JP3506236B2 - Polyester polymerization catalyst, polyester produced using the same, and method for producing polyester - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester polymerization catalyst, a polyester produced using the same, and a method for producing a polyester. More specifically, the present invention relates to a novel polyester polymerization catalyst containing no antimony compound, and a method for producing the same. The present invention relates to a polyester produced using the same and a method for producing the polyester.

[0002]

2. Description of the Related Art Polyesters, especially polyethylene terephthalate (hereinafter abbreviated as PET), have excellent mechanical and chemical properties, and have a wide range of applications, such as fibers for clothing and industrial materials, and packaging. It has been applied to various films and sheets for magnetic tapes, magnetic tapes, and molded products such as bottles and engineering plastics.

PET is industrially used to produce bis (2-hydroxyethyl) terephthalate by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, and using bis (2-hydroxyethyl) terephthalate at a high temperature under a vacuum with a catalyst. Obtained by polycondensation. Antimony trioxide is widely used as a catalyst for use in polycondensation. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity, but since metal antimony is deposited during polycondensation, it has a problem that darkening and foreign matter occur in PET. Recently, environmental issues have been pointed out regarding the safety of antimony. Under such circumstances, polyesters containing no antimony or only a very small amount thereof are desired.

Attempts have been made to use antimony trioxide as a polycondensation catalyst and to suppress the darkening of PET and the generation of foreign matter. For example, in Japanese Patent No. 2666502,
By using a compound of antimony trioxide and bismuth and selenium as a polycondensation catalyst, generation of black foreign matter in PET is suppressed. Further, in JP-A-9-291141,
It is stated that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the deposition of metallic antimony. However, these polycondensation catalysts cannot eventually achieve the purpose of polyester containing no antimony.

A polycondensation catalyst which is an alternative to antimony trioxide has also been investigated. In particular, titanium compounds typified by tetraalkoxy titanates have already been proposed, but PET produced using them has the problems that they are markedly colored and that thermal decomposition easily occurs.

[0006] As an attempt to overcome such a problem when tetraalkoxy titanate is used as a polycondensation catalyst, for example, in JP-A-55-116722, tetraalkoxy titanate is used simultaneously with a cobalt salt and a calcium salt. A method has been proposed. In addition, JP-A-8-7358
According to No. 1, a method is proposed in which a tetraalkoxy titanate is used as a polycondensation catalyst at the same time as a cobalt compound and an optical brightener is used. However, although these proposals reduce the coloring of PET when tetraalkoxy titanate is used as a polycondensation catalyst, P
Effective suppression of the thermal decomposition of ET has not been achieved.

A germanium compound has been put to practical use as a polycondensation catalyst which is an alternative to antimony trioxide and which overcomes the problems when tetraalkoxy titanate is used. There are problems that it is very expensive and that it is easy to distill out of the reaction system during the polymerization and the catalyst concentration in the reaction system changes, making it difficult to control the polymerization.

Aluminum compounds are generally known to have poor catalytic activity. Among aluminum compounds,
It has been reported that an aluminum chelate compound has higher catalytic activity as a polycondensation catalyst than other aluminum compounds, but it is said that it has sufficient catalytic activity as compared with the above-mentioned antimony compound or titanium compound. I could not say.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides a novel polycondensation catalyst other than an antimony compound, a polyester produced using the same, and a method for producing the polyester.

[0010]

Means for Solving the Problems As a result of intensive investigations aimed at solving the above-mentioned problems, the authors of the present invention have found that aluminum compounds are originally inferior in catalytic activity. Surprisingly, they have found that the polycondensation catalyst has sufficient activity, and have reached the present invention. Use of the polycondensation catalyst of the present invention makes it possible to obtain a polyester of excellent quality without using an antimony compound.

That is, as a solution to the above problems, the present invention provides a polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound, a polyester produced using the same, and a method for producing the polyester.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a novel polycondensation catalyst other than an antimony compound, a polyester produced using the same, and a method for producing the polyester. The polycondensation catalyst of the present invention is a polyester polymerization catalyst composed of an aluminum compound and a phosphorus compound.

The aluminum compound constituting the polycondensation catalyst of the present invention is not particularly limited, but examples thereof include aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate,
Aluminum laurate, aluminum stearate,
Aluminum benzoate, aluminum trichloroacetate,
Carboxylates such as aluminum lactate, aluminum citrate and aluminum salicylate, aluminum chloride,
Inorganic acid salts such as aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-
Aluminum alkoxides such as butoxide, aluminum t-butoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide and other aluminum chelate compounds, trimethylaluminum, triethylaluminum and other organic aluminum compounds. And partial hydrolysates thereof, aluminum oxide, metallic aluminum and the like. Among these, carboxylates, inorganic acid salts and chelate compounds are preferable, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferable.

The amount of the aluminum compound of the present invention used is preferably 5 × 10 ^{-7 to} 0.01 mol based on the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. , And more preferably 1 × 10 ^{−6 to} 0.005 mol.

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

The phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds referred to in the present invention are represented by the following formulas (4) to (9), respectively. A compound having a structure represented by

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

Examples of the phosphonic acid compound of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate and diethyl benzylphosphonate. To be Examples of the phosphinic acid compound of the present invention include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate,
Phenylphosphinic acid, methyl phenylphosphinate,
Examples include phenyl phenylphosphinate and the like. Examples of the phosphine oxide compound of the present invention include:
Examples thereof include diphenylphosphine oxide, methyldiphenylphosphine oxide and triphenylphosphine oxide.

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

As the phosphorus compound constituting the polycondensation catalyst of the present invention, compounds represented by the following general formulas (1) to (3) are preferably used because the effect of improving the catalytic activity is particularly large.

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

(In the formulas (1) to (3), R ¹ , R ⁴ , R ⁵ ,
R ⁶ independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including an amino group.
R ² and R ³ each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

The phosphorus compounds constituting the polycondensation catalyst of the present invention include R ¹ , R ⁴ , R ⁵ in the above formulas (1) to (3),
A compound in which R ⁶ is a group having an aromatic ring structure is particularly preferable.

Examples of the phosphorus compound constituting the polycondensation catalyst of the present invention include 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,
Examples thereof include triphenylphosphine oxide.
Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferable.

The amount of the phosphorus compound of the present invention to be used is based on the number of moles of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester.
5 × 10 ^-7 ~ 0.01 mol is preferred, more preferably 1 × 10 ^-6
~ 0.005 mol.

In addition to the aluminum compound and phosphorus compound which are the polycondensation catalyst of the present invention, one or more metal compounds selected from the group consisting of alkali metals or their compounds or alkaline earth metals or their compounds are added. Coexistence is preferable because the catalyst activity can be further improved.

As the alkali metal or the compound thereof or the alkaline earth metal or the compound thereof of the present invention, in addition to the alkali metal or the alkaline earth metal,
Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba is not particularly limited as long as it is one or two or more compounds selected from compounds, for example, formic acid of these metals, acetic acid, Saturated aliphatic carboxylates such as propionic acid, butyric acid and oxalic acid, unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid,
Aromatic carboxylic acid salts such as benzoic acid, halogen-containing carboxylic acid salts such as trichloroacetic acid, hydroxycarboxylic acid salts such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphoric acid Hydrogen, hydrogen sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid,
Inorganic acid salts such as bromic acid, 1-propanesulfonic acid, 1-pentanesulfonic acid, organic sulfonic acid salts such as naphthalenesulfonic acid, organic sulfates such as lauryl sulfuric acid, methoxy,
Examples include alkoxides such as ethoxy, n-propoxy, iso-propoxy, n-butoxy and t-butoxy, chelate compounds such as acetylacetonate, oxides and hydroxides, among which saturated aliphatic carboxylates are Preference is further given to the acetate salt, and the acetate salt is particularly preferred.

The amount of these alkali metals or their compounds or alkaline earth metals or their compounds to be used is based on the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polyvalent carboxylic acid of the obtained polyester. It is preferably in the range of 1 × 10 ^{−6 to} 0.1 mol, and more preferably in the range of 5 × 10 ^{−6 to} 0.05 mol.

The polyester according to the present invention can be produced by a conventionally known method. For example, in the case of producing PET, after esterification of terephthalic acid and ethylene glycol, polycondensation, or after performing an ester exchange reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, Any method of polycondensation can be used. Also,
The apparatus for polymerization may be a batch type or a continuous type.

The catalyst of the present invention has catalytic activity not only in polycondensation reaction but also in esterification reaction and transesterification reaction. The transesterification reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol is usually performed in the presence of a transesterification catalyst such as zinc, but instead of these catalysts or coexisting with these catalysts. Then, the catalyst of the present invention can also be used. Further, the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization.

The polycondensation catalyst of the present invention is preferably added before the start of the polycondensation reaction, but may be added to the reaction system before the start of the esterification reaction or transesterification reaction and at any stage during the reaction. .

The method for adding the polycondensation catalyst of the present invention may be in the form of powder or neat, or may be in the form of slurry or solution of a solvent such as ethylene glycol, and is not particularly limited. Further, a mixture of an aluminum compound and a phosphorus compound may be added in advance, or these may be added separately. Further, a mixture of these compounds and an alkali metal or a compound thereof or an alkaline earth metal or a compound thereof may be added in advance, or these may be added separately.

When the polyester is polymerized using the polymerization catalyst of the present invention, an antimony compound or a germanium compound may be used in combination. However, the antimony compound is preferably added in an amount of 50 ppm or less as an antimony atom with respect to the polyester obtained by polymerization. More preferably, it is added in an amount of 30 ppm or less. When the amount of antimony added is 50 ppm or more, precipitation of metallic antimony occurs, resulting in darkening and foreign matter on the polyester, which is not preferable. The germanium compound is preferably added in an amount of 20 ppm or less as a germanium atom in the polyester obtained by polymerization. More preferably, it is added in an amount of 10 ppm or less. It is not preferable to add germanium in an amount of 20 ppm or more, which is disadvantageous in terms of cost.

Examples of the antimony compound used in the present invention include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoside, etc. Of these, antimony trioxide is preferred. Further, examples of the germanium compound include germanium dioxide and germanium tetrachloride, and among these, germanium dioxide is preferable.

The polymerization catalyst of the present invention is a titanium compound,
It is possible to coexist other polymerization catalysts such as tin compounds and cobalt compounds within a range that does not impair the thermal stability and color tone of the polyester.

The polyester referred to in the present invention is one or more selected from polyvalent carboxylic acids containing dicarboxylic acids and their ester-forming derivatives, and one or more selected from polyhydric alcohols containing glycols. Or a hydroxycarboxylic acid and an ester-forming derivative thereof, or a cyclic ester.

As the dicarboxylic acid, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic 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, and ester-forming properties thereof Unsaturated aliphatic dicarboxylic acids exemplified by derivatives, fumaric acid, maleic acid, itaconic acid or the like, or 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'-biphenyl sulfone dicarboxylic acid, 4,4'-biphe Aromatic dicarboxylic acids exemplified by nyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, and ester-forming derivatives thereof. Of these, terephthalic acid and naphthalenedicarboxylic acid, especially 2,6 naphthalenedicarboxylic acid are preferred.

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

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-cyclohexane Dimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc. Examples of aliphatic glycol, hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl)
Sulfone, bis (p-hydroxyphenyl) ether,
Bis (p-hydroxyphenyl) sulfone, bis (p-
Aromatic glycols such as hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalene diol, and glycols obtained by adding ethylene oxide to these glycols are exemplified. Of these glycols, ethylene glycol and 1,4-butylene glycol are preferred.

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

As the hydroxycarboxylic acid, lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, Alternatively, ester-forming derivatives thereof and the like can be mentioned.

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

The polyester of the present invention may contain a known phosphorus compound as a copolymerization component. As the phosphorus-based compound, a bifunctional phosphorus-based compound is preferable, and examples thereof include dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxyethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, and (2-methoxy). Methyl carboxylethyl) phenylphosphinate, methyl (4-methoxycarbonylphenyl) phenylphosphinate, ethylene glycol ester of [2- (β-hydroxyethoxycarbonyl) ethyl] methylphosphinic acid, (1,2-dicarboxyethyl) dimethyl Phosphine oxide, 9,10-dihydro-10-oxa-
Examples include (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide. By including these phosphorus compounds as a copolymerization component, it is possible to improve the flame retardancy and the like of the obtained polyester.

Examples of the ester-forming derivative of polyvalent carboxylic acid or hydroxycarboxylic acid 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 naphthalene dicarboxylic acid or its ester-forming derivative, and whose main glycol component is alkylene glycol. A polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalene dicarboxylic acid or its ester-forming derivative means that terephthalic acid or its ester-forming derivative and naphthalene dicarboxylic acid or its ester-forming component are used for all acid components. A polyester containing 70 mol% or more of the total amount of the functional derivative is preferable, a polyester containing 80 mol% or more is more preferable, and a polyester containing 90 mol% or more is more preferable. The polyester whose main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is a polyester containing 90 mol% or more.
The alkylene glycol referred to herein may have a substituent or an alicyclic structure in the molecular chain.

Examples of the naphthalenedicarboxylic acid or its ester-forming derivative used in the present invention include 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedicarboxylic acid, 1,5 naphthalenedicarboxylic acid, and 2,6 naphthalenedicarboxylic acid. Acid, 2,7 naphthalene dicarboxylic acid,
Alternatively, ester-forming derivatives thereof are preferable.

As the alkylene glycol used in the present invention, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,
3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol,
1, 12 dodecanediol and the like can be mentioned. Two or more of these may be used at the same time.

The polyester of the present invention contains oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid as acid components other than terephthalic acid or its ester-forming derivative, naphthalenedicarboxylic acid or its ester-forming derivative. Suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid,
1,3-Cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer Saturated aliphatic dicarboxylic acids exemplified by acids and their ester-forming derivatives, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like, ester-forming derivatives thereof, orthophthalic acid, isophthalic acid Acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ) Ethane-p, p'-dicarboxylic acid, pamoic acid, anthra Aromatic dicarboxylic acids exemplified by sendicarboxylic acid or their ester-forming derivatives, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′ ,
A polyvalent carboxylic acid exemplified by 4′-biphenyltetracarboxylic acid and the like and ester-forming derivatives thereof and the like can be contained as a copolymerization component. Further, hydroxycarboxylic acids exemplified by lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid and the like. Alternatively, an ester-forming derivative thereof may be included.
In addition, ε-caprolactone, β-propiolactone, β-
Cyclic esters such as methyl-β-propiolactone, δ-valerolactone, glycolide and lactide may also be included.

The polyester of the present invention contains, as glycol components other than alkylene glycol, aliphatic glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene glycol and polytetramethylene glycol, hydroquinone, and 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, Aromatic glycols such as bisphenol A, bisphenol C, 2,5 naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexane. A polyhydric alcohol exemplified by triol and the like can be contained as a copolymerization component.

The polyester of the present invention may contain a known phosphorus compound as a copolymerization component. As the phosphorus-based compound, a bifunctional phosphorus-based compound is preferable, and examples thereof include dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxyethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, and (2-methoxy). Methyl carboxylethyl) phenylphosphinate, methyl (4-methoxycarbonylphenyl) phenylphosphinate, ethylene glycol ester of [2- (β-hydroxyethoxycarbonyl) ethyl] methylphosphinic acid, (1,2-dicarboxyethyl) dimethyl Phosphine oxide, 9,10-dihydro-10-oxa-
Examples include (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide. By including these phosphorus compounds as a copolymerization component, it is possible to improve the flame retardancy and the like of the obtained polyester.

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

The polyester of the present invention may contain an antioxidant such as a phenol type or aromatic amine type,
By containing one or more of these,
For example, the thermal stability of polyester can be increased. As a phenolic antioxidant, tetrakis- [methyl-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl)
Propionate] methane, 4,4'-butylidene bis- (3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,
6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like can be mentioned.

In the polyester of the present invention, any other polymer, stabilizer, antioxidant, antistatic agent, antifoaming agent, dyeability improving agent, dye, pigment, matting agent, optical brightener, Other additives may be contained.

[0061]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the intrinsic viscosity (IV) of the polyester in each example and comparative example was measured as follows. It was measured at a temperature of 30 ℃ using a 6/4 mixed solvent (weight ratio) of phenol / 1,1,2,2-tetrachloroethane.

Example 1 Bis (2-hydroxyethyl)
For terephthalate, as a catalyst, 3 g / l ethylene glycol solution of aluminum chloride was added as 0.015 mol% as aluminum to the acid component in the polyester, and then dimethyl phenylphosphonate was added as 0.02 mol% to the acid component in the polyester. Then, the mixture was stirred at normal pressure at 245 ° C. for 10 minutes. Then, the pressure of the reaction system was gradually reduced to 0.1 mmHg while raising the temperature to 275 ° C over 50 minutes, and the temperature and pressure were adjusted to 3 mm.
A time polycondensation reaction was performed. The physical properties of the obtained polymer are shown in Table 1.

(Examples 2 to 7 and Comparative Examples 1 and 2) Polyester was polymerized in the same manner as in Example 1 except that the catalyst was changed. The physical properties of the obtained polymer are shown in Table 1.

[0064]

[Table 1]

[0065]

Industrial Applicability According to the present invention, a novel polycondensation catalyst other than an antimony compound and a polyester produced using the same are provided. The polyester of the present invention can be applied to fibers for clothing, fibers for industrial materials, various films, sheets, various molded products such as bottles and engineering plastics, and paints and adhesives.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-10-231357 (JP, A) JP-A-8-325364 (JP, A) JP-A-8-193127 (JP, A) JP-A-2000-63504 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 63/00-63/91 WPI / L (QUESTEL)

Claims (9)

(57) [Claims] 1. A polyester polymerization catalyst comprising an aluminum compound and a phosphorus compound. 2. The phosphorus compound is one or more selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds and phosphine compounds. The polyester polymerization catalyst according to claim 1, which is a compound of 1. 3. The polyester polymerization catalyst according to claim 1, wherein the phosphorus compound is one kind or two or more kinds of phosphonic acid compounds. 4. The polyester polymerization catalyst according to claim 1, wherein the phosphorus compound is a compound having an aromatic ring structure. 5. A phosphorus compound is represented by the following general formulas (1) to (3).
The polyester polymerization catalyst according to claim 1, which is one kind or two or more kinds selected from the group consisting of compounds represented by: [Chemical 1] [Chemical 2] [Chemical 3] (In the formulas (1) to (3), R ¹ , R ⁴ , R ⁵ , and R ⁶ each independently include hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. It represents a hydrocarbon group having 1 to 50 carbon atoms, R ² and R ³ each independently represent hydrogen, and a hydrocarbon group having 1 to 10 carbon atoms.
However, the hydrocarbon group may include an alicyclic structure or an aromatic ring structure. ) 6. The polyester polymerization catalyst according to claim ⁵ , wherein R ¹ , R ⁴ , R ⁵ and R ⁶ are groups having an aromatic ring structure. 7. The one or more metals and / or metal compounds selected from the group consisting of alkali metals or their compounds or alkaline earth metals or their compounds coexist. 6. The polyester polymerization catalyst according to any one of 6. 8. A polyester produced using the catalyst according to any one of claims 1 to 7. 9. A method for producing a polyester, the method according to claim 1.
7. A method for producing a polyester, which comprises using the catalyst according to any one of 7 above.