MXPA00010105A - Catalyst composition comprising a titanium compound, a phosphorus compound and a solubility promoter;preparation and use thereof - Google Patents

Abstract

A catalyst composition is disclosed. The composition comprises a titanium compound, a solubility promoter selected from the group consisting of orthosilicates, orthozirconates, and combinations thereof, a phosphorus source, a solvent, and optionally a sulfonic acid, a cocatalyst, or both. The cocatalyst can be a cobalt/aluminum catalyst, and 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 phosporous 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

COMPOSITION OF CATALYST CONTAINING A COMPOUND OF TITANIUM, A COMPOSITE OF PHOSPHORUS AND A SOLUBILITY PROMOTER; YOUR PREPARATION AND USE.

FIELD OF THE INVENTION This invention relates to a catalyst composition containing a titanium compound, to a process for producing the composition, and to a process for using the composition, for example, in esterification, transesterification, or polymerization of a compound of carbonyl.

BACKGROUND OF THE INVENTION Polyesters such as, for example, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), generally referred to as "polyalkylene terephthalates", are a class of industrial polymers. important They are widely used in thermoplastic fibers, films and molding applications.

Polyalkylene terephthalates can be produced by transesterification of a dialkyl terephthalate ester with a glycol or by direct esterification of terephthalic acid with the selected glycol followed by polycondensation. A catalyst is used to catalyze the esterification, transesterification or polycondensation. Ref: 122676 selected glycol followed by polycondensation. A catalyst is used to catalyze the esterification, transesterification or polycondensation. Many commercial processes use manganese or zinc salts as the catalyst for the transesterification step. Antimony, in the form of antimony oxide glycol solution, is typically used as the polycondensation catalyst either in the transesterification or direct esterification process outlined above. However, antimony forms insoluble antimony complexes that clog the nozzles for spinning fibers. In addition, the use of antimony catalysts is generally related as less environmentally tolerable, articles related to heavy metals could arise in applications that are in contact with food. Organic titanates, such as tetraisopropyl and tetra n-butyl titanates, are known to be effective polycondensation catalysts for preparing polyalkylene terephthalates in general, and are often the catalyst of choice. However, organic titanates are not generally used to produce PET, because residual titanate tends to react with trace impurities, such as aldehydes, formed during polycondensation and PET processing, thus generating undesirable yellow discoloration. Additionally, many organic titanate catalysts are also substantially insoluble in a polymerization mixture, thus creating a non-uniform distribution of catalyst in the mixture. Therefore, there is a growing need for the development of a new catalyst that is substantially soluble, efficient, and that produces a polymer with reduced color. An advantage of the catalyst composition of the present invention is that, when used to produce a particular polyalkylene terephthalate, it has a high reactivity and the polymer produced therefrom has improved optical properties (eg, less undesirable color) compared to the polymer produced using previously known organic titanate catalysts. Other advantages will become more apparent as the invention is more fully described.

BRIEF DESCRIPTION OF THE INVENTION According to a first embodiment of the present invention, a catalyst composition is provided, which can be used as a catalyst esterification or transesterification, or as a polycondensation catalyst to produce polyalkylene terephthalates. The composition contains an organic titanium compound, a solubility promoter, and a phosphorus source. The composition may further contain a sulfonic acid, and optionally a cocatalyst, wherein the solubility promoter is selected from the group consisting of ortho-silicates, ortho zirconates, and combinations thereof. According to a second embodiment of the present invention, a process for the production of a catalyst composition is provided. The process comprises combining a solvent, an organic titanium compound, a phosphorus source, a solubility promoter, and optionally a sulfonic acid, a cocatalyst, or combinations thereof, wherein the solubility promoter is selected from the group consists of ortho silicates, ortho zirconates and combinations thereof. According to a third embodiment of the present invention, there is provided a process that can be used, for example, in the production of an ester or polyester. The process comprises contacting, in the presence of a catalyst composition, a compound of . ^ -7 .. carbonyl with an alcohol. The catalyst composition is the same as that described above.

DETAILED DESCRIPTION OF THE INVENTION According to the first embodiment of the present invention, a catalyst composition is provided. The composition may contain an organic titanium compound, a solubility promoter, a phosphorus source, and optionally a sulfonic acid, a cocatalyst, or a combination thereof. The composition may also consist essentially or consist of an organic titanium compound, a solubility promoter, a phosphorus source, and a sulfonic acid. The solubility promoter may be selected from the group consisting of ortho silicates, ortho zirconates, and combinations thereof, and the cocatalyst may be selected from the group consisting of a cobalt / aluminum catalyst as described in US 5,674,801, an antimony compound , and combinations thereof. The catalyst composition of this invention is substantially soluble in a solvent. The term "substantially" means more than trivial. It is preferred that the composition be completely soluble in the solvent. However, a substantial portion of the composition can also be suspended or f 'dispersed in the solvent. According to the present invention, the titanium compounds currently preferred are organic titanium compounds. Titanium tetrahydrocarbyloxides are currently the most preferred organic titanium compounds because they are readily available and effective. Examples of suitable titanium tetrahydrocarbyloxide compounds include those expressed by the general formula Ti (OR) lr where each R is independently selected from the group consisting of an alkyl radical, a cycloalkyl radical, an aralkyl hydrocarbon radical, and combinations of two or more of them. Each radical may contain from 1 to about 30, preferably from 2 to about 18, and more preferably from 2 to 12 carbon atoms per radical, and each R may be the same or different. Titanium tetrahydrocarbyloxides in which the hydrocarbyl group contains from 2 to about 12 carbon atoms per radical, and which is a linear or branched alkyl radical, are most preferred because they are relatively inexpensive, readily available and effective to form the solution. Suitable titanium tetrahydrocarbyloxides include, but are not limited to, tetraethoxide of titanium, titanium propoxide, titanium isopropoxide, titanium tetra-n-butoxide, titanium tetrahexoxide, titanium tetra-2-ethylhexoxide, titanium tetraoxide, and combinations of two or more thereof. generally the presence of a halide, or other active substituent, in the R group since such substituents can interfere with catalytic reactions or form undesirable by-products, which can contaminate the polymer when the titanium compound is used to produce a polymer when The titanium compound is used to produce a polymer. Currently, it is also preferred that each R group is identical to facilitate the synthesis of the organic titanate. In some cases two or more R groups may be of a common chemically bonded compound, together with a different one in the titanium atom (ie, multi-indented ligands such as triethanolamine, citric acid, lactic acid, malic acid, tartaric acid, hydroxy glycine, a salt of the acid, and combinations of two or more thereof). The titanium tetrahydrocarbyloxides suitable for use in the present invention can also be produced, for example, by mixing titanium tetrachloride and an alcohol in the presence of a base, such as ammonia, to form the tetraalkyl titanate. He alcohol is typically ethanol, n-propanol, isopropanol, n-butanol or isobutanol. In general, methanol is not used, because the resulting tetramethyl titanate is insoluble in the reaction mixture., complicating its isolation. The tetraalkyl titanates thus produced can be recovered by first stirring the byproducts of ammonium chloride by any means known to one skilled in the art, such as filtration followed by distillation of the tetraalkyl titanate from the reaction mixture. This process can be carried out at a temperature in the range of about 0 to about 150 ° C. Titanates having larger alkyl groups can also be produced by transesterification of those having R to C4 groups, with alcohols having more than 4 carbon atoms per molecule. Examples of commercially available organic titanium compounds include, but are not limited to, TYZORFTPT and TYZOROTBT (tetra isopropyl titanate and tetra n-butyl titanate, respectively) available from E.I. duPont de Nemours and Company, Wilmington, Delaware, U.S.A. It is currently preferred that the phosphorus source be selected from a phosphonic acid, a phosphinic acid, a phosphine, or combinations thereof. Without intending to relate to theory, it appears that the phosphorus compounds bind to an organic titanium compound during the preparation of the catalyst composition, thereby improving the solubility of the titanium compound and aiding in the control of the optical properties of the polyester produced using these compounds. Phosphonic acid, phosphinic acid, or phosphine may have an alkyl, alkenyl, alkaryl, arialkyl or aryl group directly attached to the phosphorus atom. Typically each group may contain from 1 to about 25, preferably from 1 to about 20, and more preferably from 1 to 15 carbon atoms per group. For example, methyl group, ethyl group, phenyl group, or naphthyl group may be present. These groups can be further substituted with substituent groups that do not unduly interfere with the preparation of the catalyst composition or subsequent reactions employing the catalyst. In addition, the hydroxy group of the acid can also be substituted. For example, one or two OH groups attached to the phosphorus atom of a phosphonic acid can be esterified. Organic phosphonic acids tend to be chelating agents stronger than phosphinic acids, and can be used for applications where a strong bond between the phosphorus compound and the organic titanium compound is desired. It has been found that phenyl phosphinic acid, diphenyl phosphinic acid and 3- (hydroxyphenylphosphinyl) propanoic acid provide an excellent balance between the reaction rate and the prevention of color generation in applications where the catalyst system is used as a polycondensation catalyst for the preparation of polyalkylene terephthalates in general, and PET in particular. Examples of suitable phosphines include, but are not limited to, 1,2-bis-diphenylphosphinoethane, 1,3-bis-diphenylphosphinopropane, 1,4-bis-diphenylphosphinobutane, bis-4-tolylphosphine oxide, bis-3 oxide, 5-xylylphosphine, or combinations of two or more thereof. Any solvent that can substantially dissolve the catalyst composition described above can be used in the present invention. The presently preferred solvent is an alcohol having the formula R '(0H) n, an alkylene glycol of formula (OH) nA (OH) ", a polyalkylene glycol or alkoxylated alcohol having the formula of ^ [CH2CH (R1) O] "H, or combinations of two or more thereof, in which each R1 may be the same or different and is a hydrocarbyl radical having from 0.1 to about 10, preferably from 1 to about 8, and more preferably from 1 to 5 carbon atoms per radical. The currently preferred R1 is an alkyl radical, either branched or straight chain. A may have from 2 to about 10, preferably from 2 to about 7, and more preferably from 2 to 4 carbon atoms per molecule. Each n may be the same or different and is independently a number in the range of 1 to about 10, preferably 1 to about 7, and more preferably 1 to 5. Examples of suitable solvents include, but are not limited to ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, 2-ethyl hexanol, and combinations of two or more of them. The currently preferred solvent is ethylene glycol for the polyester produced therefrom, it has a wide range of industrial applications.

The currently preferred solubility promoter can be an organic silicate, organic zirconate, or combinations thereof. Currently, it is preferred more than a solubility promoter can facilitate the dissolution of essentially all of the titanium present in the catalyst composition in a solvent used to prepare the composition, at room temperature (about 25 ° C), in concentrations of the catalyst composition that are desired for the particular application. The components are typically selected to form a catalyst composition that dissolves in concentrations of at least 3 grams, preferably at least 5 grams, of catalyst per 100 grams of solvent, to minimize the amount of solvent introduced into a process employing the catalyst . The most preferred solubility promoters currently include, but are not limited to, organic ortho silicates, organic ortho zirconates, or combinations thereof. The organic ortho silicates have the formula of SifOR and the organic ortho-zirconates have the formula of Zr (0R1) 4 in which each R1 is the same as that described above. These solubility promoters are generally commercially available or can be produced, for example, by introducing a silicon tetrachloride or zirconium tetrachloride in a solvent described above, to replace the chlorides with R 1 groups in the solvent. Examples of promoters of Suitable solubilities include, but are not limited to, tetraethi ortho-silicate &gf ortho-n-propyl silicate, tetra-n-propyl ortho-zirconate, tetra-n-butyl ortho zirconate, and combinations of two or more of the same. Ortho-tetraethyl silicate and tetra-n-propyl ortho silicate are commercially available. Ortho tetra-n-propyl zirconate and tetra-n-butyl ortho zirconate are commercially available organic zirconates in E.I. du Pont de Nemours and Company, under the trade name "TYZOR®". The particular selection of ortho silicate or zirconate will vary with the particular reaction to be promoted. For example, an ortho silicate is preferred over an ortho zirconate to prepare PET, although it has less of an effect on the rate of condensation. A sulfonic acid or salt thereof may optionally be used in the present invention. Presently preferred sulfonic acids can be any of aryl or alkyl sulfonic acid, which can be substantially soluble in a solvent described above. Examples of suitable sulfonic acids include, but are not limited to, p-toluene sulphonic acid, benzene sulphonic acid, methane sulphonic acid, ethane sulphonic acid, propran acid sulfonic acid, sulphanic acid, and combinations of two or more of the same. The sulfonic acid salt may be an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or combinations of two or more thereof. The catalyst composition may also contain a cocatalyst. Examples of cocatalysts include, but are not limited to, cobalt / aluminum catalysts, antimony compounds, and combinations thereof. The cobalt / aluminum catalyst contains a cobalt salt and an aluminum compound, wherein the molar ratio of aluminum to cobalt is in the range of 0.25: 1 to 16: 1. The cobalt / aluminum catalyst is described in U.S. Pat. No. 5,674,801, the description of which is incorporated herein by reference. The currently preferred antimony compound can be any antimony compound that is substantially soluble in a solvent described above. Examples of suitable antimony compounds include, but are not limited to, antimony oxides, antimony hydroxides, antimony halides, antimony sulfides, antimony carboxylates, antimony ethers, antimony glycollates, antimony alcoholates, antimony nitrates, sulfates antimony, antioxin phosphates, and combinations of two or more thereof. According to the first embodiment of the present invention, the molar ratio of phosphorus source to titanium compound, measured as P: Ti, may be in the range of about 0.1: 1 to about : 1, preferably around 0.5: 1 to about 7: 1, and more preferably 1: 1 to 4: 1 The molar ratio of solubility promoter to titanium compound (Si: Ti or Zr: Ti) may be in the range of about 0.1: 1 to about 10: 1, preferably about 0.5: 1 to about 7: 1, and more preferably from 1: 1 to 4: 1. The molar ratio of sulfonic acid to titanium compound (S03: Ti) is generally preferred to be less than or equal to 2: 1. However, the ratio may also be in the range of about 0.1: 1 to about 4: 1, preferably about 0.5: 1 to about 3: 1, and more preferably of about 1: 1 to about 2: 1. The molar ratio of cocatalyst to titanium compound, such as Sb: Ti or Co: Ti, may be in the range of about 0.01: 1 to about 10: 1. The molar ratio of phosphorus source to solubility promoter (Si: P or Zr: P) is generally greater or equal to about 0.5: 1 if the catalyst composition is used in the production of a polyalkylene terephthalate, because lower ratios can cause discoloration in the polyalkylene terephthalate. Alternatively, the titanium compound can be present in the catalyst composition in the range of from about 0.01 to about 15, preferably from about 0.1 to about 10, and more preferably from 0.5 to 5 percent (%), based on the total weight of the catalyst. the composition as 100%. According to the present invention, the catalyst composition, especially the one containing a sulfonic acid, may also contain water. The water-containing composition possesses a high degree of activity and aids in the control of the optical properties of the polyester produced using the composition. The molar ratio of water, when present, to titanium compound may be in the range of about 0.01: 1 to about 6: 1, preferably of about 0.1: 1 to about 4: 1, and more preferably of about 1. : 1 to about 2: 1. Since the catalyst composition has been described in detail for its preferred application, as a polycondensation catalyst for the manufacture of polyalkylene terephthalates B the composition also has general utility as an esterification or transesterification catalyst in conventional processes that require a highly active catalyst. For example, the catalyst composition could be employed in the reaction of phthalic anhydride and octyl alcohol to form dioctyl phthalate, a plasticizer of polyvinyl chloride, which has low opacity. The relative ratios of the catalyst components can be adjusted to meet the requirements of a particular application. The catalyst composition can be produced by any means known to one skilled in the art. However, it is preferred to produce it by the process described in the second embodiment of the present invention. The catalyst composition can be produced in a solvent that is compatible with or does not interfere with an esterification or transesterification or polycondensation reaction. For example, if the catalyst composition is used as a polycondensation catalyst to produce PET, the composition is preferably produced in ethylene glycol; if the catalyst composition is used to produce PBT, the composition is preferably produced in 1,4-butanediol; and if the Catalyst composition is used to produce polypropylene terephthalate (PPT), the composition is preferably produced in 1,3-propylene glycol. For the production of dioctylphthalate, 2-ethylhexyl alcohol is the preferred alcohol. Since the individual components can be combined in any order, it is preferred to first combine a solubility promoter and a solvent to produce a first mixture. The first mixture is then combined with a phosphorus source to produce a second mixture, because the solubility promoter helps the phosphorus source to dissolve. In general, the combination for producing the first or second mixture can be stirred and can be carried out at a temperature in the range from about 0 ° C to about 100 ° C, preferably from about 30 ° C to about 50 ° C. In general, any amount of solvent can be used as long as the amount can substantially dissolve the composition and can be in the range of about 5 to about 50, preferably about 10 to about 30, and more preferably 10 to 20 moles per mole of the titanium compound used in the composition. The titanium compound can be combined after with the second mixture to produce the catalyst composition of the present invention. This step is preferably carried out in an inert atmosphere, such as nitrogen, carbon dioxide, helium or combinations of two or more thereof, to prevent the release of an inflammable alcohol because this step is exothermic causing the temperature increase from 10 to 30 ° C. This step can be carried out by stirring for a sufficient period of time to substantially dissolve the titanium compound, generally about 5 minutes to about 20 hours or more, followed by cooling to room temperature. The catalyst composition can then be combined with a sulfonic acid, a cocatalyst, or both to produce an optional catalyst composition. The sulfonic acid can also be combined contemporaneously with the phosphorus source and the first mixture to produce the second mixture. Alternatively, the phosphorus source can be combined with a solvent and a titanium compound to form a complex. The complex can be isolated from the solvent by any conventional means, such as filtration, to produce an isolated complex. The isolated complex can then be combined with a mixture containing a solvent, solubility promoter, sulfonic acid, or cocatalyst, or combinations of two or more thereof, to produce the catalyst composition of the present invention. The amounts of individual components may vary with the selected compounds, and in general may be such that the molar ratio of each component to titanium in the catalyst compound produced is within the range described above. The structure of the catalyst system has not been established. However, based on the observed exotherm it is believed that the components have reacted or have complexed in some way to form binary or tertiary composition (s), at least to some degree, which makes the catalyst composition especially useful as a catalyst of polycondensation in the manufacture of polyalkylene terephthalates in general, and polyethylene terephthalate (PET) in particular. According to the third embodiment of the present invention, there is provided a process that can be used in, for example, the production of an ester or polyester. The process comprises contacting, in the presence of a catalyst composition, a carbonyl compound with an alcohol. The composition is the same as described above in the first embodiment of the present invention. v 'f According to the third embodiment of the invention, any carbonyl compound that can react with an alcohol to produce an ester can be used. In general, such carbonyl compounds include, but are not limited to, acids, esters, amides, acid anhydrides, acid halides, oligomers or polymers having repeating units derived from an acid, or combinations of two or more thereof. . The currently preferred acid is an organic acid. Presently preferred processes are (1) the production of an ester such as, for example, bis (2-ethylhexyl) phthalate from phthalic anhydride and 2-ethylhexanol, and (2) the polymerization of an acid or an ester and a alcohol for the production of a polyester.

A preferred process for producing an ester or polyester comprises, consists essentially of, or consists of contacting a reaction medium with a composition described above in the first embodiment of the invention. The reaction medium may comprise, consist essentially of, or consist of (1) either an organic acid or an ester thereof and an alcohol, or (2) an alcohol and an oligomer having repeating units derived from an organic acid or ester.

The carbonyl compound, organic acid or ester thereof, may have the formula of (H0) "R2 (COOR ') p wherein m is a number from 0 to about 10, preferably from 0 to about 5, and more preferably from 0 to 3; each R2 and R 'can be independently (1)? idrogen, (2) hydrocarbyl radical having a carboxylic acid group in the term, (3) hydrocarbyl radical, or (4) combinations of two or more thereof in which each radical can be substituted or unsubstituted; each radical has from 1 to about 30, preferably from about 3 to about 15 carbon atoms per radical, which may be alkyl, alkenyl, aryl, alkaryl, aralkyl radical, or combinations of two or more thereof; and p can be an integer from 1 to a number that equals the number of carbon atoms in R2. Any organic acid anhydride can also be used. The presently preferred organic acid is an organic acid having the formula wherein A1 is an alkylene group, an arylene group, an alkenylene group, or combinations of two or more thereof. Each A1 has from about 2 to about 30, preferably from about 3 to about 25, more preferably from about 4 to about 20, and more preferably from 4 at 15 carbon atoms per group. Examples of acids are not limited to terephthalic acid, softwood acid, naphthalic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, acrylic acid, oxalic acid, benzoic acid, maleic acid, propenoic acid, 4-hydroxybenzoic acid, 12-hydroxydecanoic acid, 6-hydroxyhexanoic acid, 4-hydroxycinnamic acid, 4-hydroxymethylbenzoic acid, 4-hydroxyphenylacetic acid, azelaic acid, salicylic acid, caproic acid, stearic acid, palmitic acid, fumaric acid, naphthalene dicarboxylic acid, citric acid, trimesic acid, pamoic acid, sebacic acid, any anhydride of these acids, and combinations of two or more thereof. The currently preferred organic diacid is terephthalic acid, because the polyesters produced therefrom have a wide range of industrial applications. Examples of suitable esters include, but are not limited to, dimethyl adipate, dimethyl phthalate, dimethyl terephthalate, methyl benzoate, dimethyl glutarate, and combinations of two or more thereof. Any alcohol that can esterify an acid to produce an ester or polyester can be used in the present invention. The preferred alcohol currently has the formula of R3 (0H) n, an alkylene glycol of formula (OH) "A (OH)", or combinations thereof, wherein each R3 may be the same or different and is a hydrocarbyl radical having 1 to approximately 10, preferably from 1 to about 8, and more preferably from 1 to 5 carbon atoms per radical. The currently preferred R3 is an alkyl radical, either branched or straight chain. A may have from 2 to about 10, preferably from 2 to about 7, and more preferably from 2 to 4 carbon atoms per molecule. Each n may be the same or different and is independently a number in the range from 1 to about 10, preferably from 1 to about 7, and more preferably from 1 to 5. Examples of suitable alcohols include, but are not limited to, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, 2-ethyl hexanol, stearyl alcohol, butylene glycol, 1,6-hexanediol, glycerol, pentaerythritol, and combinations of two or more thereof. The most preferred alcohol currently is alkylene glycol, such as ethylene glycol, for the polyester produced therefrom, it has a wide range of industrial applications.

* M asm¡ ^ ^ ^^ The contacting of the reaction medium with the catalyst can be carried out by any suitable means. For example, the individual compositions of the reaction medium can be combined before they are contacted with the catalyst. However, it is currently preferred that j00Tcatalyst be dissolved or dispersed first in an alcohol by any suitable means, such as mixing or mechanical stirring to produce a solution or dispersion followed by combining the solution or dispersion with (1) an organic acid, an ester , an oligomer of an organic acid, or combinations of two or more thereof, and (2) an alcohol under a condition sufficient to effect the production of an ester or polyester. According to the present invention, the reaction medium, if a sulphonic acid is present in the catalyst composition, can also contain water. The amount of water, if present, is the same as that described above. The oligomer of the diacid and alkylene glycol generally has a total of from about 1 to about 100, preferably from about 2 to about 10, repeating units derived from the diacid and alkylene oxide. An adequate condition to effect production of a polyester can include a temperature in the range of about 150 ° C to about 350 ° C, preferably of about 200 ° C to about 300 ° C, and more preferably 250 ° C to 300 ° C, low a pressure in the range of about 0.001 to about 10 atmospheres for a period of time from about 1 to about 20, preferably about 1 to about 15, and more preferably from 1 to 10 hours. The molar ratio of the alcohol (or alkylene glycol) to carbonyl compound (or organic acid or ester) can be any ratio, as large as the ratio can effect the production of a polyester. In general, the ratio can be in the range of from about 0.1: 1 to about 10: 1, preferably from about 0.5: 1 to about 5: 1, and more preferably from about 1: 1 to about 3: 1. The molar ratio of the alcohol (or alkylene glycol) to carbonyl compound (or organic acid or ester), for the oligomer having repeating units derived from the carbonyl compound (or organic acid or ester), to alcohol (alkylene glycol) may have the same relation of q: (q-1) in which q may be in the range of about 2 to about 20, preferably of about 2 to 10, and more preferably j? g "2 to 5. The catalyst may be in the range of about 0.0001 to about 30,000 parts per million by weight (ppmp) of the polymerization medium, preferably from about 0.001 to about 1,000 ppmpm, and more preferably from 0.1 to 100 ppmp Other ingredients may also be present to increase the stability or performance of the catalyst Since the advantages of the catalyst can be obtained with polyalkylene terephthalates in general, the advantages are particularly evident, as a substitute for most of antimony in the manufacture of PET, since color purity is an important criterion for commercial articles typically made of PET The catalyst composition can be used to produce esters or polyesters using any of the conventional melt or solid state techniques. catalyst compositions are compatible with esterification catalysts and tr conventional ansesterification (e.g., manganese, cobalt and / or zinc salts) and could be introduced to the countercurrent production process with, or after, the introduction of the esterification catalyst. The catalyst compositions have also been found to be effective to promote the esterification reaction, and could be used as a substitute for some or all of the esterification catalysts, as well as the polycondensation catalyst. The following Examples are provided to further illustrate the present invention, and are not constructed to unduly limit the scope of the invention.

EXAMPLES Dimethyl terephthalate was transesterified with ethylene glycol, using a zinc acetate catalyst, according to Example IA to form DMT oligomer. New catalysts of this invention, synthesized according to Examples 2 to 15, were used as polycondensation catalysts for the DMT of Example IA following the procedure of Example IB. The results were recorded in Table 1, along with four (4) control runs. The color of the resulting polymer was measured in terms of the L value and b value, using an instrument such as SP-78 Spectrophotometer. The L value shows brightness, with the highest numerical value showing the highest brightness (desirable). Preferably, the value L will be equal to or higher than that of the polymer done using antimony catalyst. The b value shows the degree of yellowing, with a higher numerical value showing a higher (undesirable) degree. Preferably, the b value will be that of the polymer made using antimony catalyst. Because the measurement of color is well known to one skilled in the art, the description thereof is omitted here for the sake of brevity.

Example IA Preparation of DMT oligomer without antimony: The oligomers used in these examples contained dimethyl terephthalate, ethylene glycol, without adding antimony. It was prepared as follows: An autoclave was charged with 45.4 Kg (100 lbs) of dimethyl terephthalate, 30.4 Kg (67 lbs) of ethylene glycol and 4.4 g of zinc acetate dihydrate. The batch was heated to 240 ° C at a stirring speed of 15 rpm, and 15.0 kg (33 lbs) of methanol and 6.5 kg (14.3 lbs) of ethylene glycol were removed. The load was then heated to 275 ° C over the course of 90 minutes, and the remaining ethylene glycol was removed at 285 ° C and below 2 mm Hg vacuum. Once it was judged that the condensation mass was complete, the melt was Extruded in a water bath pa-solidify the product. The resulting polymer was dried to remove residual moisture before using * Example IB Oligomer catalyst test: A 1 liter resin kettle was provided with a Jiffy Mixer, rotating at 40 rpm, a thermocouple, condenser and nitrogen flow. To this cauldron was added the catalyst to be tested, 115 ml of ethylene glycol, and 400 gm of DMT oligomer as prepared in Example IA. The stirrer was turned on and the temperature was increased to 275 ° C over a period of about 2.5 hours. The content was polymerized keeping stirring at 275 ° C and a pressure of 120 torr for 20 minutes, and at 280 ° C and a pressure of 30 torr for an additional 20 minutes. The content was then maintained under agitation at 285 ° C from 1 to 2 mm Hg of pressure for a sufficient time to reach the torsional force of 15 oz-in (ounces-inches), which was measured by an electro-torsional force controller. Craft Motomatic. The time of this step was recorded as the Final Time, and varied with the catalyst used. The molten polymer was then poured into a water bath to solidify the melt, and the resulting solid was set at 150 ° C for 12 hours, and rotated to pass through a 2 mm filter for color measurements using the previously described spectrophotometer. The comparison of results of "l Final Time in minutes and Color jaique was measured spectrophotometrically is given in the Table 1 later. The following examples describe the preparation of various tested catalyst compositions: Example 2 A 500 ml flask, equipped with an agitator, condenser, drip funnel and N2 purge, was charged with 240 g (3.87 mol) of ethylene glycol. Stirring was started and 25 g (0.176 moles) of phenylphosphinic acid were added. The suspension was heated to 35-45 ° C until the solid dissolved, then 50 g (0.176 mole) of tetraisopropyl titanate (TYZOR®TPT, available from EI du Pont de Nemours and Co.) was added dropwise during 1 hour at 35 ° C. When the addition was complete the reaction mass was stirred for 30 minutes, and then 36.6 g (0.176 moles) of tetraethyl orthosilicate (TEOS) was added over 30 minutes. A clear solution containing 2.4% titanium was obtained.

Example 3 Example 2 was forwarded, except that 73.2 g of TEOS were added. A clear solution containing 2.17% titanium was obtained.

Example 4 A 1 liter flask equipped as in Example 2 was charged with 240.2 g (3.87 mol) of ethylene glycol. Stirring was started and 50 g (0.352 moles) of phenylphosphinic acid was charged. The suspension was heated from 30 ° C to 35 ° C to dissolve the solid, and then 50 g (0.176 mol) of TYZOROTPT was added dropwise during 1 hour at 45 ° C. The clear solution contained 2.48% titanium.

Example 5 A 500 ml flask, equipped as in Example 2, was charged with 240 g (3.87 mol) of ethylene glycol. Stirring was started and 50 g (0.352 mole) of phenylphosphinic acid was added. The suspension was heated from 35 ° C to 45 ° C until the solid dissolved. Then 50 g (0.176 mol) of TYZOR®TPT were added dropwise during 1 hour with cooling to 40 ° C or less. When the addition was complete, the reaction mass was stirred for 1 hour. At 50 g of the above reaction mass is they added 5.4 g of tetraethyl orthosilicate at room temperature. After mixing, a clear solution was obtained which contained 2.24% titanium with a molar ratio of Ti: P: Si of 1: 2: 1.

Example 6 A 100 ml flask, equipped as in Example 2, was charged with 35.3 g (0.569 mol) of ethylene glycol. Stirring was started and 7.3 g (0.052 mole) of phenylphosphinic acid was added. The reaction mass was heated to 35 ° C to dissolve the solid and then 7.4 g (0.026 mole) of TYZOROTPT was added dropwise at 45 ° C for 15 minutes. When the addition was complete, 10.77 g (0.052 moles) of TEOS were added. The resulting clear solution contained 2.04% titanium.

Example 7 A 100 ml flask, equipped as in Example 2, was charged with 35.3 g (0.569 moles) of ethylene glycol. Stirring was started and 7.3 g (0.052 mole) of phenylphosphinic acid was added. The reaction mass was heated to 45 ° C to dissolve the solid and then 7.4 g (0.026 moles) of TYZOR®TPT were added dropwise over 15 minutes. Then they were added 16. 2 g (0.078 moles) of TEOS. The resulting clear solution contained 1.87.% Titanium. "4.

Example 8 A 500 ml flask, equipped as in Example 2, was charged with 240.2 g (3.869 mol) of ethylene glycol. Stirring was started and 75 g (0.528 mole) of phenylphosphinic acid was added. The reaction mass was heated to 45 ° C until the solid dissolved and then 50 g (0.175 mol) of TYZ0R®TPT were added dropwise at 45 ° C for 1 hour. Then 36.6 g (0.176 moles) of TEOS were added to give a clear solution containing 2.1% titanium.

Example 9 Example 8 was repeated, except that 73.2 g (0.352 mole) of TEOS was used to give a clear solution containing 1.92% titanium.

Example 10 Example 8 was repeated, except that 99.8 g (0.528 mole) of TEOS were added to give a clear solution containing 1.77% titanium.

Example 11 A 500 ml flask, equipped as in Example 2, was charged with 240.2 g (3.869 mol) of ethylene glycol. Stirring was started and 100 g (0.703 mole) of phenylphosphinic acid was added. The reaction mass was heated to 35 ° C to dissolve the solids, then 50 g (0.175 moles) of TYZOR®TPT were added dropwise over 1 hour to give a clear solution containing 2.16% titanium.

Example 12 Example 11 was repeated, only 36.6 g (0.176 moles) of TEOS were added to the reaction mixture, after TYZOR®TPT, to give a clear solution containing 1.97% titanium.

Example 13 Example 11 was repeated, except that 53.2 g (0.352 mole) of TEOS were added, after adding the TYZOR®TPT, to give a clear solution containing 1.82% titanium.

Example 14 A 500 ml flask, equipped as in Example 2, was charged with 240.2 g (3.869 mol) of ethylene glycol. The stirring was started and 100 g (0.703 mol) of phenylphosphinic acid was added. The reaction mass was heated to 45 ° C to dissolve the solids, and then 109.9 g (0.528 moles) of TEOS were added. Then 50 g (0.176 moles) of TYZOR®TPT were added dropwise over 1 hour at 38 ° C to give a clear solution containing 1.68% titanium.

Example 15 A 100 ml flask, equipped as in Example 2, was charged with 40 g (0.0135 mol) of a titanium tetra-phenylphosphinic acid solution in ethylene glycol / ethanol solution. Stirring was started and 11.27 g (0.0541 mol) of tetraethyl orthosilicate were added dropwise. The resulting solution was stirred at room temperature for 1 hour and unwound to give 51.3 g of a pale yellow liquid, which contained 1.26% titanium. In the following table, the Ti component was tetraisopropyl titanate, the phosphorus component was phenylphosphinic acid, and component A was tetraethyl ortho silicate. The amount of titanium was 25 parts per million (ppm) based on the weight of the oligomer. The final time is the residence time at the given pressure and temperature until it is reached the desired degree of condensation. The oligomer of the pre-condensation composition was prepared as described in Example IA, and the catalyst was tested as in Example IB. Except where indicated, all catalysts in these runs were soluble glycol.

TABLE 1 Catalyst Comparison for Times of Completion and Color of oligomer based on DMT, lmm Hs. 285C. 25ppm of Ti Notes: 1. This is a Control Run that uses antimony oxide solution in ethylene glycol at 300 ppm antimony. 2. This is a Control Run that uses tetraisopropyl titanate only at 25 ppm Ti. 3. This is a Control Run without phenylphosphinic acid and using a mixture of tetraisopropyl titanate and tetraethyl orthosilicate in a molar ratio of 1: 3 to 25 ppm Ti. 4. This is a test in which silicate was not used (without period), resulting in an insoluble product in glycol. 5. In these runs Ti refers to the titanium of tetraisopropyl titanate (TPT), P refers to phenyl phosphinic acid (PPA) and Si refers to tetraethyl ortho silicate (TEOS). The catalysts were prepared, except where indicated, by adding TEOS (when present) to an ethylene glycol solution of a mixture of PPA and TPT. The catalyst was evaluated at 25 ppm Ti. 6. In these runs, the Si: P ratio was = or > 1, which led to decrease the color L and / or increase the color b in the polymer.

The above table shows that when tetraisopropyl titanate (TPT) is used it produces only unsatisfactory polymer with a lower L color and higher b than antimony. In addition, tetraethyl orthosilicate (TEOS) improves the L color of TPT, but has little effect on color b. When PPA is used in combination with TPT and TEO ?, both the L and b colors improve dramatically. At a higher Si / Ti ratio, for a point, better color L and / or b. When the Si / P ratio equals or exceeds 1.0, the color L and / or b is noticeably worse.

Example 16 A. The catalyst of Example 14 (3.69% Ti) was used to catalyze the esterification of phthalic anhydride and 2-ethyl hexanol. 152.88 g of phthalic anhydride were added to 334.04 g of 2-ethyl hexanol in a 1000 mL resin flask, equipped with a Stark N2 gas receiver diffuser and stirrer. The mixture was heated with gentle stirring. The mixture was heated with gentle stirring. The temperature of the reaction was stably elevated until it reached 141 ° C. At this point, the temperature suddenly dropped to 137 ° C. Then, the temperature began to increase steadily again, and the distillate began to collect in the receiver. At 143 ° C, a 3 mL sample was removed from the reaction flask. Fifteen minutes later the first sample was removed, a 2 mL sample was removed followed by the immediate addition of 1.30 g of catalyst at 151 ° C. 1.30 g of catalyst correspond to 313.8 ppm of Ti for phthalic anhydride. The final product of this reaction was colorless and had very limited opacity. No sign of precipitation that caused the opacity appeared.

B. As a control, TYZOR®TBT was used as the catalyst in the esterification of phthalic anhydride and 2-ethyl hexanol. Reaction was run similar to the esterification of Example 16A as mentioned above. 313.3 ppm of TBT were used. The product of this reaction was colorless, but had a slight opacity that appeared to be a suspended precipitate.

Example 17 A 500 ml flask, equipped as in example 2, was charged with 75 g (0.528 moles) of phenylphosphinic acid and 218.6 g of ethylene glycol. Stirring was started and the mixture was heated to 45 ° C to dissolve the solids. Once the solids were dissolved, 50 g (0.176 mol) of TYZOR® TPT were added dropwise during 30 min, maintaining the temperature at 45 +/- 2 ° C. When the addition was complete, 110 g (0.534 mole) of tetraethylorthosilicate (TEOS) were added dropwise during 30 min, maintaining the temperature at 45 ° +/- 2 ° C. When the addition of TEOS was complete, 33.5 g (0.176 moles) of p-toluenesulfonic acid was added and stirring was continued until the solids dissolved to give a pale yellow solution containing 1.74% Ti.

Example 18 Example 17 was repeated, except that 50 were used g (0.352 moles) of phenylphosphinic acid instead of 75 g. The resulting pale yellow solution contained 1.83% Ti.

Example 19 Example 17 was repeated, except that 50 g (0.352 mole) of phenylphosphinic acid was used instead of 75 g and 67 g (0.352 mole) of p-toluenesulfonic acid instead of 33.5 g. The resulting pale yellow solution contained 1.70% Ti.

Example 20 Example 17 was repeated, except 25 g (0.176 moles) of phenylphosphinic acid was used instead of 75 g. The resulting pale yellow solution contained 1.93% Ti. The results of the previous examples are summarized in the following Table 2.

TABLE 2 Comparison of Catalysts in Times of Termination and Color of oligomer based on DMT, lmm Ho. 28SC. 25ppm of Ti al Control run using antimony oxide solution in ethylene glycol at 300 antimony. 2. T = tetraisopropyl titanate; P = phenyl phosphinic acid; S = TEOS; and SA = p-toluenesulfonic acid.

Table 2 shows an improved polymerization rate compared to the run using antimony as a catalyst.

Examples 21-28 In examples 21 to 28, various combinations miss her ». shown in Table 1 were retested using 2 mm Hg pressure. The results are shown in Table 3.

Table 3 Comparison of Antimony Catalysts for Finishing and Color Times of Oligomers Based on DMT i ">" "" "i "1. Control run using antimony oxide. 2. See footer? in Table 2. 3. Second control run. 4. Corresponding to Example 14, Table 1. 5. Corresponding to Example 6, Table 1.

The results in Table 3 show a greater reduction in the completion time obtained using combination (s) of a titanium compound, phosphinic acid, ortho silicate and antimony.

Example 29 A 500 ml flask, equipped as in example 2, was charged with 50 g (0.352 mol) of phenylphosphinic acid and 218.6 g of 1,3-propanediol. Agitation was started and the mixture was heated to 45 ° C to dissolve the solids. When all the solids were dissolved, 110 g (0.528 mole) of tetraethylorthosilicate was added dropwise during 30 minutes. Then 50 g (0.176 moles) of TYZOR® TPT were added dropwise over 30 minutes. Finally, 33.5 g of p-toluenesulfonic acid were added and the reaction mass was allowed to stir until all was dissolved. The final yellow solution contained 1.8% Ti.

Example 30 A 500 ml flask & equipped as in example 2, was charged with 100 g (0.704 mol) of phenylphosphinic acid and 109.4 g of 1,3 propylene glycol. Agitation began and the most < The reaction medium was heated to 50 C and held there until all the solids dissolved. Then, 100 g (0.528 mole) of tetraethylorthosilicate and 50 g (0.176 mole) of TYZOR®TPT were added dropwise in a similar manner to Example 29. The final product was a pale yellow liquid containing 2.3% Ti.

Example 31 A 500 ml flask, equipped as in example 2, was charged with 40 g (0.282 mol) of phenylphosphinic acid and 174.7 g of 1,3-propylene glycol. Then 53.5 g of p-toluenesulfonic acid (PTSA) was added. The solution was stirred until the PTSA was dissolved, and then 40 g (0.141 mol) of TYZ0R®TPT was added dropwise at less than 40 ° C. The reaction mass was maintained at 40 ° C 1 hr and then then cooled to give a pale yellow solution which contained 2.2% Ti.

Example 32 In a similar manner, the ethylene glycol in examples 14 and 18 is replaced with similar amounts of 1,4-butanediol or linear or branched alcohols, such as ethyl alcohol, or isopropyl alcohol to give pale yellow solutions, which functioned similarly to its ethylene glycol counterparts.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (25)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A composition containing a titanium compound, a solubility promoter, a phosphorus source, and a solvent, characterized in that the solubility promoter is selected from the group consisting of ortho silicates, ortho zirconates, and combinations thereof, and the The phosphorus source is selected from the group consisting of a phosphonic acid, a phosphinic acid, a phosphine and combinations of two or more thereof.

A composition according to claim 1, characterized in that the composition is produced by combining an organic titanium compound, a phosphorus compound, a solubility promoter, and a solvent, wherein the solubility promoter is selected from the group consisting of of organic ortho silicates, organic ortho zirconates, and combinations thereof.

3. A composition according to claim 1 or 2, characterized in that the solvent is an alcohol.

4. A composition according to claim 3, characterized in that the solvent is selected from the group consisting of ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol. , and combinations of two or more thereof.

5. A composition according to any of claims 1 to 4, characterized in that the titanium compound has the formula Ti (0R) 4 wherein each R is independently selected from the group consisting of an alkyl radical, a cycloalkyl radical, a Aralkyl radical, and combinations of two or more thereof, and contains from 1 to about 30 carbon atoms per radical.

6. A composition according to claim 5, characterized in that the titanium compound is selected from the group consisting of tetra isopropyl titanate, tetra n-butyl titanate and combinations thereof.

7. A composition according to any of claims 1 to 6, characterized in that it also contains sulphonic acid.

8. A composition in accordance with the claim 7, characterized in that the sulfonic acid is selected from the group consisting of p-toluene sulphonic acid, benzene sulfonic acid, methane sulfonic acid, ethen sulfonic acid, prophane sulphonic acid, and combinations of two or more thereof.

9. A composition according to any of claims 1 to 8, characterized in that the phosphorus compound is selected from the group consisting of phosphonic acid, phosphinic acid, a phosphine and combinations thereof.

10. A composition according to any of claims 1 to 9, characterized in that it also contains a cocatalyst selected from the group consisting of a cobalt / aluminum catalyst, an antimony compound and combinations thereof.

11. A process comprising combining a titanium compound, a solubility promoter, a phosphorus source and a solvent to produce a combination, characterized in that the solubility promoter is selected from the group consisting of ortho silicates, ortho zirconates, and combinations of same, and the phosphorus source is selected from the group consisting of a phosphonic acid, a phosphinic acid, a phosphine and combinations of two or more thereof.

12. A process in accordance with the claim 11, characterized in that the solvent is an alcohol.

13. A process according to claim 11, characterized in that the solvent is selected from the group consisting of ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol, and combinations of two or more of them.

A process according to claim 11, 12 or 13, characterized in that it further comprises combining the combination with a sulfonic acid to produce a second combination, wherein the sulfonic acid is selected from the group consisting of p-toluene sulphonic acid, benzene sulfonic acid, methane sulphonic acid, ethane sulphonic acid, prophane sulfonic acid, and combinations of two or more thereof.

15. A process according to any of claims 11 to 14, characterized in that the titanium compound has the formula Ti (OR) 4 wherein each R is independently selected from the group consisting of an alkyl radical, a cycloalkyl radical, an aralkyl radical , and combinations of two or more thereof, and contains from 1 to about 30 carbon atoms per radical.

16. A process in accordance with the claim 15, characterized in that the titanium compound is selected from the group consisting of tetra isopropyl titanate, tetra n-butyl titanate and combinations thereof.

17. A process according to any of claims 11 to 16, characterized in that it further comprises combining the combination or second combination with a cocatalyst selected from the group consisting of a cobalt / aluminum catalyst, an antimony compound and combinations thereof. .

18. A process comprising contacting, in the presence of a catalyst composition, a carbonyl compound and an alcohol, characterized in that the catalyst is recited in any of claims 1 to 10.

19. A process according to claim 18, characterized in that the catalyst composition is produced by the process recited in any of claims 11 to 17.

20. A process according to claim 18 or 19, characterized in that the carbonyl compound is selected from the group consisting of (OH) nRJ (COOR ') p, acid anhydride and combinations of two or more thereof; the alcohol is selected from the group consisting of R5 (OH) n, (OH) nA (OH) ", and combinations thereof; m is a number from 0 to about 10; R4 and R 'are each independently selected from the group consisting of hydrogen, a hydrocarbyl radical having a carboxylic acid group at the terminus of the radical, a hydrocarbyl radical, and combinations of two or more thereof; each radical has from 1 to about 30 carbon atoms and is selected from the group consisting of alkyl radical, aryl radical, alkaryl radical, aralkyl radical, alkenyl radical, and combinations of two or more thereof; p is an integer of 1 to a number equal to the number of carbon atoms of R "; A is selected from the group consisting of alkylene group, arylene group, alkylene group, and combinations of two or more thereof; is a branched or linear alkyl radical

21. A process according to claim 20, characterized in that the alcohol is selected from the group consisting of ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol, diethylene glycol, triethylene glycol, 2-ethyl hexanol, stearyl alcohol, 1,6-hexanediol, glycerol, pentaerythritol and combinations of two or more thereof.

22. A process according to claim 21, characterized in that the alcohol is selected from the group consisting of ethylene glycol, 2-ethyl hexanol and combinations thereof.

23. A process in accordance with the claim 20, characterized in that the carbonyl compound is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalic acid, succinic acid, adipic acid, phthalic acid, glutaric acid, acrylic acid, oxalic acid, benzoic acid, maleic acid, propenoic acid , 4-hydroxybenzoic acid, 12-hydroxydecanoic acid, 6-hydroxyhexanoic acid, 4-hydroxycinnamic acid, 4-hydroxymethylbenzoic acid, 4-hydroxyphenylacetic acid, azelaic acid, salicylic acid, caproic acid, stearic acid, palmitic acid, fumaric acid, acid dicarboxylic naphthalene, citric acid, trimesic acid, pamoic acid, sebacic acid, any anhydride of these acids, any ester of these acids and combinations of two or more thereof.

24. A process according to claim 20, characterized in that the carbonyl compound is selected from the group consisting of terephthalic acid, dimethyl terephthalate and combinations thereof.

25. A process of compliance with any of the claims 18 to 24, characterized in that the catalyst composition further contains water, and the molar ratio of water to titanium compound is in the range of about 0.01: 1 to about 6: 1.