JP2007056133A - Polyester polymerization catalyst and polyester produced therewith and method for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester polymerization catalyst which is excellent in catalyst activity and gives polyesters giving molded articles having excellent transparency, to provide a polyester produced therewith, and to provide a method for producing a polyester. <P>SOLUTION: This polyester polymerization catalyst comprising a solution containing an aluminum compound and a phosphorus compound is characterized by using a specific phosphorus compound. A polyester produced therewith, and a method for producing the polyester. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyester polymerization catalyst, a polyester produced using the same, and a method for producing the polyester. More specifically, the present invention relates to a novel polyester polymerization catalyst that does not use germanium or an antimony compound as a catalyst main component, and uses the same. It is related with the polyester manufactured by this, and the manufacturing method of polyester.

  Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET), has excellent mechanical and chemical properties, and is used for many purposes, such as textiles for clothing and industrial materials, packaging, and magnetic tape. It is applied to various films and sheets, molded products such as bottles and engineering plastics.

  PET industrially produces bis (2-hydroxyethyl) terephthalate by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, and polycondensates this using a catalyst at high temperature under vacuum. Can be obtained.

  As a catalyst used at the time of polycondensation, antimony trioxide is widely used. Antimony trioxide is an inexpensive catalyst having excellent catalytic activity. However, since metal antimony is precipitated during polycondensation, it has a problem that darkening and foreign matter are generated in PET. Recently, environmental problems related to antimony safety have been pointed out. Under such circumstances, a polyester containing no antimony or only a very small amount is desired.

  Attempts have been made to use antimony trioxide as a polycondensation catalyst and suppress the occurrence of darkening and foreign matter in PET. For example, in patent document 1, the production | generation of the black foreign material in PET is suppressed by using the compound of antimony trioxide, bismuth, and selenium as a polycondensation catalyst. Patent Document 2 states that when antimony trioxide containing an oxide of sodium and iron is used as a polycondensation catalyst, precipitation of metal antimony is suppressed. However, these polycondensation catalysts cannot achieve the purpose of a polyester containing no antimony after all.

Studies are also underway on polycondensation catalysts to replace antimony trioxide. In particular, titanium compounds typified by tetraalkoxy titanate have already been proposed. However, PET produced using such a compound has a problem that it is extremely colored and easily decomposes thermally.

  As an attempt to overcome such problems when tetraalkoxytitanate is used as a polycondensation catalyst, for example, Patent Document 3 proposes a method in which tetraalkoxytitanate is used simultaneously with a cobalt salt and a calcium salt. Further, according to Patent Document 4, a method of using tetraalkoxy titanate as a polycondensation catalyst simultaneously with a cobalt compound and using a fluorescent brightening agent has been proposed. However, in these proposals, although coloring of PET when tetraalkoxy titanate is used as a polycondensation catalyst is reduced, on the other hand, effective suppression of thermal decomposition of PET has not been achieved.

Japanese Patent No. 2666502 JP-A-9-291141 JP-A-55-116722 JP-A-8-73581

  As a polycondensation catalyst that replaces antimony trioxide and a polycondensation catalyst that overcomes the problems of using tetraalkoxy titanate, a germanium compound has been put into practical use, but this catalyst is very expensive. And the problem that the catalyst concentration in the reaction system changes and it becomes difficult to control the polymerization because it tends to distill out of the reaction system during the polymerization.

  Aluminum compounds are generally known to have poor catalytic activity. Among aluminum compounds, aluminum chelate compounds have been reported to have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but they have sufficient catalytic activity compared to the antimony compounds and titanium compounds described above. However, polyesters polymerized over a long period of time using an aluminum compound as a catalyst can sufficiently avoid problems such as poor thermal stability and problems such as foreign matters and coloration derived from aluminum compounds. There wasn't.

  The present invention provides a novel polyester polymerization catalyst that does not use germanium or an antimony compound as a main catalyst component, a polyester produced using the same, and a method for producing the polyester.

  As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors have found that aluminum compounds are originally inferior in catalytic activity, but the catalyst is obtained by using a mixture of aluminum and a specific phosphorus compound in a solution. It has been found that the polyester polymerization catalyst is excellent in activity and has reached the present invention.

（式（化２）中、Ｒ¹は炭素数１〜５０の脂肪族炭化水素基（直鎖状あるいは脂環構造あるいは分岐構造であってもよい）あるいは炭素数６〜５０の芳香環構造あるいは炭素数４〜５０の複素環構造を表し、該脂肪族炭化水素あるいは芳香環構造あるいは複素環構造は置換基を有していてもよい。また、脂肪族炭化水素基の構造中に異種の置換基を含んでもよい。具体的には、−Ｏ−、−ＯＣＨ₂−、−ＳＯ₂−、−ＣＯ−、−ＣＯＣＨ₂−、−ＣＨ₂ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−、−ＮＨＣＯＮＨ−、−ＮＨＳＯ₂−、−ＮＨＣ₃Ｈ₆ＯＣＨ₂ＣＨ₂Ｏ−から選ばれる。Ｒ²およびＲ³はそれぞれ独立に、水素原子、炭素数１〜２０の炭化水素基、水酸基またはアルコキシル基を含む炭素数１〜２０の炭化水素基を表す。炭化水素基は脂環構造や分岐構造や芳香環構造を有していてもよい。）
（２）式（化２）のＲ¹が炭素数１〜５０の脂肪族炭化水素（直鎖状あるいは脂環構造あるいは分岐構造であってもよい）であることを特徴とするポリエステル重合触媒。
（３）式（化２）中で表されるリン化合物の置換基において、ハロゲン置換された炭素数１〜５０の炭化水素基、水酸基、炭素数１〜１０のアルコキシル基およびアルカノール基、ハロゲン基、ニトリル基、シアノアルキル基、アミノ基（炭素数1〜１０のアルキルあるいはアルカノール置換されていてもかまわない）あるいはニトロ基あるいはカルボキシル基あるいは炭素数１〜１０の脂肪族カルボン酸エステル基あるいはホルミル基あるいはアシル基あるいはスルホン酸基、スルホン酸アミド基（炭素数1〜１０のアルキルあるいはアルカノール置換されていてもかまわない）から選ばれる１種もしくは２種以上であることを特徴とする請求項１または２のいずれかに記載のポリエステル重合触媒。
（４）上記脂肪族炭化水素基が炭素数１〜１８の炭化水素基から選ばれることを特徴とする請求項１〜３のいずれかに記載のポリエステル重合触媒。
（５）前記Ｒ²およびＲ³の少なくとも一方が水素原子であることを特徴とする請求項１〜５のいずれかに記載のポリエステル重合触媒。
（６）前記（１）〜（５）のいずれかに記載の重合触媒を用いることを特徴とするポリエステルの製造方法。
（７）前記（１）〜（５）のいずれかに記載の重合触媒を用いて製造されたポリエステル。
（８）前記（１）〜（５）のいずれかに記載のポリエステル重合触媒を用いることを特徴とするポリエステルの製造方法。
である。 That is, the present invention
(1) A polyester polymerization catalyst comprising a solution containing aluminum and a compound thereof and a phosphorus compound, and including at least one phosphorus compound represented by the following general formula (Formula 2).

(In the formula (Chemical Formula 2), R ¹ is an aliphatic hydrocarbon group having 1 to 50 carbon atoms (which may be linear, alicyclic or branched), an aromatic ring structure having 6 to 50 carbon atoms, or It represents a heterocyclic structure having 4 to 50 carbon atoms, and the aliphatic hydrocarbon, aromatic ring structure or heterocyclic structure may have a substituent, and the structure of the aliphatic hydrocarbon group may have different substituents. In particular, —O—, —OCH ₂ —, —SO ₂ —, —CO—, —COCH ₂ —, —CH ₂ OCO—, —NHCO—, —NH—, —NHCONH may be included. —, —NHSO ₂ —, —NHC ₃ H ₆ OCH ₂ CH ₂ O— R ² and R ³ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group having 1 to 20 carbon atoms to be contained. Ring structure, branched structure and aromatic ring structure may have.)
(2) A polyester polymerization catalyst, wherein R ^{1 in the} formula (Chemical Formula 2) is an aliphatic hydrocarbon having 1 to 50 carbon atoms (which may be linear, alicyclic or branched).
(3) In the substituent of the phosphorus compound represented by the formula (Chemical Formula 2), a halogen-substituted hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkanol group, and a halogen group , Nitrile group, cyanoalkyl group, amino group (which may be substituted with alkyl or alkanol having 1 to 10 carbon atoms), nitro group or carboxyl group, aliphatic carboxylic acid ester group or formyl group having 1 to 10 carbon atoms Or one or more selected from an acyl group, a sulfonic acid group, and a sulfonic acid amide group (which may be substituted with alkyl or alkanol having 1 to 10 carbon atoms). The polyester polymerization catalyst according to any one of 2 above.
(4) The polyester polymerization catalyst according to any one of claims 1 to 3, wherein the aliphatic hydrocarbon group is selected from hydrocarbon groups having 1 to 18 carbon atoms.
(5) The polyester polymerization catalyst according to any one of claims 1 to 5, wherein at least one of R ² and R ³ is a hydrogen atom.
(6) A method for producing a polyester, wherein the polymerization catalyst according to any one of (1) to (5) is used.
(7) Polyester manufactured using the polymerization catalyst in any one of said (1)-(5).
(8) A polyester production method using the polyester polymerization catalyst according to any one of (1) to (5).
It is.

  According to the present invention, a polyester that provides a polyester having excellent catalytic activity, excellent transparency of a molded article, excellent color tone, and reduced foreign matter, although the conventional antimony, germanium and titanium catalysts are not used as main catalysts. A polymerization catalyst, a polyester produced using the polymerization catalyst, and a method for producing the polyester are provided.

  The polymerization catalyst of the present invention is a polyester polymerization catalyst comprising at least one selected from the group consisting of aluminum compounds and at least one selected from phosphorus compounds, and a solution in which an aluminum compound and a phosphorus compound are mixed in a solvent in advance or A polyester polymerization catalyst comprising a slurry. More preferably, it is a polyester polymerization catalyst comprising a solution or slurry in which at least one of the aluminum compound and the phosphorus compound is preliminarily heat-treated in a solvent.

(Method for preparing phosphorus compound)
Although the temperature of heat processing is not specifically limited, It is preferable that it is the range of 20-250 degreeC. More preferably, it is the range of 100-200 degreeC. The upper limit of the temperature is preferably around the boiling point of the solvent used. Although the heating time varies depending on conditions such as temperature, the heating temperature is preferably in the range of 1 minute to 50 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 to 5 hours. Range. The pressure of the heat treatment system may be normal pressure, higher or lower, and is not particularly limited. The concentration of the solution is preferably 1 to 500 g / l as a phosphorus compound, more preferably 5 to 300 g / l, and still more preferably 10 to 100 g / l. The heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen. The storage temperature of the solution or slurry after heating is not particularly limited, but is preferably in the range of 0 ° C to 100 ° C, and more preferably in the range of 20 ° C to 60 ° C. It is preferable to store the solution in an atmosphere of an inert gas such as nitrogen.

The solvent used when the phosphorus compound constituting the polyester polymerization catalyst of the present invention is preliminarily heat-treated is preferably at least one selected from the group consisting of water and alkylene glycol, and a solvent that dissolves the phosphorus compound is used. It is preferable. As the alkylene glycol, it is preferable to use glycol which is a constituent component of the target polyester such as ethylene glycol. The heat treatment in the solvent is preferably performed after dissolving the phosphorus compound, but may not be completely dissolved. Moreover, it is not necessary for the compound to retain the original structure after the heat treatment.

  The solvent used when mixing the aluminum compound and the phosphorus compound of the present invention is preferably at least one selected from the group consisting of water and alkylene glycol, and a solvent that dissolves the aluminum compound and the phosphorus compound is used. preferable. As the alkylene glycol, it is preferable to use glycol which is a constituent component of the target polyester such as ethylene glycol. It is possible to obtain a solution or slurry polymerization catalyst by stirring and mixing an ethylene glycol solution or slurry of an aluminum compound and an ethylene glycol solution or slurry of the phosphorus compound. Furthermore, you may heat-process the said solution or slurry. The solution or slurry obtained by these operations can be used as the polymerization catalyst of the present invention.

（式（化３）中、Ｒ¹は炭素数１〜５０の脂肪族炭化水素基（直鎖状あるいは脂環構造あるいは分岐構造であってもよい）あるいは炭素数６〜５０の芳香環構造あるいは炭素数４〜５０の複素環構造を表し、該脂肪族炭化水素あるいは芳香環構造あるいは複素環構造は置換基を有していてもよい。また、脂肪族炭化水素基の構造中に異種の原子を含んでもよい。具体的には、−Ｏ−、−ＯＣＨ₂−、−ＳＯ₂−、−ＣＯ−、−ＣＯＣＨ₂−、−ＣＨ₂ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−、−ＮＨＣＯＮＨ−、−ＮＨＳＯ₂−、−ＮＨＣ₃Ｈ₆ＯＣＨ₂ＣＨ₂Ｏ−などから選ばれる。Ｒ²およびＲ³はそれぞれ独立に、水素原子、炭素数１〜２０の炭化水素基、水酸基またはアルコキシル基を含む炭素数１〜２０の炭化水素基を表す。炭化水素基は脂環構造や分岐構造や芳香環構造を有していてもよい。） The polyester polymerization catalyst of the present invention is a polyester polymerization catalyst comprising a solution or slurry containing aluminum and a compound thereof and a phosphorus compound, and containing at least one phosphorus compound represented by the following general formula (Formula 3). is there.

(In the formula (Chemical Formula 3), R ¹ is an aliphatic hydrocarbon group having 1 to 50 carbon atoms (which may be a linear or alicyclic structure or a branched structure), an aromatic ring structure having 6 to 50 carbon atoms, or It represents a heterocyclic structure having 4 to 50 carbon atoms, and the aliphatic hydrocarbon, aromatic ring structure or heterocyclic structure may have a substituent, and a heterogeneous atom in the structure of the aliphatic hydrocarbon group. Specifically, —O—, —OCH ₂ —, —SO ₂ —, —CO—, —COCH ₂ —, —CH ₂ OCO—, —NHCO—, —NH—, —NHCONH— , —NHSO ₂ —, —NHC ₃ H ₆ OCH ₂ CH ₂ O—, etc. R ² and R ³ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group containing 1 to 20 carbon atoms. Alicyclic structure, branched structure and aromatic ring structure may have.)

The substituent of the phosphorus compound represented by the formula (Chemical Formula 3) is a halogen-substituted hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkanol group, a halogen group, or a nitrile group. , A cyanoalkyl group, an amino group (which may be substituted with an alkyl or alkanol having 1 to 10 carbon atoms), a nitro group, a carboxyl group, an aliphatic carboxylic acid ester group with 1 to 10 carbon atoms, a formyl group or an acyl group Or it is preferable that it is 1 type, or 2 or more types chosen from a sulfonic acid group and a sulfonic acid amide group (It is C1-C10 alkyl and the alkanol substitution may be carried out.).
R ² and R ³ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group, and the hydrocarbon group has an alicyclic structure. Or a branched structure or an aromatic ring structure, at least one of which is preferably a hydrogen atom.
However, even if both of R ² and R ^{3 in} the general formula (Chemical Formula 3) are a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or an alkoxyl group, an alkylene group When heat-treating in glycol in advance, it can be suitably used as the phosphorus compound of the present invention.

The aliphatic hydrocarbon group is preferably a hydrocarbon group having 1 to 18 carbon atoms because of high catalytic activity and improved physical properties. More preferably, it is a 3-12 hydrocarbon group, More preferably, it is a 6-8 hydrocarbon group.

  Specific examples of the phosphorus compound of the present invention include the following.

  By using a phosphorus compound having such a specific structure, an antimony compound or a germanium compound is not included as a main component of the catalyst, aluminum is the main metal component, and the catalyst activity is excellent, and the catalyst is deactivated or removed. Polyester polymerization that gives polyester with excellent thermal stability and excellent hydrolysis resistance, and also has excellent transparency and physical properties. A catalyst is obtained.

  By using the phosphorus compound of the present invention in combination, a catalyst exhibiting a sufficient catalytic effect can be obtained even when the amount of addition as aluminum in the polyester polymerization catalyst is small.

  As the usage-amount of the phosphorus compound of this invention, 0.0001-0.1 mol% is preferable with respect to the number-of-moles of all the structural units of the polycarboxylic acid component of polyester obtained, 0.005-0.05 mol% More preferably. If the addition amount of the phosphorus compound is less than 0.0001 mol%, the addition effect may not be exhibited. If the addition amount exceeds 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may decrease. The tendency of the change varies depending on the amount of aluminum used.

  A technology that uses an aluminum compound as the main catalyst component without using a phosphorus compound, and reduces the amount of aluminum compound used, and further reduces the thermal stability when an aluminum compound is used as the main catalyst by adding a cobalt compound. Although there is a technique for preventing coloration due to oxidization, if a cobalt compound is added to such an extent that it has sufficient catalytic activity, the thermal stability is also lowered. Therefore, it is difficult to make both compatible 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 matter, and the addition amount of the metal-containing component as aluminum is sufficient. A polymerization catalyst having a catalytic effect is obtained, and by using this polymerization catalyst, thermal stability at the time of melt molding of hollow molded articles such as polyester films and bottles, fibers and engineering plastics is improved. Even if a phosphoric acid ester such as phosphoric acid or trimethyl phosphoric acid is added in place of the phosphorous compound of the present invention, the effect of addition is not observed and it is not practical. Further, even when the phosphorus compound of the present invention is used in combination with a metal-containing polyester polymerization catalyst such as a conventional antimony compound, titanium compound, tin compound, and germanium compound within the range of the addition amount of the present invention, the melt polymerization reaction is promoted. The effect is not recognized. In addition, even if it uses the phosphorus compound of this invention independently within the range of the addition amount of this invention, catalyst activity is not recognized.

  As the aluminum compound constituting the polymerization catalyst of the present invention, known aluminum compounds can be used without limitation.

  Specific examples of aluminum compounds include aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, Carboxylates such as aluminum tartrate and aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate and aluminum phosphonate, aluminum methoxide, aluminum Etoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide Id, aluminum alkoxide such as aluminum t-butoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate diiso-propoxide, and other organic chelate compounds, organoaluminum compounds such as trimethylaluminum and triethylaluminum And their partial hydrolysates, reaction products comprising aluminum alkoxides and aluminum chelate compounds and hydroxycarboxylic acids, aluminum oxide, ultrafine aluminum oxide, aluminum silicate, aluminum and titanium, silicon, zirconium, alkali metals and alkaline earths Examples thereof include complex oxides with metals. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

  Among these aluminum compounds, aluminum acetate, aluminum chloride, aluminum hydroxide, and aluminum hydroxide chloride having a high aluminum content are preferable. From the viewpoint of solubility, aluminum acetate, basic aluminum acetate, aluminum chloride, and aluminum hydroxide chloride are preferable. preferable. Furthermore, the use of aluminum acetate or basic aluminum acetate is particularly preferred from the viewpoint of not corroding the device.

Here, aluminum hydroxide chloride is a general term for what is generally called polyaluminum chloride or basic aluminum chloride, and those used for water supply can be used. These are represented by, for example, the general structural formula [Al ₂ (OH) _n Cl _6-n ] _m (where 1 ≦ n ≦ 5). Among these, those having a low chlorine content are preferable from the viewpoint of not corroding the device.

  The above-mentioned aluminum acetate is a general term for those having a structure of an aluminum salt of acetic acid represented by basic aluminum acetate, aluminum triacetate, aluminum acetate solution, etc. Among these, from the viewpoint of solubility and solution stability The use of basic aluminum acetate is preferred. Of the basic aluminum acetates, aluminum monoacetate, aluminum diacetate, or those stabilized with boric acid are preferred. When using the one stabilized with boric acid, it is preferable to use one stabilized with boric acid in an amount of equimolar or less with respect to basic aluminum acetate, and in particular, 1/2 to 1/3 molar amount. The use of basic aluminum acetate stabilized with boric acid is preferred. Examples of basic aluminum acetate stabilizers include urea and thiourea in addition to boric acid. Any of the above basic aluminum acetates solubilized in a solvent such as water or glycol, particularly those solubilized in water and / or ethylene glycol are preferably used from the viewpoint of catalytic activity and the quality of the resulting polyester.

  Solvents that can be used in the present invention are water and alkylene glycols. Examples of alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, ditrimethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyl glycol, and the like. . Preferably, they are ethylene glycol, trimethylene glycol, tetramethylene glycol, more preferably ethylene glycol.

Below, the specific example of the preparation method of a basic aluminum acetate solution is shown.
(1) Preparation example of aqueous solution of basic aluminum acetate Water is added to basic aluminum acetate and stirred at room temperature for several hours or more. The stirring time is preferably 12 hours or longer. Thereafter, stirring is performed at 60 ° C. or more for several hours or more. The temperature in this case is preferably in the range of 60 to 80 ° C. The stirring time is preferably 3 hours or more. The concentration of the aqueous solution is preferably 10 g / l to 30 g / l, particularly preferably 15 g / l to 20 g / l.
(2) Preparation Example of Ethylene Glycol Solution of Basic Aluminum Acetate Ethylene glycol is added to the above aqueous solution. The amount of ethylene glycol added is preferably 1 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 2-3 times. The solution is stirred at room temperature for several hours to obtain a uniform water / ethylene glycol mixed solution. Thereafter, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 60 ° C or higher, and preferably 120 ° C or lower. More preferably, the water is distilled off by stirring at 80 to 110 ° C. for several hours. More preferably, heating is performed under reduced pressure and / or an inert gas atmosphere such as nitrogen or argon, and water is distilled off to prepare a catalyst solution or slurry.

  The above-mentioned aluminum lactate is preferably solubilized in a solvent such as water or glycol, particularly those solubilized in water and / or ethylene glycol, from the viewpoint of catalytic activity and the quality of the resulting polyester.

Below, the specific example of the preparation method of the ethylene glycol solution of aluminum lactate is shown.
An aqueous solution of aluminum lactate is prepared. The preparation may be performed at room temperature or under heating, but is preferably performed at room temperature. The concentration of the aqueous solution is preferably 20 g / l to 100 g / l, particularly preferably 50 to 80 g / l. Ethylene glycol is added to the aqueous solution. The amount of ethylene glycol added is preferably 1 to 5 times the volume ratio of the aqueous solution. More preferably, the amount is 2-3 times. After stirring the solution at room temperature to obtain a uniform water / ethylene glycol mixed solution, the solution is heated and water is distilled off to obtain an ethylene glycol solution. The temperature is preferably 80 ° C. or higher, and preferably 120 ° C. or lower. More preferably, the water is distilled off by stirring at 90 to 110 ° C. for several hours.

  The amount of the aluminum compound used in the present invention is preferably 0.001 to 0.05 mol% with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polyvalent carboxylic acid of the obtained polyester. Preferably it is 0.005-0.02 mol%. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exerted. If the amount used is 0.05 mol% or more, thermal stability or thermal oxidation stability is lowered, resulting from aluminum. Occurrence of foreign matters or increased coloring may be a problem. As described above, the polymerization catalyst of the present invention has a great feature in that it exhibits a sufficient catalytic activity even when the addition amount of the aluminum component is small. As a result, the thermal stability and thermal oxidation stability are excellent, and foreign matters and coloring caused by aluminum are reduced.

  In the present invention, it is preferable to use an alkali metal, an alkaline earth metal, or a compound thereof in addition to aluminum or a compound thereof. The alkali metal or alkaline earth metal constituting these substances is preferably at least one selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, The use of compounds is more preferred. When an alkali metal or a compound thereof is used, the use of Li, Na, or K is particularly preferable.

  Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylic acids such as acrylic acid and methacrylic acid. Salts, aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, Inorganic acid salts such as hydrogen phosphate, hydrogen sulfate, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, organic sulfonic acids such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid Alkoxy such as salt, organic sulfate such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, t-butoxy Id, chelate compounds such as acetylacetonate, oxides, hydroxides, and the like.

  Among these alkali metals, alkaline earth metals or their compounds, when using strongly alkaline ones such as hydroxides, these tend to be difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. Therefore, it must be added to the polymerization system in an aqueous solution, which may cause a problem in the polymerization process. Furthermore, when a strongly alkaline material such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be colored, and the hydrolysis resistance also decreases. Tend. Accordingly, the alkali metal or their compounds or alkaline earth metals or their compounds suitable for the present invention are preferably saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, aromatics of alkali metals or alkaline earth metals. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, inorganic acid salt, organic sulfate, alkoxide, chelate compound, and oxide. Among these, from the viewpoints of ease of handling and availability, saturated aliphatic carboxylates of alkali metals or alkaline earth metals are preferable, and acetates are particularly preferable.

When alkali metals, alkaline earth metals and compounds thereof are added, the amount M (mol%) used is 1 × 10 ⁻⁶ or more and 0.1 mol% with respect to the number of moles of all polycarboxylic acid units constituting the polyester. Is preferably 5 × 10 ^{−6 to} 0.05 mol%, more preferably 1 × 10 ^{−5 to} 0.03 mol%, and particularly preferably 1 × 10 ^−5. -0.01 mol%. Since the addition amount of the alkali metal or 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. When the amount M of the alkali metal, alkaline earth metal and its compound is 0.1 mol% or more, the thermal stability and hydrolysis resistance decrease, the generation of foreign matters and the increase in coloring may cause problems in product processing. appear. When M is less than 1 × 10 ⁻⁶ , the effect is not clear even when added.

  In the polyester polymerization catalyst of the present invention, it is further preferable to add a cobalt compound as a cobalt atom in an amount of less than 10 ppm based on the polyester. More preferably, it is added in an amount of less than 5 ppm, more preferably 3 ppm or less.

  Although it is known that a cobalt compound itself has a certain degree of polymerization activity, if it is added to such an extent that a sufficient catalytic effect is exhibited as described above, the thermal stability is lowered. According to the present invention, the polyester obtained has good thermal stability, but by adding the cobalt compound in such a small amount as an addition amount that does not clearly show the catalytic effect, the resulting polyester can be colored. It can be erased more effectively. The cobalt compound in the present invention is for the purpose of eliminating coloration, and the addition time may be any stage of the polymerization, and may be after the polymerization reaction is completed.

  The cobalt compound is not particularly limited, and specific examples include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof. Of these, cobalt acetate tetrahydrate is particularly preferred.

  The production of the polyester according to the present invention can be carried out by a method having a conventionally known process 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, after polycondensation, or after transesterification of alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, Any method of polycondensation can be performed. The polymerization apparatus may be a batch type or a continuous type.

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

  The polymerization catalyst of the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system at any stage before and during the esterification reaction or transesterification reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In particular, aluminum or a compound thereof is preferably added immediately before the start of the polycondensation reaction.

  The addition method of components other than aluminum and phosphorus, which is the polycondensation catalyst of the present invention, may be in the form of powder or neat, or in the form of a slurry or solution of a solvent such as ethylene glycol. There is no particular limitation. Moreover, what mixed beforehand the aluminum compound which is the polymerization catalyst of this invention, a phosphorus compound, and the other component may be added, and these may be added separately, but what mixed each component previously Is preferably used. It is more preferable to perform heat treatment after mixing. Further, the aluminum compound, phosphorus compound and other components which are the polymerization catalyst of the present invention may be added to the polymerization system at the same addition time, or may be added at different addition times.

  The polymerization catalyst of the present invention is not suitable for other polymerization catalysts such as antimony compounds, titanium compounds, germanium compounds, tin compounds, etc. The addition of these components causes problems in the products such as polyester characteristics, processability and color tone as described above. The coexistence within the range of no added amount is advantageous and preferable in improving productivity by shortening the polymerization time.

  However, the antimony compound can be added in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polymerization. More preferably, it is added in an amount of 30 ppm or less. When the addition amount of antimony is more than 50 ppm, metal antimony is precipitated, and darkening and foreign matter are generated in the polyester.

  As a titanium compound, it is possible to add in the range of 10 ppm or less with respect to the polymer obtained by superposition | polymerization. More preferably, it is added in an amount of 5 ppm or less, more preferably 2 ppm or less. If the amount of titanium added is more than 10 ppm, the thermal stability of the resulting resin is significantly reduced.

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

  When the polyester is polymerized using the polymerization catalyst of the present invention, one or more antimony compounds, titanium compound manium compounds and tin compounds can be used.

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

  Specifically, examples of the antimony compound include antimony trioxide, antimony pentoxide, antimony acetate, and antimony glycoloxide. Of these, antimony trioxide is preferable.

  Examples of titanium compounds include 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. Of these, tetra-n-butoxy titanate is preferred.

  Examples of the germanium compound include germanium dioxide and germanium tetrachloride. Among these, germanium dioxide is preferable.

  In addition, the tin compounds include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin adduct, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin Examples thereof include sulfide, dibutylhydroxytin oxide, methylstannic acid, ethylstannic acid and the like, and the use of monobutylhydroxytin oxide is particularly preferable.

  The polyester referred to in the present invention is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols containing glycol. Or consisting of a hydroxycarboxylic acid and an ester-forming derivative thereof, or consisting of a cyclic ester.

  Dicarboxylic acids include succinic 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-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acids exemplified, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid Acid 5- (Al Limetal) 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′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, pamoic acid, anthracene Aromatic dicarboxylic acids exemplified by dicarboxylic acids and the like, or ester-forming derivatives thereof.

  Of these dicarboxylic acids, terephthalic acid and naphthalenedicarboxylic acid, particularly 2,6-naphthalenedicarboxylic acid, are preferable from the viewpoint of the physical properties of the resulting polyester, and other dicarboxylic acids are used as constituents as necessary.

  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, And ester-forming derivatives thereof.

  As glycols, 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 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2- Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethyleneglycol Aliphatic glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxy) Phenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, Aromatic glycols exemplified by 2,5-naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, and the like can be mentioned.

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

  Examples of polyhydric alcohols other than these glycols include 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 these Examples thereof include ester-forming derivatives.

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

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

  The polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalene dicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol. More preferably, it is a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol.

  The polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalene dicarboxylic acid or its ester-forming derivative is terephthalic acid or its ester-forming derivative and naphthalene dicarboxylic acid or its ester formation with respect to all acid components It is preferable that it is polyester containing 70 mol% or more in total of the functional derivatives, more preferably polyester containing 80 mol% or more, and still more preferably polyester containing 90 mol% or more. The polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof with respect to the total acid component, more preferably 80 Polyesters containing at least mol%, more preferably polyesters containing at least 90 mol%.

  The polyester whose main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of the total amount of alkylene glycol 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 here may contain a substituent or an alicyclic structure in the molecular chain.

  The naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention includes 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 1,7-naphthalenedicarboxylic acid or their 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, 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-cyclohexane Examples include dimethanol, 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 at the same time.

  The polyester of the present invention is preferably 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 this copolymer are particularly preferred.

  The polyester of the present invention can contain a known phosphorus compound as a copolymerization 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 copolymerization components, it is possible to improve the flame retardancy of the resulting polyester.

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

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

  As for the copolymerization amount of a metal sulfonate group containing compound, 0.3-10.0 mol% is preferable with respect to the acidic component which comprises polyester, More preferably, it is 0.80-5.0 mol%. If the amount of copolymerization is too small, the dyeability of the basic dye is inferior, and if it is too large, not only the yarn-making property is inferior, but also sufficient strength as a fiber cannot be obtained due to the thickening phenomenon. Further, when the metal sulfonate-containing compound is copolymerized in an amount of 2.0 mol% or more, it is possible to impart atmospheric pressure dyeability to the resulting modified polyester fiber. Moreover, it is possible to reduce the usage-amount of a metal sulfonate group containing compound suitably by selecting a suitable easily dyeable monomer. Although it does not specifically limit as an easily dyeable monomer, The aliphatic dicarboxylic acid represented by the long-chain glycol compound represented by polyethyleneglycol and polytetramethylene glycol, adipic acid, sebacic acid, and azelaic acid is mentioned.

  After polyester polymerization 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 by deactivating the catalyst by adding a phosphorus compound or the like.

  The polyester of the present invention can contain organic, inorganic, and organometallic toners, and a fluorescent brightening agent. By containing one or more of these, yellowing of the polyester is possible. Etc. can be suppressed to a further excellent level. It may also contain other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. Good. As antioxidants, aromatic amines, phenols and other antioxidants can be used, and as stabilizers, phosphoric acid and phosphoric acid ester-based phosphorous, sulfur-based, amine-based stabilizers, etc. Can be used.

  Although the preparation method of a polymerization catalyst is shown below, it is not restrict | limited to this.

(Preparation example 1 of aluminum compound)
Prepared by heat treatment at 80 ° C. for 2 hours under stirring, and an equivalent amount (volume ratio) of ethylene glycol to 20 g / l aqueous solution of basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich) The flask was charged and stirred at room temperature for 6 hours, and then water was distilled off from the system while stirring at 90 to 110 ° C. for several hours under reduced pressure (133 Pa) to prepare an ethylene glycol solution of 20 g / l aluminum compound.

(Preparation Example 1 of phosphorus compound)
As a phosphorus compound, diethyl n-hexylphosphonate represented by (Chemical Formula 7) was charged into a flask together with ethylene glycol, and heated at reflux temperature for 3 hours with stirring under nitrogen substitution, to obtain an ethylene glycol solution of 30 g / l phosphorus compound. Prepared.

(Preparation example of a mixture of ethylene glycol solution of aluminum compound / ethylene glycol solution of phosphorus compound)
The respective ethylene glycol solutions obtained in Preparation Example 1 for the aluminum compound and Preparation Example 1 for the phosphorus compound were charged into a flask and mixed at room temperature so that the molar ratio of aluminum atoms to phosphorus atoms was 1: 2. A catalyst solution was prepared by stirring for 1 day.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples from the first. In each example and comparative example, the intrinsic viscosity (IV) of the polyester was measured as follows. Measurement was performed at a temperature of 30 ° C. using a 6/4 mixed solvent (weight ratio) of phenol / 1,1,2,2-tetrachloroethane.

(Measurement of oligomer AVo (acid value))
The oligomer is pulverized and dried under reduced pressure at 110 ° C. for 15 hours or more. Weigh accurately 1 g of sample and add 20 ml of pyridine. Boil at reflux for 15 minutes to dissolve. After dissolution, 10 ml of pure water is added and allowed to cool to room temperature. Titrate with N / 10-NaOH using phenolphthalein as an indicator. Do the same for the blank without the sample.
According to the following formula, AV0 = (A−B) × 0.1 × f × 1000 / W
(A = drop constant (ml), B = blank drop constant (ml), f = factor N / 10-NaOH, W = weight of sample (g))

(Measurement of oligomer 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 a sample is accurately weighed and 10 ml of an acetylating agent (acetic anhydride pyridine solution 0.5 mol% / L) 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 allowed to cool to room temperature. Titrate with N / 5-NaOH using phenolphthalein as an indicator. Do the same for the blank without the sample.
According to the following formula, OHV0 = {(BA) × 0.2 × f × 1000 / W} + AV0
(A = drop constant (ml), B = blank drop constant (ml), f = factor of N / 5-NaOH, W = weight of sample (g))

(Calculation of oligomer OH%)
OH (%) = OHVo / (OHVo + AVo) × 100

(PET color tone)
The color tone of the obtained polymer was evaluated using a visual two-step evaluation method as shown below.
○: Excellent in transparency and color tone ×: Colored inferior in transparency

(Example 1)
High-purity terephthalic acid and ethylene glycol were charged, and esterification was performed according to a conventional method to obtain an oligomer mixture in which the oligomer had an OH% of about 54%. As the polycondensation catalyst for this oligomer mixture, the polymerization catalyst of the above “Preparation Example of Mixture of Aluminum Compound Ethylene Glycol Solution / Phosphor Compound Ethylene Glycol Solution” was used as the aluminum atom and the phosphorus atom respectively for the acid component in the polyester. It added so that it might become the value of Table 1, and then it stirred at 260 degreeC by the normal pressure in nitrogen atmosphere for 10 minutes. Thereafter, while the temperature was raised to 275 ° C. over 40 minutes, the pressure of the reaction system was gradually lowered to 0.3 mmHg, and a polycondensation reaction was further performed at the same temperature and pressure for 3 hours. Table 1 shows the physical property values of the obtained polymer.

(Example 2)
A polyester was polymerized in exactly the same manner as in Example 1 except that the catalyst was changed. The catalyst was prepared in exactly the same manner as the above-mentioned "Preparation Example 1 of Aluminum Compound, Preparation Example 1 of Phosphorus Compound, and Preparation Example of Mixture of Aluminum Compound in Ethylene Glycol Solution / Phosphorus Compound in Ethylene Glycol". Table 1 shows the physical property values of the obtained polymer.

(Comparative Examples 1-2)
A polyester was polymerized in the same manner as in Example 1 except that an aluminum compound or a phosphorus compound was used alone as a catalyst. Table 1 shows the physical property values of the obtained polymer.

(Comparative Example 3)
Using the aluminum compound and phosphorus compound described in Example 1 as the catalyst, the polyester was polymerized in exactly the same manner as in Example 1 without mixing them both in advance. Table 1 shows the physical property values of the obtained polymer.

  The polymerization catalyst of the present invention is excellent in catalytic activity, excellent in transparency, and gives a polyester molded product excellent in color tone. For example, a film or sheet for clothing, industrial materials, packaging, magnetic tape, etc. It can be used in a wide range of fields, such as bottles that are hollow molded products, casings for electrical and electronic parts, and other engineering plastic molded products.

Claims (10)

A polyester polymerization catalyst comprising a solution or slurry containing at least one selected from the group consisting of aluminum and its compounds and at least one selected from phosphorus compounds, and represented by the following general formula (Formula 1) A polyester polymerization catalyst comprising at least one compound.

(In the formula (Chemical Formula 1), R ¹ represents an aliphatic hydrocarbon group having 1 to 50 carbon atoms, an aromatic ring structure having 6 to 50 carbon atoms, or a heterocyclic structure having 4 to 50 carbon atoms. R ² and R ³ Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group. A polyester polymerization catalyst, wherein R ^{1 in the} formula (Chemical Formula 1) is an aliphatic hydrocarbon having 1 to 50 carbon atoms. The substituent in R ^{1 of the} phosphorus compound represented by the formula (Chemical Formula 1) is a halogen-substituted hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms and an alkanol group, halogen 1 group selected from a group, a nitrile group, a cyanoalkyl group, an amino group, a nitro group, a carboxyl group, an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms, a formyl group, an acyl group, a sulfonic acid group, or a sulfonic acid amide group Or it is 2 or more types, The polyester polymerization catalyst in any one of Claim 1 or 2 characterized by the above-mentioned.   The polyester polymerization catalyst according to any one of claims 1 to 3, wherein the aliphatic hydrocarbon group is selected from hydrocarbon groups having 1 to 18 carbon atoms. Polyester polymerization catalyst according to claim 1, at least one of R ² and R ^3, characterized in that a hydrogen atom.   A method for producing a polyester comprising using the polymerization catalyst according to claim 1.   The polyester manufactured using the polymerization catalyst in any one of Claims 1-5.   A hollow molded article made of the polyester according to claim 7.   A fiber comprising the polyester according to claim 7.   A film comprising the polyester according to claim 7.