JP2006316179A - Method for producing polyetherester block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a polyetherester block copolymer which has a low terminal COOH concentration in the formed copolymer, and good heat stability and resistance to hydrolysis, and reduces turbidity. <P>SOLUTION: In producing a polyetherester block copolymer by performing the transesterification reaction of (a) a lower alkyl ester of an aromatic dicarboxylic acid and/or a lower alkyl ester of an alicyclic dicarboxylic acid, (b) an aliphatic glycol and/or an alicyclic glycol, and (c) a polyalkylene ether glycol with the use of a titanium compound and a magnesium compound as catalysts and the consecutive polycondensation reaction, (d) an organic carboxylic acid is added in an amount of meeting formula (1) äwherein [d] is a molar fraction of (d) component and [a] is a molar fraction of (a) component}. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polyetherester block copolymer. Specifically, (a) a lower alkyl ester of an aromatic dicarboxylic acid and / or an alicyclic dicarboxylic acid or a lower alkyl ester thereof, (b) an aliphatic glycol and / or an alicyclic glycol, (c) a polyalkylene ether glycol The present invention relates to a method for producing a polyetherester block copolymer.

  The polyether ester block copolymer is composed of a crystalline polyester unit (hard segment) composed of a short-chain glycol and an aromatic dicarboxylic acid, and an amorphous polyester unit composed of a polyalkylene ether glycol and an aromatic dicarboxylic acid to be a long-chain glycol. (Soft segment). Such a polyetherester block copolymer has excellent mechanical properties, flexibility, and elastic recovery, and is thermoplastic and easy to mold, so it can be used for fibers, films, sheets, tubes, automobile parts, and electrical and electronic equipment. It is used in various fields such as parts.

A general method for producing a polyetherester block copolymer includes a direct polymerization method in which a dicarboxylic acid, a glycol, and a polyalkylene ether glycol are esterified, followed by a polycondensation reaction, a dicarboxylic acid diester, a glycol, and a polyester. A transesterification method in which an alkylene glycol is transesterified and then a polycondensation reaction is known. In any reaction, it is known to use a titanium compound as a catalyst. (See Patent Document 2)
On the other hand, when the polyether ester block copolymer is used to obtain a copolymer having a higher molecular weight and the reaction temperature is excessively increased or the reaction time is prolonged in the polycondensation reaction, the obtained ester is reversed. Bonds may break and terminal COOH groups may increase. If many such terminal COOH groups remain in the copolymer, the thermal stability and hydrolysis resistance of the obtained copolymer are adversely affected, which becomes a serious problem in use. On the other hand, it has been proposed to use a titanium compound and a magnesium compound that is 0.2 to 3 mole times the amount of titanium as a catalyst (see Patent Document 1).
JP 2000-191758 A Japanese Patent Publication No.54-20982

  Even if the polyether ester block copolymer is produced using the technique proposed in Patent Document 1, the concentration of the terminal COOH group is certainly suppressed to some extent when the titanium compound and the magnesium compound are used in combination. However, in the polymerization using the transesterification method used in the present invention, when a magnesium compound is used, white turbidity due to precipitation of the catalyst occurs and the polymerization rate is greatly reduced as compared with the case where only the titanium compound is used. I also found that there was a case. That is, it is considered that the magnesium compound is denatured and aggregates and precipitates in the reaction system, which further promotes the precipitation of the titanium compound. Therefore, it is still difficult to achieve both the reduction of the terminal COOH group concentration and the polymerization of the polyether ester block copolymer having a higher molecular weight.

  The object of the present invention is to provide a method for efficiently producing a polyetherester block copolymer having a low concentration of terminal COOH groups in the produced copolymer, good thermal stability and hydrolysis resistance, and low cloudiness. There is to do.

  As a result of intensive studies to solve the above-mentioned problems peculiar to the polymerization of the polyether ester block copolymer using the transesterification method, the present inventors surprisingly made the organic carboxylic acid coexist at the time of production. The inventors have found that the catalyst can be remarkably improved against the remarkable catalyst precipitation and the decrease in polymerization activity that occur when a magnesium compound is used, and the present invention has been completed.

  That is, the gist of the present invention is that (a) a lower alkyl ester of an aromatic dicarboxylic acid and / or a lower alkyl ester of an alicyclic dicarboxylic acid, (b) an aliphatic glycol and / or an alicyclic glycol, (c) poly In producing a polyetherester block copolymer by performing an ester exchange reaction and a subsequent polycondensation reaction using an alkylene ether glycol as a catalyst with a titanium compound and a magnesium compound, (d) an organic carboxylic acid is represented by the following formula (1): A method for producing a polyetherester block copolymer, wherein the polyetherester block copolymer is added in a range satisfying the above.

([D] indicates the mole fraction of the component (d), and [a] indicates the mole fraction of the component (a).)

  According to the present invention, a polyether ester block copolymer having a high degree of polymerization can be efficiently obtained, and a block copolymer having good heat resistance and hydrolysis resistance and less turbidity can be obtained.

Hereinafter, the present invention will be described in detail.
<(A) Lower alkyl ester of aromatic dicarboxylic acid and / or lower alkyl ester of alicyclic dicarboxylic acid>
Examples of the aromatic dicarboxylic acid component used in the present invention include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, Phenoxydicarboxylic acid, 5-sulfoisophthalic acid, etc. are mentioned, Preferably terephthalic acid and naphthalene-2,6-dicarboxylic acid are mentioned, More preferably, it is terephthalic acid. Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid. These lower alkyl esters are used. Two or more of these aromatic dicarboxylic acid components or alicyclic dicarboxylic acid components may be used in combination. As the lower alkyl ester component, one or more of the above-mentioned dicarboxylic acid components such as methyl ester, ethyl ester, propyl ester, and butyl ester may be mixed, and can be arbitrarily selected depending on the purpose. In addition, a small amount of aliphatic dicarboxylic acid components such as succinic acid, adipic acid, oxalic acid and sebacic acid may be added, and these may be used alone or in combination of two or more and may be arbitrarily selected according to the purpose. be able to. Further, a tri- or higher functional polycarboxylic acid component such as trimellitic acid, pyromellitic acid or trimesic acid may be used. A small amount of an acid anhydride such as trimellitic anhydride may be used. When using a component other than the main component, it is usually preferable to charge it at the same time as the main component.

<(B) Aliphatic glycol and / or alicyclic glycol>
The aliphatic diol or alicyclic diol component used in the present invention includes ethylene glycol, 1,4-butanediol, 1,3-propanediol, pentamethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, deca Examples include methylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tricyclodecane dimethanol, diethylene glycol, triethylene glycol, etc., but ethylene glycol, 1,4-butanediol, 1,3- Propanediol and 1,6-cyclohexanedimethanol are preferred. A small amount of a polyhydric alcohol component such as trimethylolpropane or glycerin may be used.

<(C) Polyalkylene ether glycol>
Examples of the polyalkylene ether glycol used in the present invention include polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polytrimethylene ether glycol, polyneopenylene ether glycol, block or random copolymer of ethylene oxide and propylene oxide. And a block copolymer or a random copolymer of ethylene oxide and THF. Polytetramethylene ether glycol and polytrimethylene ether glycol are particularly preferable. It is polytrimethylene ether glycol that exhibits a particularly remarkable effect. The number average molecular weight of these polyalkylene ether glycols is usually 400 or more, preferably 600 or more, more preferably 800 or more, and usually 6000 or less, preferably 4000 or less, and more preferably 3000 or less. When this number average molecular weight is less than 400, the melting point drop becomes severe and the heat resistance may be adversely affected. On the other hand, when the number average molecular weight exceeds 6000, the viscosity of the polyalkylene ether glycol increases, so that phase separation in the polyether ester block copolymer using the same becomes remarkable, and the physical properties of the copolymer molded product are May decrease. The “number average molecular weight (Mn)” used herein refers to the esterification of the hydroxyl group at the polyalkylene ether glycol end with phthalic anhydride and the decomposition of unreacted phthalic anhydride into phthalic acid. The hydroxyl value is obtained by back titration with alkali (terminal group titration method) and is calculated from the value.

  Further, the amount (weight ratio) used in the copolymer of polyalkylene ether glycol is usually 5% to 95%, preferably 10% to 90%, more preferably 20% to 80%. It is. When the amount used is lower than the lower limit, the properties of the copolymer as an elastic body derived from the soft segment may be reduced. On the other hand, if the amount used exceeds the upper limit, the copolymer may become too soft, making it difficult to use as a polymer.

<Catalyst>
Examples of the titanium compound used in the present invention include titanium potassium oxalate, alkoxy titanium compound, titanium carbonate compound, titanium halide compound, titanium acetylacetonate, titanium lactate and the like. Of these, titanium potassium oxalate, alkoxy titanium compounds, titanium acetylacetonate, and titanium lactate are preferable, and alkoxy titanium compounds are most preferable. Among these, tetraalkyl titanate (tetraalkoxytitanium) is preferable, and specifically, tetara-n-propyl titanate, tetraisopropylisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetra Cyclohexyl titanate, tetrabenzyl titanate, or mixed titanates thereof. Of these, tetra-n-propyl titanate, tetroilopropyl titanate, and tetra-n-butyl titanate are preferable, and tetra-n-butyl titanate is most preferable. Two or more of these titanium compounds may be used in combination.

  The addition amount of the titanium compound is usually 10 ppm or more and 400 ppm or less, preferably 20 ppm or more and 350 ppm or less, more preferably 30 ppm or more and 300 ppm or less with respect to the polyether ester copolymer produced as the amount of titanium. If the amount of the catalyst to be added is less than the lower limit, the reaction may be difficult to proceed and the productivity may be deteriorated. If the amount exceeds the upper limit, the produced polyetherester block copolymer may be colored or the copolymer. The surface appearance of the molded product may be deteriorated by bumps or the like.

  Examples of the magnesium compound used in the present invention include magnesium halides such as magnesium hydroxide, magnesium oxide, magnesium sulfate, magnesium carbonate, magnesium hydrogen carbonate, and magnesium chloride, magnesium hydrogen phosphate, magnesium acetate, and propionic acid. Examples thereof include organic acid salts such as magnesium and magnesium butyrate, alkoxides such as magnesium methoxide, magnesium ethoxide, magnesium propoxide and magnesium butoxide, and magnesium acetylacetonate. From the viewpoint of solubility, magnesium acetate, magnesium alkoxide, and magnesium acetylacetonate salt are preferable, and magnesium acetate is more preferable.

  The amount of magnesium compound used is usually 0.01 or more, preferably 0.2 or more, more preferably 0.5 or more, and usually 8.0 or less, preferably as a metal atomic weight as a molar ratio to titanium. 5.0 or less, more preferably 3.0 or less. If the amount of the magnesium compound to be added is less than the lower limit, it may be difficult to exert the effect of reducing terminal COOH. If the amount exceeds the upper limit, precipitation of the magnesium compound increases and the reaction rate is remarkably reduced. The surface appearance of the copolymer molded product may be deteriorated due to bumps or the like.

<(D) Organic carboxylic acid>
(D) Examples of organic carboxylic acids include aliphatic saturated monocarboxylic acids such as acetic acid, propionic acid, butyric acid, hexanoic acid, stearic acid, and behenic acid, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. Aliphatic saturated dicarboxylic acids such as suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, and dodecadicarboxylic acid and their anhydrides, aliphatic unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their anhydrides, Aliphatic polycarboxylic acids such as tricarballylic acid and anhydrides thereof, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid and anhydrides thereof, benzoic acid, t- Aromatic monocarboxylic acids such as butylbenzoic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sulfoisophthalic acid Aromatic dicarboxylic acids such as sodium oxalate, terephthalic acid, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 2,6-naphthalenedicarboxylic acid and their anhydrides, Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid and their anhydrides, and for example, glycolic acid, lactic acid, citric acid, malic acid, gallic acid, p-hydroxybenzoic acid, p- Examples thereof include hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid and alkoxycarboxylic acids. Among these, aromatic carboxylic acids and alicyclic carboxylic acids are preferable, dicarboxylic acids in the ester used in (a) and / or isomers thereof are more preferable as the main raw material, and in the ester used in (a) Dicarboxylic acids are most preferred.

  (D) The usage-amount of organic carboxylic acid is used in the range with which following formula (1) is satisfy | filled.

([D] indicates the mole fraction of the component (d), and [a] indicates the mole fraction of the component (a).)
When it is smaller than the above range, the catalyst activity cannot be sufficiently lowered and the polymerization rate may be lowered. When it is larger than the above range, catalyst association and precipitation may occur due to water by-produced by the reaction of the organic carboxylic acid, leading to a decrease in polymerization rate. Accordingly, it is usually preferably 0.2 or more, more preferably 0.5 or more, most preferably 1.0 or more, and usually preferably 8.0 or less, more preferably 6.0 or less, and most preferably 4. 0 or less.

<Polymerization reaction>
The method for producing the polyetherester copolymer of the present invention comprises: (a) a lower alkyl ester of an aromatic dicarboxylic acid and / or a lower alkyl ester of an alicyclic dicarboxylic acid, (b) an aliphatic glycol and / or an alicyclic. A polyether ester copolymer is produced in a transesterification method in which a glycol and (c) a polyalkylene ether glycol are transesterified, followed by a polycondensation reaction, but these reaction conditions are not particularly limited. The known reaction conditions are applied as they are.

  For example, the molar ratio of glycol component / lower alkyl ester component of dicarboxylic acid is 2.5 or less, preferably 1.0 or more and 2.2 or less, and 120 ° C. or more and 245 ° C. or less, preferably 150 ° C. or more and 230 or less as transesterification. It is performed for 2 to 4 hours at a temperature not higher than 0C. In this case, if the temperature falls below the lower limit reaction temperature, the reaction may hardly proceed and the productivity may deteriorate, and if the temperature exceeds the upper limit reaction temperature, the glycol component may distill out and adversely affect the polycondensation reaction. . Also, if the reaction time is short, the transesterification reaction may not proceed sufficiently and the subsequent polycondensation reaction may not proceed. Is sufficiently advanced, the production efficiency may deteriorate.

  Following the transesterification reaction, a polycondensation reaction is performed. The conditions are usually performed under a reduced pressure of 0.4 kPa or less, a temperature of 230 ° C. or more and 250 ° C. or less, and a polymerization time of 2 to 8 hours. At this time, if the pressure is exceeded, the reaction may not proceed easily and the productivity may deteriorate. Moreover, when it exceeds the said upper limit reaction temperature, the polyetherester block copolymer to produce | generate may color. In addition, when the reaction time is shorter than 2 hours, the degree of polymerization of the copolymer generated due to insufficient progress of the polycondensation reaction may be extremely low. When the reaction time is longer than 8 hours, the copolymer is generated. The polymer may be colored or a depolymerization reaction may occur to lower the degree of polymerization of the polymer.

  The titanium compound may be added before the start of the transesterification reaction, during the reaction, before the start of the polycondensation reaction, during the polycondensation reaction, etc., but dividedly added before the start of the transesterification reaction and before the start of the polycondensation reaction. Alternatively, it is preferably added before the start of the transesterification reaction or before the start of the polycondensation reaction. The magnesium compound may be added before the start of the transesterification reaction, during the reaction, before the start of the polycondensation reaction, during the polycondensation reaction, etc., but is added separately before the start of the transesterification reaction and before the start of the polycondensation reaction. Alternatively, it is preferably added before the start of the transesterification reaction or before the start of the polycondensation reaction. The magnesium compound may be added in combination with the titanium compound or may be added separately. Further, a tin compound, a zinc compound, an antimony compound, a germanium compound, or the like may be added.

(D) The organic carboxylic acid may be added as a mixture with a titanium compound or a magnesium compound, or may be added separately.
(D) The organic carboxylic acid is preferably added immediately before the magnesium compound is added or mixed with the magnesium compound. (D) The organic carboxylic acid reacts with the magnesium compound to form a salt, which is considered to have a function of preventing the magnesium compound from being modified and precipitated in the reaction system, and the addition time is particularly important. When (d) organic carboxylic acid is added after adding the magnesium compound, the precipitation of the magnesium compound occurs first, the effect of suppressing the catalyst precipitation is small, haze is deteriorated, and the reaction rate may be slow. . In addition, (d) If organic carboxylic acid is added long before the magnesium compound, the organic carboxylic acid reacts with the glycol component in the reaction system before forming a salt with the magnesium compound, thus suppressing catalyst precipitation. May not be effective.

When a magnesium compound is used, the terminal COOH group concentration is 25 eq / ton or less, and heat stability at melting, heat aging resistance, hydrolysis resistance and the like are improved. Preferably it is 20 eq / ton or less, More preferably, it is 18 eq / ton or less.
In the polyether ester block copolymer of the present invention, various additives such as a heat stabilizer, an antioxidant, a crystal nucleating agent, a flame retardant, an antistatic agent, a release agent, as long as the properties are not impaired. An ultraviolet absorber or the like may be added, and the addition timing is not particularly limited, and may be during polymerization or after polymerization.

The reaction format in the present invention can be applied to a batch facility or a continuous facility such as a plug flow method.
In addition, the polyether ester block copolymer of the present invention obtained by melt condensation polymerization as described above is usually held at a temperature equal to or higher than the melting point, and sequentially molded by discharge, pelletizing, etc. from the reaction vessel. . In addition, you may further solid-phase-polymerize the pellet obtained here as needed.

<Application>
The polyether ester block copolymer of the present invention can be used in various fields such as fibers, films, sheets, tubes, industrial parts, automobile parts, and electric / electronic parts. For example, textile products such as clothing fibers and various filters, film products such as biaxially stretched films and conductive films, various hoses such as hydraulic hoses and pneumatic hoses, automobile parts such as constant velocity joint boots and suspension boots, Various seals / packings, flexible couplings, conveyor belts, timing belts, industrial parts such as compression springs, precision mechanical parts such as gears, mobile phone housings, vibration control materials, anti-vibration materials, keyboard pads, conductive pads, OA rolls There are electrical and electronic parts such as telephone curl cords, daily necessities such as hair brushes, hot curlers, ski shoe soles, and shoe inner soles.

Further, the obtained copolymer can be dispersed in water using a solvent or an appropriate emulsifier and used for coating applications such as a binder. In particular, the fact that there is little white turbidity in the use of thin materials such as fibers, films, and sheets has a good appearance and contributes to improvement of mechanical properties such as breaking strength and breaking elongation.
In particular, the fiber is also effective in preventing yarn breakage in the spinning process. The fiber can be formed by melt spinning and drawing. For example, using an extruder type melt spinning apparatus, the melt is melted at a temperature 15 to 80 ° C. higher than the melting point of the polymer, discharged from the spinneret, cooled and solidified, and then the undrawn yarn is wound up through a roller. Next, the undrawn yarn is drawn unheated or using a heated roller depending on the properties of the polymer, and subjected to relaxation heat treatment as necessary. Yarn breakage is a trouble that occurs in conjunction with yarn cutting when such a spinning process is continuously performed.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “part” means “part by weight”. Inherent viscosity ηinh, terminal COOH group, and solution haze were carried out based on the following method.
(1) Inherent viscosity Using an Ubbelohde viscometer, the inherent viscosity was determined in the following manner. That is, using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1), at 30 ° C., the polymer solution having a concentration of 0.5 g / dl and the number of falling seconds of the solvent alone were measured, and the following formula was obtained. .

ηinh = lnηrel / c
ηrel = seconds of dropping of polymer solution / seconds of falling of solvent
c = concentration (g / dl)
(2) Terminal COOH group 0.5 g of a polyetherester block copolymer was dissolved in 25 ml of benzyl alcohol, and titrated using a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

(3) Solution haze 0.2 g of polyetherester block copolymer was dissolved in 20 ml of phenol / tetrachloroethane (weight ratio 1/1), and measured using a turbidimeter (NDH2000) manufactured by Nippon Denshoku Industries Co., Ltd. did.
Production Example 1
<Method for producing polytrimethylene ether glycol (Mn = 2166)>
Distilled and purified 1,3-propanediol (50 g) was charged into a 100 ml four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a thermometer and a stirrer while supplying nitrogen at 100 Nml / min. To this was added 0.0348 g of sodium carbonate, and then 0.678 g of concentrated sulfuric acid (95%) was slowly added with stirring. The flask was immersed in an oil bath and heated to 162 ° C. After the liquid temperature was adjusted to 162 ° C. ± 2 ° C. and held for 18 hours to react, the flask was removed from the oil bath and allowed to cool to room temperature. Water produced during the reaction was distilled off accompanying nitrogen. The reaction liquid cooled to room temperature was transferred to a 300 ml eggplant type flask using 50 g of tetrahydrofuran, 50 g of demineralized water was added thereto, and the mixture was gently refluxed for 1 hour to hydrolyze the sulfate ester. After cooling to room temperature and cooling, the lower layer (water tank) separated into two layers was removed. After adding 0.5 g of calcium hydroxide to the upper layer (oil layer) and stirring at room temperature for 1 hour, 50 g of toluene was added and heated to 60 ° C., and tetrahydrofuran, water and toluene were distilled off under reduced pressure. The obtained oil layer was dissolved in 100 g of toluene and filtered through a 0.45 μm filter to remove insoluble matters. The filtrate was heated to 60 ° C. and vacuum dried for 6 hours.

Example 1
A reactor equipped with a nitrogen inlet and a vacuum port was charged with 39.4 parts of dimethyl terephthalate, 23.5 parts of 1,4-butanediol, and 109.0 parts of polytrimethylene ether glycol produced by the method of Production Example 1. Then, 0.107 parts of tetrabutyl titanate (100 ppm / polymer as Ti metal) and 0.067 parts of magnesium acetate tetrahydrate (50 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)) ) Was dissolved in a small amount of 1,4-butanediol and added. After substituting under reduced pressure, the temperature was increased from 150 ° C. to 230 ° C. over 3 hours under nitrogen to conduct a transesterification reaction. Thereafter, 0.7 part of terephthalic acid, 0.160 part of tetrabutyl titanate (150 ppm / polymer as Ti metal) and 0.101 part of magnesium acetate tetrahydrate (75 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)), Irganox 1330 (antioxidant manufactured by Ciba Geigy Co., Ltd.) 0.27 part was mixed with 1,4-butanediol, and the polycondensation reaction was started.

In the polycondensation reaction, the pressure was gradually reduced from normal pressure to 0.07 kPa over 90 minutes, and at the same time, the temperature was raised to a predetermined polymerization temperature of 245 ° C. Thereafter, 0.07 kPa was maintained, and when the predetermined stirring torque was reached, the reaction was terminated and the contents were taken out. Table 1 shows the polymerization time, solution viscosity, terminal COOH group, and solution haze of the obtained polyetherester copolymer.
Example 2
A reactor equipped with a nitrogen inlet and a vacuum port was charged with 39.0 parts of dimethyl terephthalate, 20.1 parts of 1,4-butanediol, and 109.0 parts of polytrimethylene ether glycol produced by the method of Production Example 1. Then, 0.107 parts of tetrabutyl titanate (100 ppm / polymer as Ti metal) and 0.067 parts of magnesium acetate tetrahydrate (50 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)) ) Was dissolved in a small amount of 1,4-butanediol and added. After substituting under reduced pressure, the temperature was increased from 150 ° C. to 230 ° C. over 3 hours under nitrogen to conduct a transesterification reaction. Thereafter, 1.03 part of terephthalic acid, 0.160 part of tetrabutyl titanate (150 ppm / polymer as Ti metal) and 0.101 part of magnesium acetate tetrahydrate (75 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)), Irganox 1330 (antioxidant manufactured by Ciba Geigy Co., Ltd.) 0.27 part was mixed with 1,4-butanediol, and the polycondensation reaction was started.

In the polycondensation reaction, the pressure was gradually reduced from normal pressure to 0.07 kPa over 90 minutes, and at the same time, the temperature was raised to a predetermined polymerization temperature of 245 ° C. Thereafter, 0.07 kPa was maintained, and when the predetermined stirring torque was reached, the reaction was terminated and the contents were taken out. Table 1 shows the polymerization time, solution viscosity, terminal COOH group, and solution haze of the obtained polyetherester copolymer.
Example 3
A reactor equipped with a nitrogen inlet and a vacuum port was charged with 39.0 parts of dimethyl terephthalate, 32.8 parts of 1,4-butanediol, and 109.0 parts of polytrimethylene ether glycol produced by the method of Production Example 1. It is. There, 0.107 parts of tetrabutyl titanate (100 ppm / polymer as Ti metal) and 0.067 parts of magnesium acetate tetrahydrate (50 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)) ), 0.35 part of terephthalic acid was added to 1,4-butanediol. After substituting under reduced pressure, the temperature was increased from 150 ° C. to 230 ° C. over 3 hours under nitrogen to conduct a transesterification reaction. Thereafter, 0.86 part of terephthalic acid, 0.08 part of tetrabutyl titanate (75 ppm / polymer as Ti metal) and 0.05 part of magnesium acetate tetrahydrate (34 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)), Irganox 1330 (antioxidant manufactured by Ciba Geigy Co., Ltd.) 0.27 part was mixed with 1,4-butanediol, and the polycondensation reaction was started.

In the polycondensation reaction, the pressure was gradually reduced from normal pressure to 0.07 kPa over 90 minutes, and at the same time, the temperature was raised to a predetermined polymerization temperature of 245 ° C. Thereafter, 0.07 kPa was maintained, and when the predetermined stirring torque was reached, the reaction was terminated and the contents were taken out. Table 1 shows the polymerization time, solution viscosity, terminal COOH group, and solution haze of the obtained polyetherester copolymer.
Comparative Example 1
A reactor equipped with a nitrogen inlet and a vacuum port was charged with 40.2 parts of dimethyl terephthalate, 25.0 parts of 1,4-butanediol, and 109.0 parts of polytrimethylene ether glycol produced by the method of Production Example 1. Then, 0.107 parts of tetrabutyl titanate (100 ppm / polymer as Ti metal) and 0.067 parts of magnesium acetate tetrahydrate (50 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)) ) Was dissolved in 1,4-butanediol and added. After vacuum replacement, from 150 ° C. under nitrogen, 0.160 parts of tetrabutyl titanate (150 ppm / polymer as Ti metal) and 0.101 parts of magnesium acetate tetrahydrate (75 ppm / polymer as Mg metal, Mg / Ti = 1.0 (molar ratio)), Irganox 1330 (Antioxidant manufactured by Ciba Geigy) 0.27 part is mixed with 1,4-butanediol, and the pressure is gradually reduced over 90 minutes. The polymerization temperature was raised to 245 ° C. Thereafter, 0.07 kPa was maintained, and when the predetermined stirring torque was reached, the reaction was terminated and the contents were taken out. Table 1 shows the polymerization time, solution viscosity, terminal COOH group, and solution haze of the obtained polyetherester copolymer.

Claims (3)

(A) Lower alkyl ester of aromatic dicarboxylic acid and / or lower alkyl ester of alicyclic dicarboxylic acid, (b) aliphatic glycol and / or alicyclic glycol, (c) polyalkylene ether glycol and titanium compound In producing a polyetherester block copolymer by carrying out a transesterification reaction and a subsequent polycondensation reaction using a magnesium compound as a catalyst, (d) adding an organic carboxylic acid in a range satisfying the following formula (1): A method for producing a polyetherester block copolymer.

([D] indicates the mole fraction of the component (d), and [a] indicates the mole fraction of the component (a).)   (D) The method for producing a polyetherester block copolymer according to claim 1, wherein the organic carboxylic acid is added immediately before the magnesium compound is added or mixed with the magnesium compound. .   The method for producing a polyetherester block copolymer according to claim 1 or 2, wherein (d) the organic carboxylic acid is a dicarboxylic acid in the ester used in (a).