JP2003096176A - Polyester polymerization catalyst and method of preparing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester polymerization catalyst, which does not contain any antimony or germanium compound as a main catalytic component, contains aluminum and cobalt as principal metallic components, is cheap and excellent in catalytic activity, causes less corrosion to the equipment, and gives a polyester with reduced formation of a foreign matter that is insoluble in the polyester, and a method of preparing the same. SOLUTION: The polyester polymerization catalyst comprises at least one selected from the group consisting of cobalt and compounds thereof and a solution formed by dissolving at least one selected from the group consisting of an aluminum carboxylate in water and/or an organic solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester polymerization catalyst and a method for producing the same, and further relates to a polyester produced using the polymerization catalyst and a method for producing the polyester.

[0002]

2. Description of the Related Art Polyethylene terephthalate (PE
T), polyesters represented by polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like are excellent in mechanical properties and chemical properties, and depending on the properties of each polyester, for example, for clothing or It is used in a wide range of fields such as fibers for industrial materials, films and sheets for packaging and magnetic tape, bottles that are hollow molded products, casings for electric and electronic parts, and other engineering plastic molded products.

A typical polyester having aromatic dicarboxylic acid and alkylene glycol as main constituents is, for example, polyethylene terephthalate (PE).
In the case of T), bis (2-hydroxyethyl) terephthalate is produced by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, which is polycondensed with a catalyst at high temperature and under vacuum. It is industrially produced by the polycondensation method or the like.

Conventionally, antimony trioxide has been widely used as a polyester polymerization catalyst used in such polycondensation of polyester. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity,
If this is used as the main component, that is, in an addition amount such that a practical polymerization rate is exhibited, since metal antimony is precipitated during polycondensation, there is a problem that darkening and foreign matter occur in the polyester. There is. Under such circumstances, polyesters containing no antimony or no antimony as a catalyst main component are desired.

The above-mentioned foreign matter in polyester causes the following problems. (1) In the polyester for a film, the deposition of metal antimony becomes a foreign substance in the polyester, which not only causes stain on the die during melt extrusion, but also causes a surface defect of the film. Further, when used as a raw material for a hollow molded article or the like, it is difficult to obtain a hollow molded article having excellent transparency. (2) The foreign matter in the polyester for the fiber becomes a foreign matter that causes a decrease in strength in the fiber, and becomes a cause of stain on the spinneret during spinning. In the production of polyester fibers, a polyester polymerization catalyst that does not generate foreign matter is required mainly from the viewpoint of workability.

As a method for solving the above problems, attempts have been made to use antimony trioxide as a catalyst and suppress the darkening of PET and the generation of foreign matter. For example, in Japanese Patent No. 2666502, by using a compound of antimony trioxide and bismuth and selenium as a polycondensation catalyst, generation of black foreign matter in PET is suppressed. Further, JP-A-9-291141 describes that when antimony trioxide containing an oxide of sodium and iron is used as a polycondensation catalyst, precipitation of metal antimony is suppressed. However, these polycondensation catalysts cannot eventually achieve the purpose of reducing the content of antimony in the polyester.

As a method for solving the problems of antimony catalysts in applications requiring transparency such as PET bottles, Japanese Patent Laid-Open No. 6-279579 discloses, for example,
A method is disclosed in which the transparency is improved by defining the amount ratio of the antimony compound and the phosphorus compound used. However, the hollow molded article made of polyester obtained by this method does not have sufficient transparency.

Further, Japanese Unexamined Patent Publication No. 10-36495 discloses a continuous production method of polyester having excellent transparency by using antimony trioxide, phosphoric acid and sulfonic acid compounds. However, the polyester obtained by such a method has a problem that the thermal stability is poor and the obtained hollow molded article has a high acetaldehyde content.

[0009] Polycondensation catalysts replacing antimony-based catalysts such as antimony trioxide have also been studied, and titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. Further, polyester has a problem that it is susceptible to thermal deterioration during melt molding and that the polyester is markedly colored.

As an attempt to overcome the above problems when a titanium compound is used as a polycondensation catalyst, for example, in JP-A-55-116722, a method in which a tetraalkoxy titanate is used at the same time as a cobalt salt and a calcium salt is used. Is proposed. In addition, JP-A-8-7358
No. 1 proposes a method in which a tetraalkoxy titanate is used as a polycondensation catalyst at the same time as a cobalt compound and an optical brightener is used. However, although these techniques reduce the coloring of PET when tetraalkoxy titanate is used as a polycondensation catalyst,
Effective suppression of thermal decomposition of T has not been achieved.

As another attempt to suppress thermal deterioration during melt molding of a polyester polymerized by using a titanium compound as a catalyst, for example, in JP-A-10-259296, a phosphorus compound is used after polymerizing a polyester by using a titanium compound as a catalyst. Methods of adding compounds are disclosed. But,
It is not only technically difficult to effectively mix an additive into a polymer after polymerization, but also it is not practically used because of cost increase.

Germanium compounds have already been put into practical use as catalysts which give polyesters having excellent catalytic activity and thermal stability other than antimony compounds, but this catalyst is very expensive. In addition, there is a problem that the catalyst concentration in the reaction system changes and the control of the polymerization becomes difficult because it is easy to distill out from the reaction system during the polymerization, and there is a problem in using it as a catalyst main component.

Further, as a method for suppressing thermal deterioration of polyester during melt molding, a method of removing a catalyst from polyester can be mentioned. As a method of removing the catalyst from the polyester, for example, Japanese Patent Application Laid-Open No. 10-251394 discloses a method of bringing a polyester resin into contact with an extractant which is a supercritical fluid in the presence of an acidic substance.
However, the method using such a supercritical fluid is not preferable because it is technically difficult and leads to an increase in cost.

Based on the above-mentioned circumstances, it is a polymerization catalyst having a metal component other than antimony and germanium as a main metal component of the catalyst, and has excellent catalytic activity and excellent thermal stability that hardly causes thermal deterioration during melt molding. Polymerization catalysts that provide polyesters are desired.

On the other hand, Japanese Patent Laid-Open No. 10-324741 and Japanese Patent Laid-Open No. 11-507694 propose a catalyst in which an aluminum compound and a cobalt compound are used in combination. Examples of the aluminum compound include aluminum chelate compounds such as aluminum acetylacetonate, inorganic acid salts such as aluminum chloride and aluminum hydroxide, carboxylic acid aluminum salts, and aluminum alkoxide. Among these, aluminum chelate compounds such as aluminum acetylacetonate are generally expensive, and because the aluminum content in the compound is low, the cost is increased and the solubility in solvents such as ethylene glycol is low and the addition method is limited. Have the problem of Aluminum hydroxide and aluminum alkoxide have problems that they have low solubility in the system and low catalytic activity, and that insoluble foreign matters are generated in the polyester. Inorganic acid salts containing chlorine, such as aluminum chloride, are relatively excellent in catalytic activity, but have the problem that they are highly corrosive to equipment and that the resulting polymer is highly colored.

On the other hand, examples of the aluminum salt of carboxylic acid include aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum benzoate and the like. These are generally inexpensive and have low corrosiveness with respect to equipment, but with respect to polyester. Since the solubility is low, the catalyst activity is inferior and the resulting polyester becomes turbid, which is a problem when used as a catalyst. For example, Japanese Unexamined Patent Publication No. 10-324741 describes that a polyester using aluminum acetate as a catalyst easily forms an insoluble foreign substance, which causes a problem of poor spinnability.

[0017]

DISCLOSURE OF THE INVENTION The present invention does not contain an antimony compound or a germanium compound as a main component of a catalyst, but contains aluminum and cobalt as main metal components, is inexpensive, has excellent catalytic activity, and has little corrosion on equipment,
Further, the present invention provides a polyester polymerization catalyst and a method for producing the same, which gives a polyester in which the formation of insoluble foreign matters is reduced. The present invention also provides a method for producing polyester using the catalyst and the polyester.

[0018]

[Means for Solving the Problems] The authors of the present invention have made extensive studies aiming at improving the activity of a catalyst comprising an aluminum salt of a carboxylic acid and a cobalt compound, and as a result, the aluminum salt of a carboxylic acid was previously prepared. The inventors have found that the catalytic activity is improved by using a catalyst dissolved in water or an organic solvent in combination with a cobalt compound, and have proposed the present invention. That is, as a solution to the above problems, the present invention dissolves at least one selected from the group consisting of cobalt and its compounds and at least one selected from the group consisting of aluminum carboxylic acid salts in water and / or an organic solvent. Provided are a polyester polymerization catalyst comprising a solution and a method for producing the solution.

[0019]

Specific examples of the carboxylic acid aluminum salt of the present invention include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, and stearic acid. Aluminum, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, aluminum tartrate, aluminum salicylate, and the like. Among these, those having the structure of an aluminum salt of acetic acid such as aluminum acetate and basic aluminum acetate, Aluminum lactate is preferable from the viewpoint of solubility in the system and catalytic activity.

Examples of the use of an aluminum salt of a carboxylic acid as a polyester polymerization catalyst include aluminum acetate, basic aluminum acetate, aluminum lactate, and aluminum benzoate.
Since all of them have low solubility in polyester, they have a problem that they are inferior in catalytic activity and insoluble foreign matter is generated in the obtained polyester, and there is a problem in using these compounds as a catalyst as they are. It was The present invention is characterized in that it is possible to impart sufficient catalytic activity by using a pre-dissolved product of these in water and / or an organic solvent in combination with a cobalt compound as a catalyst.

The aluminum carboxylic acid salt of the present invention must be dissolved in water and / or an organic solvent in advance before being added to the polymerization system of polyester, and then added to the polymerization system. As the organic solvent, glycols are preferably used, and in the case of producing PET, ethylene glycol is preferably used. The above solution of the aluminum carboxylic acid salt and the cobalt compound may be mixed in advance and added to the polymerization system, or both may be added separately. When a mixture of a solution of a carboxylic acid aluminum salt and a cobalt compound is added to the polymerization system, the cobalt compound may be added to a solution of the aluminum compound prepared in advance, or the aluminum compound is added to the solution of the cobalt compound prepared in advance. May be dissolved. Alternatively, both solutions may be mixed and prepared, or both may be simultaneously dissolved in a solvent. When the solution of the aluminum carboxylic acid salt and the cobalt compound are separately added to the polymerization system, the cobalt compound may be added in the form of powder or neat, or in the form of slurry or solution of a solvent such as ethylene glycol. May be added and is not particularly limited.

Examples of those having the structure of an aluminum salt of acetic acid include basic aluminum acetate, aluminum triacetate, and an aluminum acetate solution. Among them, from the viewpoint of solubility and solution stability, basic The use of aluminum acetate is preferred. Among the basic aluminum acetates, monoaluminum acetate or aluminum diacetate is preferably used. It is necessary to use as a catalyst any basic aluminum acetate dissolved in water and / or an organic solvent. By using the catalyst having such a constitution, it becomes possible to obtain a polyester having excellent catalytic activity and excellent quality. As the solvent, use of water or diols is preferable, and in the case of producing PET, use of water and / or ethylene glycol is preferable.

In another aspect of the present invention, when the aluminum carboxylic acid salt stabilized with boric acid or the like is used in combination with the cobalt compound as a catalyst, the solubility and the stability of the solution are excellent and the catalytic activity is excellent. It is characterized by the fact that it is possible to obtain a polyester having excellent quality and excellent quality. As the carboxylic acid aluminum salt, those having a structure of an aluminum salt of acetic acid are preferable, and of these, use of basic aluminum acetate is preferable. Examples of the stabilizer include urea and thiourea in addition to boric acid, and boric acid is preferably used. When using a boric acid-stabilized one, it is preferable to use a boric acid-stabilized one having an equimolar amount or less with respect to aluminum. The use of stabilized aluminum compounds is preferred. When an aluminum carboxylic acid salt stabilized with boric acid or the like is used as a catalyst in combination with a cobalt compound, it may be added to the polymerization system in a state of being dissolved in water and / or an organic solvent in advance. It is preferable from the viewpoint of activity and quality of polyester. As the organic solvent, glycols are preferably used, and in the case of producing PET, ethylene glycol is preferably used.

In order to produce a solution of the aluminum carboxylate of the present invention dissolved in water and / or an organic solvent, it is preferable to use a solution of the aluminum carboxylate previously dissolved in water. It is preferable to add an organic solvent such as a diol to the aqueous solution, if necessary. The aqueous solution may be added as it is to the polymerization system, but in order to reduce the heat shock at the time of addition, the aqueous solution diluted with a diol such as ethylene glycol is added to the polymerization system, or It is preferable to add a solution obtained by distilling water by liquid-liquid exchange of the diluted solution to the polymerization system.

When the aqueous solution of aluminum carboxylic acid salt is diluted with diols such as ethylene glycol, it is preferable to dilute with 0.5 to 50 times the volume of diols with respect to water. Further, it is preferable that the concentration of the solution of the carboxylic acid aluminum salt added to the polymerization system is 0.01 to 1 mol / liter in terms of aluminum atom because the generation of insoluble foreign matter in the obtained polyester is particularly suppressed. .

When the carboxylic acid aluminum salt is dissolved in water and / or an organic solvent, or in a dissolved solution,
It is preferable to add a stabilizer such as boric acid or an acid such as citric acid, lactic acid or oxalic acid because the solubility and the stability of the solution are increased.

Specific examples of the method for preparing a solution in which the basic aluminum acetate used in the present invention is dissolved in water and / or an organic solvent will be shown below. (1) Preparation Example of Aqueous Solution of Basic Aluminum Acetate Water is added to basic aluminum acetate and stirred at room temperature for several hours or longer. The stirring time is preferably 12 hours or more. Then, the mixture is stirred at 60 ° C. or higher for several hours or longer. The temperature in this case is preferably in the range of 60 to 80 ° C. The stirring time is preferably 3 hours or more. The concentration of the aqueous solution is preferably 5 g / l to 100 g / l, especially 1
0 g / l to 30 g / l is preferred. (2) Preparation example of ethylene glycol solution of basic aluminum acetate Ethylene glycol is added to the above aqueous solution. Addition amount of ethylene glycol is 1 by volume ratio to the aqueous solution.
It is preferably ˜5 times. More preferably, it is 2-3 times the amount. By stirring the solution at room temperature for several hours, a uniform water / ethylene glycol mixed solution is obtained. Then, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 80 ° C or higher, 120
C. or less is preferable. More preferably, the water is distilled off by stirring at 90 to 110 ° C. for several hours.

Specific examples of the method for preparing the ethylene glycol solution of aluminum lactate used in the present invention are shown below. Prepare an aqueous solution of aluminum lactate. The preparation may be performed at room temperature or under heating, but preferably at room temperature. The concentration of the aqueous solution is preferably 20 g / l to 100 g / l, 50 to 80
g / l is particularly preferred. Ethylene glycol is added to the aqueous solution. The amount of ethylene glycol added is preferably 1 to 5 times the volume of the aqueous solution. More preferably 2
~ 3 times the amount. The solution is stirred at room temperature to obtain a uniform water / ethylene glycol mixed solution, and then the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 80 ° C or higher, and preferably 120 ° C or lower. More preferably, the water is distilled off by stirring at 90 to 110 ° C. for several hours.

When the polyester is produced according to the method of the present invention, the amount of the aluminum compound to be used is such that the aluminum is used with respect to the number of moles of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. The atom content is preferably 0.001 to 0.05 mol%, and more preferably 0.005 to 0.02 mol%. When the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited, and when the amount used is more than 0.05 mol%, thermal stability and thermal oxidation stability are deteriorated and aluminum is caused. Occurrence of foreign matter and increase in coloring sometimes become a problem.

When the polyester is produced according to the method of the present invention, the amount of the cobalt compound used is 1 to 50 pp as a cobalt atom based on the polyester obtained.
The range is preferably m, and more preferably 5 to 40 ppm. When the amount used exceeds 50 ppm, the thermal stability and color tone of the obtained polyester tend to deteriorate, which is not preferable. If the amount used is less than 1 ppm, the catalytic activity may not be sufficiently exhibited.

When the polyester is produced according to the method of the present invention, the addition ratio of the aluminum compound and the cobalt compound is such that the molar ratio of aluminum atom / cobalt atom is 0.1.
It is preferable to set it to be from 100 because the obtained polyester has excellent color tone and heat stability. It is more preferably 0.5 to 50, still more preferably 1 to 20.

The cobalt compound used in the present invention is not particularly limited, but specific examples thereof include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and hydrates thereof. To be Among them, cobalt acetate tetrahydrate is particularly preferable.

The polyester according to the present invention can be produced by a method including conventionally known steps except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, in the case of producing PET, a direct esterification method in which terephthalic acid is directly reacted with ethylene glycol and, if necessary, other copolymerization components to distill off water for esterification, and then polycondensate under reduced pressure. Alternatively, it is produced by a transesterification method in which dimethyl terephthalate is reacted with ethylene glycol and, if necessary, other copolymerization components to distill off methyl alcohol for transesterification, and then polycondensation is performed under reduced pressure. It Further, solid phase polymerization may be carried out to increase the intrinsic viscosity, if necessary. In order to accelerate crystallization before solid-phase polymerization, the melt-polymerized polyester may be adsorbed with moisture and then crystallized by heating, or steam may be directly blown onto the polyester chips to be crystallized by heating.

The melt polycondensation reaction may be carried out in a batch reactor or a continuous reactor.
In any of these methods, the esterification reaction or transesterification reaction may be carried out in one step, or may be carried out in multiple steps. The melt polycondensation reaction may be carried out in one step or may be carried out in multiple steps.
The solid phase polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus as in the melt polycondensation reaction. The melt polycondensation and solid phase polymerization may be carried out continuously or may be carried out separately.

The catalyst of the present invention has catalytic activity not only in polycondensation reaction but also in esterification reaction and transesterification reaction. For example, polymerization by transesterification reaction between an alkyl ester of dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol is usually performed in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. Alternatively, or together with these catalysts, the catalyst of the present invention can be used. Further, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and polyester can be produced by any method.

The catalyst of the present invention can be used at any stage of the polymerization reaction,
For example, it can be added to the reaction system before the start of the esterification reaction or transesterification reaction and at any stage during the reaction or immediately before the start of the polycondensation reaction or during the reaction. The solution of the aluminum compound constituting the catalyst of the present invention and the cobalt compound may be added to the polymerization system at the same addition time, or may be added at different addition times.
In particular, the aluminum compound is preferably added immediately before the start of the polycondensation reaction. Further, the whole amount of the catalyst may be added at once or may be added in plural times.

In the present invention, the compound other than the aluminum compound and the cobalt compound may be added in the form of powder or neat, or the addition of a solvent such as ethylene glycol in the form of slurry or solution. It may be present and is not particularly limited. Further, the catalyst solution of the aluminum compound of the present invention and other compounds may be added as a premixed mixture, or they may be added separately. Further, the catalyst solution of the aluminum compound of the present invention and the other compound may be added to the polymerization system at the same addition time, or the respective components may be added at different addition times.

When the polyester is produced according to the method of the present invention, another polycondensation catalyst such as an antimony compound, a germanium compound or a titanium compound is added, and the addition of these components makes it possible to obtain the properties, processability and color tone of the polyester as described above. It is preferable to coexist within the range of the addition amount that does not cause a problem in the product, etc., because it is effective in improving productivity by shortening the polymerization time.

The antimony compound is preferably added in an amount of 50 ppm or less as antimony atom with respect to the polyester obtained by polymerization. A more preferable addition amount is 30 ppm or less. The amount of antimony added is 50
If it is more than ppm, metal antimony will be deposited,
It is not preferable because darkening and foreign matter are generated on the polyester.

The germanium compound has a germanium atom content of 20 pp with respect to the polyester obtained by polymerization.
It is preferably added in an amount of m or less. A more preferable addition amount is 10 ppm or less. When the addition amount of germanium is 20 ppm or more, it becomes disadvantageous in terms of cost, which is not preferable.

The titanium compound is preferably added in an amount of 5 ppm or less in terms of titanium atom with respect to the polyester obtained by polymerization. More preferable addition amount is 3 ppm
It is below, and more preferably below 1 ppm. When the amount of titanium added is 5 ppm or more, the polyester obtained is significantly colored, and the thermal stability is significantly reduced, which is not preferable.

The antimony compound that can be used in the present invention is not particularly limited, but preferable compounds include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoxide and the like, and the use of antimony trioxide is particularly preferable. Is preferred. The germanium compound is not particularly limited, but examples thereof include germanium dioxide and germanium tetrachloride, and germanium dioxide is particularly preferable. Both crystalline and amorphous germanium dioxide can be used.

The titanium compound usable in the present invention is not particularly limited, but tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n
-Butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate, lithium oxalate titanate, potassium oxalate titanate, ammonium titanate oxalate, titanium oxide,
Complex oxides of titanium with silicon, zirconium, alkali metals, alkaline earth metals, etc., titanium orthoesters or condensed orthoesters, reaction products of titanium orthoesters or condensed orthoesters and hydroxycarboxylic acids, titanium ortho Reaction product consisting of ester or condensed orthoester, hydroxycarboxylic acid and phosphorus compound, reaction product consisting of titanium orthoester or condensed orthoester and polyhydric alcohol having at least two hydroxyl groups, 2-hydroxycarboxylic acid and base Examples thereof include a complex oxide of titanium and silicon, a complex oxide of titanium and magnesium, a reaction product of a titanium orthoester or a condensed orthoester, a hydroxycarboxylic acid and a phosphorus compound.

As the tin compound, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditinoxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, Examples thereof include dibutyltin sulfide, dibutylhydroxytin oxide, methylstannonic acid and ethylstannonic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

The polyester referred to in the present invention is one or two or more kinds selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof and one or two kinds selected from polyhydric alcohols containing glycol. The above-mentioned ones, those consisting of hydroxycarboxylic acids and their ester-forming derivatives, or those consisting of cyclic esters.

As the dicarboxylic acid, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adibic acid, vimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid Acid, 1,
2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, saturated aliphatic dicarboxylic acids exemplified by dimer acid, or ester-forming derivatives thereof, Unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4 -Naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,
4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-
Examples thereof include aromatic dicarboxylic acids exemplified by p, p′-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof.

Among the above-mentioned dicarboxylic acids, use of terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid is particularly preferable in view of physical properties of the obtained polyester, and if necessary, other dicarboxylic acid may be used as a constituent component. To do.

As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ', 4'-biphenyltetra Examples thereof include carboxylic acids and their ester-forming derivatives.

As glycol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1, 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2
-Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,
1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol,
Aliphatic glycols such as polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) ) Sulfone, bis (p-hydroxyphenyl)
Ether, bis (p-hydroxyphenyl) sulfone,
Bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol,
Aromatic glycols such as glycols in which ethylene oxide is added to these glycols, and the like are included.

Among the above glycols, ethylene glycol, 1,3-propylene glycol, 1,
It is preferable to use 4-butylene glycol or 1,4-cyclohexanedimethanol as a main component.

As polyhydric alcohols other than these glycols, trimethylolmethane, trimethylolethane,
Trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like can be mentioned.

Examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and 4-hydroxycyclohexanecarboxylic acid. , Or ester-forming derivatives thereof and the like.

Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide and lactide.

Examples of the ester-forming derivative of polycarboxylic acid or hydroxycarboxylic acid include alkyl esters, acid chlorides, acid anhydrides and the like.

The polyester used in the present invention is preferably a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalene dicarboxylic acid or its ester-forming derivative, and whose main glycol component is alkylene glycol.

The polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is a polyester which contains terephthalic acid or an ester-forming derivative thereof in a total amount of 70 mol% or more based on all acid components. A polyester containing 80 mol% or more is more preferable, and a polyester containing 90 mol% or more is more preferable. Similarly, the polyester whose main acid component is naphthalene dicarboxylic acid or its ester-forming derivative is preferably a polyester containing 70 mol% or more of naphthalene dicarboxylic acid or its ester-forming derivative in total, and more preferably 80 It is a polyester containing at least mol%, more preferably 90 mol% or more.

The polyester whose main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total based on all glycol components, more preferably 80 mol% or more. And more preferably a polyester containing 90 mol% or more. The alkylene glycol referred to herein may have a substituent or an alicyclic structure in the molecular chain.

Examples of the naphthalenedicarboxylic acid or its ester-forming derivative used in the present invention include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid exemplified in the above dicarboxylic acids. 2,6-naphthalenedicarboxylic acid,
2,7-naphthalenedicarboxylic acid or ester-forming derivatives thereof are preferred.

Examples of the alkylene glycol used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, which are exemplified as the above-mentioned glycols.
1,3-Putylene glycol, 2,3-Putylene glycol, 4,4-Putylene glycol, 1,5-Pentanediol, Neopentyl glycol, 1,6-Hexanediol, 1,2-Cyclohexanediol, 1, 3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol,
The use of 1,10-decamethylene glycol, 1,12-dodecanediol and the like is preferable. You may use 2 or more types at the same time.

The polyester of the present invention includes polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Are preferred, and polyethylene terephthalate and copolymers thereof are particularly preferred.

The polyester of the present invention may contain a known phosphorus compound as a copolymerization component. As the phosphorus compound, a bifunctional phosphorus compound is preferable, for example, (2-carboxyethyl) methylphosphinic acid,
(2-carboxylethyl) phenylphosphinic acid,
9,10-Dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10
-Oxide and the like. By including these phosphorus compounds as a copolymerization component, it is possible to improve the flame retardancy and the like of the obtained polyester.

As a constituent of the polyester of the present invention,
In order to improve the dyeability when polyester is used as the fiber, it is a preferred embodiment to use a polycarboxylic acid having an alkali metal sulfonate as a copolymerization component.

The metal sulfonate group-containing compound used as the copolymerization monomer is not particularly limited, but it is 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfo. Examples thereof include terephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, and lower alkyl ester derivatives thereof. In the present invention, it is particularly preferable to use 5-sodium sulfoisophthalic acid or its ester-forming derivative.

The copolymerization amount of the metal sulfonate group-containing compound is 0.3 to 1 with respect to the acid component constituting the polyester.
0.0 mol% is preferable, and 0.80 is more preferable.
It is 5.0 mol%. If the copolymerization amount is too small, the dyeability of the basic dye will be poor, and if it is too large, when it is made into fibers, not only the spinnability will be poor, but also sufficient strength as fibers cannot be obtained due to the thickening phenomenon. Further, by copolymerizing the metal sulfonate group-containing compound in an amount of 2.0 mol% or more, it is possible to impart atmospheric pressure dyeability to the obtained modified polyester fiber. In addition, it is possible to appropriately reduce the amount of the metal sulfonate group-containing compound used by selecting an appropriate dyeing monomer. The easily dyeable monomer is not particularly limited, and examples thereof include long-chain glycol compounds typified by polyethylene glycol and polytetramethylene glycol, and aliphatic dicarboxylic acids typified by adipic acid, sebacic acid, and azelaic acid.

The thermal stability of the polyester can be further enhanced by polymerizing the polyester according to the method of the present invention, and then removing the catalyst from the polyester or deactivating the catalyst by adding a phosphorus compound or the like. .

The polyester of the present invention may contain a bluing agent, an organic type, an inorganic type or an organic metal type dye, a pigment, an optical brightening agent, etc., and one or more of these may be contained. By doing so, it is possible to suppress coloring such as yellowing of the polyester. In addition, any other polymer or antistatic agent, antifoaming agent, dyeability improving agent, dye, pigment, matting agent, optical brightener, stabilizer, antioxidant,
Other additives may be contained. As the antioxidant, aromatic amine-based and phenol-based antioxidants can be used, and as the stabilizer, phosphoric acid and phosphoric ester-based stabilizers such as phosphorus-based, sulfur-based and amine-based stabilizers can be used. Can be used.

These additives can be added during or after the polymerization of the polyester, or at any stage during the molding of the polyester. Which stage is suitable depends on the characteristics of the compound and the requirements of the polyester molded product. Different depending on the performance.

[0068]

EXAMPLES The constitution and effects of the present invention will be described below based on examples, but the present invention is not limited to these examples. In each example, the intrinsic viscosity (IV) of the polyester was determined by dissolving the polyester in a 6/4 (weight ratio) mixed solvent of phenol / 1,1,2,2-tetrachloroethane, and heating it to a temperature of 30 ° C. Measured.

(Example 1)

(Preparation example of water / ethylene glycol mixed solution of basic aluminum acetate) Basic aluminum acetate (hydroxyaluminum diacetate; manufactured by ALDRICH)
Deionized water was added at a ratio of 50 ml to 1 g, and the mixture was stirred at room temperature for 12 hours. Then, the mixture was stirred at about 70 ° C. for 6 hours to obtain a clear aqueous solution. Add 3 volumes (volume ratio) of ethylene glycol to this aqueous solution 1, and add 6 times at room temperature.
After stirring for a time, a catalyst solution was obtained.

(Polymerization Example of Polyester) 2 with Stirrer
High-purity terephthalic acid and twice the molar amount of ethylene glycol were charged into a litter stainless steel autoclave,
Add 0.3 mol% of triethylamine to the acid component, add 0.25M
A mixture of bis (2-hydroxyethyl) terephthalate (BHET) and an oligomer with an esterification rate of about 95% (hereinafter referred to as BHET mixture) by performing an esterification reaction while distilling water out of the system at 245 ° C under Pa pressure. I got). For this BHET mixture, a water / ethylene glycol mixed solution of the above basic aluminum acetate as a polycondensation catalyst was added as an aluminum atom to the acid component in the polyester in an amount of 0.03.
A 20 g / l ethylene glycol solution of cobalt acetate and tetrahydrate was added as a cobalt atom to the acid component in an amount of 0.01 mol%, and 245 at a normal pressure under a nitrogen atmosphere.
The mixture was stirred at 0 ° C for 10 minutes. Then, the pressure of the reaction system is gradually reduced while raising the temperature to 275 ° C over 50 minutes, and the pressure is increased to 66.5 Pa (0.5 Torr).
As r), the polycondensation reaction was further carried out at 275 ° C. and 66.5 Pa.
The polycondensation time required to obtain PET having an IV of 0.61 dl / g was 105 minutes, and the present catalyst had practical catalytic activity.

(Comparative Example 1) As a polycondensation catalyst, about 10 g / l ethylene glycol slurry of basic aluminum acetate (hydroxyaluminum diacetate; manufactured by ALDRICH) was used as an aluminum atom in an amount of 0.03 mol% with respect to the acid component in the polyester. The same operation as in Example 1 was performed, except that a 20 g / l ethylene glycol solution of cobalt acetate tetrahydrate was added in an amount of 0.01 mol% as cobalt atoms to the acid component. 180 polycondensation reaction
After more than a minute, the IV did not reach 0.61 dl / g.

(Example 2)

(Preparation example of ethylene glycol solution of basic aluminum acetate) Basic aluminum acetate (CH ₃ COO
Al (OH) ₂ .1 / 3H ₃ BO ₃ ; manufactured by ALDRICH) was stirred in ethylene glycol at about 70 ° C. for 5 hours to obtain an ethylene glycol solution having a concentration of about 5 g / l.

(Polyester Polymerization Example) A mixture of bis (2-hydroxyethyl) terephthalate and an oligomer prepared by a conventional method from high-purity terephthalic acid and ethylene glycol was used, and 5 g / l ethylene of the above basic aluminum acetate was used as a polycondensation catalyst. The glycol solution is used as an aluminum atom with respect to the acid component in the polyester of 0.01.
0.005 mol% of 5 mol% and a 20 g / l ethylene glycol solution of cobalt acetate tetrahydrate as a cobalt atom was added to the acid component, and the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, the temperature of the reaction system was gradually decreased while raising the temperature to 275 ° C. over 50 minutes to reach 13.3 Pa (0.1 Torr) and further 275
A polycondensation reaction was carried out at 13.3 Pa at 13.degree. IV is 0.6
The polycondensation time required to obtain 0 dl / g PET was 150 minutes, and the present catalyst had practical catalytic activity.

(Evaluation Results) From the examples and comparative examples of the present invention, when a solution prepared by previously dissolving an aluminum carboxylic acid salt in water or an organic solvent in combination with a cobalt compound was used as a catalyst, the polymerization activity was On the other hand, when a catalyst obtained by using a carboxylate aluminum salt in combination with a cobalt compound without previously dissolving it is used as a catalyst, the polymerization activity is inferior.

[0077]

According to the present invention, an antimony compound or a germanium compound is not contained as a catalyst main component, and aluminum and cobalt are the main metal components.
Provided are a polyester polymerization catalyst and a method for producing the same, which provides a polyester having excellent catalytic activity, less corrosion to a device, and excellent quality. Further, a method for producing polyester using the catalyst and the polyester are provided. The polyester of the present invention includes, for example, textiles for clothing, curtains, carpets, textiles for interior and bedding typified by futon cotton, fibers for industrial materials typified by tire cords, ropes, various woven fabrics, various knitted fabrics, short fabrics, etc. Fibers such as fiber non-woven fabric, long fiber non-woven fabric, packaging film, industrial film, optical film, magnetic tape film, photographic film, can laminating film, content film, heat shrink film, gas barrier film, white film, Films such as easy-cut films, non-heat-resistant stretched bottles, heat-resistant stretched bottles, direct blow bottles, gas barrier bottles, pressure-resistant bottles, pressure-resistant bottles, and other hollow molded bodies, sheets such as A-PET and C-PET, and glass fiber reinforced polyester. , Engineering plastics such as elastomers Various molded articles, and paints and adhesives can be applied to such.

Continued front page    F-term (reference) 4J029 AA01 AB04 AC01 JF221                       JF571

Claims (6)

[Claims] 1. A polyester polymerization catalyst comprising at least one selected from the group consisting of cobalt and its compounds, and a solution in which at least one selected from the group consisting of aluminum carboxylic acid salts is dissolved in water and / or an organic solvent. . 2. The polyester polymerization catalyst according to claim 1, wherein the aluminum carboxylic acid salt is at least one selected from the group consisting of compounds having a structure of an aluminum salt of acetic acid. 3. The polyester polymerization catalyst according to claim 1, wherein the carboxylic acid aluminum salt is aluminum lactate. 4. The method for producing a polyester polymerization catalyst according to claim 1, wherein a solution prepared by previously dissolving at least one selected from the group consisting of aluminum carboxylic acid salts in water is used. 5. When producing polyester, the method according to claim 1
3. A method for producing polyester, which comprises using the polyester polymerization catalyst according to any one of 3 above. 6. A polyester produced by using the polyester polymerization catalyst according to claim 1.