JP2002322255A - Method for producing polyester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyester using a new polyester polymerization catalyst other than antimony. SOLUTION: This method for producing the polyester is characterized by adding the polyester polymerization catalyst comprising at least one kind selected from aluminum and its compounds as a metal-containing component and at least one kind selected from phenolic compounds to an oligomer satisfying specific viscosity conditions, specific acid value conditions, specific hydroxyl value conditions, specific molecular-weight conditions or specific esterification ratio conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyester, and more particularly, to a novel polyester polymerization catalyst not using germanium or an antimony compound as a catalyst main component, and a method for producing a polyester produced using the same. It relates to a manufacturing method.

[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 and 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 example of a polyester comprising an aromatic dicarboxylic acid and an alkylene glycol as main components is, for example, in the case of polyethylene terephthalate (PET), by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol. Producing bis (2-hydroxyethyl) terephthalate,
This is industrially manufactured by a polycondensation method of polycondensing this using a catalyst at a high temperature and in a vacuum. Conventionally, antimony trioxide has been widely used as a polyester polymerization catalyst used at the time of such polycondensation of polyester. Antimony trioxide is a catalyst which is inexpensive and has excellent catalytic activity.However, if this is used as a main component, that is, in an amount added so as to exhibit a practical polymerization rate, metal antimony during polycondensation is used. Has a problem that blackening or foreign matter is generated in the polyester.
Under such circumstances, a polyester containing no antimony or containing no antimony as a main component of a catalyst is desired. The above-mentioned foreign matter in the polyester causes, for example, the following problem. (1) In polyester for a film, the precipitation of antimony metal becomes a foreign substance in the polyester and causes not only stains on a die at the time of melt extrusion but also surface defects on the film. In addition, when a raw material such as a hollow molded article is used, it is difficult to obtain a hollow molded article having excellent transparency. (2) Foreign matter in the polyester for fibers becomes a foreign matter that causes a decrease in strength in the fibers, and causes stains on a spinneret during yarn production. In the production of polyester fibers, a polyester polymerization catalyst free of foreign matter is required mainly from the viewpoint of operability. As a method for solving the above problem, an attempt has been made to use antimony trioxide as a catalyst and to suppress the occurrence of darkening or foreign matter in PET. For example, in Japanese Patent No. 2666502, generation of black foreign matter in PET is suppressed by using a compound of antimony trioxide, bismuth, and selenium as a polycondensation catalyst.
JP-A-9-291141 describes that when antimony trioxide containing sodium and iron oxides is used as a polycondensation catalyst, the precipitation of antimony metal is suppressed. However, these polycondensation catalysts cannot ultimately achieve the purpose of reducing the content of antimony in the polyester. For applications requiring transparency such as PET bottles, as a method for solving the problems of the antimony catalyst, for example, JP-A-6-279 describes
No. 579 discloses a method in which the transparency is improved by defining the amount ratio of the antimony compound to the phosphorus compound. However, the hollow molded article made of the polyester obtained by this method cannot be said to have sufficient transparency. Also, JP-A-10-36495 discloses that
A continuous process for producing a polyester having excellent transparency using antimony trioxide, phosphoric acid and a sulfonic acid compound is disclosed. However, the polyester obtained by such a method has a problem that heat stability is poor and the acetaldehyde content of the obtained hollow molded article is high. Studies have been made on polycondensation catalysts replacing antimony-based catalysts such as antimony trioxide, and titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. There is a problem that the polyester is susceptible to thermal deterioration during melt molding and the polyester is significantly colored. In an attempt to overcome such problems when a titanium compound is used as a polycondensation catalyst, for example, Japanese Patent Application Laid-Open No. 55-116 discloses
No. 722 proposes a method of using a tetraalkoxy titanate simultaneously with a cobalt salt and a calcium salt. JP-A-8-73581 proposes a method in which a tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst, and a fluorescent brightener is used. However, in these techniques, PET when tetraalkoxy titanate is used as a polycondensation catalyst is used.
Although the coloring of the PET is reduced, it has not been achieved to effectively suppress the thermal decomposition of PET. Other attempts to suppress thermal degradation during melt molding of polyesters polymerized using a titanium compound as a catalyst include, for example, JP-A-10-2
No. 59296 discloses a method of adding a phosphorus compound after polymerizing a polyester using a titanium compound as a catalyst. However, it is not only technically difficult to effectively mix additives into the polymer after polymerization,
At present, it has not been put into practical use due to cost increase. It is known that aluminum compounds generally have poor catalytic activity. Among aluminum compounds, chelating compounds of aluminum are reported to have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but have sufficient catalytic activity as compared to the above-mentioned antimony compounds and titanium compounds. I ca n’t say
In addition, there is a problem that the polyester which is polymerized for a long time using an aluminum compound as a catalyst has poor thermal stability. A technique of adding an alkali metal compound to an aluminum compound to obtain a polyester polymerization catalyst having sufficient catalytic activity is also known. The use of such a known catalyst provides a polyester having excellent thermal stability.However, a catalyst using this alkali metal compound in combination requires a large amount of addition thereof in order to obtain practical catalytic activity. As a result, at least one of the following problems occurs due to the alkali metal compound in the obtained polyester polymer. 1) The amount of foreign matters increases, and when used for fibers, the spinning properties and yarn properties are deteriorated, and when used for films, the film properties and the like are deteriorated. 2) The hydrolysis resistance of the polyester polymer decreases, and the transparency decreases due to the generation of foreign substances. 3) Poor color tone of the polyester polymer, that is, a phenomenon in which the polymer is colored yellow occurs, and when used for a film, a hollow bottle, or the like, there is a problem that the color tone of a molded product is deteriorated. . 4) The filter pressure at the time of melting and producing a molded article increases due to clogging of foreign matter, and the productivity also decreases. Germanium compounds have already been put into practical use as catalysts that provide polyesters that have excellent catalytic activity other than antimony compounds and do not have the above-mentioned problems, but these catalysts are very expensive, There is a problem in that the catalyst concentration in the reaction system changes and it becomes difficult to control the polymerization because it easily distills out of the reaction system inside, and there is a problem in using it as the main component of the catalyst. Further, as a method of suppressing thermal deterioration during melt molding of polyester, a method of removing a catalyst from polyester can also be mentioned. As a method for removing a catalyst from polyester, for example, Japanese Patent Application Laid-Open
Japanese Patent Publication No. 0-251394 discloses a method in which a polyester resin is brought into contact with an extractant which is a supercritical fluid in the presence of an acidic substance. However, such a method using a supercritical fluid is not preferable because it is technically difficult and leads to an increase in product cost. In view of the circumstances described above, a production method that provides a polyester that is a polymerization catalyst containing a metal component other than antimony and germanium as a main metal component of the catalyst, has excellent catalytic activity, has a small amount of foreign matter, and has excellent transparency. It is rare.

[0003]

SUMMARY OF THE INVENTION The present invention provides a novel polyester polymerization catalyst other than an antimony compound, and a method for producing a polyester produced using the same. In addition, the present invention provides a polymerization catalyst which provides a polyester which contains aluminum as a main metal component, has excellent catalytic activity, generates little foreign matter, has excellent transparency, and further has excellent color tone, and a polyester production method using the same. I do. The present invention is also directed to the polyester polymerization catalyst, wherein the catalyst is used, a film, a hollow molded article such as a bottle, a fiber, the generation of foreign matter when performing melt molding of an engineering plastic, and the like, and the productivity is improved. And a method for producing a polyester using the same.

[0004]

Means for Solving the Problems The present inventors have proposed that an aluminum compound having poor catalytic activity is polycondensed by combining an aluminum compound with a phenolic compound, a phosphorus compound or a phosphorus compound having a phenol moiety in the same molecule. The inventors have found that the catalyst has sufficient activity as a catalyst, and have reached the present invention. Further, by using the polymerization catalyst and the production method of the present invention, it is possible to obtain a polyester excellent in quality without using an antimony compound.

That is, the present invention provides a polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound or a phenolic compound, particularly a phosphorus compound having a phenol moiety in the same molecule, and a process for producing the same using the same. Provided is a method for producing a polyester.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a polyester produced using a novel polycondensation catalyst other than an antimony compound. The production method of the present invention
A polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound or a phenolic compound, particularly a phosphorus compound having a phenol moiety in the same molecule, and a method for producing a polyester using the same.

As the aluminum or aluminum compound constituting the polycondensation catalyst of the present invention, known aluminum compounds can be used without limitation in addition to metallic aluminum.

Specific examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, and aluminum trichloroacetate. , Aluminum lactate,
Carboxylates such as aluminum citrate and aluminum salicylate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate and aluminum phosphonate; aluminum methoxide, aluminum ethoxide, and aluminum n -Propoxide, aluminum is
Aluminum chelates such as o-propoxide, aluminum n-butoxide, aluminum t-butoxide, aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate di-iso-propoxide, trimethyl aluminum, Organoaluminum compounds such as triethylaluminum and partial hydrolysates thereof,
Aluminum oxide and the like can be mentioned. Of these, carboxylate, inorganic acid salt and chelate compound are preferred,
Among these, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

The amount of the aluminum or aluminum compound used in the present invention is 0.001 to 0.05 mol based on the total number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. %, More preferably 0.005 to 0.0%
2 mol%. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited. If the amount used is 0.05 mol% or more, the thermal stability and thermo-oxidation stability decrease, and aluminum is caused. In some cases, the generation of foreign matter and the increase in coloring may become a problem. As described above, even when the addition amount of the aluminum component is small, the polymerization catalyst of the present invention is greatly characterized in that it exhibits a sufficient catalytic activity. As a result, thermal stability and thermal oxidation stability are excellent, and foreign matter and coloring due to aluminum are reduced.

The phenolic compound constituting the polycondensation catalyst of the present invention is not particularly limited as long as it has a phenolic structure. For example, 2,6-di-tert-butyl-4-methylphenol, 2 , 6-Di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-
tert-amyl-4-methylphenol, 2,6-di-tert-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-
n-octylphenol, 2-isopropyl-4-methyl-6-te
rt-butylphenol, 2-tert-butyl-2-ethyl-6-tert
-Octylphenol, 2-isobutyl-4-ethyl-6-tert-
Hexylphenol, 2-cyclohexyl-4-n-butyl-6-
Isopropylphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3-
(3,5-di-tert-butyl-4,4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert
-Butyl-4-hydroxy-hydrocinnamide), 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5- Di-tert-
Butyl-4-hydroxybenzyl) isocyanurate, 1,
3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-
Di-tert-butyl-4-hydroxy) hydrocinnamate]
Methane, bis [(3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid) glycol ester, N, N'-bis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyl] hydrazine, 2,2'-oxazamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-
Methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl
-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl2- {β- (3-t
ert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3 , 5-di-tert-
Butyl-4-hydroxycinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, thiodiethylene-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-
Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3 ′ -tert-butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane. These can be used in combination of two or more at the same time. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3 ′, 5 ′) -Di-tert-butyl
4-Hydroxyphenyl) propionate] methane and thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

The addition of these phenolic compounds during the polymerization of the polyester improves the catalytic activity of the aluminum compound and also improves the thermal stability of the polymerized polyester.

The phenolic compound of the present invention is used in an amount of 5 × 10 ^{−7 to} 0.01 mol per mol of all the constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. Preferably, it is more preferably 1 × 10 ^{−6 to} 0.005 mol. In the present invention, a phosphorus compound may be used together with the phenolic compound.

The phosphorus compound constituting the polycondensation catalyst of the present invention is not particularly limited.
Phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds,
It is preferable to use one or more compounds selected from the group consisting of phosphine-based compounds because the effect of improving the catalytic activity is large. Among these, the use of one or two or more phosphonic acid compounds is particularly preferable because the effect of improving the catalytic activity is particularly large.

The phosphonic acid-based compound, phosphinic acid-based compound, phosphine oxide-based compound, phosphonous acid-based compound, phosphinous acid-based compound and phosphine-based compound referred to in the present invention are represented by the following formulas 1 to 6, respectively. Refers to a compound having a structure.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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The phosphonic acid compounds of the present invention include, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate and the like. Can be Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
And phenyl phenylphosphinate. As the phosphine oxide compound of the present invention, for example,
Examples include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds and phosphine compounds, the phosphorus compounds of the present invention are represented by the following chemical formulas (7) to (12). Preferably, a compound is used.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the phosphorus compound constituting the polycondensation catalyst of the present invention, the compounds represented by the following general formulas (13) to (15) are particularly preferable since they greatly improve the catalytic activity.

[0031]

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[0032]

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[0033]

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(Wherein R ¹ , R ⁴ , R ⁵ , R ⁶
Are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group or an amino group.
R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to 1 carbon atoms including a hydroxyl group or an alkoxyl group.
Represents 50 hydrocarbon groups. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the phosphorus compound constituting the polycondensation catalyst of the present invention, R ¹ , R ⁴ , R ⁵ ,
Compounds in which R ⁶ is a group having an aromatic ring structure are particularly preferred.

The phosphorus compounds constituting the polycondensation catalyst of the present invention include, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate,
Diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
Phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide,
Triphenylphosphine oxide and the like.
Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

As the phosphorus compound constituting the polycondensation catalyst of the present invention, it is preferable to use a phosphorus compound having a phenol moiety in the same molecule. The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid-based compound, a phosphinic acid-based compound, and a phosphine oxide-based compound having a phenol moiety in the same molecule. It is preferable to use one or more compounds selected from the group consisting of compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds because the effect of improving the catalytic activity is large. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferred because the effect of improving the catalytic activity is particularly large. Examples of the phosphorus compound having a phenol moiety in the same molecule that constitutes the polycondensation catalyst of the present invention include compounds represented by the following general formulas 16 to 1
The use of the compound represented by 8 is preferred because the catalytic activity is particularly improved.

[0038]

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[0039]

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[0040]

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(Wherein R ¹ represents a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group or a halogen group, a substituent such as an alkoxyl group or an amino group, and 1 carbon atom including a phenol moiety. Represents a hydrocarbon group of 50 to 50. R ⁴ , R ⁵ , and R ⁶ each independently represent hydrogen, and have 1 to 5 carbon atoms.
C 1 -C 1 including a substituent such as a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
Represents 50 hydrocarbon groups. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may include a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The terminals of R ² and R ⁴ may be bonded to each other. )

Examples of the phosphorus compound of the present invention having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonate.
Diphenyl hydroxyphenylphosphonate, bis (p
-Hydroxyphenyl) phosphinic acid, bis (p-hydroxyphenyl) phosphinic acid methyl, bis (p-hydroxyphenyl) phosphinic acid phenyl, p-hydroxyphenylphenylphosphinic acid, p-hydroxyphenylphenylphosphinic acid methyl, p-hydroxyphenyl Phenyl phenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis ( and (p-hydroxyphenyl) methylphosphine oxide, and compounds represented by the following formulas (19) to (22). Among these, a compound represented by the following formula (21) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0043]

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[0044]

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[0045]

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[0046]

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As the compound represented by the above formula 21, SANKO-220 (manufactured by Sanko Co., Ltd.) is available.

By adding a phosphorus compound having such a phenol moiety in the same molecule during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved and the thermal stability of the polymerized polyester is also improved.

In the present invention, it is preferable to use a metal salt compound of phosphorus as the phosphorus compound. The metal salt compound of phosphorus is not particularly limited as long as it is a metal salt of a phosphorus compound, but the use of a metal salt of a phosphonic acid-based compound is preferred because the effect of improving the catalytic activity is large. Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

In the above-mentioned phosphorus compounds, the metal part of the metal salt is Li, Na, K, Be, Mg, Sr,
It is preferable to use one selected from Ba, Mn, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

As the phosphorus metal salt compound constituting the polymerization catalyst of the present invention, it is preferable to use at least one selected from compounds represented by the following general formula (23) since the effect of improving the catalytic activity is large.

[0052]

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(In Formula 23, R ¹ is hydrogen, and has 1 to 5 carbon atoms.)
And represents a hydrocarbon group having 1 to 50 carbon atoms including 0 hydrocarbon group, hydroxyl group, halogen group, alkoxyl group or amino group. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 50 carbon atoms.
Represents a hydrocarbon group. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l is 1
M is an integer of 0 or 1 or more, and l + m is 4
It is as follows. M represents a (l + m) -valent metal cation. n is 1
Represents the above integer. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. R ³
Examples of O ^- include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

It is preferable to use at least one compound selected from the compounds represented by the following general formula 24 among the compounds represented by the above general formula 23.

[0056]

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(In Formula 24, R ¹ is hydrogen, and has 1 to 5 carbon atoms.
And represents a hydrocarbon group having 1 to 50 carbon atoms including 0 hydrocarbon group, hydroxyl group, halogen group, alkoxyl group or amino group. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion,
Examples include acetate ion and acetylacetone ion.

Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

In the above formula 24, M is Li, N
a, K, Be, Mg, Sr, Ba, Mn, Ni, Cu,
It is preferable to use a material selected from Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

The phosphorus metal salt compounds of the present invention include lithium [ethyl (1-naphthyl) methylphosphonate],
Sodium [ethyl (1-naphthyl) methyl phosphonate], magnesium bis [(1-naphthyl) methyl phosphonate], potassium [ethyl (2-naphthyl) methyl phosphonate], magnesium bis [(2-naphthyl) methyl phosphonate], Lithium [ethyl benzyl phosphonate], sodium [ethyl benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], beryllium bis [ethyl benzyl phosphonate],
Strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [ethyl (9-anthryl) methylphosphonate], magnesium bis [(9-anthryl) ) Ethyl methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis [ethyl 4-hydroxybenzylphosphonate], sodium [phenyl chlorobenzylphosphonate], ethyl magnesium bis [4-chlorobenzylphosphonate] ], Sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis [phenylphosphonate] Ethyl phosphate], zinc bis [phenylphosphonic acid ethyl] and the like. Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], lithium [ethyl benzylphosphonate], Sodium [ethyl benzylphosphonate],
Magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate and magnesium bis [benzylphosphonic acid] are particularly preferred.

The metal salt compound of phosphorus, which is another preferable phosphorus compound constituting the polymerization catalyst of the present invention, is at least one selected from compounds represented by the following general formula 25.

[0063]

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[0064] ((in formalized 25, R ^1, R ² are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
R ⁴ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents 50 hydrocarbon groups. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among them, it is preferable to use at least one selected from compounds represented by the following general formula (26).

[0066]

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(In Formula 26, M ^{n +} represents an n-valent metal cation. N represents 1, 2, 3, or 4.)

In the above formulas (25) and (26), M
Are Li, Na, K, Be, Mg, Sr, Ba, Mn,
It is preferable to use one selected from Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, Li,
Na and Mg are particularly preferred.

The specific phosphorus metal salt compounds of the present invention include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-t-t
ethyl ert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [3,5-di-tert-butyl]
-Butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-]
Ethyl hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl], Strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-
Phenyl di-tert-butyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4
-Ethyl ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4]
-Ethyl ethyl hydroxybenzylphosphonate] and zinc bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate]. Among them, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

Another embodiment of the present invention is a method for producing a polyester, comprising at least one selected from aluminum salts of phosphorus compounds. An aluminum salt of a phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound or the like. The aluminum salt of the phosphorus compound of the present invention is not particularly limited as long as it is a phosphorus compound having an aluminum portion. However, the use of an aluminum salt of a phosphonic acid compound is preferred because the effect of improving the catalytic activity is large. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

Of the above-mentioned aluminum salts of phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the aluminum salt of the phosphorus compound constituting the polymerization catalyst of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula 27 since the effect of improving the catalytic activity is large.

[0073]

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((In Formula 27, R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. R ³ is hydrogen, carbon number 1-50
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, an alkoxyl group or a carbonyl. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and l + m is 3
It is. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

The aluminum salt of the phosphorus compound of the present invention includes aluminum salt of ethyl (1-naphthyl) methylphosphonate, aluminum salt of ethyl (1-naphthyl) methylphosphonate, aluminum salt of ethyl (2-naphthyl) methylphosphonate, benzyl Aluminum salt of ethyl phosphonate, aluminum salt of benzylphosphonic acid, (9
Aluminum salt of ethyl -anthryl) methylphosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, aluminum salt of phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate Aluminum salt of ethyl 4-methoxybenzylphosphonate, aluminum salt of ethyl phenylphosphonate, and the like. Among them, (1-
Naphthyl) aluminum salt of ethyl methylphosphonate,
Aluminum salts of ethyl benzylphosphonate are particularly preferred.

Another embodiment of the present invention is a compound represented by the following general formula 2.
A polyester polymerization catalyst comprising at least one selected from aluminum salts of specific phosphorus compounds represented by No. 8 and a polyester production method using the same.
The aluminum salt of the phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound, or the like. The aluminum salt of a specific phosphorus compound constituting the polymerization catalyst of the present invention means at least one selected from compounds represented by the following general formula 28.

[0078]

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[0079] ((in formalized 28, R ^1, R ² are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
R ⁴ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents 50 hydrocarbon groups. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula 29.

[0081]

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(In Formula 29, R ³ is hydrogen, and has 1 to carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups or alkoxyl groups. R ⁴ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and l + m is 3. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group and a naphthyl group, and a group represented by —CH ₂ CH ₂ OH. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

Examples of the aluminum salt of the specific phosphorus compound of the present invention include aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-t-t
Aluminum salt of methyl ert-butyl-4-hydroxybenzylphosphonate, aluminum salt of isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzyl Aluminum salt of phenyl phosphonate, 3,5-di-tert-
Aluminum salt of butyl-4-hydroxybenzylphosphonic acid; Of these, 3,5-di-ter
Aluminum salts of ethyl t-butyl-4-hydroxybenzylphosphonate and aluminum salts of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

In the present invention, it is preferable to use a phosphorus compound having at least one P-OH bond as the phosphorus compound. A phosphorus compound having at least one P-OH bond,
There is no particular limitation as long as it is a phosphorus compound having at least one P-OH in the molecule. Among these phosphorus compounds,
Use of a phosphonic acid-based compound having at least one P-OH bond is preferred because the effect of improving the catalytic activity is large.

Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the phosphorus compound having at least one P-OH bond constituting the polymerization catalyst of the present invention, when at least one selected from compounds represented by the following general formula (30) is used, the effect of improving the catalytic activity is improved. Large and preferred.

[0088]

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(In Formula 30, R ¹ is hydrogen, and has 1 to 5 carbon atoms.)
0 represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. R ² is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 50 carbon atoms.
Represents a hydrocarbon group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH.

Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is large.

The phosphorus compounds having at least one P-OH bond according to the present invention include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid,
Ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, ethyl (9-anthryl) methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate , Methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate, and the like. Of these, (1
-Naphthyl) ethyl methylphosphonate and ethyl benzylphosphonate are particularly preferred.

[0093] Preferred phosphorus compounds used in the present invention include specific phosphorus compounds having at least one P-OH bond. The specific phosphorus compound having at least one P-OH bond refers to at least one compound selected from the compounds represented by the following general formula 31.

[0094]

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[0095] ((in formalized 31, R ^1, R ² are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among them, it is preferable to use at least one selected from compounds represented by the following general formula 32.

[0097]

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(In Formula 32, R ³ is hydrogen, and has 1 to carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups or alkoxyl groups. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group and a naphthyl group, and a group represented by —CH ₂ CH ₂ OH.

Specific phosphorus compounds having at least one P-OH bond according to the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl-ethyl. Methyl 4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Phenyl hydroxybenzylphosphonate, 3,5-di-ter
Octadecyl t-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like can be mentioned. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

A preferred phosphorus compound is represented by the following chemical formula 3.
And a phosphorus compound represented by 3.

[0102]

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[0103] (in formalized 33, R ¹ represents a hydrocarbon group having 1 to 49 carbon atoms containing a hydrocarbon group or a hydroxyl group or a halogen group, an alkoxyl group, or an amino group, of 1 to 49 carbon atoms, R ^2, R ³ is each independently hydrogen, carbon number 1-5
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a 0 hydrocarbon group, a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. )

Further, more preferably, in the chemical formula 33,
At least one of R ¹ , R ² and R ³ is a compound containing an aromatic ring structure.

Specific examples of the phosphorus compound used in the present invention are shown below.

[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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The phosphorus compound used as a polycondensation catalyst in the present invention has a higher molecular weight and is more effective because it is less likely to be distilled off during polymerization.

Another phosphorus compound desirably used in the present invention is at least one phosphorus compound selected from compounds represented by the following general formula 40.

[0114]

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[0115] (in the formalized 40, R ^1, R ² are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
R ⁴ is each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 50 carbon atoms.
Represents a hydrocarbon group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Of the above general formulas 40, the use of at least one compound selected from the compounds represented by the following general formulas 41 is preferred because the effect of improving the catalytic activity is high.

[0117]

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(In the above formula 41, R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrogen group may include an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

R ³ and R ⁴ are, for example, short-chain aliphatic groups such as hydrogen, methyl group and butyl group, long-chain aliphatic groups such as octadecyl, phenyl group, naphthyl group and substituted phenyl group. aromatic groups such as groups or naphthyl group, -CH ₂ CH ₂
And a group represented by OH.

The specific phosphorus compounds of the present invention include 3,5
-Di-tert-butyl-4-hydroxybenzylphosphonate diisopropyl, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate di-n-butyl, 3,5-di-ter
dioctadecyl t-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the like. Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-
Diphenyl hydroxybenzylphosphonate is particularly preferred.

Another phosphorus compound that is desirably used in the present invention is at least one phosphorus compound selected from the compounds represented by Chemical Formulas 42 and 43.

[0122]

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[0123]

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As the compound represented by the chemical formula 42, Irganox 1222 (manufactured by Ciba Specialty Chemicals) is commercially available, and as the compound represented by the chemical formula 43, Irganox 142
5 (manufactured by Ciba Specialty Chemicals) is commercially available and can be used.

By using the phosphorus compound described in the present invention in combination, a polymerization catalyst which exhibits a sufficient catalytic effect even when the amount of aluminum added in the polyester polymerization catalyst is small, and a polyester production method can be obtained.

The amount of the phosphorus compound of the present invention to be used is preferably 0.0001 to 0.1 mol% with respect to the total number of moles of all constituent units of the polycarboxylic acid component of the obtained polyester.
More preferably, it is 0.005 to 0.05 mol%. When the addition amount of the phosphorus compound is less than 0.0001 mol%, the effect of addition may not be exhibited. When the addition amount exceeds 0.1 mol%, on the contrary, the catalytic activity as a polyester polymerization catalyst may decrease. The tendency changes depending on the amount of aluminum used and the like.

This is a technique in which an aluminum compound is used as a main catalyst component without using a phosphorus compound. In this technique, the amount of the aluminum compound used is reduced, and a cobalt compound is added to make the heat stable when the aluminum compound is used as the main catalyst. Although there is a technique for preventing coloring due to a decrease in the properties, if the cobalt compound is added to such an extent that it has a sufficient catalytic activity, the thermal stability also decreases. Therefore, it is difficult to achieve both with this technique.

According to the present invention, the use of the phosphorus compound having the above-mentioned specific chemical structure does not cause problems such as a decrease in thermal stability and the generation of foreign matters, and the addition amount of the metal-containing component as aluminum is small. However, a polymerization catalyst having a sufficient catalytic effect can be obtained, and by using this polymerization catalyst, the thermal stability at the time of melt molding of hollow molded articles such as polyester films and bottles, and fibers and engineering plastics can be improved. Even if a phosphoric acid ester such as phosphoric acid or trimethyl phosphoric acid is added in place of the phosphorus compound of the present invention, the effect of addition is not seen and it is not practical. Further, even when the phosphorus compound of the present invention is used in combination with a conventional antimony compound, a titanium compound, a tin compound, a metal-containing polyester polymerization catalyst such as a germanium compound in the range of the addition amount of the present invention, the melt polymerization reaction is promoted. No effect is observed.

It is preferable that the above-mentioned catalyst does not contain an alkali metal, an alkaline earth metal, or a compound thereof. On the other hand, in a preferred embodiment of the present invention, a small amount of at least one selected from alkali metals, alkaline earth metals and compounds thereof is coexisted as the second metal-containing component in addition to aluminum or its compound. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity in addition to the effect of suppressing the production of diethylene glycol, and therefore, a catalyst component having a higher reaction rate is obtained, which is effective for improving the productivity. .

It is known that a catalyst having sufficient catalytic activity can be obtained by adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound. The use of such a known catalyst can provide a polyester having excellent thermal stability. However, the known catalyst using an alkali metal compound or an alkaline earth metal compound in combination is not suitable for obtaining a practical catalytic activity. When an alkali metal compound is used, the amount of foreign matter caused by the alkali metal compound increases, and when used for fibers, the spinning properties and yarn properties, and when used for films, the film properties, transparency, and heat stability Properties, thermal oxidation stability, hydrolysis resistance, etc. are deteriorated. Further, the color tone of a melt-formed product such as a fiber or a film deteriorates.
In addition, when an alkaline earth metal compound is used in combination, the thermal stability and thermal oxidative stability of the obtained polyester are reduced in order to obtain practical activity, the coloring due to heating is large, and the amount of foreign matter generated is also small. More.

When an alkali metal, an alkaline earth metal or a compound thereof is added, the amount of use M (mol%) is
It is preferably from 1 × 10 ^{−6 to} less than 0.1 mol%, more preferably from 5 × 10 ^{−6 to} 0.05, based on the number of moles of all the polycarboxylic acid units constituting the polyester.
Mol%, more preferably 1 × 10 ^{−5 to} 0.03.
Mol%, particularly preferably 1 × 10 ^{−5 to} 0.01.
Mol%. Since the added amount of the alkali metal and the alkaline earth metal is small, the reaction rate can be increased without causing problems such as a decrease in thermal stability, generation of foreign matter, and coloring. Further, the reaction rate can be increased without causing a problem such as a decrease in hydrolysis resistance. When the amount M of the alkali metal, alkaline earth metal or compound thereof is 0.1 mol% or more, there is a problem in product processing such as a decrease in thermal stability, an increase in generation of foreign matter and coloring, and a decrease in hydrolysis resistance. Cases occur. If M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if added.

The alkali metal and alkaline earth metal constituting the second metal-containing component which is preferably used in addition to aluminum or its compound in the present invention include Li, Na, K, Rb, Cs, Be, Mg, Ca,
It is preferably at least one selected from Sr and Ba, and more preferably an alkali metal or a compound thereof. When an alkali metal or a compound thereof is used, it is particularly preferable to use Li, Na, and K. Examples of the alkali metal or alkaline earth metal compounds include, for example, saturated aliphatic carboxylate such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid. Aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, hydroxycarboxylate such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as oxyhydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid, and organic sulfonic acid salts such as 1-propanesulfonic acid, 1-pentanesulfonic acid, and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n
-Propoxy, iso-propoxy, n-butoxy, t
alkoxides such as tert-butoxy, chelate compounds with acetylacetonate and the like, hydrides, oxides,
Hydroxide and the like.

When strong alkalis such as hydroxides are used among these alkali metals, alkaline earth metals or compounds thereof, they are less likely to be dissolved in organic solvents such as diols such as ethylene glycol or alcohols. Therefore, an aqueous solution must be added to the polymerization system, which may cause a problem in the polymerization step. Further, when a strong alkali such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be easily colored, and the hydrolysis resistance is also reduced. Tend to. Accordingly, the alkali metal or a compound thereof or an alkaline earth metal or a compound thereof suitable for the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, or an aromatic salt of an alkali metal or an alkaline earth metal. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid,
It is an inorganic acid salt selected from chloric acid and bromic acid, an organic sulfonate, an organic sulfate, a chelate compound, and an oxide. Among these, from the viewpoints of ease of handling and availability, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly an acetate.

In a preferred embodiment, a cobalt compound is added to the polyester polymerization catalyst of the present invention in an amount of less than 10 ppm as a cobalt atom to the polyester. More preferably, it is less than 5 ppm, and still more preferably 3 ppm or less.

It is known that the cobalt compound itself has a certain degree of polymerization activity. However, when the cobalt compound is added to such an extent that a sufficient catalytic effect is exhibited, the brightness of the polyester polymer obtained is lowered. And thermal stability decreases. The polyester obtained according to the present invention has good color tone and thermal stability, but can be obtained by adding a cobalt compound in an amount such that the catalytic effect of the addition by a small amount as described above is not clear. The coloring can be more effectively eliminated without lowering the brightness of the polyester. The purpose of the cobalt compound in the present invention is to eliminate coloration, and it may be added at any stage of the polymerization or after the completion of the polymerization reaction.

The cobalt compound is not particularly limited, but specific examples thereof include cobalt acetate, cobalt nitrate,
Cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof are exemplified. Among them, cobalt acetate tetrahydrate is particularly preferred.

The amount of the cobalt compound to be added is such that the total of the aluminum atoms and the cobalt atoms is 50 ppm or less and the cobalt atoms are 10 pp to the finally obtained polymer.
It is preferably less than m. More preferably, the total of aluminum atoms and cobalt atoms is 40 ppm or less,
The cobalt atom is 8 ppm or less, more preferably the total of the aluminum atom and the cobalt atom is 25 ppm or less, and the cobalt atom is 5 ppm or less. From the viewpoint of the thermal stability of the polyester, the total of aluminum atoms and cobalt atoms is less than 50 ppm,
It is preferably 0 ppm or less. In order to have sufficient catalytic activity, the total amount of aluminum atoms and cobalt atoms is preferably more than 0.01 ppm.

The production of the polyester according to the present invention can be carried out by a method having conventionally known steps except that the polyester polymerization catalyst of the present invention is used as a catalyst. For example, when producing PET, after esterification of terephthalic acid and ethylene glycol, a method of polycondensation, or after performing an ester exchange reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, Any of the polycondensation methods can be used. Also, the polymerization apparatus is a batch type,
It may be a continuous type.

The catalyst of the present invention has catalytic activity not only in polymerization but also in esterification and transesterification. For example, polymerization by transesterification of an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate with a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. Alternatively, or in combination 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 it is possible to produce polyester by any method.

The polymerization catalyst of the present invention needs to be added to the reaction system with IV ≦ 0.40. Addition of IV> 0.4 is not preferable because the viscosity of the reaction system is too high, and not only does the catalyst not uniformly disperse, but also the polymerization rate becomes slow. More preferably, IV ≦ 0.3, and IV ≦
Particularly preferred is 0.2. However, the above IV
If it satisfies the range of ≦ 0.40, it can be added to the reaction system 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 the transesterification reaction and at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. Further, as long as the above-mentioned range of IV ≦ 0.40 is satisfied, each component of the mixed catalyst can be added simultaneously or separately. In particular, aluminum or its compound immediately before the start of the polycondensation reaction, that is, 0.03 ≦ IV ≦
It is preferably added to 0.20.

As another embodiment of the production method of the present invention,
Phosphorus compound 42 is preferably added at IV ≦ 0.1. Compound 42 is not preferred because if it is added with IV> 0.1, the amount remaining in the reaction system is small and the polymerization rate is significantly reduced. IV ≦ 0.05 is more preferable, and IV ≦ 0.03 is particularly preferable. Further, it is preferable to add phosphorus compounding 43 so that 0.01 ≦ IV ≦ 0.20.
Compounding 43 is not preferable if added at IV <0.01 because the carboxylic acid terminal reacts with the catalyst metal to increase the amount of foreign substances. Further, if IV> 0.2, the polymerization rate is undesirably reduced. 0.02 ≦ IV ≦ 0.15 is more preferable, and 0.03 ≦ IV ≦ 0.12 is particularly preferable.

As another embodiment of the production method of the present invention,
The polymerization catalyst is preferably added to a reaction system satisfying 10 ≦ AVo ≦ 3000. If AVo <10, the viscosity of the reaction system is too high, and not only is the catalyst not uniformly dispersed, but also the polymerization rate is undesirably low. Also, A
If Vo> 3000, the carboxylic acid terminal and the catalyst metal react with each other to increase the amount of foreign substances, which is not preferable. More preferably, it is added at 50 ≦ AVo ≦ 2000. Also, 10
It is particularly preferable to add in a range of 0 ≦ AVo ≦ 1500.
However, if it satisfies the above range of 10 ≦ AVo ≦ 3000, it can be added to the reaction system 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 the transesterification reaction and at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In addition, the above 10 ≦ A
As long as the range of Vo ≦ 3000 is satisfied, each component of the mixed catalyst can be added simultaneously or separately.
In particular, it is preferable to add aluminum or its compound immediately before the start of the polycondensation reaction, that is, at 100 ≦ AVo ≦ 500.

As another embodiment of the production method of the present invention,
It is preferable to add the phosphorus compound conversion 42 at AVo> 3000. Compound 42 is not preferable when added at AVo ≦ 3000 because the amount remaining in the reaction system is small and the polymerization rate is significantly reduced. In addition, the conversion to phosphorus compound 43 is 10
It is particularly preferable to add in a range of 0 ≦ AVo ≦ 1000.
Compounding 43 is not preferable when added at AVo> 1000 because the carboxylic acid terminal reacts with the catalyst metal to increase the amount of foreign substances. Addition of AVo <100 is not preferable because the polymerization rate decreases.

As another embodiment of the production method of the present invention,
The polymerization catalyst is preferably added to a reaction system satisfying 50 ≦ OHVo ≦ 7000. When OHVo <50, the viscosity of the reaction system is too high, so that not only is the catalyst not uniformly dispersed, but also the polymerization rate is slow, which is not preferable. On the other hand, if OHVo> 7000, not only the productivity is lowered due to excess ethylene glycol, but also the polymer is undesirably colored. More preferably, 500 ≦
Add with OHVo ≦ 6000. Also, 1000 ≦ OH
It is particularly preferred to add at Vo ≦ 5000. However, if it satisfies the range of 50 ≦ OHVo ≦ 7000, it can be added to the reaction system 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 the transesterification reaction and at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. Of course, the above 50 ≦ O
If the range of HVO ≦ 7000 is satisfied, each component of the mixed catalyst can be added simultaneously or separately. In particular, it is preferable to add aluminum or its compound immediately before the start of the polycondensation reaction, that is, at 1000 ≦ OHVo ≦ 5000.

As another embodiment of the production method of the present invention,
Phosphorus compound 42 is preferably added when OVO> 7000. Compound 42 is not preferable because if it is added at OHVo ≦ 7000, the amount remaining in the reaction system is small and the polymerization rate is significantly reduced. Further, it is particularly preferable to add the phosphorus compound conversion 43 so that 1000 ≦ OHVo ≦ 5000. The compounding 43 is not preferable because if the OHV o> 5000 is added, the carboxylic acid terminal reacts with the catalyst metal to increase the amount of foreign substances. On the other hand, if OHVo <1000, the polymerization rate is undesirably reduced.

The polymerization catalyst of the present invention has an average polymerization degree Pn ≦ 5.
It is preferable to add 0 to the reaction system. Addition of Pn> 50 is not preferred because the viscosity of the reaction system is too high, and not only does the catalyst not uniformly disperse, but also the polymerization rate becomes slow. More preferably, Pn ≦ 12, and Pn ≦ 8
Is particularly preferred. However, the above Pn ≦ 50
Can be added to the reaction system 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 the transesterification reaction and at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. Also,
As long as the above-mentioned range of Pn ≦ 50 is satisfied, each component of the mixed catalyst can be added simultaneously or separately. In particular, aluminum or its compound is preferably added immediately before the start of the polycondensation reaction, that is, at 2 ≦ Pn ≦ 8.

As another embodiment of the production method of the present invention,
It is particularly preferable to add the phosphorus compound 42 at Pn <1. Compounding 42 is not preferable if Pn ≧ 1 is added because the amount remaining in the reaction system is small and the polymerization rate is significantly reduced. It is particularly preferable to add the phosphorus compounding compound 43 so that 2 ≦ Pn ≦ 8. Compound 43 has Pn <2
If added, the carboxylic acid terminal reacts with the catalyst metal and the amount of foreign substances increases, which is not preferable. Further, if Pn> 8, the polymerization rate is undesirably reduced.

As another embodiment of the production method of the present invention,
The polymerization catalyst is preferably added to the reaction system satisfying the esterification ratio Es (%) ≧ 60. If Es (%) <60, the carboxylic acid terminal and the catalyst metal react with each other to increase the amount of foreign substances, which is not preferable. More preferably, Es (%) ≧ 80 is added. It is particularly preferable to add Es (%) ≧ 90. However, if the above range of Es (%) ≧ 60 is satisfied,
It can be added to the reaction system 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 the transesterification reaction and at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In addition, the above Es (%) ≧
As long as the range of 60 is satisfied, each component of the mixed catalyst can be added simultaneously or separately. In particular, it is preferable to add aluminum or its compound immediately before the start of the polycondensation reaction, that is, when Es (%) ≧ 90.

As another embodiment of the production method of the present invention,
It is preferable that the compound 42 for phosphorus compound is added by Es (%) ≦ 90. It is not preferable that the compound 42 is added when Es (%) ≧ 90 because the amount remaining in the reaction system is small and the polymerization rate is significantly reduced. In addition, the conversion of phosphorus compound 43 into Es
(%) ≧ 90 is particularly preferred. Compounding 4
The addition of Es (%) <90 is not preferable because the carboxylic acid terminal reacts with the catalyst metal to increase the amount of foreign substances.

The shape of the polymerization catalyst of the present invention needs to be a solution. If it is not added as a solution, not only the dispersion in the reaction system becomes non-uniform, but also it is difficult to supply quantitatively, which is not preferable. The solvent is not particularly limited as long as it can dissolve the polymerization catalyst of the present invention even in a small amount. However, a diol component which forms a polyester which does not become a foreign substance or an impurity even when remaining in the polyester, or a diol component which is distilled out of the system during the production of the polyester is preferable.

As the solvent, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butyl glycol 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,
Aliphatic glycols exemplified by 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc., 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 naphthalene diol, and aromatic glycols exemplified by ethylene glycol added to these glycols.
Also, lower aliphatic alcohols such as methanol, ethanol, isopropanol, propanol, isobutyl alcohol, butanol, pentanol, hexanol, chloroform, carbon tetrachloride, dichloromethane, perchloroethylene, trichloroethane, trichloroethylene, toluene, benzene, acetone, and acetonitrile ,
Dimethylformamide, ethyl acetate, amyl alcohol, amyl acetate, benzyl alcohol, water, cyclohexanone, dimethylacetamide, dimethylformamide, dioxane, dimethylsulfoxide, ethers such as diethyl ether, formaldehyde, glycerin, hexane, isopropyl acetate,
Examples include methyl ethyl ketone, pentane, phenol, pyridine, xylene, tetrahydrofuran and the like.

The method for preparing the solution is not particularly limited. Physical conditions such as heating, stirring, and dissolution time depend on the compound,
It can be freely selected according to the solvent. For example, liquid-liquid replacement from a readily soluble solvent is also possible. Also, the stability of the solution,
Various additives can be added to improve the solubility.

For example, in the case of an aluminum compound, if the aluminum compound is previously mixed with water containing an alkali compound, an organic solvent or a mixture of water and an organic solvent, and then added to the reaction system, the formation of foreign substances in the polyester of the aluminum compound is further suppressed. This is preferable. In particular, it is preferable to mix an aluminum compound with the aqueous solution after mixing the alkali compound with water to form an aqueous solution, since the aluminum compound is uniformly dispersed or dissolved in the aqueous solution, and the generation of foreign substances in the polyester is further suppressed. It is also preferable to dilute the aqueous solution containing the aluminum compound with a diol component forming a polyester such as ethylene glycol and then add it to the reaction system, since local concentration or the like due to a rapid temperature change hardly occurs. Further, when the compound volatilizes at a temperature of 280 ° C. or lower, the residual amount in the finally obtained polyester decreases, and the color tone of the polyester is more favorable, which is preferable.

As the alkali compound mentioned here, specifically, ammonia, diethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrapropylammonium hydroxide, Examples include tetrabutylammonium, trimethylbenzylammonium hydroxide, ethylenediamine, tetraethylenediamine, hexamethylenediamine, pyridine, quinoline, pyrroline, pyrrolidone, and piperidine.

As other additives, for example, ligand exchange can be carried out wholly or partially to improve the solubility and dispersion of the polymerization catalyst. In particular, ligands are formed by carboxylic acids such as acetic acid and benzoic acid, alcohols, diol components forming polyester, phosphoric compounds such as phosphoric acid, trimethyl phosphate and phenylphosphonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. It is preferable to perform exchange in terms of solution stability.

When the concentration of the solution is 0.01 to 20% by weight in terms of the metal atom of the catalyst, the solution stability,
The color tone of the obtained polyester composition is good and preferable.

A solution in which aluminum metal or its compound and another component, preferably the phenolic compound or phosphorus compound of the present invention are mixed in advance may be used. You may add in shape. Further, additives such as a polyester stabilizer, a surfactant, a coloring inhibitor, and a coloring agent may be appropriately added to the solution. In particular, the use of a cobalt compound is preferable because the polycondensation reaction proceeds more quickly and the color tone of the obtained polyester is further improved.

As another embodiment of the present invention, the shape of the polymerization catalyst of the present invention needs to be a slurry. When added in a slurry, not only is it possible to maintain appropriate fluidity and facilitate quantitative addition, but also the amount of solvent to be added to the reaction system can be suppressed, so that the temperature of the reaction system does not drop significantly, which is preferable in production. The solvent is not particularly limited as long as it has a proper fluidity. However, a diol component which forms a polyester which does not become a foreign substance or an impurity even when remaining in the polyester, or a diol component which is distilled out of the system during the production of the polyester is preferable.

As the solvent, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butyl glycol 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,
Aliphatic glycols exemplified by 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc., 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 naphthalene diol, and aromatic glycols exemplified by ethylene glycol added to these glycols.
Also, lower aliphatic alcohols such as methanol, ethanol, isopropanol, propanol, isobutyl alcohol, butanol, pentanol, hexanol, chloroform, carbon tetrachloride, dichloromethane, perchloroethylene, trichloroethane, trichloroethylene, toluene, benzene, acetone, and acetonitrile ,
Dimethylformamide, ethyl acetate, amyl alcohol, amyl acetate, benzyl alcohol, water, cyclohexanone, dimethylacetamide, dimethylformamide, dioxane, dimethylsulfoxide, ethers such as diethyl ether, formaldehyde, glycerin, hexane, isopropyl acetate,
Examples include methyl ethyl ketone, pentane, phenol, pyridine, xylene, tetrahydrofuran and the like.

The method for preparing the slurry is not particularly limited. For example, physical conditions such as heating, stirring, and preparation time can be freely selected according to the compound and the solvent. In addition, aluminum metal or a compound thereof and other components, preferably a slurry in which the phenolic compound or the phosphorus compound of the present invention is preliminarily mixed may be used, or these may be formed into separate slurries or may be formed into separate shapes. It may be added.

The shape of the slurry particles is not particularly limited. However, from the viewpoint of the sedimentation stability of the slurry, the volume-weighted average particle size of the catalyst powder is preferably 500 μm or less. More preferably, it is 300 μm or less, particularly preferably 100 μm or less, most preferably 50 μm or less. In addition, additives such as a dispersant, a stabilizer, a surfactant, a coloring inhibitor, and a color stabilizer of the slurry and the polyester may be appropriately added to the slurry. In particular, the use of a cobalt compound is preferable because the polycondensation reaction proceeds more quickly and the color tone of the obtained polyester is further improved.

The concentration of the slurry is preferably 0.05 to 50% by weight in terms of the metal atom of the catalyst because the slurry stability and fluidity are good. More preferably,
0.1 to 20% by weight.

In another embodiment of the present invention, the polymerization catalyst of the present invention needs to be in the form of a powder.
A powder is preferable not only in that the catalyst has excellent stability over time but also in that the solvent is not added to the reaction system, so that the temperature of the reaction system does not decrease and thus the production is low. If the polymerization catalyst is solid, the shape of the particles is not particularly limited. However, when adding the particles to the reaction system, it is preferable to process the particles into a tablet or lump, or to wrap the particles in a film or the like to facilitate the addition. Further, aluminum metal or a compound thereof and another component, preferably a powder obtained by previously mixing the phenolic compound or the phosphorus compound of the present invention, may be a separate powder, or may be in a separate form. It may be added. Further, additives such as a stabilizer for the powder and polyester, a surfactant, a coloring inhibitor, and a coloring agent may be appropriately mixed with the powder. In particular, the use of a cobalt compound is preferable because the polycondensation reaction proceeds more quickly and the color tone of the obtained polyester is further improved.

In another embodiment of the present invention, the polymerization catalyst of the present invention needs to be in the form of a melt. If it is a melt, it is not only easy to maintain a suitable fluidity and easy to add quantitatively, but also because no solvent is added to the reaction system,
Since the temperature of the reaction system does not decrease, it is preferable in production. Further, additives such as a stabilizer for the melt and the polyester, a surfactant, a coloring inhibitor, and a tinting agent may be appropriately mixed with the melt. In particular, the use of a cobalt compound is preferable because the polycondensation reaction proceeds more quickly and the color tone of the obtained polyester is further improved.

The method for preparing the melt is not particularly limited. Physical conditions such as heating temperature, stirring, and preparation time can be freely selected according to the compound. However, in view of the stability of the compound, the heating temperature is preferably equal to or lower than the melting point + 20 ° C, more preferably equal to or lower than the melting point + 10 ° C, and most preferably equal to or lower than the melting point + 5 ° C. On the other hand, if the preparation time exceeds 30 minutes, the decomposition of the compound becomes remarkable, and coloring is caused, which is not preferable. The preparation time is preferably within 30 minutes, more preferably within 20 minutes, and most preferably within 10 minutes.

Further, a molten metal in which aluminum metal or its compound and another component, preferably the phenolic compound or phosphorus compound of the present invention are mixed in advance may be used. You may add in a separate form. When added in the form of a melt, it is particularly preferable to add them separately from the viewpoint of the stability of the compound.

The method of adding the polycondensation catalyst of the present invention may be a powdery or neat addition, or a slurry or solution addition of a solvent such as ethylene glycol. Not limited. Further, a mixture of aluminum metal or a compound thereof and another component, preferably a phenolic compound or a phosphorus compound of the present invention, may be added in advance, or they may be added separately. Further, the aluminum metal or its compound and another component, preferably a phenolic compound or a phosphorus compound, may be added to the polymerization system at the same time, or they may be added at different times.

The polymerization catalyst of the present invention comprises an antimony compound,
Other polymerization catalysts such as titanium compounds, germanium compounds, and tin compounds are allowed to coexist within the range of the addition amount in which the addition of these components does not cause a problem in the properties of the polyester, processability, color tone, etc. as described above. The use is advantageous and preferable in improving productivity by shortening the polymerization time.

However, as the antimony compound, as an antimony atom, a polyester obtained by polymerization is used.
It can be added in an amount of 50 ppm or less. More preferably 30 ppm
It is to be added in the following amount. The amount of antimony added
If it exceeds 50 ppm, precipitation of metallic antimony occurs, and blackening or foreign matter is generated in the polyester, which is not preferable.

The titanium compound can be added in a range of 10 ppm or less based on the polymer obtained by polymerization. More preferably 5ppm or less, more preferably 2ppm
It is to be added in the following amount. Add 10ppt titanium
If it is larger than m, the thermal stability of the obtained resin is significantly reduced.

The germanium compound can be added to a polyester obtained by polymerization in an amount of 20 ppm or less as a germanium atom. More preferably 10
It is to be added in the amount of ppm or less. If the amount of germanium added is more than 20 ppm, it is not preferable because it is disadvantageous in terms of cost.

When polymerizing a polyester using the polymerization catalyst of the present invention, one or more of an antimony compound, a titanium compound, a germanium compound, and a tin compound can be used.

The antimony compound, titanium compound, germanium compound and tin compound used in the present invention are not particularly limited.

Specifically, antimony compounds include:
Examples include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycooxide, and the like. Of these, antimony trioxide is preferable.

Further, as the titanium compound, tetra-n-
Propyl titanate, tetraisopropyl titanate,
Tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, titanium oxalate and the like.
-Butoxytitanate is preferred.

Examples of the germanium compound include germanium dioxide, germanium tetrachloride and the like, among which germanium dioxide is preferable.

Examples of the tin compound include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, and monobutyltin trioxide. Examples thereof include chloride, dibutyltin sulfide, dibutylhydroxytin oxide, methylstannoic acid, and ethylstannoic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

The polyester referred to in the present invention is one or more selected from polycarboxylic acids containing dicarboxylic acids and their ester-forming derivatives and one or more selected from polyhydric alcohols containing glycol. Or those composed of hydroxycarboxylic acids and their ester-forming derivatives, or those composed of cyclic esters.

As the dicarboxylic acid, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, dodecane dicarboxylic acid, tetradecane dicarboxylic acid, hexadecane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-cyclo Pentanedicarboxylic acid,
Saturated aliphatic dicarboxylic acids exemplified by 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, and the like, or their ester-forming properties Derivatives, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like and ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic 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'-biphenylsulfone dicarboxylic acid, 4,4'-biphe Aromatic dicarboxylic acids exemplified by enyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof are exemplified.

Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6 naphthalenedicarboxylic acid, are preferred in view of the physical properties of the resulting polyester, and other dicarboxylic acids may be used as a component if necessary.

Examples of polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid. Examples include carboxylic acids and their ester-forming derivatives.

As the 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,
Aliphatic glycols exemplified by 4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc., 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-hydroxy Phenyl) methane, 1,2-bis (p
-Hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5 naphthalene diol, and aromatic glycols exemplified by ethylene glycol added to these glycols.

Of these glycols, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol and 1,4-cyclohexanedimethanol are preferred.

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

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

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

Examples of the ester-forming derivatives of polycarboxylic acids or hydroxycarboxylic acids include these alkyl esters, acid chlorides and acid anhydrides.

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

The polyester in which the main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative refers to terephthalic acid or its ester-forming derivative and naphthalenedicarboxylic acid or It is preferable that the polyester is a polyester containing at least 70 mol% of the ester-forming derivative in total, more preferably a polyester containing at least 80 mol%, more preferably
It is a polyester containing 90 mol% or more.

The polyester in which the main glycol component is an alkylene glycol is preferably a polyester containing alkylene glycol in a total amount of at least 70 mol% based on all glycol components, more preferably
It is a polyester containing 80 mol% or more, and more preferably a polyester containing 90 mol% or more. The alkylene glycol mentioned here may contain a substituent or an alicyclic structure in the molecular chain.

The naphthalenedicarboxylic acid or its ester-forming derivative used in the present invention includes 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, and 2,6 naphthalenedicarboxylic acid Acid, 2,7 naphthalene dicarboxylic acid,
Alternatively, these ester-forming derivatives 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, 1,3-butylene glycol,
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 and the like. Two or more of these may be used simultaneously.

The polyester of the present invention includes polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexane dimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Of these, polyethylene terephthalate and its copolymer are particularly preferred.

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

As the constituent components of the polyester of the present invention,
In a preferred embodiment, a polycarboxylic acid having a sulfonate alkali metal base is used as a copolymer component in order to improve dyeability when polyester is used as a fiber.

The metal sulfonate group-containing compound used as the copolymerizable monomer is not particularly limited, but is preferably 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, or 2-lithium sulfoisophthalic acid. Examples thereof include terephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, and lower alkyl ester derivatives thereof. In the present invention, use of 5-sodium sulfoisophthalic acid or an ester-forming derivative thereof is particularly preferred.

The amount of the metal sulfonate group-containing compound to be copolymerized is 0.3 to 10.0 with respect to the acid content of the polyester.
Mol% is preferred, and more preferably 0.80 to 5.0 mol%. If the copolymerization amount is too small, the dyeability of the basic dye is inferior. If the copolymerization amount is too large, not only the spinning properties are poor, but also the fiber does not have sufficient strength due to the thickening phenomenon. The metal sulfonate-containing compound was 2.0 mol%
By copolymerizing as described above, it is also possible to impart normal pressure dyeability to the obtained modified polyester fiber. It is possible to appropriately reduce the amount of the metal sulfonate group-containing compound by selecting an appropriate dye for facilitating dyeing. Examples of the easily dyeable monomer include, but are not particularly limited to, long-chain glycol compounds represented by polyethylene glycol and polytetramethylene glycol, and aliphatic dicarboxylic acids represented by adipic acid, sebacic acid, and azelaic acid.

After the polyester is polymerized according to the method of the present invention, the thermal stability of the polyester can be further enhanced by 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 an organic, inorganic, or organometallic toner, a fluorescent whitening agent, and the like. Coloration such as yellowishness can be suppressed to a more excellent level. Also, any other polymer, antistatic agent, defoamer, dyeability improver, dye,
Pigments, matting agents, optical brighteners, stabilizers, antioxidants and other additives may be included. As the antioxidant, an aromatic amine type, a phenol type or the like antioxidant can be used, and as the stabilizer, a phosphorus type such as phosphoric acid or a phosphoric ester type, a sulfur type, an amine type or the like can be used. Can be used.

[0200]

According to the present invention, a method for producing a polyester using a novel polycondensation catalyst other than an antimony compound is provided. The polyester of the present invention may be, for example, fibers for interior materials and bedding represented by clothing fibers, curtains, carpets, futon, etc., fibers for industrial materials represented by tire cords, ropes, etc., various woven fabrics, various knits, and short fibers. Fibers such as fibrous nonwoven fabrics and long-fiber nonwoven fabrics, packaging films, industrial films, optical films, magnetic tape films, photographic films, can laminating films, contensor films, heat shrink films, gas barrier films, white films, Films such as easy-cut films, non-heat-resistant stretched bottles, heat-resistant stretched bottles, direct blow bottles, gas barrier bottles, pressure-resistant bottles, hollow molded articles such as heat-resistant pressure bottles, sheets such as A-PET and C-PET, glass fiber reinforced polyester Engineering plastics such as Various molded articles, and paints and adhesives can be applied to such.

[0201]

EXAMPLES (Example 1) The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In Examples, “parts” means “parts by weight” and “%” means “percent by weight”.

(Measurement of Intrinsic Viscosity (IV)) Polyester was heated and dissolved at a mixed solvent of phenol / 1,1,2,2-tetrachloroethane at 6/4 (weight ratio) 80-100 ° C. At a temperature of 30 ° C. The concentration was measured at several points around 4 g / l, and the obtained reduced viscosity was plotted against the concentration. When the obtained straight line was extrapolated to zero concentration, the value of the reduced viscosity was calculated as the intrinsic viscosity (I
V).

(Measurement of AVo (acid value)) The oligomer is pulverized and dried under reduced pressure at 110 ° C for 15 hours or more. Approximately 1 g of sample
Is weighed accurately and 20 ml of pyridine are added. Dissolve by boiling for 15 minutes. After dissolution, 10 ml of pure water is added and the mixture is left to cool to room temperature. Phenolphthalein as indicator
Titrate with N / 10-NaOH. Do the same for the blanks without any sample. When the oligomer does not dissolve in pyridine, the reaction is performed in benzyl alcohol. AVo (eq / ton) is calculated according to the following equation. AVo = (AB) × 0.1 × f × 1000 / W (A = liter constant (ml), B = liter constant of blank (ml), f =
NaOH factor, W = sample weight (g))

(Measurement of OHVo (OH value)) The oligomer is pulverized and dried under reduced pressure at 110 ° C. for 15 hours or more. About 0.5 g of the sample is precisely weighed, and 10 ml of an acetylating agent (0.5 mol% / L of acetic anhydride pyridine solution) is added. After immersing in a water bath at 95 ° C. or higher for 1.5 hours, 10 ml of pure water is added, and the mixture is allowed to cool to room temperature. N / 5 with phenolphthalein as indicator
-Titrate with NaOH solution. Do the same for the blanks without any sample. OHVo (eq / ton) is calculated according to the following equation. OHVo = [(BA) × 0.2 × f × 1000 / W] + A
Vo (A = liter constant (ml), B = blank constant (ml), f =
N / 5-NaOH solution factor, W = sample weight (g))

(Calculation of Pn) Pn (average degree of polymerization) = [MW + 26−88 × [OHVo / (A
Vo + OHVo)]] / (192 + 44E) where MW (molecular weight (g / mol)) = 10 ⁶ × 2 / (AVo + O
HVo) E = DEG / (EG + DEG) E is the diethylene glycol production mole fraction. DEG is the number of moles of diethylene glycol in the polymer, and EG is the number of moles of ethylene glycol.

(Calculation of Es (%)) Es conversion rate = {1−AVo / Pn × (AVo + OHVo)} × 1
00

(Color Measurement) The color of the chip was indicated by L value, a value, and b value by a Hunter color difference meter. The larger the L value, the stronger the whiteness, and the b value (hereinafter, Co-
(described as a b value) indicates that the larger the value, the stronger the yellow color.

(Evaluation of Foreign Material) After the resin was melted and formed into a film, the foreign material was observed with a transmission microscope. The evaluation was made in 10 steps, with 10 indicating little foreign matter and 1 indicating extremely large amount of foreign matter.

(Measurement of Volume Weighted Average Particle Size) Particles are dispersed by ultrasonic waves in a solvent in which powder is not dissolved,
The volume-weighted average particle size was measured using Model A-9220 (Nikkiso). The aluminum trisacetylacetonate powder was dispersed and measured using Nisseki Mitsubishi Super Malpas 5K2OJ2 as a solvent.

(Example 1) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a heating medium circulation type 2-liter stainless steel autoclave equipped with a stirrer, and triethylamine was added at 0.3 mol% to the acid component. 0.25Mpa
The esterification reaction was carried out while distilling water out of the system at 245 ° C. under the pressure of, and a mixture of bis (2-hydroxyethyl) terephthalate (BHET) and oligomer as shown in Table 1 (hereinafter referred to as BHET mixture) Obtained. For this BHET mixture, 2.
5 g / l of an ethylene glycol solution was added to the acid component in the polyester in an amount of 0.008 mol% as an aluminum atom, and the 10 g / l ethylene glycol solution of the above-mentioned phosphorus compound 43 was converted to a phosphorus compound with respect to the acid component in the polyester. 43
0.012 mol% at normal pressure under nitrogen atmosphere at 245 ° C
Stir for 15 minutes. Then, over 60 minutes, the temperature of the reaction system was gradually lowered while the temperature was raised to 275 ° C. to 0.1 Torr, and a polycondensation reaction was further performed at 275 ° C. and 0.1 Torr. Various physical properties were measured using the PET resin chip obtained by the above polycondensation. Table 2 shows the results.

(Examples 2 and 3) A polymer was polymerized in the same manner as in Example 1 except that the esterification end time was changed. Table 2 shows the results. The higher the AVo and the lower the Es (%), the faster the polymerization time and the lower the Co-b value.

(Examples 4 to 6) In Example 2, the charged ethylene glycol / high-purity terephthalic acid ratio (hereinafter referred to as E
G / TPA) except that the polymer was polymerized in the same manner. Table 2 shows the results. Example 5 having a low EG / TPA has a low Co-b value.

(Examples 7 and 8) A polymer was polymerized in the same manner as in Example 2 except that the amount of the catalyst was changed.
Table 2 shows the results. Increasing the amount of catalyst tends to shorten the polymerization time, but tends to slightly increase the Co-b value.

(Examples 9 to 12) Polymers were polymerized in the same manner as in Example 2 except that the amount of the catalyst added was changed. Table 2 shows the results. When the addition amount of aluminum trisacetylacetonate is fixed, the polymerization time is slow when the addition amount of phosphorous compound 43 exceeds 1 to 2 times the range of aluminum trisacetylacetonate. Also, the Co-b value tended to increase as the amount of the added phosphorus compound 43 increased.

(Examples 13 and 14)
A polymer was polymerized in the same manner as in Example 1 except that the phosphorus compound was changed to Chemical formula 42 and the amount of the catalyst added was changed as shown in Table 1. In Example 14, phosphorus compound 42 was added at the time of preparation before the esterification reaction. Table 2 shows the results. When phosphorus compound 42 was used, the polymerization time was shorter when the catalyst was added before the esterification reaction.

(Example 15) A polymer was polymerized in the same manner as in Example 2, except that a 30 g / l ethylene glycol slurry of aluminum trisacetylacetonate having a volume-weighted average particle size of 1.5 µm was used. The polymer physical properties were almost the same as in Example 2. The sedimentation of the slurry was at a practically acceptable level.

(Example 16) In Example 2, aluminum trisacetylacetonate was converted to a phosphorus compound.
The polymer was polymerized in the same manner except that the powder was wrapped in a polyester film and added. The polymer physical properties were almost the same as in Example 2.

Example 17 A polymer was polymerized in the same manner as in Example 2, except that a melt obtained by melting aluminum trisacetylacetonate at a melting point of + 3 ° C. was added. Although the b value was slightly higher, other physical properties were as in Example 2.
It was almost the same.

The production method of the present invention may be a batch type or a continuous type as long as it is a conventionally known polymerization apparatus.
Examples 18 to 21 are polymerization methods assuming a continuous system.

(Examples 18 to 21) In Example 2,
284 parts of ethylene glycol was charged to 346 parts of high-purity terephthalic acid, and an esterification reaction was carried out in the same manner as in Example 2 to obtain a BHET mixture. For this BHET mixture,
Again, 87 parts of high-purity terephthalic acid was added, and normal pressure esterification was performed at 260 ° C. for a predetermined time.
An ET mixture was obtained. To this BHET mixture, an ethylene glycol solution of 2.5 g / l of aluminum trisacetylacetonate was added in an amount of 0.008 mol% as an aluminum atom with respect to the acid component in the polyester.
A 10 g / l ethylene glycol solution of No. 3 was added to the acid component in the polyester in an amount of 0.012 mol% as a phosphorus compound 43, followed by stirring at 245 ° C. for 15 minutes under a normal pressure under a nitrogen atmosphere.
Then, the temperature of the reaction system was gradually lowered while raising the temperature to 275 ° C. over 60 minutes to 0.1 Torr, and the temperature was further increased to 275 ° C. and 0.1 Torr.
To carry out a polycondensation reaction. Various physical properties were measured using the PET resin chip obtained by the above polycondensation. Table 4 shows the results. As the AVo of the reaction system to which the catalyst is added is higher, the Co-b value is lower but the amount of foreign substances increases. The polymerization time is
In the case of Example 14 where Avo of the reaction system is around 500, it is the slowest. As compared with the batch type examples 1 to 17, the continuous type examples 18 to 21 have a considerable amount of foreign matter.

Example 22 The procedure of Example 18 was repeated, except that the phosphorus compound was changed to Chemical formula 42, the amount of aluminum trisacetylacetonate was changed to 0.014 mol%, and the added amount of Chemical formula 42 was changed to 0.02 mol%. The polymer was polymerized as in Example 18. As a result, the amount of foreign substances was very small, and the result of foreign substance observation was 10.

Example 23 Example 23 was repeated except that the phosphorus compound was changed to Chemical formula 42, the amount of aluminum trisacetylacetonate was changed to 0.014 mol%, and the added amount of Chemical formula 42 was changed to 0.02 mol%. The polymer was polymerized as in Example 21. As a result, the polymerization time was longer than in Example 22. When phosphorous compound 42 is used, AVo
Polymerization time is shorter when a catalyst is added to a reaction system having a higher value. The amount of foreign matters was very small, and the result of foreign matter observation was 10.

[0223]

[Table 1]

[0224]

[Table 2]

[0225]

[Table 3]

[0226]

[Table 4]

[0227]

According to the present invention, a method for producing a polyester using a novel polycondensation catalyst other than an antimony compound is provided. The polyester of the present invention includes, for example, textiles for clothing, curtains, carpets, fibers for interior and bedding represented by futon, etc., fibers for industrial materials represented by tire cords, ropes, etc., various fabrics, various knits, and short fibers. Fibers such as fibrous nonwoven fabrics and long-fiber nonwoven fabrics, packaging films, industrial films, optical films, magnetic tape films, photographic films, can laminating films, contensor films, heat shrink films, gas barrier films, white films, Films such as easy-cut films, non-heat-resistant stretched bottles, heat-resistant stretched bottles, direct blow bottles, gas barrier bottles, pressure-resistant bottles, hollow molded products such as heat-resistant pressure bottles, sheets such as A-PET and C-PET, glass fiber reinforced polyester Engineering plastics such as Various molded articles, and paints and adhesives can be applied to such.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Shoichi Katamai 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory 4J029 AE01 AE02 AE03 AE11 AE13 BA02 BA03 BA04 BA05 BB05A BB10A BB12A BB13A BB15A BC05A BD03A BF03 BF08 BF09 BF18 BF25 BH02 CA02 CA03 CA04 CA05 CA06 CB04A CB05A CB06A CB10A CB12A CC05A CC06A CC09 CD03 CF03 CH02 CH06 DB02 DB12 FC03 FC03 J03 FC02 FC03 J02 FC04 FC03 J02 FC04 JC551 JC561 JC571 JC601 JF221 JF371 JF411 JF571 KH08

Claims (14)

[Claims] An oligomer having an intrinsic viscosity IV satisfying the following formula (1): A polyester polymerization catalyst containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds. A method for producing a polyester, characterized in that it is added to a polyester. IV ≦ 0.40 (1) (where IV in the formula indicates an intrinsic viscosity.) 2. An oligomer having a polyester polymerization catalyst containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds, having an acid value AVo satisfying the following formula (2): A method for producing a polyester, characterized in that it is added to a polyester. 10 ≦ AVo ≦ 3000 (2) (where, AVo in the formula indicates an acid value (eq / ton).) 3. A polyester polymerization catalyst containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds, has a hydroxyl value OHVo satisfying the following formula (3). A method for producing a polyester, which is added to an oligomer. 50 ≦ OHVo ≦ 7000 (3) (However, OHVo in the formula indicates an OH value (eq / ton).) 4. A polyester polymerization catalyst containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds, wherein the average polymerization degree Pn satisfies the following formula (4). A method for producing a polyester, which is added to an oligomer. Pn ≦ 50 (4) (Pn (average degree of polymerization) = [MW + 26−88 × [OHVo /
(AVo + OHVo)]] / (192 + 44E) However, MW (molecular weight (g / mol)) = 10 6 × 2 / (AVo + O
HVo) E = DEG / (EG + DEG) E is the diethylene glycol production mole fraction. DEG is the number of moles of diethylene glycol in the polymer, and EG is the number of moles of ethylene glycol. ) 5. A polyester polymerization catalyst containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds, wherein an esterification ratio Es satisfies the following formula (4). A method for producing a polyester, which is added to an oligomer. Es (%) ≧ 60 (5) (However, Es (%) in the formula indicates an esterification rate (%).) 6. A polyester polymerization catalyst solution containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds, and adding the solution. Polyester manufacturing method. 7. A polyester polymerization catalyst slurry containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds, and adding the slurry. Polyester manufacturing method. 8. A polyester polymerization catalyst powder containing at least one selected from aluminum and its compounds as a metal-containing component and at least one selected from phenolic compounds, and adding the powder. Polyester manufacturing method. 9. A melt of a polyester polymerization catalyst containing at least one selected from aluminum and its compounds as a metal-containing component and containing at least one selected from phenolic compounds, and adding the melt. Characteristic polyester production method. 10. The polymerization catalyst according to claim 1, which is a polyester polymerization catalyst containing at least one selected from aluminum and its compounds as a metal-containing component and at least one selected from phosphorus compounds. The method for producing a polyester according to claim 1. 11. The method according to claim 1, wherein the polymerization catalyst according to claim 1 is a phosphorus compound. 12. The phosphorus compound according to claim 10 or 11, wherein the phosphorus compound is a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound,
The method for producing a polyester according to claim 10 or 11, wherein the method is one or two or more compounds selected from the group consisting of phosphinous acid compounds and phosphine compounds. 13. The phosphorus compound according to claim 10, wherein the phosphorus compound is one or more phosphonic acid compounds.
13. The method for producing a polyester according to any one of items 12 to 12. 14. The phosphorus compound according to claim 10, wherein the phosphorus compound is a compound having an aromatic ring structure.
14. The method for producing a polyester according to any one of 0 to 13.