Methods of preparing a catalyst utilizing hydrated reagents

Abstract

A method of preparing a catalyst comprising a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution; b) contacting the solution with a chrominated silica-support to form a pre-catalyst; and c) thermally treating the pre-catalyst by heating to a temperature of from about 400 C. to about 1000 C. for a time period of from about 1 minute to about 24 hours to form the catalyst.

Claims

1. A method of preparing a pre-catalyst comprising: a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution, wherein the solvating agent comprises a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, or a combination thereof; and b) contacting a silica support, a chromium-containing compound and the solution to form the pre-catalyst.

2. The method of claim 1 wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6 ##STR00008## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

3. The method of claim 1 wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

4. The method of claim 1 wherein the titanium-containing compound comprises a titanium tetraalkoxide.

5. The method of claim 1 wherein a weight ratio of solvating agent to silica of the silica support is from about 0.5:1 to about 10:1.

6. The method of claim 1 wherein the solvent is an aqueous solvent, a nonaqueous solvent, an alcohol or a combination thereof.

7. A method of preparing a pre-catalyst comprising: a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution, wherein the solvating agent comprises a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, or a combination thereof; b) contacting the solution with a chromium-containing compound to form a titanium-chromium solution; and c) contacting the titanium-chromium solution with a silica support to form the pre-catalyst.

8. The method of claim 7 wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6 ##STR00009## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

9. The method of claim 7 wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

10. The method of claim 7 wherein the titanium-containing compound comprises a titanium tetraalkoxide.

11. The method of claim 7 wherein a weight ratio of solvating agent to silica of the silica support is from about 0.5:1 to about 10:1.

12. The method of claim 7 wherein the solvent is an aqueous solvent, a nonaqueous solvent, an alcohol or a combination thereof.

13. A method of preparing a titantated-silica support comprising: a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution, wherein the solvating agent comprises a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, or a combination thereof; and b) contacting the solution with a silica support to form a titantated-silica support.

14. The method of claim 13 wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6 ##STR00010## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

15. The method of claim 13 wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

16. The method of claim 13 wherein the titanium-containing compound is characterized by a general formula Ti(OR.sup.1).sub.2(acac).sub.2 wherein OR.sup.1 is ethoxide, isopropoxide, n-propoxide, butoxide, or a combination thereof and acac is acetylacetonate.

17. The method of claim 13 wherein the titanium-containing compound is characterized by a general formula Ti(OR.sup.1).sub.2(oxal) wherein OR.sup.1 is ethoxide, isopropoxide, n-propoxide, butoxide, or a combination thereof and oxal is oxalate.

18. The method of claim 13 wherein the titanium-containing compound comprises a titanium tetraalkoxide.

19. The method of claim 18 wherein the titanium tetraalkoxide comprises titanium ethoxide Ti(OEt).sub.4, titanium isopropoxide Ti(OiPr).sub.4, titanium n-propoxide Ti(nOPr).sub.4, titanium butoxide Ti(OBu).sub.4, titanium 2-ethylhexoxide, or combinations thereof.

20. A titanated silica support composition comprising: a) a solvated titanium wherein the solvated titanium comprises a titanium-containing compound and a solvating agent wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof; and b) a silica support.

21. A reactant composition forming a titanated silica support comprising: a) a titanium-containing compound; b) a solvating agent wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof; c) a solvent; and d) a silica support.

Description

EXAMPLES

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

Example 1

(2) In the following experiments, the solvating agents listed in Table 1 were investigated by dissolving in the solvent system as listed to form a solution. Ti(OiPr).sub.4 was then added and dissolution was attempted in order to form a titanium solution. A pre-catalyst was prepared by depositing the titanium-cation solution onto a chrominated silica-support (HW30A, W. R. Grace and Company). The pre-catalyst was then dried and calcined in air for three hours at 650 C. prior to use in polymerization experiments. HW30A, the solvating agents and solvents were used as received and were not dried prior to use.

(3) Polymerization tests were conducted in a 2.2 liter stainless-steel reactor equipped with a marine stirrer rotating at 500 rpm. The reactor was surrounded by a steel jacket, through which a mixture of cold water and steam was passed to precisely control the temperature to within half a degree centigrade, with the aid of electronic control instruments.

(4) Unless otherwise stated, a small amount (0.01 to 0.10 grams normally) of the solid catalyst prepared as described herein was first charged under nitrogen to the dry reactor. Next 1.2 liter of isobutane liquid was charged and the reactor and heated to 105 C. Finally ethylene was added to the reactor to maintain a fixed pressure, 550 psig (3.8 MPa), during the experiment. The mixture was stirred continuously for the specified time, usually around one hour, and the activity was noted by recording the flow of ethylene into the reactor to maintain the set pressure.

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

(6) The results of polymerization runs are shown in Table 1. The table lists each solvating agent and solvent system along with various polymer properties including high load melt index and I.sub.10 melt index. I.sub.10 melt index (g/10 min) is the polymer flow rate using a 10 kg weight and was determined in accordance with ASTM D1238 at 190 C. with a 10 kg weight. The high load melt index (HLMI) represents the rate of flow of a molten resin through an orifice of 0.0825 inch diameter when subjected to a force of 21,600 grams at 190 C. The HLMI values were determined in accordance with ASTM D1238-82 condition F.

(7) Comparative run CM-1 used no titanium and provided baseline levels for the catalyst productivity, activity, and melt index values for the resultant polymer. The melt index values I.sub.10 and HLMI indicate the extent of titanation upon the silica-support where higher melt index values indicate more effective (i.e., greater), titanation. Comparative runs CM-2 and CM-3 used no solvating agent: the lack of improvement in HLMI and/or I.sub.10 indicate that effective titanation was not achieved with an alcohol solvent or a water solvent. Comparative runs CM-4, CM-5, CM-6, CM-7, & CM-12 used a water solvent and none of the potential solvating agents tested displayed effective titanation. Comparative runs CM-8-CM-11 used a water solvent and none of the potential solvating agents tested were capable of dissolving the Ti(IV) reagent. Comparative runs CM-13 & CM-14 used a mixed solvent system with 2 equivalents ascorbic acid but did not provide effective titanation. The polymers produced using the catalysts of the present disclosure, runs IN-1 & IN-2, displayed highly effective titanation using 4 equivalents ascorbic acid as the solvating agent in either a water solvent or an alcohol solvent.

(8) TABLE-US-00001 TABLE 1 Productivity Activity HLMI I.sub.10 Run Wt. % Solvating Agent Molar Equiv. SA/ g PE/g g PE/g- g/10 g/10 No. Ti (SA) Ti Solvent catalyst h min min CM-1 0 None None 2973 2973 5.5 0.87 CM-2 3.5* None Water 2488 2650 5.2 0.80 CM-3 3.5 None n-PrOH 2765 2614 6.1 0.98 CM-4 3.5 Glycolic acid 4 Water 3098 3320 5.7 0.97 CM-5 3.5 Glyoxilic acid 2 Water 2186 2851 2.9 0.37 CM-6 3.5 HNO.sub.3 1 Water 2846 2339 1.1 0.08 CM-7 3.5 Phosphono-acetic 2 Water 867 627 6.0 1.14 acid CM-8 3.5 Malic acid 4 Water Ti would not dissolve CM-9 3.5 Malonic acid 4 Water Ti would not dissolve CM-10 3.5 Maleic acid 4 Water Ti would not dissolve CM-11 3.5 Aspartic acid 3 Water Ti would not dissolve CM-12 3.5 Citric acid 3 Water 2303 2607 3.9 0.48 CM-13 3.5 Ascorbic acid 2 9/1 nPrOH/water 3236 3034 4.6 0.76 (v/v) CM-14 3.5 Ascorbic acid 2 2/1 nPrOH/water 3258 2874 6.2 1.07 (v/v) IN-1 3.5 Ascorbic acid 4 Water 2927 3444 12.8 2.53 IN-2 3.5 Ascorbic acid 4 MeOH 3635 2167 9.6 1.84 *indicates TiO.sub.2 precipitated out of solution

ADDITIONAL DISCLOSURE

(9) The following enumerated aspects of the present disclosures are provided as non-limiting examples.

(10) Aspect A

(11) A first aspect which is a method of preparing a catalyst comprising: a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution; b) contacting the solution with a chrominated silica-support to form a pre-catalyst; and c) thermally treating the pre-catalyst by heating to a temperature of from about 400 C. to about 1000 C. for a time period of from about 1 minute to about 24 hours to form the catalyst.

(12) A second aspect which is the method of the first aspect, wherein the solvating agent comprises a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, or a combination thereof.

(13) A third aspect which is the method of any of the first through second aspects wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6

(14) ##STR00002##

(15) wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, tert-butyl or a combination thereof.

(16) A fourth aspect which is the method of the third aspect wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

(17) A fifth aspect which is the method of any of the first through fourth aspects wherein the titanium-containing compound comprises a titanium tetraalkoxide.

(18) A sixth aspect which is the method of the fifth aspect wherein the titanium tetraalkoxide comprises titanium n-propoxide, titanium n-butoxide, titanium isopropoxide or a combination thereof.

(19) A seventh aspect which is the method of any of the first through sixth aspects wherein a weight ratio of solvating agent to silica comprising the chrominated silica-support is from about 0.5:1 to about 10:1.

(20) An eighth aspect which is the method of any of the first through seventh aspects wherein the solvent is an aqueous solvent, a nonaqueous solvent, an alcohol or a combination thereof.

(21) A ninth aspect which is the method of any of the first through eighth aspects wherein the chrominated silica-support is characterized by a surface area of from about 100 m.sup.2/gram to about 1000 m.sup.2/gram and a pore volume of from about 1.0 cm.sup.3/gram to about 2.5 cm.sup.3/gram.

(22) A tenth aspect which is the method of any of the first through ninth aspects wherein an amount of chromium present in the catalyst may range from about 0.01% to about 10% by weight of the catalyst and an amount of titanium present in the catalyst may range from about 0.01% to about 10% by weight of the catalyst.

(23) An eleventh aspect which is the method of any of the first through tenth aspects wherein the chrominated silica-support is a not thermally treated prior to contacting with the solution.

(24) A twelfth aspect which is a method of forming a polymer comprising contacting the catalyst of the first aspect with a monomer under conditions suitable for formation of a polymer and recovering the polymer.

(25) A thirteenth aspect which is the method of the twelfth aspect wherein the monomer comprises an ethylene monomer and the polymer comprises an ethylene polymer.

(26) A fourteenth aspect which is the method of any of the twelfth through thirteenth aspects wherein the polymer has a high load melt index that is from about 1.5 to about 2.5 times greater than the high load melt index of a polymer produced by utilizing an otherwise similar catalyst produced in the absence of a solvating agent.

(27) A fifteenth aspect which is the a method of preparing a catalyst comprising: a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution; b) contacting the solution with a silica-support to form a titanated support; c) contacting the titanated support with a chromium-containing compound to form a pre-catalyst; and d) thermally treating the pre-catalyst by heating to a temperature of from about 400 C. to about 1000 C. for a time period of from about 1 minute to about 24 hours to form the catalyst.

(28) A sixteenth aspect which is the method of the fifteenth aspect wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

(29) A seventeenth aspect which is the method of any of the fifteenth through sixteenth aspects wherein the titanium-containing compound comprises a titanium tetraalkoxide.

(30) An eighteenth aspect which is the method of any of the fifteenth through seventeenth aspects wherein a weight ratio of solvating agent to silica comprising the silica-support is from about 0.5:1 to about 10:1.

(31) A nineteenth aspect which is the method of any of the fifteenth through eighteenth aspects wherein the solvent is an aqueous solvent, a nonaqueous solvent, an alcohol or a combination thereof.

(32) A twentieth aspect which is the method of any of the fifteenth through nineteenth aspects wherein the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, tertiary butyl chromate, a diarene chromium (0) compound, biscyclopentadienyl chromium(II), chromium (III) acetylacetonate, or a combination thereof.

(33) A twenty-first aspect which is the method of any of the fifteenth through twentieth aspects wherein the silica-support is not thermally treated prior to contacting with the solution.

(34) A twenty-second aspect which is a method of preparing a catalyst comprising: a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution; b) contacting a silica-support, a chromium-containing compound and the solution to form a pre-catalyst; and c) thermally treating the pre-catalyst by heating to a temperature of from about 400 C. to about 1000 C. for a time period of from about 1 minute to about 24 hours to form the catalyst.

(35) A twenty-third aspect which is a method of preparing a catalyst comprising: a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution; b) contacting a silica-support and a chromium-containing compound to form a chrominated support; c) contacting the solution of step (a) with the chrominated support of step (b) to form a pre-catalyst; and d) thermally treating the pre-catalyst by heating to a temperature of from about 400 C. to about 1000 C. for a time period of from about 1 minute to about 24 hours to form the catalyst.

(36) A twenty-fourth aspect which is a method of preparing a catalyst comprising: a) contacting a silica-support, a chromium-containing compound, a titanium-containing compound, a solvating agent, and a solvent to form a pre-catalyst; and b) thermally treating the pre-catalyst by heating to a temperature of from about 400 C. to about 1000 C. for a time period of from about 1 minute to about 24 hours to form the catalyst.

(37) A twenty-fifth aspect which is a method of preparing a catalyst comprising: a) contacting Ti(OiPr).sub.4, water, and ascorbic acid to form a solution; b) contacting the solution with a chrominated silica-support to form a pre-catalyst; and c) thermally treating the pre-catalyst by heating to a temperature of from about 400 C. to about 1000 C. for a time period of from about 1 minute to about 24 hours to form the catalyst.

(38) Aspect B

(39) A first aspect which is a method of preparing a pre-catalyst comprising a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution, wherein the solvating agent comprises a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, or a combination thereof, and b) contacting the solution with a chrominated silica-support to form the pre-catalyst.

(40) A second aspect which is the method of the first aspect wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6

(41) ##STR00003## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

(42) A third aspect which is the method of any of the first and the second aspects wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

(43) A fourth aspect which is the method of any of the first through the third aspects wherein the titanium-containing compound comprises a titanium tetraalkoxide.

(44) A fifth aspect which is the method of the fourth aspect wherein the titanium tetraalkoxide comprises titanium n-propoxide, titanium n-butoxide, titanium isopropoxide or a combination thereof.

(45) A sixth aspect which is the method of any of the first through the fifth aspects wherein a weight ratio of solvating agent to silica of the chrominated silica-support is from about 0.5:1 to about 10:1.

(46) A seventh aspect which is the method of any of the first through the sixth aspects wherein the solvent is an aqueous solvent, a nonaqueous solvent, an alcohol or a combination thereof.

(47) An eighth aspect which is the method of any of the first through the seventh aspects wherein the chrominated silica-support is characterized by a surface area of from about 100 m.sup.2/gram to about 1000 m.sup.2/gram and a pore volume of from about 1.0 cm.sup.3/gram to about 2.5 cm.sup.3/gram.

(48) A ninth aspect which is the method of any of the first through the eighth aspects wherein the chrominated silica-support is not thermally treated prior to contacting with the solution.

(49) A tenth aspect which is a method of preparing a pre-catalyst comprising a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution, wherein the solvating agent comprises a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, or a combination thereof, b) contacting the solution with a silica-support to form a titanated support, and c) contacting the titanated support with a chromium-containing compound to form the pre-catalyst.

(50) An eleventh aspect which is the method of the tenth aspect wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS

(51) ##STR00004## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

(52) A twelfth aspect which is the method of any of the tenth and the eleventh aspects wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

(53) A thirteenth aspect which is the method of any of the tenth through the twelfth aspects wherein the titanium-containing compound comprises a titanium tetraalkoxide.

(54) A fourteenth aspect which is the method of any of the tenth through the thirteenth aspects wherein a weight ratio of solvating agent to silica comprising the silica-support is from about 0.5:1 to about 10:1.

(55) A fifteenth aspect which is the method of any of the tenth through the fourteenth aspects wherein the solvent is an aqueous solvent, a nonaqueous solvent, an alcohol or a combination thereof.

(56) A sixteenth aspect which is the method of any of the tenth through the fifteenth aspects wherein the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, tertiary butyl chromate, a diarene chromium (0) compound, biscyclopentadienyl chromium(II), chromium (III) acetylacetonate, or a combination thereof.

(57) A seventeenth aspect which is the method of any of the tenth through the sixteenth aspects wherein the silica-support is not thermally treated prior to contacting with the solution.

(58) An eighteenth aspect which is a method of preparing a pre-catalyst comprising a) contacting a titanium-containing compound, a solvating agent, and a solvent to form a solution, wherein the solvating agent comprises a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, or a combination thereof, and b) contacting a silica support, a chromium-containing compound and the solution to form the pre-catalyst.

(59) A nineteenth aspect which is the method of the seventeenth aspect wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6

(60) ##STR00005## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

(61) A twentieth aspect which is the method of the eighteenth aspect wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

(62) A twenty-first aspect which is a pre-catalyst composition comprising a) a titanium-containing compound, b) a solvating agent selected from the group consisting of a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, and a combination thereof, and c) a chrominated silica-support.

(63) A twenty-second aspect which is the pre-catalyst of the twenty-first aspect wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6

(64) ##STR00006## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

(65) A twenty-third aspect which is the pre-catalyst of any of the twenty-first and the twenty-second aspects wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

(66) A twenty-fourth aspect which is a titanated, chominated silica-support comprising a solvating agent selected from the group consisting of a -hydroxy-,-unsaturated carbonyl-containing compound, an ,-dihydroxy-,-unsaturated carbonyl-containing compound, and a combination thereof.

(67) A twenty-fifth aspect which is the titanated, chominated silica-support of the twenty-fourth aspect wherein the solvating agent has Structure CS 1, Structure CS 2, Structure CS 3, Structure CS 4, Structure CS 5, or Structure CS 6

(68) ##STR00007## wherein R.sup.1 is a C.sub.1 to C.sub.12 organyl group or a C.sub.6 to C.sub.12 aryl group, R.sup.2 and R.sup.3 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, R.sup.4 is OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.5 is CH(OR.sup.6)CH.sub.2OR.sup.7, OH, OCH.sub.2OCH.sub.3, OCH.sub.2SCH.sub.3, OSiY.sub.3, hydrogen, a C.sub.2 to C.sub.12 organyl group, or a C.sub.6 to C.sub.12 aryl group, R.sup.6 and R.sup.7 are each independently be hydrogen, CH.sub.2OCH.sub.3, CH.sub.2SCH.sub.3, or SiY.sub.3, and Y is methyl, isopropyl, t-butyl or a combination thereof.

(69) A twenty-sixth aspect which is the titanated, chominated silica-support of any of the twenty-fourth through the twenty-fifth aspects wherein the solvating agent comprises ascorbic acid, L-ascorbic acid, D-ascorbic acid, L-isoascorbic acid, D-isoascorbic acid, D-erythorbic acid, oxytetronic acid, reductic acid or a combination thereof.

(70) While various aspects of the present disclosures have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The aspects of the present disclosures described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of the term optionally with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc.

(71) Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an aspect of the present disclosure of the present invention. Thus, the claims are a further description and are an addition to the aspect of the present disclosures of the present disclosure. The discussion of a reference in the present disclosure is not an admission that it is prior art to the present disclosure, especially any reference that may have a publication date after the priority date of this application. The present disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein.