TW592811B - Titanium-containing catalyst composition and processes therefor and therewith - Google Patents

Abstract

A catalyst composition is disclosed. The composition comprises a titanium compound, a solubility promoter, a phosphorus source, a solvent, and optionally a sulfonic acid, a cocatalyst, or both. The cocatalyst can be a cobalt/aluminum catalyst, an antimony compound, or combinations thereof. Also disclosed is a process for producing the composition. The process comprises combining a titanium compound, a solubility promoter, a phosphorus source, a solvent, and optionally a sulfonic acid, a cocatalyst, or both. Further disclosed is a process for using the composition which comprises contacting a carbonyl compound, in the presence of the composition, with an alcohol under a condition suitable for esterification, transesterification, polymerization, or combinations thereof.

Description

592811 Amendment No. 88106251 V. Description of the invention (1) Scope of the invention The present invention relates to a catalyst composition containing a titanium compound, a method for manufacturing the composition, and in, for example, esterification, transesterification, or polymerization of a carbonyl compound Method of using composition. BACKGROUND OF THE INVENTION Polyesters commonly referred to as π-polyalkylene terephthalate, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are important Industrial Polymer Classification. It is widely used in thermoplastic fibers, films, and molding applications.

Polyalkylene terephthalate can be produced by transesterification of dialkyl p-dimonate with ethylene glycol or by direct esterification of terephthalic acid with selected ethylene glycol after polyconcentration . A catalyst is used to catalyze esterification, transesterification or polyconcentration. Many commercial processes use magnesium or zinc salts as catalysts for the transesterification step. Typically, antimony is used as the antimonylated ethylene glycol as a polycondensation catalyst in transesterification or in the direct esterification indicated above. However, antimony can form insoluble antimony complexes that block fiber spinnerets. Moreover, the use of antimony catalysts is generally considered to be environmentally unfavorable, and controversial heavy metals may appear in food contact applications. Organic titanates, such as tetraisopropylacetate and tetra-n-butyltitanate, are known to be effective polycondensation catalysts for the preparation of polyalkylene terephthalates, and are often the catalysts of choice. However, organic titanates are generally not used in the manufacture of PET because the residual titanates are reacted with small amounts of impurities formed during polyconcentration and PET processing, such as aldehydes, and thus form undesired yellow discoloration. In addition, many organic titanate catalysts are essentially insoluble in polymerization

O: \ 58 \ 58096-910820.ptc Page 6 592811 _Case No. 88106251 Θ 丨 Year P Month Day Amendment_ V. Description of the invention (2) In the mixture, an unevenly distributed catalyst is formed in the mixture. . Therefore, there is an increasing demand for new catalysts for the development of polymers that are substantially soluble, potent, and that produce polymers with reduced colors. One advantage of the catalyst composition of the present invention is that it has high reactivity when used in the manufacture of special polyalkylene terephthalates, and the polymers made therefrom have improved optical properties (e.g., less desirable) Color) when compared to polymers made using previously known organic titanate catalysts. Other advantages of the present invention will become more apparent from the following more complete disclosure. # SUMMARY OF THE INVENTION · According to the first embodiment of the present invention, it provides a catalyst that can be used as an esterification or transesterification catalyst, or as a polyconcentration catalyst for the production of polyalkylene terephthalate. Catalyst composition used. The composition contains an organic titanium compound, a dissolution promoter, and a phosphorus source. The composition further includes a sulfonic acid and an optional catalyst, wherein the solvent accelerator is selected from the group consisting of orthosilicate, orthozirconate, and combinations thereof. According to a second embodiment of the present invention, a method for manufacturing a catalyst composition is provided. The method comprises combining a solvent, an organic titanium compound, a source of phosphorus, a dissolution promoter, and optionally a sulfonic acid, a cocatalyst, or a combination thereof, wherein the dissolution promoter is selected from the group consisting of orthosilicate, orthophosphonate, and a combination thereof And so on. According to a third embodiment of the present invention, it is provided a method which can be used in the production of, for example, polyester. The method includes contacting a carbonyl compound with an alcohol in the presence of a catalyst composition. The catalyst composition is the same as the composition disclosed above. Detailed description of the invention

O: \ 58 \ 58096-910820.ptc Page 7 592811 Amendment No. 88106251 V. Description of the Invention (3) According to a first embodiment of the present invention, a catalyst composition is provided. The composition may include an organic titanium compound, a dissolution promoter, a source of phosphorus, and optionally a sulfonic acid, a cocatalyst, or a combination thereof. The composition basically consists of or consists of an organic titanium compound, a dissolution accelerator, a source of phosphorus, and a sulfonic acid. The dissolution accelerator may be selected from the group consisting of orthosilicate, orthorammate, and a combination thereof, and the co-catalyst may be free of cobalt as described in U.S. Patent Application No. 5,6 7 4,8 01. Each is composed of an aluminum catalyst, an antimony compound, and a composition thereof. The catalyst composition of the present invention is substantially soluble in a solvent. In terms of π, the term π is more trivial. The composition is preferably completely soluble in a solvent. However, a substantial part of the composition may be suspended or dispersed in a solvent. According to the present invention, the currently preferred titanium compound is an organic titanium compound. Tetrahydrocarbyl titanium oxide is currently the best organic titanium compound because it is easily available and effective. Examples of suitable tetrahydrocarbyl titanium oxide compounds include those represented by the general formula T i (OR) 4, where one R is independently selected from the group consisting of alkyl, cycloalkyl, aralkyl, and two or more of them. And so on. Each radical may include from 1 to about 30 carbon atoms, preferably each radical has from 2 to about 18 carbon atoms, and most preferably from 2 to 12 carbon atoms, and each R may be the same or different. Among them, tetrahydrocarbyl titanium oxide containing 2 to about 12 carbon atoms per hydrocarbon group and a linear or branched alkyl group is most preferable because it is relatively inexpensive, easier to obtain, and effectively forms a solution. Suitable tetrahydrocarbon-based titanium oxides include tetraethoxytitanium, propoxytitanium, isopropoxytitanium, tetra-n-butoxytitanium, tetrahexyltitanium, tetra2-ethylhexyltitanium, tetraoctyltitanium and any two or more Its composition, but not limited to this. The presence of halides or other reactive substituents is usually avoided in the R group, because

O: \ 58 \ 58096-910820.ptc Page 8 592811 Amendment No. 88106251 V. Description of the invention (4) Because these substitutions may interfere with the reaction of the catalyst or form unexpected by-products, polymers are produced using titanium compounds As a result, it may contaminate the polymer. At present, it is also ideal to make each R group the same, which is helpful for the synthesis of organic titanates. In some examples, two or more R groups may be derived from common compounds that are not chemically bonded together on the titanium atom (i.e. multi-ligands, such as triethanolamine, citric acid, lactic acid, maleic acid, tartaric acid, hydroxyglycine , Acid salts and two or more of them). For example, titanium tetrachloride is mixed with an alcohol in the presence of a base (such as ammonia) to form a tetraalkyl titanate, and a tetrahydrocarbyl titanium oxide suitable for use in the present invention can also be produced. Alcohols are typically ethanol, n-propanol, isopropanol, n-butanol or isobutanol. Methanol is generally not used because the tetramethyl titanate produced is insoluble in the reaction mixture and complicates the separation. In any manner known to those skilled in the art (e.g., filtration), first removing the gasified ammonium by-product and then distilling out the titanate titanate from the reaction mixture, the titanate titanate can be recovered. The method can be carried out at a temperature ranging from about 0 to about 150 ° C. It is possible to produce titanates having a high-carbon alkyl group by transesterification of 1? Groups with at most C4 and alcohols having more than 4 carbon atoms per molecule. Examples of commercially available organic titanium compounds include TYZOR® TPT and TYZOR® TBT (tetraisopropyl titanate and tetra-n-butyl titanate, respectively) from EI du Pont de Nemours, Wilmington, Delaware, USA ), But not limited to this. The phosphorus source is currently preferably selected from phosphonic acid, phosphinic acid, phosphine, or a combination thereof. Without wishing to be bound by theory, it is clear that phosphorus compounds will bond with organic titanium compounds during the preparation of the catalyst composition, thereby improving the solubility of the titanium compounds and helping to control the optical characteristics of polyesters made from these compounds.

O: \ 58 \ 58096-910820.ptc Page 9 592811 _Case No. 88106251 5 Rev. P7 M7_ V. Description of the invention (5) Phosphonic acid, phosphinic acid or phosphine may have a direct bond to a phosphorus atom Alkyl, alkenyl, aralkyl or aryl. Each radical may typically include from 1 to about 25 carbon atoms, preferably from 1 to about 20 carbon atoms, and most preferably from 1 to about 15 carbon atoms. For example, fluorenyl, ethyl, phenyl or naphthyl can occur. These groups may be further substituted with a group which does not interfere with the preparation of the catalyst composition at all or which is followed by a reaction using the catalyst. Moreover, it is also possible to replace the hydroxyl group of the acid. For example, one or two OH groups of a phosphorus atom bonded to a phosphonic acid can be esterified. Organic phosphonic acid has a tendency to be a stronger chelating agent than phosphinic acid, and can be used in applications where a strong bond between a phosphorus compound and an organic titanium compound is desired. It has been found that phenylphosphinic acid, diphenylphosphinic acid, and 3- (hydroxyphenylphosphiphosino) propionic acid provide an excellent balance between reaction speeds and avoid using the catalyst system as a conventionally-produced polymer Alkyl terephthalates and polyconcentrate catalysts, especially PET, are used to produce color. Examples of suitable phosphines include 1,2-bis-diphenylphosphinoethane, 1,3-bis-diphenylphosphinopropane, 1,4-bis-diphenylphosphinobutane, bis-4- Tolylphosphine oxide, bis-3,5-bisfluorenylphenylphosphine oxide, or two or more thereof, but is not limited thereto. Any solvent that can dissolve the catalyst composition disclosed above can be used in the present invention. The currently preferred solvents are alcohols with the chemical formula RKOH), alkylene glycols with the chemical formula, alkoxylated alcohols with the formula RiOCCI ^ CiURDOLH, or two or more of their compositions, where each R1 may be the same or not Similarly, it is a hydrocarbon group having 1 to about 10 carbon atoms per group, preferably 1 to about 8 carbon atoms, and most preferably 1 to about 5 carbon atoms. Currently preferred are R1 or branched, or linear alkyl. A may have 2 to about 10 carbon atoms per molecule, with 2 to about 7 carbon atoms compared

O: \ 58 \ 58096-910820.ptc Page 10 592811 Case No. 88106251 Amendment V. Description of the Invention (6) is good, and it is the same with 2 to about 4 carbon atoms, which is alone to be from 1 to about 1, and 1 to 5 is best. Suitable alcohols, butanol, ethylene glycol, propylene glycol, pentanediol, diethylene glycol, triethylene glycol are not limited thereto. The B of the purpose of making S is currently preferred or a combination thereof. Catalyst composition Concentration The dissolution promoter introduced into the gram catalyst using the catalyst composition at room temperature is, but is not limited to. Sour vinegar is chemical. These dissolved chlorite or tetrakis R1 substituted tetraethyl chloride, tetra-n-butyl chloride and di- ortho- and tetra- and tetra-n-butyl orthosilicate monoethyl ether, 2-the currently preferred diols. Dissolving Accelerator Currently the best method of titanium (2 5 ° C) dissolving agent is to make the components dissolve in concentration. Organic ortho-silicic acid Organic-ortho-silicic acid type ZKOR1) * Tetra-n-propyl oxalate is produced in several combinations, and the combination of n-propyl ester can be the best from the acetic acid esters. Each η may be a number in the same or different range from 0 to 1 and more. Examples of solvents include ethanol, propanol, isopropanol, isopropanediol, butanediol, 1-fluorenyl alcohol, triethylene glycol, Diethylene glycol monoethylethylhexanol and two or more of its compositions. The solvent is used in a wide range of industrial applications. It can be an organic silicate, organic zirconate dissolution promoter that can help The catalyst composition intended for a particular application is used in the preparation of the composition. In order to reduce the amount of the solvent, it is typically selected to form the composition at least 3 and at least 5 g per 100 g of the solvent. Currently the best formula, organic orthoester or combination thereof, the ester has the chemical formula Si (OR1) 4 and organic orthocyanin, each of which R1 and the above disclosure can be obtained commercially or can, for example, be Among the solvents disclosed above, to the solvent. Examples of suitable dissolution accelerators include, but are not limited to, silicon ester, tetra-n-propyl orthoacetate, and tetra-ortho-zirconate. Tetraethyl orthosilicate was obtained commercially. Tetra-n-propyl orthanoic acid ester is commercially obtained from E.I. du Pont de

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Nemours is an organic zirconate under the trademark TYZOR®. The choice of special ortho- ortho- ortho-amarconic esters will alter the special reactions that are promoted. For example, in the preparation of PET, ortho-silicate is preferred over ortho-humic acid ester because it has a smaller effect on the concentration rate. If necessary, a sulfonic acid or a salt thereof may be used in the present invention. The currently preferred sulfonic acid can be any aryl or alkanoic acid that is substantially soluble in the solvents disclosed above. Examples of suitable dicarboxylic acids include, but are not limited to, p-benzoic acid, benzenesulfonic acid, pinanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and two or more thereof. The salts of the sulfonic acid may be an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or two or more combinations thereof. The catalyst composition may further include a co-catalyst. Examples of co-catalysts include, but are not limited to, cobalt / aluminum catalysts, antimony compounds, and combinations thereof. The cobalt / aluminum catalyst comprises a cobalt salt and an aluminum salt, wherein the molar ratio of aluminum to cobalt ranges from 0.25: 1 to 16: 1. A cobalt / aluminum catalyst is disclosed in U.S. Patent Application No. 5,6 7,4,801, which is incorporated herein by reference. The presently preferred antimony compound may be any antimony compound that is substantially soluble in the solvents disclosed above. Examples of suitable antimony compounds include antimony oxide, antimony hydroxide, antimony halide, antimony sulfide, antimony carboxylic acid, antimony ether, antimony glycolate, antimony alkyd, antimony nitrate, antimony sulfate, antimony phosphate, and two or more combinations thereof , But not limited to this. According to the first preferred embodiment of the present invention, according to the measurement of P: T i, the molar ratio of the phosphorus source to the titanium compound may be in a range from about 0.1: 1 to about 10: 1, It is preferably from about 0.5: 1 to about 7: 1, and most preferably from about 1: 1 to about 4: 1. Molar ratio of dissolution accelerator to titanium compound (S i: T i or

O: \ 58 \ 58096-910820.ptc Page 12 592811 _ Case No. 88106251_ Today / Year β Month _ ^ _ V. Description of the invention (8) Z r: T i) can be from about 0.1: 1 In the range from about 10: 1, about 0.5: 1 to about 7: 1 is preferred, and most preferably from about 1: 1 to about 4: 1. The molar ratio (S i 03: T i) of the sulfonic acid to the titanium compound is usually preferably less than or equal to 2 ·· 1. However, the ratio may also be in a range from about 0.1: 1 to about 4: 1, preferably in a range of about 0.5: 1 to about 3: 1, and about 1: 1 to about 2: 1 is the best. The molar ratio of the co-catalyst to the titanium compound, such as Sb: Ti or C0: Ti, can be in a range from about 0.01: 1 to about 10: 1. If the catalyst composition is used in the production of polyalkylene terephthalate, the molar ratio (S i: P or Z r: P) of the phosphorus source to the dissolution promoter is usually greater than or equal to about 0.5: 1, because lower proportions may cause the discoloration of polyalkylene terephthalates. The titanium compound may optionally be present in the catalyst composition in a range from about 0. 0 1 0 to about 15% based on the total weight of the composition as 100%, preferably about 0.1 to about 10%, And the best is 0.5 to 5%. According to the present invention, the catalyst composition may further contain water, especially a composition containing sulfonic acid. Water-containing compositions have high activity and help control the optical characteristics of polyesters made from the compositions. When water is present, the molar ratio of water to titanium compound may range from about 0.01: 1 to about 6: 1, preferably about 0.1: 1 to about 4: 1, and It is preferably from about 1: 1 to about 2: 1. Although it has been described in detail as a catalyst composition for a polycondensation catalyst for producing a polyalkylene terephthalate with its preferred application, the composition also has an esterification or an ester as a well-known method requiring a highly active catalyst General purpose of base transfer catalyst. For example, a catalyst composition can be used in the reaction of phthalic anhydride and octanol to form dioctyl terephthalate, a plasticizer of polyvinyl chloride, and have low haze. The relative proportions of the catalyst composition can be adjusted to meet the requirements of special applications.

O: \ 58 \ 58096-910820.ptc Page 13 592811 _Case No. 88106251 Issued February 1991 Modified_ V. Description of the invention (9) The catalyst composition can be produced in any manner known to those skilled in the art. However, it is preferable to manufacture it by the method disclosed in the second embodiment of the present invention. The catalyst composition can be produced in a solvent compatible or non-interfering with the esterification or transesterification or polyconcentration reaction. For example, if the catalyst composition is used as a polyconcentrated catalyst for manufacturing PET, it is better to manufacture the composition in ethylene glycol; if the catalyst composition is used to manufacture PBT, it is used in 1,4-butanediol It is preferable to produce a composition; when a polypropylene glycol terephthalate (PPT) is produced using a catalyst composition, it is preferable to produce the composition in 1,3-propanediol. Regarding the production of dioctyl terephthalate, 2-ethylhexanol is the preferred alcohol. Although the components can be combined in any order, it is preferred to combine the dissolution accelerator and solvent first to produce the first mixture. The first mixture is then combined with the phosphorus source to produce a second mixture because the dissolution promoter helps dissolve the phosphorus source. The combination that produces the first or second mixture can usually be stirred and can be performed at a temperature ranging from about 0 ° C to about 100 ° C, with a temperature of about 30 ° C to about 50 ° C. good. Generally, any amount of solvent may be used as long as the composition is substantially soluble, and the titanium compound used in the composition may range from about 5 to about 50 moles per mole, and from about 10 to About 30 is preferred, and most preferably about 10 to about 20. The titanium compound can then be combined with a second mixture to produce the catalyst composition of the present invention. This step is preferably performed under an inert gas, such as nitrogen, carbon dioxide, helium, or two or more of them, to avoid the generation of flammable alcohols, as this step will exotherm and cause a temperature increase of 10 to 30 ° C. This step is performed by stirring for a time sufficient to allow the titanium compound to be almost dissolved.

O: \ 58 \ 58096-910820.ptc Page 14 592811 _Case No. 88106251 9 丨 Only Month and Day Amendment_ V. Description of the invention (10) Often about 5 minutes to about 20 hours or longer, and then cooled to Room temperature. The catalyst composition may then be combined with a sulfonic acid, a cocatalyst, or both to produce a catalyst composition as desired. It is also possible to combine the sulfonic acid with the phosphorus source and the first mixture simultaneously to produce a second mixture. Optionally, the phosphorus source can be combined with a solvent and a titanium compound to form a complex. The complex can be separated from the solvent in any well-known manner (e.g., filtration) to produce an isolated complex. The separated complex can then be combined with a mixture containing a solvent, a dissolution promoter, a continuous acid or co-catalyst, or a mixture of two or more of its compositions to produce the catalyst composition of the present invention. The amount of each component may vary depending on the selected compound, and the molar ratio of each component to titanium in the prepared catalyst compound is usually within the range disclosed above. The structure of the catalyst system has not been established. However, on the basis of the exothermicity discovered by ^, the Xianxin components have reacted or compounded in some ways to form a binary or ternary composition (etc.), making the catalyst composition particularly suitable as at least to some extent in the manufacture Polycondensation catalyst for polyalkylene terephthalate, especially polyethylene terephthalate (PET). According to a third embodiment of the present invention, it provides a method which can be used, for example, in the manufacture of esters or polyesters. The method includes contacting a carbonyl compound with an alcohol in the presence of a catalyst composition. The composition is the same as that disclosed in the first embodiment of the present invention. According to a third embodiment of the present invention, any carbonyl compound which can react with an alcohol to produce an ester can be used. These carbonyl compounds are usually in contact with alcohols. The composition is the same as that disclosed in the first embodiment of the present invention.

O: \ 58 \ 58096-910820.ptc Page 15 592811 _Case No. 88106251 F Year Minute ^ Day Amendment_ V. Description of the Invention (11) According to the third embodiment of the present invention, any reaction with alcohol can be used An ester carbonyl compound is produced. Generally these several base compounds include, but are not limited to, acids, esters, amidines, anhydrides, acid halides, agglomerates or polymers having repeat units derived from an acid, or two or more of them. The currently preferred acids are organic acids. The presently preferred method is (1) Manufactured from esters of phthalic anhydride and 2-ethylhexanol, such as exemplified bis (2-ethylhexyl) terephthalate and (2) acids or esters and alcohols. Polymerization to make polyester. A preferred method for making an ester or polyester comprises or consists essentially of contacting a reaction medium with the composition disclosed in the first embodiment of the invention above. The reaction medium may contain or consist essentially of (1) or an organic acid, or an ester and an alcohol thereof, or (2) an alcohol and a polymer having a repeating unit derived from an organic acid or an ester, and the like. A carbonyl compound, an organic acid or an ester thereof may have a chemical formula (HO) mR2 (COOR,) p, where m is a number from 0 to about 10, preferably from 0 to about 5, and most preferably from 0 to 3, Each of R2 and R 'may be (1) hydrogen, (2) a hydrocarbon group having a carboxyl group at the terminal, (3) a hydrocarbon group, or (4) two or more combinations thereof, each of which may be substituted or not Substituted; each group has 1 to about 30 carbon atoms, preferably about 3 to 15 carbon atoms, which may be alkyl, alkenyl, aryl, alkaryl, aralkyl, or two or Several of its compositions; and p may be an integer from 1 to equal to the number of carbon atoms in R2. Any anhydride of organic acids can also be used. The currently preferred organic acids are those having the chemical formula HOJAiCOd, where A1 is an alkylene, an arylene, an alkenyl or two or more of them. Each A1 has about 2 to about 30 carbon atoms, preferably about 3 to about 25 carbon atoms, more preferably about 4 to about 20 carbon atoms, and about 4 to about 15 carbon atoms. Atomic best. Examples of suitable organic acids include terephthalic acid,

O: \ 58 \ 58096-910820.ptc Page 16 592811 Amendment No. 88106251 V. Description of the invention (12) Phthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, acrylic acid , Oxalic acid, phenylarsinic acid, maleic acid, propionic acid, 4-hydroxyphenylarsinic acid, 1 2-hydroxydecanoic acid, 6-hydroxyhexanoic acid, 4-hydroxycinnamic acid, 4-hydroxyfluorenylbenzoic acid, 4 -Hydroxyphenylacetic acid, azelaic acid, salicylic acid, caproic acid, stearic acid, palmitic acid, fumaric acid, decalinic acid, citric acid, trimesic acid, pamoic acid, sebacic acid Any anhydride of these acids and two or more of its compositions, but are not limited thereto. The currently preferred organic diacid is phthalic acid because the polyesters made from it have a wide range of industrial applicability. Examples of suitable esters include dimethyl adipate, dimethyl phthalate, dimethyl terephthalate, methyl benzoate, dimethyl glutarate, and two or more of their compositions, but not Limited to this. The present invention can use any alcohol that can be esterified into an ester or polyester. The currently preferred alcohol has an alcohol of the formula R3 (OH) n, a formula of the formula (HO) nA (OH) n, or a combination thereof, wherein each R3 may be the same or different, and each group has 1 to about 1 A hydrocarbon group of 0 carbon atoms is preferably 1 to about 8 carbon atoms, and most preferably 1 to 5 carbon atoms. Currently preferred R3 is either branched or linear alkyl. A may have 2 to about 10 carbon atoms per molecule, preferably 2 to about 7 carbon atoms, and most preferably 2 to about 4 carbon atoms. Each η may be the same or different, it is a number ranging from 1 to about 10 alone, preferably from 1 to about 7, and most preferably from 1 to 5. Examples of suitable alcohols include ethanol, propanol, Isopropanol, butanol, ethylene glycol, propylene glycol, isopropyl glycol, butylene glycol, 1-fluorenyl propylene glycol, pentanediol, diethylene glycol, triethylene glycol, 2-ethylhexanol, stearyl alcohol , 1,6-hexanediol, glycerol, isopentaerythritol, and two or more thereof, but not limited thereto. At present, the best alcohol is alkylene glycol, such as the ethylene glycol of the polyester prepared therefrom, which has wide industrial applicability. The contacting of the reaction medium with the catalyst can be carried out in any suitable manner. example

O: \ 58 \ 58096-910820.ptc P.17 592811 _Case No. 88106251_Year February Amendment_ V. Description of the invention (13) For example, before contacting the catalyst, first combine the various components of the reaction medium . However, at present, the catalyst is first dissolved or dispersed in a solvent in any suitable manner, such as mechanical mixing or stirring to produce a solution or dispersion, and then the solution or dispersion is mixed with (1) organic acids, esters, and organic acids. The polymer or two or more of its composition and (2) the alcohol are combined under conditions sufficient to complete the manufacture of the ester or polyester. According to the present invention, when a sulfonic acid is contained in the catalyst composition, the reaction medium may contain water. If water is present, the amount of water is the same as disclosed above. The diacid polymer and alkylene glycol generally have a total of about 1 to about 100 repeat units derived from the diacid and alkylene oxide, preferably from about 2 to about 10 . Suitable conditions for completing the manufacture of polyester include temperatures ranging from about 150 ° C to about 350 ° C, preferably about 200 ° C to 300 ° C, and about 2 50 ° C to about 300 ° C is optimal and at a pressure ranging from about 0.01 to about 10 atmospheres over a time range from about 1 to about 20 hours, to from about 1 to It is preferably about 15 hours, and most preferably from 1 to 10 hours. The molar ratio of the alcohol (or alkylene glycol) to the carbonyl compound may be any ratio as long as it is a ratio that can complete the production of an ester. Usually the ratio ranges from about 0.1: 1 to about 10: 1, preferably from about 0.5: 1 to about 5: 1, and most preferably from about 1: 1 to about 3: 1 . Regarding the molar ratio of the polymer to alcohol (or alkylene glycol) derived from alcohol carbonyl compounds (or organic acids or esters), alcohol (or alkylene glycol) to carbonyl compounds (or organic acids) The molar ratios of the esters or esters can have the same q: (q-1) ratio, where q can range from about 2 to about 20, preferably about 2 to 10, and most preferably 2 to 5.

O: \ 58 \ 58096-910820.ptc Page 18 592811 Case No. 88106251 V. Description of the invention (14)-The catalyst can be used per million polymerizations, and the rainwater outlet is 4 times, the weight of the shell is about 0.0001 to 30, 000 = Ϊ (PP =) is the stock of the range, from about 0.001 to about 2: ° 0? Mw is the best. There may also be other components that increase the reminder ϊ i ϊ 彳 ϋ. Although the advantages of polyisocyanate and terephthalic acid are usually used to obtain catalytic dysprosium, it is obvious that when producing PET, it will be better than Λ, because color purity is typically based on PET clothing. Business. 〇 Important criteria for objects. Tian: ί Γ: ϊ ί well-known melting or solid state technology for the manufacture of esters or polyesters

Hit! Ϊ: Bu,] composition. The catalyst composition may be compatible with well-known esterification or picotransfer catalysts (e.g., magnesium, cobalt, and / or zinc oxide), and the acetification catalyst may be introduced into the manufacturing process simultaneously or later. Also: It has been found that the catalyst composition has the effect of promoting the esterification reaction, and can be used as a substitute for part or all of the lamination catalyst and polyconcentration catalyst. The following examples are provided to further illustrate the present invention and are not to be construed as improperly limiting the scope of the invention. EXAMPLES According to Example A1, zinc acetate was catalyzed with ethylene glycol to purify diethylene terephthalate 'to form Dragon T polymer. The novel catalyst of the present invention synthesized according to Examples 2 to 15 was used as a polyconcentrated catalyst for DMT according to Example 丨 A and subsequent to step IB of Example IB. The results are recorded in Table 1 along with the four control experiments. The color of the resulting polymer is measured using an instrument such as an SP-spectrophotometer at l-value and b-value angles. The L-value represents brightness, with larger values indicating higher brightness (desired). The 1-value will preferably be equal to or greater than the polymer prepared using the catalyst. b-value represents yellowness, as a value

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Case No. 88106251 V. Description of the invention (16) Maintain a period of time sufficient to achieve 15 ounce-inch torque under agitation (as measured by the Electro-Craft Motomatic torque controller). The time of ^ step is recorded as the final time 'and varies with the catalyst used. The molten polymer is poured into a water bath, the melt is solidified, and the resulting solid is annealed at 150 t for 12 hours, and the mill is passed through a 2 millimeter transition device to use the spectrophotometer previously described Meter to measure color. The results compared with the final time in minutes and the color measured spectrophotometrically are provided in Table 1 below. Example 2 A 40 ml beaker of 2.40 g (3.87 mol) of ethylene glycol was equipped with a stirrer, a concentrator, a dropping funnel and a N 2 rinse. Initiation was initiated and 25 grams (0.176 mol) of phenylphosphinic acid was added. Heat the mud to 3 5-4 5 ° C until the solids dissolve, and then add 50 g (0.116 mol) of titanium titanate dropwise at 35 ° C in a small amount. Isopropyl ester (from TYZ OR® TPT by E. j du Pont de Nemours). When the addition was complete, the reaction mass was stirred for 30 minutes, and then 36.6 g (0.176 mol) of tetraethylorthoacetate (TEOS) was added over 30 minutes. A clear solution containing 2.4% Chin will be obtained. Example 3 Example 2 was repeated, except that 73.2 g of TEOS was added. A clear solution containing 2.17% titanium will be obtained.

Example 4 240.2 g (3.87 moles) of ethylene glycol was charged into a 1 liter beaker prepared as described in Example 2. Stirring was started and charged with 50 grams (0.352 mol) of phenyl hypopic acid. The mud is heated for 30 to 3 5 C ′ until the solid is dissolved

O: \ 58 \ 58096-910820.ptc Page 21 592811 Amendment_Case No. 88106251 V. To the description of the invention (17), and then add 50 grams (0 · 17) dropwise at 1 hour at 45 ° C 6 mol) of TYZOR® TPT. A clear solution containing 2.48% titanium will be obtained. Example 5 240 g (3.87 moles) of ethylene glycol were charged into a 500 ml beaker equipped with the same as in Example 2. Start agitation and add 50 grams (0.352 moles) of phenylphosphinic acid. Heat the mud at 30 to 35 ° C until the solids are dissolved. It is then cooled to 40. (: 50 grams (0.176 mol) of TYZOR® TPT is added dropwise at 1 hour or lower at 1 hour. When the addition is complete, the reaction block is stirred for 1 hour. At room temperature, 5 · 4 grams of raw silicon Tetraethyl acid is added to the reaction block above 50 grams. After mixing, a clear solution containing 2.24% titanium will be obtained, which has a molar ratio of T i: P: S i of 1: 2: 1 Example 6 35.3 grams (0.569 moles) of ethylene glycol was charged into a 100 ml beaker equipped as in Example 2. Agitation was started and 7.3 grams (0.052 moles) was added. ) 的 phenyl phosphinic acid. The reaction block was heated to 3 5 ° C until the solids were dissolved, and then 7.4 grams (0 · 0 2 6 mole) was added dropwise at 45 ° C over 15 minutes. TYZOR® TPT. When the addition was complete, 10.77 grams (0.052 moles) of TEOS was added. The resulting clear solution contained 2.04% titanium. Example 7

35.3 grams (0.569 mol) of ethylene glycol was charged into a 100 ml beaker equipped with the same as in Example 2. Begin agitation and add 7.3 g (0.052 mol) of phenylphosphinic acid. The reaction block was heated to 45 ° C until the solids were dissolved, and then 7.4 grams (0.026 moles) of TYZOR® TPT was added dropwise over 15 minutes. Then add 16.2 grams (0.078 moles) of T EOS. Raw

O: \ 58 \ 58096-910820.ptc Page 22 592811 ------- # 1¾ 88106251_September I M_Revision V. Description of the invention (18) The resulting clear solution contains 1.87% titanium. Example 8 240.2 g (3.869 mol) of ethylene glycol was charged into a 500 ml beaker equipped with the same as in Example 2. Agitation was started and 75 grams (0.528 mol) of phenylphosphinic acid was added. The reaction block was heated to 45 ° C until the solids were dissolved 'and then 50 grams (0 · 76 mole) of TYZOR® TPT was added dropwise over 1 hour at 45 ° C. Then 36.6 grams (0.176 moles) of TEOS was added to obtain a clear solution containing 2.1% titanium. Example 9 Example 8 was repeated, except that 73.2 g (0.352 mol) of Ding EOS was used 'to obtain a clear solution containing 1.92% titanium. Example 10 Example 8 was repeated, except that 99.8 g (0.528 mol) of τ E0s was added 'to obtain a clear solution containing 1.77% titanium. Example 11 1 2 40 · 2 g (3.89 mol) of ethylene glycol was charged into a 500 ml beaker equipped with the same as in Example 2. Begin agitation and add 100 g (0.707 mol) of Benzoylpic acid. The reaction block was heated to 35 ° C until the solid was dissolved, and then 50 grams (0.176 mol) of TYZOR® TPT was added dropwise over 1 hour to obtain a clear solution containing 2.16% titanium . Example 1 2 Example 11 was repeated, except that 36.6 grams (0.176 mol) of TEOS was added to the reaction mixture after TYZOR® TPT to obtain a clear solution containing 182% titanium. Example 1 3

O: \ 58 \ 58096-910820.ptc Page 23 592811 _88106251_9 Year S_Revision V. Description of Invention (19) Example 11 was repeated except that 53.2 grams (〇_ 3 was added after TYZOR® TPT 5 2 moles) < TE0s to obtain a clear solution containing 182% titanium. Example 1 4 2 40 · 2 g (3.89 mol) of ethylene glycol was charged into a 500 ml beaker equipped with the same J2. Stirring was started, and 0.00 g (0.703 mol) of this basic phosphinic acid was added. The reaction block was heated to 45 ° C until the solids were dissolved, and then 109.9 g (0.528 mol) of TEOS was added. Then, 50 g (0.176 mol) of TYZOR® TP Τ was added dropwise at 38 C for 1 hour to obtain a clear solution containing 丨 68% titanium. Example 15 A 40-gram (0.0135 mole) titanium tetraphenylphosphinic acid solution in an ethylene glycol / ethanol solution was charged into a 100 ml beaker equipped with the same as in Example 2. Stirring was started, and 11.27 g (0.051 mol) of tetraethyl ortholate were added dropwise. The resulting solution was stirred at room temperature for 1 hour and decanted to obtain 5 1 · 3 g of a pale yellow liquid containing 1.26% of titanium. In the following table, the T i component is tetraisopropyl titanate, the p component is benzyl phosphinic acid and the A component is tetraethyl orthosilicate. The amount of titanium is 25 parts per million (p p m) based on the weight of the agglomerates. The final time is the time maintained at a given pressure and temperature 'until a predetermined concentration is achieved. A pre-concentrated composition polymer was prepared according to the instructions of Example 1A and a β-test catalyst was used according to Examples 丨. Except as noted, all catalysts were soluble in ethylene glycol in these tests.

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Table 1 Comparison of catalyst and oligomers based on final time. Oligomers of this component, 1 Hg, 285. 〇, 225ppmTi Mohr proportion color Example Ti P Si \ Dissolution in Ethylene ## Final time (minutes) L b Note Antimony Unknown solubility 110 71.98 7.78 1 1.0 0.0 0.0 Insoluble 75 68.80 11.57 2 1.0 0.0 3.0 soluble ----------- · 90 75.32 12.00 3 — 1.0 1.0 0.0 insoluble — 4 2 1.0 1.0 1.0 soluble 120 73.05 13.01 5 3 1.0 1.0 2.0 soluble 65 73.86 11.20 5 4 1.0 2.0 0.0 soluble 145 73.99 12.44 5 5 1.0 2.0 1.0 soluble 80 76.40 10.69 5 6 1.0 2.0 2.0 soluble 80 77.04 9.87 5 7 1.0 2.0 3.0 soluble 100 76.01 11.33 6 8 1.0 3.0 1.0 70 74.11 10.82 5 9 1.0 3.0 2.0 soluble Soluble -------- 175 70.18 8.71 5 10 1.0 3.0 3.0 _ soluble 125 70.57 11.94 6 11 1.0 4.0 0.0 soluble -------- 80 74.01 11.35 6 12 1.0 4.0 1.0 — 145 75.29 10.37 5 13 1.0 4.0 2.0 Soluble 95 76.30 9.86 5 14 1.0 4.0 3.0 _. Soluble. 120 79.77 7.98 5 15 1.0 4: 0 4.0 Soluble 130 74.38 10.94 6 Notes: 1 This is a control experiment using 3 0 0 ppm antimony. Antimony oxide solution in ethylene glycol

Page 25 ^ «11 ^« 11 Amendment V. Description of the invention (21) ^ = Control experiment, using only tetraisopropyl titanate, 2 5 ρριη Ti. Example: This is a control experiment without using phenylphosphinoic acid, using a mixture of tetraisopropylglycate gallate and tetraethylglycolate 1: 1 at a molar ratio of 1: 3, 2 & p p m T i. This is a test product. It does not use silicate (without any deadline) and produces + > by-products that are contained in ethylene glycol. In these experiments, Ti represents titanium tetraisopropyl titanate (τρτ), p-substituted phosphinic acid (PPA), and Si represents tetraethyl orthosilicate (TEOs). In addition to the main solution of η ', teos (when present) is added to a glycol solution of ppA and τρA to prepare a catalyst. The catalyst was evaluated at 25 Ppm Ti. 6. In these experiments, the ratio of si: p = or> 1, which results in lower L color and / or higher b color in the polymer. The above table shows that when using tetraisopropyl titanate (τ ρ τ) itself, it will produce unsatisfactory polymers with lower L and higher b color than antimony. When tetraethyl orthosilicate is added to TPT, the value will be improved, but it has little effect on b color 1 ~. When using pp A combined with TPT and TE 0S, ^, good L and b will be obvious. The higher the Si / Ti ratio, the more important is the B and / or color. When the S 1 / T 1 ratio is equal to or greater than 1.0, the color of Beza and / or b will be significantly worsened. A: The catalyst of Example 14 (3.69% Tm) was used to catalyze the acetic acid reaction of phthalic acid needle and 2-ethyl ^ =. The 1 52.8 8 gram cup is equipped with n2 gas spray, stark receiver, and t-bomb. The reaction temperature climbed slowly. t f = up. At this point, the temperature will suddenly drop to 137 \ L’ 4 until f c ’and then the temperature will start

592811 Amendment No. 88106251 V. Description of the invention (22) Increased steadily, and began to collect distillate in the receiver. Remove 3 ml of sample from the reaction flask at 14 ° C. 15 minutes after the first sample was taken, immediately after the addition of 1.30 g of catalyst at 15 1 ° C, a 2 ml sample was taken. 1.3 g of catalyst corresponds to 3 1 3 · 8 p pm T i terephthalic anhydride. The end product of this reaction is colorless and has very limited haze. No signs of precipitation were observed. B. As a control product, use TYZOR® TBT as a catalyst in the action of phthalic acid needle and 2-ethylhexanol ester. The reaction was carried out in a manner similar to that used for the esterification of Example 16A described above. Use 3 1 3 · 3 grams of T B T. The final product of this reaction is colorless, but it has a slight haze that appears as a suspended precipitate. Example 17 75 grams (0.528 moles) of phenylphosphinic acid and 218.6 grams of ethylene glycol were charged into a 500 ml beaker equipped with the same as in Example 2. Begin agitation and heat the mixture to 4 5 ° C to dissolve the solid. Once the solids are dissolved, the temperature is maintained at 45 + / -2. (: 50 g (0.176 mol) of TYZOR® TPT is added dropwise over 30 minutes. When the addition is complete, the temperature is maintained at 45 + / 2 ° C and added dropwise for 30 minutes. Grams (0.534 moles) of tetraethyl orthosilicate (TEOS). When TEOS addition is complete, add 33.5 grams (0.176 moles) of p-toluenesulfonic acid and keep stirring, Until the solids were dissolved, a light yellow solution containing 1.74% T i was obtained. Example 18 8 Example 7 was repeated except that 50 grams (0.352 mol) of phenylphosphine was used. Acid substitutions other than 7 5 g. The resulting pale yellow solution contains 1.83%

Ti 〇

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Page 27

592811 __ ^ Plug No. 88106251 kg 丨 afternoon c month ^ amendment _ V. Description of the invention (23) Example 1 9 Repeat Example 17 7 'Except to use 50 grams (0.32 2 Moore) of phenyl The phosphinic acid was replaced by 75 g and 67 g (0.352 mol) of p-toluenesulfonic acid was replaced by 3 3.5 g. The resulting light yellow solution contained 丨 · 70% τ i. Column 20 repeats Example 17 'except that 75 grams are replaced with 25 grams (0. 76 moles) of phenylphosphinic acid. The resulting light yellow solution contained 丨 · 9 3 Ti ° The results of the previous examples are summarized in Table 2 below. L ·!

Comparison of catalyst with final time 丨 mmHg, 285 ° C, 225ppmTi molar ratio Example Ti P SA Si Final time (minutes) L b Xu Xie 1 Antimony 95, 75.52 7.07 1 17 1.0 3.0 1.0 3.0 90 ^ 73.65 7 ^; Q 2 18 1.0 2.0 1.0 — / • 〇y 3.0 85 75.18 7.13 2 19 1.0 2.0 2.0 75 74.99 8.21 2 20 1.0 1.0 1.0 3.0 ------ 50 74.64 8.31 2

Titanium oxide on ethylene glycol, 300 ppm recorded cp = phenylphosphinic acid; Si = TEOS; and SA p 2 · T = tetrakis (2-ethylhexyl) -toluenesulfonic acid Table 2 shows the polymerization rate without improvement Compared with the use of video as a catalyst than fortunate. Example 2 1-2 8

O: \ 58 \ 58096-910820.ptc Page 28 592811 Amendment No. 88106251 V. Description of the Invention (24) In Examples 2 1-28, many combinations shown in Table 1 were retested with 2 mm Hg Thing. The results are shown in Table 3. Table 3 Comparison of the final time and color of the antimony catalyst DMT-based oligomers, 2 mm Hg mole ratio color Example Ti P SA ppm Metal urging J Ti Sb Final time (minutes) L b Note a Antimony 0 375 98 72.9 -5.7 1 21 1.0 4.0 3.0 20 100 90 62.8 -5.1 2,4 Record 0 375 92 70.5 -4.0 3 22 1.0 4.0 3.0 20 100 81 64.7 -4.4 2,4 23 1.0 4.0 3.0 20 50 95.5 74.2 1.2 2 , 4 24 1.0 4.0 3.0 20 0 93 77.5 3.2 2,4 25 1.0 2.0 2.0 20 100 81.5 72.8 0.2 2,5 26 1.0 2.0 2.0 15 188 94.5 74.1 0.7 235 27 1.0 2.0 2.0 20 375 105 '64.2 -2.3 2,5 28 1.0 2.0 2.0 12.5 0 101.5 77.7 1.8 2,5 a. Control experiment using antimony oxide 2. Refer to footnote 2 in Table 2 3 · Second control experiment 4. Example 1 corresponding to Table 1 4 5 · Correspondence Example 6 in Table 1 Orthosilicate and antimony The results in Table 3 show that the final time obtained using the titanium compound, phosphinic acid composition (etc.) is significantly shortened in Example 2 9

O: \ 58 \ 58096-910820.ptc page 29 592811 _ case number 88106251_β leap year p month > 1? _ Revision __ 5. Description of the invention (25) 50 grams (0.352 mole) of phenyl Phosphonic acid and 218.6 grams of 1,3-propanediol were placed in a 500 ml beaker equipped with the same as in Example 2. Initiate induction 'and heat the mixture to 45 ° C to dissolve the solid. When all the enzyme solids were dissolved, 110 g (0.528 mol) of tetraethyl orthoacetate was added dropwise over 30 minutes. Then, 50 grams (0.176 moles of TYZOR® TPT) was added dropwise over 30 minutes. Finally, 33.5 grams of p-xanthoxyflavonic acid was added and the reaction block was allowed to stir until it dissolved. The final yellow solution contained ° K 8% T Example 30 0 100 g (0.704 mol) of phenylphosphinic acid and ι0.9 · 4 g of 1,3-propanediol were charged to 500 ml equipped with the same as in Example 2. In the beaker. Start to infuse and heat the mixture to 45 ° C and maintain until all solids are dissolved. Then, in a similar manner as in Example 29, 100 g (0.528 mol) of raw material is added dropwise. Tetraethyl silicate and 50 grams (0176 Mo TYZOR® TPT. The final product is a light yellow solution containing 2.3% Ti. Example 31. 40 grams (0.22 Mole) of phenyl Put phosphinic acid and 174.7 grams of i 3 propylene glycol into a 500 ml beaker equipped as in Example 2. Then 53.5 grams of p-toluenesulfonic acid (PTSA) was added. The solution was stirred, Until the σ PTSA is dissolved, and then 40 g (0.141 mol) of TY is added dropwise below 40 t. ZOR® TPT. The reaction block was maintained at 40 t hours, and then 40 grams (41 mol, TYZOR® TPT) was added dropwise below 400 c. The reaction block was maintained at hours, and then, To obtain a pale yellow solution containing 2.2% T i. Example 3 2

592811 _ Case No. 88106251 Rev. P ^^^ 4 of the year _ V. Description of the invention (26) ^ In the same way, the ethylene glycol in Examples 14 and 18 will be the same, the amount of 1, 4-butanediol or linear or branched alcohol substitution, such as ethanol or isopropanol, to give a pale yellow solution, which was tested in an amount similar to its ethylene glycol.

O: \ 58 \ 58096-910820.ptc Page 31 592811 _Case No. 88106251 β 丨 year $ month > € 7th Amendment Simple diagram description Page 32 O: \ 58 \ 58096-910820.ptc

Claims (1)

592811 I Chong No. 88106251 ft · xian. Li Λ, read Qin Lifan ui: ri- month said modified beauty ^ warehouse ^ containing compound, dissolution promoter, structural source The dissolution promoter is orthosilicate, the source of phosphorus Is selected from the group consisting of an acid, a phosphine, and two or more combinations thereof, the titanium chemical formula Ti (0R) 4, wherein each R is independently selected from the group consisting of an alkane, an aralkyl group, and two or more combinations thereof 1: 1 至 1 Each of the substances includes from 1 to 30 carbon atoms, wherein the source of phosphorus to the titanium compound ranges from 0.1: 1 to 1 0: 1, and the ratio of the dissolution promoter to the titanation ranges from 0.1 to 1 to 1 0: 1. The composition according to item 1 of the patent, wherein the composition is manufactured by combining an organic phosphorus source, a dissolution promoter, and a solvent, and the additive is an organic orthosilicate. The composition of claim 1 or 2, wherein the solvent is 1. A composition and a solvent whose phosphonic acid, phosphinate compound has a chemical group, a cycloalkyl group and a mole ratio of each base Moore 2. According to Shen Ti compounds, the dissolution promotes 3. According to Shen an alcohol. 4. The composition according to item 3 of the scope of patent application, wherein the solvent is selected from the group consisting of ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropyl glycol, butanediol, 1-methylpropanediol, Pentylene glycol and each of two or more combinations thereof. 5. The composition according to item 1 of the scope of the patent application, wherein the titanium compound is selected from the group consisting of tetraisopropyl titanate, tetra-n-butyl titanate, and combinations thereof. 6. The composition according to item 1 or 2 of the scope of the patent application, which further comprises acid. 7. The composition according to item 6 of the scope of the patent application, wherein the acid is selected from free p-benzoic acid, benzoic acid, acetic acid, acetic acid, and propane. O: \ 58 \ 58096-910820.ptc Page 33 592811 Case No. 88106251 One year? Month Amendment 6. Scope of patent application Sulfuric acid and two or more of its combinations. 8. The composition according to item 1 or 2 of the scope of the patent application, wherein the phosphorus compound is selected from the group consisting of phosphonic acid, phosphinic acid, phosphine, and combinations thereof. 9. The composition according to item 1 or 2 of the patent application scope, further comprising a co-catalyst selected from the group consisting of a cobalt / aluminum catalyst, a titanium compound, and a combination thereof. 1 0. A method for manufacturing a composition according to item 1 of the scope of patent application, which comprises combining a titanium compound, a dissolution promoter, a source of phosphorus, and a solvent at a temperature of 0 to 100 ° C to manufacture a composition, wherein the The dissolution accelerator is an organic orthosilicate, and the phosphorus compound is selected from the group consisting of phosphonic acid, phosphinic acid, phosphine, and two or more combinations thereof. The titanium compound has the chemical formula Ti (OR) 4, each of which R is independently selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group, and two or more combinations thereof, and each group includes from 1 to 30 carbon atoms, in which the source of phosphorus is mole of titanium The ratio ranges from 0.1: 1 to 10: 1, and the molar ratio of the dissolution accelerator to the titanium compound ranges from 0.1: 1 to 10: 1. 1. The method according to item 10 of the scope of patent application Where the solvent is an alcohol. 1 2. The method according to item 10 of the application, wherein the solvent is selected from the group consisting of ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropyl glycol, butanediol, and 1-methylpropanediol. , Pentanediol, and two or more of them. 1 3. The method according to item 10, 11 or 12 of the scope of patent application, further comprising combining the composition with sulfonic acid to produce a second composition, O: \ 58 \ 58096-910820.ptc Page 34 592811 Amendment No. 88106251 VI. In the scope of the patent application, the sulfonic acid is selected from the group consisting of p-toluenesulfonic acid, benzenesulfonic acid, oxanesulfonic acid, and ethanesulfutenic acid. , Propionic acid, and two or more of them in combination. 14. The method according to item 10 of the application, wherein the titanium compound is selected from the group consisting of tetraisopropyl titanate, tetra-n-butyl titanate, and combinations thereof. j 1 5. The method according to item 10, 11 or 12 of the scope of the patent application, further comprising combining the composition or the second composition with a co-catalyst selected from the group consisting of a cobalt / aluminum catalyst, antimony Each of the compounds and their combinations is included in the presence of a catalyst composition. The catalyst composition is described in item 1 of the scope of the patent application by contacting a carbonyl compound with an alcohol in accordance with 16.-A method for producing a polyester. 1 7. The method according to item 16 of the scope of patent application, wherein the catalyst component is manufactured according to the method described in item 10 of the scope of patent application. 1 8. The method according to item 16 or 17 of the scope of the patent application, wherein the carbonyl compound is selected from the group consisting of the chemical formula (0H) mR4 (C00R ') p, the chemical formula HVCCAiCC ^, acid anhydride, and two or more combinations thereof. The alcohol is selected from the group consisting of R5 (ΟΗ) η, (ΗΟ) ηΑ (ΟΗ) η, and combinations thereof; m is a number from 0 to about 10, and each of R4 and R 'is independently selected from Argon, a hydrocarbyl group having a carboxyl group at the terminal of the radical, a hydrocarbyl group, and two or more combinations thereof, each group having 1 to 30 carbon atoms and its system is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkene And each of two or more combinations thereof; p is an integer from 1 to equal to R4 carbon atoms; A is selected from the group consisting of an alkylene, an arylene, an alkenyl, or two or more combinations thereof Each; and R5 is a branched or straight bond. O: \ 58 \ 58096-910820.ptc Page 35 592811 _ Case No. 88106251 4 丨 amended on the month and day _ 6, the scope of the patent application 19. According to the method of the 18th scope of the patent application, the solvent is selected Free ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropyl glycol, butanediol, 1-methylpropanediol, pentanediol, diethylene glycol, triethylene glycol, 2-ethyl Hexanol, stearyl alcohol, 1,6-hexanediol, glycerol, isopentaerythritol, and two or more of them. 20. The method according to item 19 of the application, wherein the solvent is selected from the group consisting of ethylene glycol, 2-ethylhexanol, and combinations thereof. 2 1. The method according to item 18 of the scope of patent application, wherein the carbonyl compound is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, phthalic acid, glutaric acid Acid, acrylic acid, oxalic acid, phenylarsinic acid, maleic acid, propionic acid, 4-hydroxyphenylarsinic acid, 12-hydroxydecanoic acid, 6-hydroxyhexanoic acid, 4-hydroxycinnamic acid, 4-hydroxyfluorenylbenzene Acid, 4-hydroxyphenylacetic acid, azelaic acid, salicylic acid, hexanoic acid, stearic acid, palmitic acid, fumaric acid, decalinic acid, citric acid, trimesic acid, pamoic acid, Sebacic acid, any anhydride of these acids, and each of two or more combinations thereof. 2 2. The method according to item 18 of the scope of patent application, wherein the carbonyl compound is selected from the group consisting of terephthalic acid, dimethyl terephthalate, and combinations thereof. 2 3. The method according to item 16 or 17 of the scope of the patent application, wherein the catalyst composition further comprises water, and the molar ratio of water to titanium compound ranges from 0.01: 1 to 6: 1. O: \ 58 \ 58096-910820.ptc Page 36