reactor systems of the present invention may include one type of reactor in the system, or multiple reactors of the same or different types operating in any suitable configuration. The production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transport system that allows transfer of the resulting polymers from the first polymerization reactor to the second reactor. Alternatively, multi-reactor polymerization may involve transporting, manually or automatically, the polymer from one reactor to the next reactor or reactors for further polymerization. Alternatively, the multi-stage or multi-stage polymerization may take place in a single reactor in which the conditions are changed so that another polymerization reaction proceeds.

[0067] The required polymerization conditions in one of the reactors may be the same or different from the operating conditions in any other reactors involved in the overall polymer production process of the present 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 reactors. Several reactors may operate in series or in parallel. According to one aspect of the present invention, any arrangement and/or any combination of reactors can be used to produce the polymer of the present invention.

[0068] According to one aspect of the present invention, the polymerization reactor system may include at least one loop slurry reactor. Such reactors are conventional and may contain vertical or horizontal loops. In general, continuous processes may include continuously introducing monomer, olefin polymerization catalyst and/or diluent into a polymerization reactor and continuously removing from such reactor a slurry containing polymer particles and diluent. The monomer, diluent, olefin polymerization catalyst, and optionally any comonomer can be continuously fed into the slurry loop reactor in which the polymerization occurs. The reactor effluent may be flashed to remove diluent containing liquids from the solid polymer, monomer and/or comonomer. Various technologies can be used for this separation step, including, but not limited to, flash evaporation, which can include any combination of heat and pressure reduction; separation by cyclonic action in either a cyclone or a hydrocyclone; separation by centrifugation; or other suitable separation method.

[0069] Exemplary slurry polymerization processes (also known as particle formation processes) are described, for example, in US Pat. Nos. 3,248,179; 4,501,885; 5,565,175; each of which is incorporated herein by reference in its entirety.

[0070] Suitable diluents for use in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons, which are liquids under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some polymerization reactions in a loop reactor can take place under high volume conditions where no diluent is used. An example is the polymerization of propylene monomer described in US Pat. No. 5,455,314, which is incorporated herein by reference in its entirety.

[0071] According to another aspect of the present invention, the polymerization reactor may include at least one gas phase reactor. Such systems may use a continuous recycle stream containing one or more monomers circulating continuously through a fluidized bed in the presence of an olefin polymerization catalyst under polymerization conditions. The recycle stream can be removed from the fluidized bed and returned back to the reactor. Simultaneously, the polymer product can be removed from the reactor and new or fresh monomer can be added to replace the polymerized monomer. Such gas phase reactors may include a multistage gas phase olefin polymerization process in which olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones while simultaneously feeding the polymer containing the olefin polymerization catalyst formed in the first polymerization zone to the second polymerization zone. One type of gas phase reactor suitable for use is described in US Pat.

[0072] According to another aspect of the present invention, the high pressure polymerization reactor may include a tubular reactor or an autoclave reactor. Tubular reactors may have multiple zones to which fresh monomer, olefin polymerization initiators or catalysts are added. The monomer can be entrained in an inert gas flow and introduced into one of the zones of the reactor. The initiators, olefin polymerization catalysts and/or catalyst components can be entrained in the gas stream and introduced into another zone of the reactor. For polymerization, the gas streams can be stirred. Heat and pressure can be appropriately used to obtain optimal polymerization reaction conditions.

[0073] According to another aspect of the present invention, the polymerization reactor may include a solution polymerization reactor in which the monomer is brought into contact with the olefin polymerization catalyst composition by suitable agitation or other means. You can use a carrier containing an organic diluent or excess monomer. If desired, the monomer can be vaporized and brought into contact with the catalytic reaction product in the presence or absence of liquid material. The polymerization zone is maintained at a temperature and pressure that will result in the formation of a polymer solution in the reaction medium. Stirring can be used to provide better temperature control and maintain uniformity of polymerization mixtures throughout the polymerization zone. Suitable means are used to remove the exothermic heat of polymerization.

[0074] Polymerization reactors suitable for use in the present invention may further include 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 polymer recovery system. Reactor systems suitable for the present invention may further include feed purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis, and process control.

[0075] Conditions controlled to ensure polymerization efficiency and polymer properties include, but are not limited to, temperature, pressure, type and amount of olefin polymerization catalyst or co-catalyst, and concentrations of various reactants. The polymerization temperature can affect catalyst performance, polymer molecular weight and molecular weight distribution. Suitable polymerization temperatures may be any temperature below the depolymerization temperature in accordance with the Gibbs free energy equation. Typically, this includes a temperature of 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.

[0076] Suitable pressures will also vary depending on the reactor and polymerization process. The pressure for carrying out liquid phase polymerization in a loop reactor is typically less than 1000 psig (6.9 MPa). Pressure for conducting gas phase polymerization is typically from about 200 psig (1.4 MPa) to 500 psig (3.45 MPa). High pressure polymerization in tubular or autoclave reactors generally proceeds at pressures ranging from about 20,000 psig (138 MPa) to 75,000 psig (518 MPa). Polymerization reactors can also operate in the supercritical region, typically occurring at higher temperatures and pressures. Operation above the critical point shown in the pressure/temperature diagram (supercritical phase) can be advantageous.

[0077] To obtain polymers with certain physical and mechanical properties, the concentration of various reagents can be controlled. The intended end use product to be made with the polymer and the method of making such a product can be modified to determine desired end product properties. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, impact resistance, creep, stress relaxation, and hardness test values. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting point, glass transition temperature, crystallization temperature, density, stereoregularity, cracking, short chain branching, long chain branching, and rheological measurements.

[0078] In general, the concentrations of monomer, comonomer, hydrogen, co-catalyst, modifiers, and electron donors are important parameters in obtaining specific polymer properties. A comonomer can be used to control the density of the product. Hydrogen can be used to control the molecular weight of the product. Co-catalysts can be used for alkylation, poison removal and/or molecular weight control. The concentration of poisons can be minimized because poisons can interfere with reactions and/or otherwise affect the properties of the polymer product. Modifiers can be used to control product properties, whereby electron donors can affect stereoregularity.

[0079] 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 prepared as described herein can be molded into industrial or end use products using methods known in the art such as extrusion, blow molding, injection molding, fiber spinning, thermoforming, and injection molding. For example, a polymer resin can be extruded into a sheet, which is then thermoformed into an end use product such as a container, cup, tray, tray, toy, or component of another product. Examples of other end-use products that can be obtained by molding polymer resins include pipes, films and bottles.

[0080] The method of the present invention includes contacting an olefin polymerization catalyst of the type described with an olefin monomer under conditions suitable for forming a polyolefin and recovering the polyolefin. In one aspect, the olefin monomer is an ethylene monomer and the polyolefin is an ethylene polymer (polyethylene).

[0081] The polyethylene prepared as described herein may have a High Shear Melt Index (HLMI) of about 1 g/10 min to about 1000 g/10 min; alternatively from about 3 g/10 min to about 300 g/10 min; alternatively from about 6 g/10 min to about 100 g/10 min; or alternatively from about 15 g/10 min to about 40 g/10 min. In a further aspect, a polyethylene made as described herein may have an HLMI that is about 1.5 to about 15 times higher than the HLMI of a polymer made using an otherwise similar olefin polymerization catalyst made in the absence of a nitrogen containing compound.

[0082] In a specific aspect, polyethylene can be made using a detaninated catalyst that has been made from a water-extracted catalyst precursor. In a further aspect, the water-extracted catalyst precursor is a catalyst precursor that has been extracted with water prior to calcination. For example, a catalyst precursor obtained as described herein can be extracted with water and then calcined to obtain a detanated catalyst (ie, an olefin polymerization catalyst obtained from a catalyst precursor extracted with water). In a further aspect, the polyethylene made using the detanated catalyst may have an HLMI in the range of about 1 dg/min to about 7 dg/min. Such a HLMI value may indicate that the amount of titanium, based on the amount of silicon dioxide in the detanated catalyst, is from about 0% wt. up to about 1% wt.; or alternatively from about 0.1% of the mass. up to about 0.5% of the mass.

[0083] The Melt Index (MI) is the flow rate of molten polymer through a 0.0825 inch (about 2.10 mm) hole when subjected to a force of 2160 grams at 190°C, as determined according to ASTM D1238-82 Condition E. I10 is the flow rate of molten polymer through a 0.0825 inch (approximately 2.10 mm) hole when subjected to a force of 10,000 grams at 190°C, as determined according to ASTM D1238-82, Condition N. HLMI (High Shear Melt Index) is the flow rate of molten polymer through a 0.0825 inch (approximately 2.10 mm) diameter hole when subjected to a force of 21600 grams at 190°C, as determined according to ASTM D1238-82, Condition F.

EXAMPLES

[0084] The following examples are given as specific aspects of the present invention to demonstrate its practical application and advantages. It is understood that these examples are given by way of illustration and are not intended to limit in any way the description or claims of the present invention.

[0085] One skilled in the art will appreciate that the surfaces of oxides, including silicon dioxide (SiO ₂ ) and titanium dioxide (TiO ₂ ), typically contain hydroxyl groups at the end, which are proton groups that can participate in acid-base reactions. Under strongly acidic conditions, hydroxyl groups can undergo protonation, creating a positive charge on the surface of the oxide. Under strongly alkaline conditions, hydroxyl groups can undergo deprotonation, creating a negative charge on the surface of the oxide. The pH value lies somewhere between the two limiting values at which there is a net zero charge on the surface of the oxide. The pH value correlating with net zero charge is the isoelectric point. Each oxide has a characteristic acidity and a specific isoelectric point, governed by the chemical properties of the oxide's metallic or non-metallic element.

[0086] The following figure shows the zeta potential as a function of the solution pH for silica and titanium dioxide along with the isoelectric point of both oxides. In addition, the Si-Ti Coulomb attraction curve is shown. The zeta potential is the electrical charge potential difference between the surface of a solid particle immersed in a conductive liquid (such as water) and the bulk of the liquid. The figure shows that titanium dioxide is positively charged and silica is negatively charged in the pH range of 3.0 to 5.0. This figure also shows that the Coulomb attraction of Si-Ti is greatest near a pH value of about 4.0. Without wishing to be limited by theory, highly efficient titanation of an aqueous Ti olefin polymerization catalyst can occur when the Coulomb attraction of Si-Ti is maximized by maintaining the pH of the solution at about 4.0. To explore such a theory, several series of experiments were carried out with the creation of conditions leading to the formation of an aqueous solution of Ti with a pH value of approximately 4.0.

[0087] All silica carrier materials, chemicals, and solvents described herein were used as shipped and were not dried prior to use.

[0088] Catalysts used in the experiments described below include ^Magnapore® (Magnapor), a commercial Cr/silica-titanium dioxide catalyst obtained from WR Grace and Company and activated at various temperatures. Magnapore ^® (Magnapor) is obtained by ter-gelation (tergellation) of Si, Ti and Cr, while the specified catalyst contains 2.5% of the mass. Ti and 1% wt. Cr has 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 μm. Another commercially available Cr/silica-titanium dioxide catalyst, referred to as C-25305HM, was obtained from Philadelphia Quartz (PQ) Corporation. It also contains 2.5% of the mass. 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 μm. The main base catalyst used in the titanation processes described below was Sylopol® ^HA30W , a commercial Cr/silica based catalyst obtained from WR Grace. This catalyst did not contain titanium, but contained 1% of the mass. cr. It had a 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 μm. In addition, three other commercial Cr/silica catalysts were used; one catalyst named EP30X from PQ Corporation, another catalyst named D-70-150A (LV) from Asahi Glass Corporation (AGC), and the third catalyst was Sylopol® ^969MPI from WR Grace. All three of these catalysts did not contain titanium, but contained 1% of the mass. cr. The pore volume of all three catalysts was about 1.6 ml/g. EP30X and 969MPI had a surface area of about 300 m ² /g and an average particle size of about 100 microns. AGC D-70-150A (LV) had a surface area of about 400 m ² /g and an average particle size of about 80 μm.

[0089] Activity tests were carried out in a 2.2 liter steel reactor equipped with a ship agitator operating at 400 rpm. The reactor was surrounded by a steel jacket in which water circulated, the temperature of which was controlled by steam-water heat exchangers. These heat exchangers were connected in an electronic feedback loop so that the reactor temperature could be maintained at +/- 0.5 °C during the reaction.

[0090] Unless otherwise noted, a small amount (typically 0.01 to 0.10 g) of solid chromium catalyst was first loaded into a dry reactor under nitrogen atmosphere. Next, about 0.25 g of sulfate-treated alumina (600 °C) was added as a poison scavenger. Then 1.2 liters of liquid isobutane were charged and the reactor was heated to the desired temperature, typically 105°C. Finally, ethylene was added to the reactor until a fixed pressure, typically 550 psig (3.8 MPa), was maintained throughout the experiment. Agitation was allowed to continue for a predetermined time, typically about one hour, and activity was noted by recording the flow of ethylene into the reactor while maintaining the set pressure.

[0091] After a predetermined time, the flow of ethylene was stopped, while the reactor was slowly depressurized and the reactor was opened to recover the granular polymer powder. In all cases the reactor was clean with no signs of scale, sedimentation or other forms of contamination on the walls. The polymer powder was then removed and weighed. Activity was reported in grams of polymer produced per gram of solid catalyst loaded per hour.

Example 1

[0092] Several control tests were conducted, with the results of these control tests are shown in Table 1. The performance properties of the experimental catalysts shown in the following examples regarding productivity, activity and melt index potential can be compared with the results of control tests. Tests 1.10-1.13 demonstrate the performance of two non-titanized catalysts, the last of which, HA30W, provides a benchmark for the performance of titanation processes in Tests 1.16-1.18. In the titanation shown in Tests 1.16-1.18, Ti(OiPr) ₄ was used to titanize HA30W. In test 1.15 titanation, the support was exposed to TiCl ₄ vapor at 250° C. in order to obtain a titanated catalyst not contaminated with organic or alcoholic by-products. In both such processes, the carrier must be dried to remove free water from the surface, typically by heat treatment at a temperature of from about 150°C to about 800°C. Otherwise, titanium will interact with free adsorbed water and will be ineffective. In tests 1.15-1.18 the catalyst was dried at 200° C. prior to titanation using either a gas phase or an anhydrous solvent (usually heptane).

Table 1: Performance properties of reference catalysts Test No. Catalyst base Treatment Ti
% wt. Activation temperature Time, min Performance
y/y Activity,
g/g-h mi,
dg/min I10, dg/min HLMI, dg/min 1.1 Magnapore ^® (Magnapore) No 2.5 eight 5362 7149 2.27 29.2 121 1.2 Magnapore ^® (Magnapore) No 2.5 eight 1921 4117 1.58 22.7 108 1.3 Magnapore ^® (Magnapore) No 2.5 7 2822 3938 0.73 13.7 66.2 1.4 Magnapore ^® (Magnapore) No 2.5 6 2071 2825 0.45 30.0 1.5 Magnapore ^® (Magnapore) No 2.5 6 1653 3672 0.58 36.3 1.6 Magnapore ^® (Magnapore) No 2.5 7 3411 5831 0.50 29.7 1.7 Magnapore ^® (Magnapore) No 2.5 7 2150 2283 0.47 26.9 1.8 PQ C-25305HM No 2.5 5 1535 1674 0.91 52.7 1.9 PQ C-25305HM No 2.5 5 1596 4352 0.86 53.9 1.10 969MPI No 0 twenty 2830 2326 1.5 8.7 1.11 969MPI No 0 eighteen 1835 1835 0.16 12.8 1.12 HA30W No 0 eleven 2973 2973 0.87 5.5 1.13 " " " eighteen 3117 2309 0.24 4.22 19.6 1.14 D-70-150A(LV) PPC C1 activation 3.0 12 3221 2577 0.35 6.3 30.5 1.15 D-70-150A(LV) Steam TiCl ₄ 3.0 6 3092 2728 0.46 8.20 36.3 1.16 HA30W Ti
(OiPr) ₄ /C7 3.5 eight 2534 2715 0.40 7.70 36.7 1.17 HA30W Ti
(OiPr) ₄ /C7 4.8 eleven 2455 1259 0.23 4.69 21.5 1.18 " " " " 5 2271 2349 0.29 5.91 28.0 Testing at 105°C, 550 psig (approximately 3.8 MPa g)

Example 2: Acid titanation

[0093] In a first series of experiments, the ability of carboxylic acids to form an acidic Ti-containing solution capable of providing efficient titanation of an olefin polymerization catalyst of the type described herein (ie, catalyst) was studied. The results are shown in Table 2. All of these experiments started with hydrated silica supports that were not heat treated prior to being contacted with any other catalyst component. The listed carboxylic acids were mixed with water or the alternative solvent system shown in the table 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 into a chromium silica support (HA30W). Then, before using in polymerization experiments, the resulting product was dried and calcined in air for three hours at 650°C.

[0094] Table 2 summarizes the results of a variety of carboxylic acids. The use of carboxylic acids alone (no base added) did not provide very efficient titanation. Test 2.2, which used acetic acid in the solvent propanol, provided the most efficient titanation. Successful results were also observed when HA30W was impregnated with an acidic Ti-containing solution and dropped into the activator tube at 300°C ("hot drop", tests 2.12-2.16). This fast drying method was moderately effective, as evidenced by the higher melt index obtained from catalyst production using this method compared to oven drying. The proposed hot drop drying method resulted in more efficient titanation when citric acid was used instead of oxalic acid. This result may have occurred because 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 makes it possible to obtain a Ti-containing solution with a pH value that is higher and closer to 4.0 compared to a Ti-containing solution obtained using oxalic acid.

Table 2: Titanation with simple acids Test No. Acid/
solvent Acid/
Ti Time, min Productivity, g/g Activity, g/g-h mi,
dg/min I10, dg/min HLMI,
dg/min 2.1 Solvent acetic acid Large excess 7 1453 1478 0.09 2.39 11.0 2.2 Acetic acid/n-propanol Large excess 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% fifteen 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 " " fourteen 2986 5599 0 1.53 9.0 2.12 " " 9 3238 1833 0 3.02 16.0 The catalysts used the primary base HA30W, the catalysts contained 3.5% of the mass. Ti, water was used as a solvent, the catalysts were activated at 650°C.
Testing was typically performed at 105°C, 550 psig (approximately 3.8 MPa g).
*Tested at 100°C using 5 ml 1-hexene, 550 psig (about 3.8 MPa g).
** These catalysts were dried by dropping into a hot activator tube, the temperature of which was set at 300°C.

Example 3: Alkaline titanation

[0095] In the following series of experiments, the ability of the base to form an alkaline Ti-containing solution capable of providing efficient titanation of the catalyst was investigated. The results obtained are shown in Table 3. The experimental approach was essentially identical to that described in Example 2. Ti dissolved in some strong bases, eg organic bases, was effective, but ammonium hydroxide and alkali metal hydroxides were ineffective. Quaternary ammonium hydroxides dissolved Ti, but uncharged primary, secondary, or tertiary amines were less effective. All melt index potentials obtained using alkaline solutions were low, similar to the non-titanized support, and thus did not show evidence of effective titanation of the chromium silica support.

Table 3: Titanation with simple bases
[0096] Test No. Base/solvent Base/Ti Time,
min Performance,
y/y Activity, g/g-h mi,
dg/min I10,
dg/min HLMI,
dg/min 3.1 _NEt4OH 4:1 34 0 0 3.2 " 4:1 0 0 0 3.3 _NEt4OH 1:1 24 2314 1876 0 0.28 2.6 3.4 NTA+NEt _4OH 1.2:2:1 Not
soluble 3.5 AcAc+NEt ₄ OH 1:1:1 eighteen 2474 2699 0.20 2.6 3.6 Dimethylglycine 4.5:1 Not
data 2749 No data 0.018 1.3 7.0 3.7 " 16 3060 3165 0.013 1.0 5.9 3.8 Triethanolamine 2:1 Not
soluble 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 Not
soluble 3.13 Arginine 4:1 Not
soluble The catalysts used the primary base HA30W, the catalysts contained 3.5% of the mass. Ti and were activated at 650°C.
Testing was typically carried out at 105° C. and 550 psig (about 3.8 MPa g).
* Tested at 100°C using 5 ml hexene-1, 550 psig (approximately 3.8 MPa g).
NTA=nitrilotetraacetic acid

Example 4 pH Adjustment with Ammonium Hydroxides

[0096] The results in Tables 2 and 3 confirmed that the addition of titania to silica can be problematic at both high and low pH. The following series of experiments was carried out to test the theory that the maximum Coulomb attraction of Si-Ti occurs at a pH value of approximately 4.0. Ti(OiPr) ₄ was hydrolyzed to give titanium dioxide, which was dissolved in an aqueous solution of oxalic acid (2 equivalents of oxalic acid per Ti) to give an acidic Ti-containing solution with a pH of about 1. Ammonium hydroxide or the quaternary derivative shown in Table 4, was added until a green color corresponding to the endpoint of the indicator bromocresol green was reached, indicating a pH value of about 4.0, to obtain a Ti solubilized mixture (STM) of the type described herein. The stoichiometry required to partially neutralize the acidic Ti-containing solution and thereby obtain STM was typically about two equivalents of base per Ti. The HA30W carrier was impregnated with STM and the resulting product was dried and calcined in air for three hours at 650° C. prior to use in polymerization experiments.

[0097] The results shown in Table 4 show that the proposed approach was successful. Quaternary ammonium hydroxides were more effective than ammonium hydroxide. This result can be explained by the lower volatility of tetraalkylammonium hydroxides. The results in Table 4 also indicate that the amount of base used to make the STM affected the melt index potential imparted by the resulting catalyst. This method also provided efficient titanation on the hydrogel rather than on the finished silica support (test 4.16). The catalyst used in test 4.6 was obtained by back addition and showed excellent performance: Ti was dissolved in aqueous NMe ₄ OH to form an alkaline solution, which was added to an aqueous solution of oxalic acid to form the STM used to impregnate the HA30W support.

Table 4: Partial neutralization with ammonium hydroxides Test No. Base Base/Ti Time, min Productivity, g/g Activity, g/g-h mi,
dg/min I10, dg/min HLMI, 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 1OA Precipitation has occurred 4.8 _NEt4OH 1.0 eighteen 2943 4772 0.14 3.39 16.9 4.9 _NEt4OH 1.5 16 3062 5104 0.20 4.22 21.0 4.10 _NEt4OH “ eleven 2182 3193 0.13 3.45 18.0 4.11 _NEt4OH 1.5 13 2415 3916 0.24 5.32 26.8 4.12 _NEt4OH 2.0 13 3165 6126 0.27 5.34 26.8 4.13 _NEt4OH 2.5 12 3226 6244 0.18 3.95 21.2 4.14 _NEt4OH 3.0 22 2865 2605 0.00 1.20 6.8 4.15 _NEt4OH 4.0 Precipitation has occurred 4.16 _NEt4OH 2.0H eighteen 2769 1678 0.25 5.48 27.8 4.17 _NEt4OH 2.0 s Cr 9 3157 2282 0.28 5.70 28.4 Ti(OiPr) ₄ was dissolved in 2 eq. oxalic acid solution, then a base was added to partially neutralize the acid. The resulting solution was then added to primary HA30W and dried. Each catalyst contained 3.5% of the mass. Ti and was activated at 650°C. Testing was performed at 105°C, 550 psig (approximately 3.8 MPa g).
R: Ti was dissolved in the base, then the acid was added.
H: A hydrogel was used in place of the prepared silica carrier.
Cr: Cr was added to the oxalic acid and was not originally present on the catalyst.

Example 5 pH Adjustment with Urea

[0098] In the following series of experiments, the ability of urea to partially neutralize an acidic Ti-containing solution and form STM capable of providing efficient titanation of the catalyst was studied. Urea easily decomposes when heated into volatile products. Replacing the carbonaceous catalyst components with urea compounds has the potential to reduce VOC and highly reactive VOC emissions from catalyst calcination. The experimental approach was essentially identical to that described in Example 4, but without the use of the bromocresol green indicator. The results obtained are shown in Table 5. The addition of urea to the acidic Ti-containing solution provided more efficient titanation as the amount of urea increased. Such an effect was not observed in the experiments that investigated the use of urea using spray drying, possibly because the urea decomposed and/or evaporated during the spray drying process. Efficient titanation was also observed with N,N'-dimethylurea, which is less volatile than urea.

Table 5: Oxalic acid with urea Test No. Base Urea/Ti Time, min Productivity, g/g Activity, g/g-h MI
dg/min I10 dg/min HLMI
dg/min 5.1 Urea 1:1 fifteen 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 ten 2553 4140 0.26 5.86 29.4 5.4 Urea 3:1 eight 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 fourteen 3712 5179 0.36 6.87 34.3 Ti(OiPr) ₄ was dissolved in 2 eq. oxalic acid solution, then a base was added to partially neutralize the acid. The resulting solution was then added to primary HA30W and dried.
Each catalyst contained 3.5% of the mass. Ti and was activated at 650°C.
Testing was performed at 105°C, 550 psig (approximately 3.8 MPa g).

Example 6 pH Adjustment with Alkanolamines

[0099] In the following series of experiments, the ability of alkanolamines to partially neutralize an acidic Ti-containing solution and form an STM capable of providing efficient titanation of the catalyst was studied. The ethanolamines and isopropanolamines were chosen because they generally have low toxicity, low cost, are readily available from a variety of sources, and have a low odor compared to most amines. The experimental approach was essentially identical to that described in Example 5, the results are shown in Table 6. Results varied, with the bulkier amines appearing to work best. Without wishing to be limited by theory, this could be the result of the lower volatility of bulkier compounds and/or the lower dielectric constant of Ti ions formed when bulkier compounds are used. Dimethylaminoethanol (DMAE) provided a relatively high melt index, was low cost, available from several vendors, and had a low odor. The catalyst obtained in test 6.11 was prepared by dissolving titanium dioxide in two equivalents of an aqueous oxalic acid solution, followed by the addition of two equivalents of DMAE to obtain a Ti solubilized solution (STM) of the type described herein. The HA30W support was impregnated with STM to obtain a titanated support, which was dried under vacuum overnight at 100°C. The resulting dried titanated support was extracted with water before calcination at 650° C. and subjected to polymerization experiments. Based on the melt index data, it is assumed that said catalyst suffered a significant loss of Ti, presumably during the water extraction step. This observation indicates that Ti may not have been completely bonded to silica after drying at 100°C and confirms previous studies that bonding of Ti and silica occurs at least partially at temperatures above 150°C.

Table 6: Oxalic acid with alkanolamines Test No. Catalyst
Base OA/Ti Base Base/Ti Time, min Performance,
y/y Activity, g/g-h mi,
dg/min I10,
dg/min HLMI,
dg/min 6.1 HA30W 2.0 ethanolamine 2.0 ten 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 ten 3157 3105 0.21 4.6 22.7 6.4 HA30W 2.0 Diethanolamine 2.0 ten 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 eight 3403 3646 0.33 6.8 34.1 6.9 HA30W 2.0 DMAE 3.0 eight 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 fifteen 2467 1495 0.09 1.3 7.0 6.12 969MS 2.0 DMAE† 2.0 ten 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 ten 2784 6425 0.66 12.4 61.1 6.15 Evonik 2.0 DMAE 2.0 fourteen 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 " " " ten 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 eq. 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% of the mass. Ti and was activated at 650°C.
Testing was performed at 105°C, 550 psig (approximately 3.8 MPa g).
* Drying was carried out at 100°C, then washed with water before drying again.
† Drying was carried out at temperatures up to 650°C in N ₂ .
†† Air drying up to 650°C.
OA: oxalic acid, DMAE: dimethylaminoethanol

Example 7 pH Adjustment with Other Amines

[00100] In the following series of experiments, the ability of a variety of other amines to partially neutralize an acidic Ti-containing solution and form an STM capable of providing efficient catalyst titanation was studied. The experimental approach was essentially identical to that described in Example 5, the results are shown in Table 7. There was a general trend towards higher performance with bulkier amines, but this was sometimes disrupted due to poor solubility of e.g. 2-ethylhexylamine or DABCO. Bases capable of delocalizing the positive charge produced by protonation have shown very good performance properties; examples include DBU, creatine and imidazole.

Table 7: Oxalic acid with other amines Test No. Base Base/Ti Time,
min Performance
y/y Activity, g/g-h mi,
dg/min I10,
dg/min HLMI,
dg/min 7.1 Hydrazine 2.00 12 3304 2643 0.00 2.3 12.4 7.2 Hydroxylamine 2.50 four 1638 1694 0.23 5.4 27.1 7.3 Trimethylamine 2.00 fifteen 3143 4013 0.38 7.2 35.5 7.4 Hexylamine 2.00 9 3312 3896 0.54 8.2 45.1 7.5 t-Butylamine + ethanolamine 1.0+1.0 ten 3257 3832 0.45 5.0 38.0 7.6 2-Ethylhexylamine 2.00 Precipitation fell out 7.7 2-Ethylhexylamine* 2.00 Precipitation fell out 7.8 Ethylenediamine 0.40 Precipitation fell out 7.9 Diethylenetriamine 2.00 Precipitation fell out 7.10 Diethylenetriamine 0.50 Precipitation fell out 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 fourteen 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 Precipitation fell out 7.17 DABCO 2.00 Precipitation fell out 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 fifteen 3150 3098 0.09 2.7 13.6 7.23 Dimethylglycine 2.00 ten 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 Precipitation fell out 7.29 uricil 2.00 Precipitation fell out 7.30 cyanuric acid 2.00 Precipitation fell out 7.31 Methyl carbamate 2.00 fourteen 2930 2980 0.14 3.5 18.2 7.32 Dimethylcarbamate 2.00 fourteen 3380 3219 0.26 5.3 25.7 Ti(OiPr) ₄ was dissolved in 2 eq. oxalic acid solution, then a base was added to partially neutralize the acid. This solution was then added to primary HA30W and dried. Each catalyst contained 3.5% of the mass. Ti and was activated at 650°C. Testing was performed at 105°C, 550 psig (approximately 3.8 MPa g).
* Ethylhexylamine was added directly to the oxalic acid solution.

Example 8 pH Adjustment with Inorganic Bases

[00101] In the following series of experiments, the ability of inorganic bases to partially neutralize an acidic Ti-containing solution and form an STM capable of providing efficient titanation of the catalyst was studied. The experimental approach was essentially identical to the method described in example 5, the results are shown in table 8. As a rule, this approach was unsuccessful. Without wishing to be bound by theory, the higher permittivity may have contributed, but the presence of divalent or trivalent metal cations may have upset the delicate surface charge equilibrium between silica and titanium dioxide. Tests 8.2 and 8.3 were partially successful, with equal amounts of Al ions and Ti ions being introduced simultaneously in these tests. Three equivalents of oxalic acid were added to dissolve two equivalents of metal (1 Ti(OiPr) ₄ +1 Al(OH) ₃ ), corresponding to a lower acid/metal ratio than most of the other experiments described herein. Test 8.3 included partial neutralization of the acid with tetraethylammonium hydroxide in an amount of 1.5 equivalents of base on Ti. This represents a lower base/metal ratio than most of the other experiments described herein, but an increase in HLMI was observed. Without wishing to be limited by theory, the deposition of titanium dioxide on alumina may be more easily achieved than the deposition of titanium dioxide on silicon dioxide. Ti and Al are both metals, and the chemical properties of the two metals are much more similar than those of Ti and Si.

Table 8: Oxalic acid with inorganic bases Test No. Description Time, min Productivity, g/g Activity, g/g-h mi,
dg/min I10,
dg/min HLMI,
dg/min 8.1 Ti+2 OA+1.2 Al(OH) ₃ ten 3333 2273 0.0 0.65 4.7 8.2 Ti+3OA+Al(OH) ₃ 17 3286 2987 0.0 1.43 8.0 8.3 Ti + 3 OA + Al (OH) ₃ +
1.5 _NEt4OH 12 3205 4274 0.0 2.04 11.2 8.4 Ti + 2 OA + 1.4 Mg (OH) ₂ 12 3199 3047 0.0 0.80 5.1 8.5 Ti+2 OA+1 Mg(OH) ₂ 12 3220 3645 0.0 1.04 6.1 8.6 Ti+2 OA+0.4 ZnO Not soluble Ti(OiPr) ₄ was dissolved in the OA solution to which other metals were added. This solution was then added to primary HA30W and dried. Each catalyst contained 3.5% of the mass. Ti and was activated at 650°C.
Testing was performed at 105°C, 550 psig (approximately 3.8 MPa g).
OA=oxalic acid

Example 9 Solvation of Ti with Other Acids

[00102] In the following series of experiments, the ability of carboxylic acids other than oxalic acid to be partially neutralized and form STM capable of providing effective titanation of the catalyst was studied. The experimental approach was essentially identical to the method described in example 4, the results are shown in table 9. In general, such experiments were less successful than experiments using oxalic acid. In several experiments, two equivalents of base on Ti were added, which was more than necessary to obtain a pH value of 4.0, since the acids studied were weaker than oxalic acid. In other experiments, the base was added until a green color was reached, corresponding to the end point of the indicator bromocresol green, indicating a pH value of 4.0. An example of such a method is test 9.7, in which the use of citric acid and tetramethylammonium hydroxide provided highly effective titanation, as evidenced by an HLMI value of almost 30. Test 9.14 showed that titanyl sulfate in the absence of carboxylic acid can be partially neutralized with DMAE, providing a moderately effective titanization.

Table 9: Solvation of Ti with other acids and partial neutralization
[00103] Test No. Description Time,
min Productivity, g/g Activity, g/g-h mi,
dg/min I10,
dg/min HLMI,
dg/min 9.1 Ti+2 maleic acid+2 NEt ₄ OH Didn't dissolve 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, endpoint, green 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 formed 9.5 Ti + 4 malic acid + 1.6 ethanolamine, endpoint, green 13 3112 2964 0.10 3.1 16.1 9.6 Ti+2 citric acid+2 NEt ₄ OH fourteen 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 end point eleven 2930 2790 0.16 3.9 19.9 9.9 Ti+5 glycolic acid+1,6 ethanolamine, green end point eight 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 glyoxalic 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* fifteen 3174 3662 0.01 0.7 4.9 9.13 Ti + dihydroxy fumaric acid Didn't dissolve 9.14 _TiOSO4 +DMAE ten 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 base. Then this solution was added to the primary HA30W and dried to obtain 3.5% of the mass. Ti followed by activation at 650°C.
*969MS
DMAE=dimethylaminoethanol

ADDITIONAL DISCLOSURE OF THE INVENTION

[00103] The following listed aspects of the present invention are given as non-limiting examples.

[00104] The first aspect is a process comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from about 1:1 to about 100:1; b) contacting a titanium-containing compound and an acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said acidic titanium mixture is from about 1:1 to about 1:4; c) contacting a nitrogen-containing compound and an acidic titanium mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said 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 chromium-silica media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to form an adduct, and drying said adduct by heating to a temperature in the range from about 50°C to about 150°C and maintaining the temperature in the range from about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[00105] The second aspect is the process of the first aspect, further comprising e) calcining the catalyst precursor by heating said catalyst precursor to a temperature in the range of about 400° C. to about 1000° C. and maintaining the temperature of the catalyst precursor 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 obtain a catalyst.

[00106] A 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 said acidic titanium mixture is about 1:2, and the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said solubilized titanium mixture is approximately 1:2.

[00107] The fourth aspect, which is a method according to any of the first three aspects, in which the pH of the solubilized titanium mixture is from about 3.5 to about 4.5.

[00108] A fifth aspect, which is a method according to any of the first four aspects, wherein (c) comprises neutralizing the acidic titanium mixture, wherein said neutralization is partial neutralization or complete neutralization.

[00109] 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 R^one, R², R³, R⁹, R^tenand R^elevenis independently hydrogen, C_one-C₁₂ organo group or C₆-C₁₂an aryl group; R^four represents C_one-C₁₂ organo group or C_one-C₆an aryl group; every R⁵ and R⁶ are independently hydrogen, C_one-C₆ organo group or C₆-C₁₂an aryl group; every R⁷ and R^eightare independently hydrogen or CH₃; R¹² is a branched C_one-C₆alkyl group, cyclic C_one-C₆alkyl group or linear C_one-C₆ an alkyl group; x is an integer from 1 to 4, y is an integer from 1 to 12, 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 ) _y OH Structure 1 Structure 2 Structure 3 NR ⁹ R ^10OH Z=C(N(R ¹¹ ) ₂ ) ₂ N(R ¹² OH) ₃ Structure 4 Structure 5 Structure 6

[00110] A seventh aspect, which is a method according to any of the first six aspects, wherein the nitrogen compound comprises an alkanolamine, an amine, ammonium hydroxide, hydroxylamine, urea, or a combination thereof.

[00111] The eighth aspect, which is the method according to any of the first seven aspects, wherein the nitrogen compound comprises 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 a combination thereof .

[00112] The ninth aspect, which is the process according to any of the first eight aspects, wherein the carboxylic acid comprises C ₁ -C ₁₅ monocarboxylic acid, C ₁ -C ₁₅ dicarboxylic acid, C ₁ -C ₁₅ tricarboxylic acid, C ₁ -C ₁₅ α-hydroxycarboxylic acid or a combination thereof.

[00113] A tenth aspect, which is a method according to any of the first nine aspects, wherein the carboxylic acid comprises acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid, or a combination thereof.

[00114] An eleventh aspect, which is a method according to any of the first ten aspects, wherein the titanium-containing compound comprises titanium hydroxide, titanic acid, titanyl sulfate, titanium (IV) alkoxide, titanyl acetylacetonate, titanium (IV) halide, or a combination thereof.

[00115] The twelfth aspect, which is a method according to any of the first eleven aspects, in which the titanium-containing compound includes titanium (IV) isopropoxide.

[00116] A thirteenth aspect, which is a method according to any of the first twelve aspects, wherein (d) further comprises spray drying the solubilized titanium mixture on a chromium silica support.

[00117] The fourteenth aspect, which is a method according to any of the first thirteen aspects, in which the chromium silica carrier has a surface area of from about 100 m ² /g to about 1000 m ² /g and a pore volume of from about 1.0 cm ³ / g to about 2.5 cm ³ /g.

[00118] 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% of the mass. up to about 10% of the mass. based on the total weight of the catalyst, and the amount of titanium present in the catalyst is from about 0.01% of the mass. up to about 10% of the mass. based on the total weight of the catalyst.

[00119] The sixteenth aspect, which is a method according to any of the first fifteen aspects, in which the solvent includes an aqueous solvent, an alcohol, an organic solvent, or a combination thereof.

[00120] The seventeenth aspect is a method for producing an ethylene polymer, comprising contacting the catalyst obtained by the method according to the second aspect with an ethylene monomer under conditions suitable for forming an ethylene polymer, and recovering the ethylene polymer.

[00121] An eighteenth aspect, which is the process of the seventeenth aspect, wherein the ethylene polymer has a high shear melt index (HLMI) that is about 1.5 to about 15 times higher than the HLMI of an ethylene polymer produced using a similar the rest of the catalyst obtained in the absence of a nitrogen-containing compound.

[00122] A nineteenth aspect, which is a process comprising a) contacting a solvent and a carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from about 1:1 to about 100:1; b) contacting a titanium-containing compound and an acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said acidic titanium mixture is from about 1:1 to about 1:4; c) contacting a nitrogen-containing compound and an acidic titanium mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said solubilized titanium mixture is from about 1:1 to about 1:4, and the pH of the solubilized titanium mixture is about 3.5 to about 4.5; d) bringing into contact silicon dioxide media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to obtain a titanated carrier and drying said titanated carrier by heating to a temperature in the range from about 50°C to about 150°C and maintaining the temperature in the range from about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to obtain a dried titanized support; and e) contacting, to form a catalyst precursor, a chromium-containing compound and at least one material selected from the group consisting of a silica support, a titanated support, and a dried titanated support.

[00123] The twentieth aspect, which is the method according to the nineteenth aspect, further comprising: f) calcining the catalyst precursor by heating to a temperature in the range from about 400°C to about 1000°C and maintaining the temperature in the range from about 400°C to about 1000 °C over a period of time from about 1 minute to about 24 hours to obtain a catalyst.

[00124] The twenty-first aspect, which is the method according to the nineteenth aspect, wherein (c) comprises neutralizing the acidic titanium mixture, wherein said neutralization is partial neutralization or complete neutralization.

[00125] A twenty-second aspect, which is a method comprising: a) bringing into contact a titanium-containing compound and a nitrogen-containing compound to form a base mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said base mixture is from about 1:1 to about 1:4; b) contacting the solvent and the carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from about 1:1 to about 100:1; c) contacting the basic mixture and the acidic mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said 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 chromium-silica media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to form an adduct, and drying said adduct by heating to a temperature in the range from about 50°C to about 150°C and maintaining the temperature in the range from about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[00126] The twenty-third aspect, which is the method of the twenty-second aspect, further comprising: e) calcining the catalyst precursor by heating said catalyst precursor to a temperature in the range of about 400° C. to about 1000° C. and maintaining the temperature of the catalyst precursor 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 obtain a catalyst.

[00127] A twenty-fourth aspect, which is a method comprising: a) bringing into contact a titanium-containing compound and a nitrogen-containing compound to form a base mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said base mixture is from about 1:1 to about 1:4; b) contacting the solvent and the carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from about 1:1 to about 100:1; c) contacting the basic mixture and the acidic mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said 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; d) bringing into contact silicon dioxide media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to obtain a titanated carrier and drying said titanated carrier by heating to a temperature in the range from about 50°C to about 150°C and maintaining the temperature in the range from about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to obtain a dried titanized support; and e) contacting, to form a catalyst precursor, a chromium-containing compound and at least one material selected from the group consisting of a silica support, a titanated support, and a dried titanated support.

[00128] The twenty-fifth aspect, which is the method of the twenty-fourth aspect, further comprising: f) calcining the catalyst precursor by heating said catalyst precursor to a temperature in the range of about 400°C to about 1000°C and maintaining the temperature of the catalyst precursor 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 obtain a catalyst.

[00129] the Twenty-sixth aspect, which is a composition of the catalyst precursor, containing: a) silica carrier containing silicon dioxide, while the amount of silicon dioxide is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier; b) chromium-containing compound, while the amount of chromium is from about 0.1% of the mass. up to about 5% of the mass. based on the amount of silicon dioxide; c) titanium-containing compound, while the amount of titanium is from about 0.1% of the mass. up to about 20% of the mass. based on the amount of silicon dioxide; d) a carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is from 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 from about 1:0.5 to about 1:10.

[00130] The twenty-seventh aspect, which is the catalyst precursor composition of the twenty-sixth aspect, wherein the carboxylic acid comprises C ₁ -C ₁₅ monocarboxylic acid, C ₁ -C ₁₅ dicarboxylic acid, C ₁ -C ₁₅ tricarboxylic acid, C ₁ -C ₁₅ α-hydroxycarboxylic acid, or a combination thereof.

[00131] The twenty-eighth aspect is the catalyst precursor composition 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.

[00132] A twenty-ninth aspect which is a catalyst precursor composition according to any of the twenty-sixth to twenty-eighth aspects, wherein the nitrogen compound comprises an alkanolamine, an amide, an amine, an alkylamine, ammonium hydroxide, aniline, a hydroxylamine, a urea, or a combination thereof.

[00133] The thirtieth aspect, which is the catalyst precursor composition according to any of the twenty-sixth to twenty-ninth aspects, wherein the nitrogen-containing compound comprises 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, hydroxyamine, 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.

[00134] The thirty-first aspect is the catalyst precursor composition according to any of the twenty-sixth to thirtieth aspects, wherein the silica support further comprises alumina.

[00135] The thirty-second aspect, which is the catalyst precursor composition according to any of the twenty-sixth to thirty-first aspects, wherein the silica support has a 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.

[00136] A thirty-third aspect, which is the catalyst precursor composition according to any of the twenty-sixth to thirty-second aspects, wherein the silica carrier comprises a hydrated silica carrier.

[00137] The thirty-fourth aspect, which is the catalyst precursor composition according to any of the twenty-sixth to thirty-third aspects, in which the silica carrier contains from about 1% of the mass. up to about 20% of the mass. water based on the total weight of silicon dioxide carrier.

[00138] Thirty-fifth aspect, which is a composition of the precursor of the catalyst, containing: a) silicon dioxide carrier containing silicon dioxide, while the amount of silicon dioxide is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier; b) chromium-containing compound, while the amount of chromium is from about 0.1% of the mass. up to about 5% of the mass. based on the amount of silicon dioxide; and c) an organotitanium salt, wherein said organotitanium salt contains titanium, a protonated nitrogen-containing compound and a carboxylate, and wherein: i) the amount of titanium is from about 0.1% by weight. up to about 20% of the mass. based on the amount of silicon dioxide; ii) an equivalent molar ratio of titanium to carboxylate is from about 1:1 to about 1:10; and iii) an equivalent molar ratio of titanium to protonated nitrogen compound is from about 1:0.5 to about 1:10.

[00139] The thirty-sixth aspect, which is the catalyst precursor composition of the thirty-fifth aspect, wherein the protonated nitrogen-containing compound comprises a protonated alkanolamine, a protonated amide, a protonated amine, a protonated alkylamine, a protonated ammonium hydroxide, a protonated aniline, a protonated hydroxylamine, a protonated urea, or a combination thereof .

[00140] The thirty-seventh aspect, which is the catalyst precursor composition of the thirty-fifth aspect, wherein the protonated nitrogen-containing compound comprises protonated acetamide, protonated acrylamide, protonated allylamine, ammonium, protonated ammonium hydroxide, protonated butylamine, protonated t-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 glycolamine , protonated hexylamine, protonated hydroxyamine, protonated imidazole, protonated isopropanolamine, protonated methacryl amide, 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.

[00141] The thirty-eighth aspect, which is the catalyst precursor composition according to any of the thirty-fifth to thirty-seventh aspects, wherein the carboxylate comprises C ₁ -C ₁₅ monocarboxylate, C ₁ -C ₁₅ dicarboxylate, C ₁ -C ₁₅ tricarboxylate, C ₁ -C ₁₅ α-hydroxycarboxylate or a combination thereof.

[00142] A thirty-ninth aspect which is a catalyst precursor composition according to any one of the thirty-fifth to thirty-eighth aspects, wherein the carboxylate comprises acetate, citrate, glycolate, oxalate, phosphonoacetate, or a combination thereof.

[00143] The fortieth aspect, which is the catalyst precursor composition according to any of the thirty-fifth to thirty-ninth aspects, wherein the silica support further comprises alumina.

[00144] The forty-first aspect is the catalyst precursor composition of any of the thirty-fifth to fortieth aspects, wherein the silica support has a surface area of about 100 ^m2 /g to about 1000 ^m2 /g and a pore volume of about 1, 0 cm ³ /g to about 2.5 cm ³ /g.

[00145] The forty-second aspect is the catalyst precursor composition according to any of the thirty-fifth to forty-first aspects, wherein the silica support comprises a hydrated silica support.

[00146] The forty-third aspect, which is the composition of the catalyst precursor according to any one of the thirty-fifth to forty-second aspects, in which the silica carrier contains from about 1% of the mass. up to about 20% of the mass. water based on the total weight of silicon dioxide carrier.

[00147] The forty-fourth aspect, which is a composition of the catalyst precursor, containing: a) silica carrier containing silicon dioxide, while the amount of silicon dioxide is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier; b) chromium-containing compound, while the amount of chromium is from about 0.1% of the mass. up to about 5% of the mass. based on the amount of silicon dioxide; c) titanium-containing compound, while the amount of titanium is from about 0.01% of the mass. up to about 0.1% of the mass. based on the amount of silicon dioxide; d) a carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is from 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 from about 1:0.5 to about 1:10.

[00148] The forty-fifth aspect, which is a catalyst precursor composition obtained by 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 said acidic mixture is from about 1:1 up to about 100:1; b) contacting a titanium-containing compound and an acidic mixture to form an acidic titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid in said acidic titanium mixture is from about 1:1 to about 1:4; c) contacting a nitrogen-containing compound and an acidic titanium mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound in said 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 chromium-silica media containing from about 0.1% of the mass. up to about 20% of the mass. water, and a solubilized titanium mixture to form an adduct, and drying said adduct by heating to a temperature in the range from about 50°C to about 150°C and maintaining the temperature in the range from about 50°C to about 150°C for a period of time from about 30 minutes to about 6 hours to obtain a catalyst precursor.

[00149] Terms in the singular, unless specifically stated otherwise, are intended to include a plurality of alternatives, such as at least one. In this document, although the methods and processes are described in terms of "comprising" various components or steps, these methods and processes can also "consist essentially of" or "consist of" various components or steps. A specific feature of the proposed subject matter can be described as follows: Feature X can be A, B, or C. It is further contemplated that, for each feature, the statement can also be formulated as a list of alternatives, for example, the statement "Feature X is A , alternatively B or alternatively C" is also an aspect of the present invention, whether or not said statement is made.

[00150] Although various aspects of the present invention have been shown and described, modifications can be made by a person skilled in the art without deviating from the essence and ideas of the present invention. The aspects of the present invention described herein are illustrative only and are not intended to be limiting. Many variations and modifications of the present invention are possible and are within its scope. When explicitly stating ranges or limitations of numerical values, it is to be understood that such explicit ranges or limitations include repetitive ranges or limitations of a similar magnitude falling within the explicitly stated ranges or limitations (e.g., "from about 1 to about 10" includes, 2, 3, 4 etc., "greater than 0.10" includes 0.11, 0.12, 0.13, etc.). The use of the term "optional" in relation to any element of the claims means that the claimed element is necessary 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 primarily of", "consisting of essentially from”, etc.

[00151] Accordingly, the scope of protection is not limited to the above description, but is limited only by the claims below, and such scope includes all equivalents of the subject matter of the claims. Each claim is included in the description as an aspect of the present invention. Thus, the claims are a further description and are in addition to the aspects of the present invention. The discussion of a reference in this specification is not an admission that it is prior art to the present invention, in particular any reference that may have a publication date after the priority date of this application. The present disclosure of all patents, patent applications, and publications cited herein is hereby incorporated by reference to the extent that such documents provide an illustrative, methodological, or other detailed description in addition to the description given herein.

[00152] All publications, patent applications and patents mentioned herein are incorporated by reference in their entirety. In case of conflict, the present description, including the definitions, is intended to take precedence. As with all ranges described herein, such ranges are intended to include any combination of the upper and lower limits given, even if no specific combination is specifically stated.

Claims (40)

1. An olefin polymerization catalyst precursor composition comprising: a) silicon dioxide media containing silicon dioxide, while the amount of silicon dioxide is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier; b) chromium-containing compound, while the amount of chromium is from 0.1% of the mass. up to 5% wt. based on the amount of silicon dioxide; c) titanium-containing compound, while the amount of titanium is from 0.1% of the mass. up to 20% wt. based on the amount of silicon dioxide; d) carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is from 1:1 to 1:10; and e) a nitrogen-containing compound containing at least one nitrogen atom, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is from 1:0.5 to 1:10. 2. The catalyst precursor composition of claim 1, wherein the carboxylic acid comprises C ₁ -C ₁₅ monocarboxylic acid, C ₂ -C ₁₅ dicarboxylic acid, C ₃ -C ₁₅ tricarboxylic acid, C ₂ -C ₁₅ α-hydroxycarboxylic acid, or their combination. 3. The catalyst precursor composition of claim 1 wherein the carboxylic acid comprises acetic acid, citric acid, glycolic acid, oxalic acid, phosphonoacetic acid, or a combination thereof. 4. The catalyst precursor composition of claim 1 wherein the nitrogen compound comprises an alkanolamine, an amide, an amine, an alkylamine, ammonium hydroxide, aniline, a hydroxylamine, urea, or a combination thereof. 5. The catalyst precursor composition of claim 1 wherein the nitrogen compound comprises acetamide, acrylamide, allylamine, ammonia, ammonium hydroxide, butylamine, t-butylamine, N,N'-dibutyl urea, creatine, creatinine, diethanolamine, diethylhydroxyamine, diisopropanolamine, dimethylaminoethanol , dimethylcarbamate, dimethylformamide, dimethylglycine, dimethylisopropanolamine, N,N'-dimethylurea, ethanolamine, ethylamine, glycolamine, hexylamine, hydroxyamine, 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. 6. The catalyst precursor composition of claim 1, wherein the silica support further comprises alumina. 7. The catalyst precursor composition of claim 1, wherein the silica support has a surface area of 100 m ² /g to 1000 m ² /g and a pore volume of 1.0 cm ³ /g to 2.5 cm ³ /g. 8. The catalyst precursor composition of claim 1, wherein the silica support comprises a hydrated silica support. 9. The composition of the catalyst precursor according to claim 1, in which the silicon dioxide carrier contains from 1 wt%. up to 20% wt. water based on the total weight of silicon dioxide carrier. 10. An olefin polymerization catalyst precursor composition comprising: a) silicon dioxide media containing silicon dioxide, while the amount of silicon dioxide is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier; b) chromium-containing compound, while the amount of chromium is from 0.1% of the mass. up to 5% wt. based on the amount of silicon dioxide; and c) an organic titanium salt, wherein said organic titanium salt contains titanium, a protonated nitrogen compound and a carboxylate, and wherein: i) the amount of titanium is from 0.1% of the mass. up to 20% wt. based on the amount of silicon dioxide; ii) the equivalent molar ratio of titanium to carboxylate is from 1:1 to 1:10; and iii) the equivalent molar ratio of titanium to protonated nitrogen-containing compound is from 1:0.5 to 1:10. 11. The catalyst precursor composition of claim 10 wherein the protonated nitrogen compound comprises a protonated alkanolamine, a protonated amide, a protonated amine, a protonated alkylamine, a protonated ammonium hydroxide, a protonated aniline, a protonated hydroxylamine, a protonated urea, or a combination thereof. 12. The catalyst precursor composition of claim 10 wherein the protonated nitrogen compound comprises protonated acetamide, protonated acrylamide, protonated allylamine, ammonium, protonated ammonium hydroxide, protonated butylamine, protonated t-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 imidazole, protonated isopropanolamine, protonated methacrylamide, protonated methylamine, protonated N-methylaniline, protonated 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 trimethylamine, protonated urea, protonated 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination thereof. 13. The catalyst precursor composition of claim 10 wherein the carboxylate comprises C ₁ -C ₁₅ monocarboxylate, C ₂ -C ₁₅ dicarboxylate, C ₃ -C ₁₅ tricarboxylate, C ₂ -C ₁₅ α-hydroxycarboxylate, or a combination thereof. 14. The catalyst precursor composition of claim 10 wherein the carboxylate comprises acetate, citrate, glycolate, oxalate, phosphonoacetate, or a combination thereof. 15. The catalyst precursor composition of claim 10 wherein the silica support further comprises alumina. 16. The catalyst precursor composition of claim 10 wherein the silica support has a surface area of 100 m ² /g to 1000 m ² /g and a pore volume of 1.0 cm ³ /g to 2.5 cm ³ /g. 17. The catalyst precursor composition of claim 10 wherein the silica support comprises a hydrated silica support. 18. The catalyst precursor composition according to claim 10, in which the silicon dioxide carrier contains from 1% wt. up to 20% wt. water based on the total weight of silicon dioxide carrier. 19. An olefin polymerization catalyst precursor composition comprising: a) silicon dioxide media containing silicon dioxide, while the amount of silicon dioxide is from about 70% of the mass. up to about 95% of the mass. based on the total weight of silicon dioxide carrier; b) chromium-containing compound, while the amount of chromium is from 0.1% of the mass. up to 5% wt. based on the amount of silicon dioxide; c) titanium-containing compound, while the amount of titanium is from 0.5% of the mass. up to 5% wt. based on the amount of silicon dioxide; d) carboxylic acid, wherein the equivalent molar ratio of titanium-containing compound to carboxylic acid is from 1:1 to 1:10; and e) a nitrogen-containing compound containing at least one nitrogen atom, wherein the equivalent molar ratio of titanium-containing compound to nitrogen-containing compound is from 1:0.5 to 1:10. 20. An olefin polymerization catalyst precursor composition prepared by a process comprising: a) contacting the solvent and the carboxylic acid to form an acidic mixture, wherein the weight ratio of solvent to carboxylic acid in said acidic mixture is from 1:1 to 100:1; b) bringing into contact a titanium-containing compound and an acidic mixture to obtain an acidic titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to carboxylic acid in said acidic titanium mixture is from 1:1 to 1:4; c) contacting a nitrogen-containing compound and an acidic titanium mixture to obtain a solubilized titanium mixture, wherein the equivalent molar ratio of the titanium-containing compound to the nitrogen-containing compound in said solubilized titanium mixture is from 1:1 to 1:4, and the pH of the solubilized titanium mixture is less than 5 ,5; and d) bringing into contact chromium-silica media containing from 0.1% of the mass. up to 20% wt. water, and a solubilized titanium mixture to obtain an addition product and drying said addition product by heating to a temperature in the range from 50°C to 150°C and maintaining the temperature in the range from 50°C to 150°C for a period of time from 30 minutes to 6 hours to obtain a catalyst precursor.

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