TWI413653B - Polyester elastomer composition and producing method thereof - Google Patents

Abstract

Disclosed are: a polyester elastomer composition which is reduced in the contents of a free acid, a free diol, a linear oligomer and tetrahydrofuran therein, and therefore which has an improved flavoring property and improved heat resistance and hardly causes the deterioration in a product or the pollution of the environment; and a method for producing the polyester elastomer composition. Specifically disclosed are: a polyester elastomer composition which comprises 0.01 to 5 wt% of an antioxidant agent, 2000 ppm or less of tetrahydrofuran, 50 ppm or less of a free dicarboxylic acid, 10 ppm or less of a free glycol, and 300 ppm or less of a linear oligomer having a molecular weight of 650 or less in a polyester elastomer produced from a dicarboxylic acid component, a glycol component mainly composed of 1,4-butanediol and having a molecular weight of less than 250 and a polyol having a number average molecular weight of 400 to 70000; and a method for producing the polyester elastomer composition.

Description

Polyester elastomer composition and preparation method thereof

The present invention relates to a polyester elastomer composition, relating to a polyester elastomer composition and a process for producing the same, wherein the amount of free dicarboxylic acid, free glycol, and linear oligomer in the polyester elastomer composition The content of tetrahydrofuran is extremely small, and the polyester elastomer composition is suitable for various uses centered on automobiles, home appliance components, and packaging materials.

A crystalline aromatic polyester unit having polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) as a hard portion, and polybutanediol (PTMG) as a soft portion A polyester elastomer of an aliphatic polyester structural unit such as an aliphatic polyether or a poly(ε-caprolactone) is widely used in automobiles, home electric appliances, films, and the like because of its excellent heat resistance and mechanical properties. field.

Conventionally, a method for producing such a polyester elastomer is usually carried out by directly esterifying a dicarboxylic acid with a diol component, or transesterifying a dicarboxylic acid alkyl ester with a diol component to obtain a hydroxy ester and/or Its oligomer, followed by a method of polymerizing it under high vacuum.

For example, the embodiment of Patent Document 1 discloses a method by using dimethyl phthalate (DMT), 1,4-butanediol (BD), tetrahydrofuran (THF), and ethylene oxide (EO). A polyester elastomer is produced by performing a transesterification reaction in the presence of a random copolymer, IRGANOX, and dibutyl titanate (TBT), followed by polymerization.

Further, Patent Documents 2 and 3 disclose a method of performing a transesterification reaction in the presence of DMT, PTMG, BD, IRGANOX, and TBT. Next, a polymerization reaction is carried out to produce a polyester elastomer. Patent Document 4 discloses a method of producing a polyester elastomer by performing a transesterification reaction in the presence of decanoic acid (TPA), PTMG, BD, IRGANOX, and TBT, followed by a polymerization reaction.

Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

However, in the polyester elastomer produced by the above method, the appearance, heat resistance, and odor change of the polymer are considered to be due to a large amount of free acid, free diol, free dicarboxylic acid glycol ester, and the like remaining. Poor questions. In particular, when the polyester elastomer is used for a food container main body for a microwave oven or a laminate film for a food container, the flavor of the content is changed (the odor is deteriorated). Further, in the polyester elastomer produced by such a method, when a hydroxytetramethylene terminal group represented by the formula (1) is present, a large amount of a tetrahydrofuran which is caused by a ring-closing reaction of the terminal group upon heating and melting is generated in a large amount. (THF).

-O(CH ₂ ) ₄ OH formula (1)

Therefore, in a refining process of a compounding process or a forming process in which a polymerization process containing a polyester elastomer of the formula (1) or a molten polymer is fragmented, and a polyester process is given a new function, Oxidation of tetrahydrofuran produced by thermal decomposition causes environmental pollution such as odor.

In order to solve the above problems, the inventors have concentrated on the results of research and development. Now, a polyester elastomer obtained by using a dicarboxylic acid component, a glycerol component having a molecular weight of less than 250 mainly composed of 1,4-butanediol, and a polyol having a number average molecular weight of 400 to 70,000 The linear oligomer containing 0.01 to 5 wt% of an antioxidant, 2000 ppm or less of tetrahydrofuran, 50 ppm or less of a free dicarboxylic acid, 10 ppm or less of a free diol, and a molecular weight of 650 or less can improve odor and heat resistance. The present invention has been completed.

That is, the present invention is as follows, [1] a polyester elastomer composition characterized by a glycol component having a molecular weight of less than 250 mainly composed of a dicarboxylic acid component and 1,4-butanediol, and The polyester elastomer obtained by the polyol having a number average molecular weight of 400 to 70,000 contains 0.01 to 5 wt% of an antioxidant, 2000 ppm or less of tetrahydrofuran, 50 ppm or less of a free dicarboxylic acid, 10 ppm or less of a free diol, and a molecular weight of The linear oligomer of 650 or less is 300 ppm or less.

[2] The polyester elastomer composition according to [1], wherein the free dicarboxylic acid is 15 ppm or less, the free diol is 2 ppm or less, and the linear oligomer having a molecular weight of 650 or less is 200 ppm or less.

[3] A method for producing a polyester elastomer composition, which comprises the polyester elastomer composition of [1] or [2], which comprises using a carboxylic acid component and 1,4-butanediol as The glycol component having a molecular weight of less than 250 and a polyol having a number average molecular weight of 400 to 70,000 are used as a raw material to melt-polymerize the polyester elastomer, and at least one of the late stage of the polymerization reaction and the completion of the polymerization reaction is added to 0.01~ 5 wt% antioxidant.

[4] A method for producing a polyester elastomer composition, which is a polyester elastomer composition of [2], which comprises a dicarboxylic acid component and mainly 1,4-butanediol. A glycol component having a molecular weight of less than 250 and a polyol having a number average molecular weight of 400 to 70,000 as a raw material, and a polyester elastomer having a comparative viscosity of 0.2 dl/g or more is transferred to a thin film evaporator or a lateral type. The biaxial reaction tank is further subjected to polymerization at 230 to 255 ° C and 2 hPa or less, and 0.01 to 5 wt % of an antioxidant is added at least one of the late stage of the polymerization reaction and the completion of the polymerization reaction.

[5] The method for producing a polyester elastomer composition according to [4], which is transferred to a thin film evaporator or a horizontal biaxial reaction tank for reaction, and then transferred to a twin screw extruder and added with an antioxidant.

[6] The method for producing a polyester elastomer composition according to [4] or [5], which comprises heating and mixing a glycol component having a molecular weight of less than 250 mainly composed of a dicarboxylic acid component and 1,4-butanediol. A polyester having a number average molecular weight of 5,000 to 50,000 and a polyol having a number average molecular weight of 400 to 70,000 are obtained, and a polyester elastomer having a comparative viscosity of 0.2 dl/g or more is transferred to a thin film evaporator or a horizontal Type biaxial reaction tank.

[7] The method for producing a polyester elastomer composition according to any one of [3] to [6] wherein the antioxidant is one or more selected from the group consisting of a hindered phenol system, a sulfur system, and a phosphorus system.

[8] The method for producing a polyester elastomer composition according to [6] or [7], wherein the polyester is selected from the group consisting of polybutylene terephthalate, polybutylene naphthalate, and polybutylene adipate. At least one type of the ester is selected from the group consisting of at least one selected from the group consisting of polytetramethylene glycol, polycarbonate diol, polypropylene glycol, and polyethylene glycol.

[9] A fibrous material characterized by extrusion molding the polyester elastomer composition of [1] or [2].

[10] A sheet characterized by comprising the polyester elastomer of [1] or [2] The object is formed by extrusion molding.

[11] A molded body characterized by comprising the polyester elastomer composition of [1] or [2].

[12] A stretched film characterized by stretching a sheet of [10] in at least one direction.

The polyester elastomer of the present invention is excellent in odor and heat resistance, and can be suitably used as a raw material of a fiber, a molded article, a sheet, and a stretched film which are required to be strict.

Moreover, when the polyester elastomer composition is produced by the present production method and contains a compound having a hydroxytetramethylene terminal group of tetrahydrofuran which is generated, the content of tetrahydrofuran can be lowered to suppress environmental pollution or deterioration of polymer quality. Further, since the content of the free acid, the free diol, and the low molecular weight oligomer is small, the polymer is excellent in appearance, heat resistance, and odor.

Best form for implementing the invention

According to the invention, the upper limit of the content of tetrahydrofuran is 2,000 ppm or less in the polyester elastomer composition. The content is the mass of tetrahydrofuran relative to the mass of the polyester elastomer composition.

The content of tetrahydrofuran is preferably 1800 ppm or less, more preferably 1500 ppm or less, and most preferably 1000 ppm or less.

When the tetrahydrofuran is more than 2,000 ppm, the flavor or flavor of the contents of the container obtained from the polyester elastomer composition tends to be extremely poor.

The polyester elastomer composition of the present invention must be added with an antioxidant at least one of the late stage of the polymerization reaction and immediately after the completion of the polymerization reaction for the tetrahydrogen The content of furan is maintained below 2000 ppm. It is considered that, in general, the function of trapping free radicals which disappears in the polymerization reaction when added before the polymerization reaction does not disappear, and contributes to the thermal stability of the terminal group of the tetrahydrofuran, and contributes to Inhibition of the closed loop reaction.

The term "polymerization" as used herein refers to a state in which the viscosity is 0.01 to 0.50 dl/g lower than the specified comparative viscosity.

The lower limit of the content of tetrahydrofuran is preferably 0, but in order to be less than 40 ppm (particularly less than 100 ppm when PTMG is used as the polyol), it is necessary to set the production conditions at the expense of productivity, which is not preferable.

In the present invention, the free dicarboxylic acid and the free diol in the polyester elastomer composition are each the same compound as the dicarboxylic acid component constituting the polyester elastomer and the glycol component having a molecular weight of less than 250. Further, the linear oligomer having a molecular weight of 650 or less is a linear oligomer in which a dicarboxylic acid molecule of a polyester elastomer and a glycol component having a molecular weight of less than 250 are bonded.

According to the present invention, the upper limit of the content of the free low molecular compound is 50 ppm or less of the free dicarboxylic acid in the polyester elastomer composition, the free diol is 10 ppm or less, and the linear oligomer having a molecular weight of 650 or less is 300 ppm or less. . These contents are the mass of each component relative to the content of the polyester elastomer composition.

The content of the free dicarboxylic acid is preferably 20 ppm or less, more preferably 15 ppm or less, most preferably 10 ppm or less, and the content of the free diol is preferably 7 ppm or less, more preferably 2 ppm or less, and 1 ppm or less. The content of the linear oligomer having a molecular weight of 650 or less is preferably 250 ppm or less, more preferably 200 ppm or less, and most preferably 170 ppm or less.

The content of free dicarboxylic acid is more than 50 ppm, and the free diol is less than When the content of the linear oligomer having a molecular weight of 650 or less is more than 300 ppm, the flavor or flavor of the content of the container or the like obtained from the polyester elastomer composition tends to be extremely poor, and the heat resistance is lowered. Propensity.

When the content of the free dicarboxylic acid is less than 15 ppm, the free diol is less than 2 ppm, and the content of the linear oligomer having a molecular weight of 650 or less is 200 ppm or less, the flavor or flavor of the content of the container or the like obtained from the polyester elastomer composition can be It is maintained for a long period of time and heat resistance is improved.

In order to make the content of the free dicarboxylic acid of the polyester elastomer composition of the present invention 50 ppm or less, the content of the free diol is 10 ppm or less, and the content of the linear oligomer having a molecular weight of 650 or less is 300 ppm, at the end of the polymerization reaction and At least one of the polymerization reaction is completed, and an antioxidant must be added. It is considered that the function of trapping the radicals by the antioxidant which is usually lost in the polymerization reaction when it is added before the polymerization reaction does not disappear, and contributes to the thermal stability of the polymer.

In order to make the content of the free dicarboxylic acid of the polyester elastomer composition of the present invention 15 ppm or less, the content of the free diol is 2 ppm or less, and the content of the linear oligomer having a molecular weight of 650 or less is 200 ppm, and it is necessary to (1) At least one of the late stage of the polymerization reaction and the completion of the polymerization reaction, an antioxidant is added, and (2) the glycol component having a molecular weight of less than 250 mainly composed of a dicarboxylic acid component and 1,4-butanediol is heated and mixed. A polyester having a number average molecular weight of 5,000 to 50,000 and a polyol having a number average molecular weight of 400 to 70,000 are obtained, and a polyester elastomer having a comparative viscosity of 0.2 dl/g or more is transferred to a thin film evaporator or a horizontal type. The biaxial reaction tank must be further polymerized at 230 to 255 ° C and below 2 hPa.

Here, the number average molecular weight is 5,000 to 50,000 when heated and mixed. The ester will partially depolymerize while being dissolved and react with the polyol.

When a dicarboxylic acid component or a glycol component having a molecular weight of less than 250 is used as a raw material in the prior DMT method or the TPA method, in order to increase the reaction rate or process stability, it is necessary to excessively add a glycol having a molecular weight of less than 250, resulting in The reactants remain and the frees become more. On the other hand, by carrying out the above (1), since the function of trapping the radicals by the antioxidant which is usually lost in the polymerization reaction when it is added before the polymerization reaction can be maintained, the heat of the polymer when taken out from the reaction tank is maintained. The decomposition is reduced, and the formation of a free dicarboxylic acid, a free diol, and a linear oligomer having a molecular weight of 650 or less can be suppressed. Further, by carrying out the above (2), it is not necessary to excessively add a glycol having a molecular weight of less than 250, and even if a glycol having a molecular weight of less than 250 is added to adjust the reaction rate, the amount of addition is small, so that the amount of free matter is small. Further, since the polymerization reaction is carried out using a thin film evaporator having a high surface renewability or a horizontal biaxial reaction tank, the reaction time can be shortened, and the free dicarboxylic acid, the free diol and the molecular weight of 650 or less which are caused by thermal decomposition can be suppressed. Formation of linear oligomers.

In addition, when the above (2) is carried out, it is possible to suppress the formation of a free dicarboxylic acid, a free diol, and a linear oligomer having a molecular weight of 650 or less due to thermal decomposition during heating and mixing or during polymerization, and to add an anti-advance in advance. An oxidizing agent is preferred.

The lower limit of the content of the free dicarboxylic acid, the free diol, and the linear oligomer having a molecular weight of 650 or less is preferably 0, and the free dicarboxylic acid is less than 3 ppm, the free diol is less than 0.6 ppm, and the molecular weight is 650. The following linear oligomers are less than 120 ppm, and manufacturing conditions must be sacrificed at the expense of productivity, which is not preferable.

Examples of the dicarboxylic acid which can be used in the present invention include oxalic acid, adipic acid, and hydrazine. Diacid, sebacic acid, dodecanedione acid, sebacic acid, succinic acid, glutaric acid, dodecanedioic acid, dimer acid, hydrogenated dimer acid, malonic acid, glutaric acid, ring Hexanedicarboxylic acid, p-citric acid, isophthalic acid, citric acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, stilbene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane dicarboxylic acid, 5-sodium sulfonate isophthalic acid and 5-tetrabutyl a dicarboxylic acid such as phosphoisophthalic acid or the like, and the like, and adipic acid, p-citric acid, naphthalene dicarboxylic acid, and the like, preferably an aromatic dicarboxylic acid. It is especially good for citric acid and dimethyl phthalate. Further, these may be used alone or in combination of two or more.

The component other than the aromatic dicarboxylic acid is preferably less than 50 mol%, more preferably less than 40 mol%, most preferably less than 30 mol%, and more than 50 mol%, the crystallinity of the polyester elastomer is There is a tendency to decrease, and the formability and heat resistance tend to be lowered.

Examples of the glycol component having a molecular weight of less than 250 include ethylene glycol, 1,3-propanediol, 1,4-butanediol, heptanediol, hexanediol, octanediol, decanediol, decanediol, and 1 , 4-cyclohexanedimethanol, neopentyl glycol, glycol, pentaerythritol, EO adduct of bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol F and TCD glycol For the compound or the like, one or more of these may be used. When the molecular weight is more than 250, the crystallinity is lowered and the formability heat resistance tends to be lowered. Among the above glycols, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferred, and 1,4-butanediol is particularly preferred. When 1,4-butanediol is mainly used, it is preferably 60 mol% or more of 1,4-butanediol, more preferably 70 mol% or more, and most preferably 80 mol% or more. When the amount is less than 60% by mole, the crystallinity is lowered and the heat resistance of the moldability tends to be lowered.

Also, it may contain glycolic acid, lactic acid, hydroxypropionic acid, hydroxyvaleric acid, A hydroxycarboxylic acid such as hydroxycaproic acid, hydroxybutyric acid or hydroxybenzoic acid is used as a copolymerization component.

The carboxylic acid can also be imparted without departing from the scope of the invention. The method of introducing a carboxyl group may be, for example, adding 1,2,4-benzenetricarboxylic anhydride, phthalic anhydride, pyrogallic anhydride, succinic anhydride, 1,8-naphthalene dicarboxylic acid, 1, after polymerizing the polyester elastomer. The acid value is added after 2-cyclohexanedicarboxylic anhydride or the like, and the modified polyester may be a chain extending method using dimethylolpropionic acid or dimethylolbutanoic acid. Further, examples thereof include 1,2,4-benzenetricarboxylic acid and pyrogolite, and examples of the glycol component include glycerin and neopentyl glycol. The amount of the above copolymerized component used is such that the polyester elastomer must substantially maintain a linear shape.

Examples of the polyhydric alcohol include polyethylene glycol, polypropylene glycol, polybutanediol, polyhexamethylene glycol, a copolymer of ethylene oxide and tetrahydrofuran, an addition polymer of ethylene oxide of polypropylene glycol, and polycarbonate. Ester diol, poly neopentyl glycol, poly 3-methyl pentane diol, poly 1,5-pentanediol, bis-A ethylene oxide adduct, double A propylene oxide adduct, double S ring Examples of the oxyethylene adduct and the like and the derivative thereof include, for example, a copolymer of polyneopentyl glycol and polyethylene glycol, among which polybutanediol, polycarbonate diol, and polypropylene glycol are polymerized. It is better.

The number average molecular weight of the polyol is from 400 to 70,000, preferably from 600 to 60,000, and particularly preferably from 1,000 to 50,000. When the number average molecular weight is 400 or more, heat resistance, elastic properties, and moldability are excellent, and when the number average molecular weight is 70,000 or less, phase separation at the time of polymerization can be lowered, and reactivity can be improved. When the polyol is a polytetramethylene glycol, the upper limit of the number average molecular weight is preferably 10,000, more preferably 4,000, and still more preferably 2,000.

In the polycarbonate diol of the present invention, an aliphatic polycarbonate diol is used. The method of adjusting the molecular weight is not particularly limited. For example, since the molecular weight of the commercially available aliphatic polycarbonate diol is lower than the preferred molecular weight range of the present invention, a commercially available low molecular weight aliphatic polycarbonate is previously used with a chain extender. It is preferred that the ester diol is polymerized to adjust the molecular weight. In other words, it is preferred to adjust the molecular weight of the aliphatic polycarbonate diol in a preferred range by using a chain extender in advance, and then supply the mixture to a block reaction.

The method of using the commercially available low molecular weight product described above is capable of producing an aliphatic polycarbonate diol of any molecular weight, and the production can be carried out on a device using the manufacturing apparatus of the thermoplastic polyester elastomer of the present invention, which is economical. The effect is great. Further, the above method has a simple method of changing the ratio of the chain extender to the aliphatic polycarbonate diol, and a commercially available low molecular weight aliphatic polycarbonate diol can be used to correspond to any desired molecular weight. advantage.

When the chain extender contains two or more active compounds having a functional group capable of reacting with a terminal hydroxyl group of an aliphatic polycarbonate diol in one molecule, it is not particularly limited, and when the number of functional groups is two or more It is not particularly limited, and a 2-functional group is preferred. Examples thereof include diphenyl carbonate, diisocyanate, and an acid anhydride of a dicarboxylic acid. A trifunctional or higher polyfunctional compound can also be used in a small amount. Instead of diphenyl carbonate, a carbonate compound such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate or dimethyl carbonate may also be used. Further, it may be a cyclic carbonate or a dithiocarbonate compound such as ethylene carbonate. Further, a carbonyl compound of a phenoxy group of diphenyl carbonate may be used instead of a nitrogen-containing compound residue such as imidazole or indoleamine.

In the above method, the low molecular weight aliphatic polycarbonate diol before the high molecular weight is preferably a commercially available product, but is not limited. For example, when a special copolymer is necessary, the aliphatic polycarbonate diol can be used in particular.

In the present invention, the method of introducing the above-mentioned active terminal group is not limited, and a method of adjusting the molecular weight of the aliphatic polycarbonate diol by using the above chain extender is to add the chain extender residue at the end. Modulation is better.

The preparation method is not limited, and after adjusting to a molecular weight lower than a desired molecular weight, the reaction is carried out under milder conditions than when a predetermined amount of chain extender is added to adjust the molecular weight, thereby causing the chain extender and the aliphatic polycarbonate. A method in which a terminal group of an ester diol is reacted and introduced. For example, the reaction is preferably carried out at 100 to 200 ° C under normal pressure or under pressure. Further, it is also possible to carry out the simultaneous introduction of the active terminal group at the time of adjusting the molecular weight by optimizing the feed ratio of the chain extender or the reaction conditions.

In the above method, the molecular weight of the obtained aliphatic polycarbonate diol is adjusted or introduced into the active terminal group, and the molecular weight of the aliphatic polycarbonate diol of the starting material and the aliphatic polycarbonate diol can be changed. The feed ratio of the chain extender is carried out. Also, it can be adjusted by the reaction time. The molecular weight of the obtained aliphatic polycarbonate diol is such that the higher the molecular weight of the starting material, and the higher the feed ratio of the chain extender, the higher the ratio. It can be appropriately set in accordance with the target molecular weight.

According to the reaction method in the above-mentioned method, if the aliphatic polycarbonate diol having a molecular weight lower than the final molecular weight is mixed with the chain extender in the reactor, the reaction conditions such as the reaction temperature, the reaction time, and the stirring conditions are not limited, for example, It is recommended to divide this molecular weight adjustment into more than two stages. The method to carry out the stage. That is, after reacting for a predetermined amount of the feed ratio for a predetermined period of time, the molecular weight of the obtained aliphatic polycarbonate diol is measured, and if the molecular weight is lower than the target molecular weight, the chain extender is additionally added, and conversely, if the molecular weight is too large When it is high, it is preferable to adjust the molecular weight by further adding an aliphatic polycarbonate diol which is a raw material, and further carrying out a reaction. By repeating this method, the adjustment accuracy of the molecular weight or the concentration of the active terminal groups can be improved.

The polyester composed of a dicarboxylic acid component and a glycol component having a molecular weight of less than 250 may, for example, be polyethylene terephthalate, polybutylene terephthalate, propylene terephthalate or polypair. Cyclodecyl dimethylene phthalate, polyisophthalic acid ethylene glycol ester, polyisophthalic acid butyl diester, polyisophthalic acid propylene glycol ester, polyethylene naphthalate, polyethylene naphthalate, Polypropylene naphthalate and other copolymers, preferably polybutylene terephthalate, polybutylene naphthalate, polyethylene adipate and polybutylene adipate, It is especially good for butylene phthalate.

The dicarboxylic acid component used in the present invention and a polyester having a number average molecular weight of 5,000 to 50,000 obtained by using a glycerol component having a molecular weight of less than 250 as a main component of 1,4-butanediol, and a polyester having the above-mentioned respective polyesters can be used. Commercial products.

As the polyester obtained from the dicarboxylic acid component and the glycol component having a molecular weight of less than 250, a recycled container or a polyester of industrial waste can be used, and a copolymer polyester can also be used.

Examples of the catalyst used in the polymerization reaction include metals such as tin, zinc, lead, titanium, lanthanum, zirconium, hafnium, tantalum, and aluminum, and derivatives thereof. The derivatives are preferably metal alkoxides, carboxylates, carbonates, oxides and halides. Specific examples thereof include tin chloride, tin octylate, zinc chloride, zinc acetate, lead oxide, lead carbonate, titanium chloride, titanium alkoxide, cerium oxide, and zirconium oxide. Among these, a titanium compound, a ruthenium compound, an aluminum compound, and a ruthenium compound are preferable, and a titanium compound is more preferable.

Specific examples of the titanium compound include tetraalkyl titanate such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, and n-tetrabutyl titanate, and partial hydrolyzates thereof, titanium acetate. , titanium oxalate, titanyl oxalate, sodium oxytitanate, potassium oxytitanate, calcium oxalate oxalate and oxytitanium oxalate, titanium oxalate, titanium 1,2,4-benzenetricarboxylate, titanium sulfate, Hydrogen chloride, titanium halide hydrolysate, titanium bromide, titanium fluoride, potassium hexafluorophosphate, ammonium hexafluorophosphate, cobalt hexafluoride, manganese hexafluorophosphate, acetonitrile Titanium, a composite oxide composed of titanium and cerium or zirconium, a reaction product of a titanium alkoxide and a phosphorus compound, and the like.

The ruthenium compound is preferably a solution obtained by using amorphous cerium oxide, crystalline cerium oxide, or dissolving crystalline cerium oxide in glycol.

Specific examples of the aluminum compound include aluminum formate, aluminum acetate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, and lemon. a mineral acid salt such as aluminophosphate or aluminum sulphate, aluminum chloride, aluminum hydroxide, aluminum chloride hydroxide, polyaluminum chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate, aluminum phosphonate, etc., methanol Aluminum, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum alkoxide such as aluminum butoxide, aluminum acetonitrile, aluminum acetate, aluminum ethyl acetoacetate, ethyl ethyl An aluminum alloy compound such as acetonitrile acetate aluminum diisopropoxide, an organoaluminum compound such as trimethyl aluminum or triethyl aluminum, or a partial hydrolyzate or alumina. Among these, a carboxylate, a mineral acid salt, and a chelating compound are preferred, and among these, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide, and aluminum acetonate are used. It is especially good.

Further, in the method for producing the polyester elastomer of the present invention, an alkali metal compound or an alkaline earth metal compound may be used in combination. The alkali metal or alkaline earth metal is preferably at least one selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba, and more preferably an alkali metal or a compound thereof. When an alkali metal or a compound thereof is used, it is particularly preferable to use Li, Na, and K. Examples of the alkali metal compound or the alkaline earth metal compound include saturated aliphatic carboxylic acid salts such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated aliphatic carboxylic acids such as acrylic acid and methacrylic acid. An aromatic carboxylate such as a salt or a benzoic acid, a carboxylate containing a halogen such as trichloroacetic acid, a hydroxycarboxylic acid salt such as lactic acid, citric acid or salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid or hydrogencarbonate. , inorganic sulphate of hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrogen bromide, hydrochloric acid, bromic acid, etc., organic sulfonate such as 1-propanesulfonic acid, 1-pentanesulfonic acid, naphthalenesulfonic acid, etc. An acid salt of an acid salt, a lauryl sulfate or the like, an alkoxide such as a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group or a third butoxy group, and an acetone A compound such as a salt, a hydride, an oxide, a hydroxide, or the like is clamped.

The polycondensation catalyst of the present invention can also be used in combination with a phosphorus compound.

The compound which can be used in combination with a catalyst is at least one phosphorus selected from the group consisting of a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphinic acid compound, a phosphinic acid compound, and a phosphine compound. The compound is preferred. When the polyester elastomer composition is polymerized, by using these phosphorus compounds, the effect of enhancing the activity of the catalyst and the effect of improving the thermal stability of the polyester can be observed. Among these, it is preferred to use a phosphonic acid compound to enhance the activity of the catalyst and to enhance the thermal stability of the polyester. Among the above phosphorus compounds, when a compound having an aromatic ring structure is used, the catalyst is active. The effect of improving the properties and the thermal stability of the polyester elastomer are improved, which is preferable.

Examples of the cerium compound include antimony trioxide, cerium acetate, cerium tartrate, cerium potassium tartrate, cerium trichloride, cerium glycolate, cerium pentoxide, and triphenyl sulfonium.

The reactor used in the melt polymerization of the polyester elastomer used in the present invention can be a well-known reactor, and can be a batch type or a continuous type, and a vertical reaction tank, an spectacles-like horizontal reaction tank, and a lattice wing can be used. Horizontal reaction tank, thin film evaporation reaction tank, stirred reaction tank, tower type reaction tank, short shaft extruder and twin shaft extruder reaction tank. In either of these modes, the melt polycondensation reaction can be carried out in one stage or in multiple stages. In order to increase the contrast viscosity, solid phase polymerization can also be carried out, and the solid phase polymerization reaction is carried out in the same manner as the melt polycondensation reaction, and can be carried out using a batch type apparatus or a continuous apparatus. The melt polycondensation and solid phase polymerization can be carried out continuously or divided.

The polymerization reaction is carried out under reduced pressure to 2 hPa or less, and it is preferred to adjust the polyester elastomer to have a viscosity of 0.2 dl/g or more before transferring to the reaction tank. When it is less than 0.2 dl/g, since the melt viscosity is too low, bumping occurs, and the low-viscosity planthopper is accumulated in the upper portion of the tank or the pressure-reducing pipe, which may cause clogging of the pollution or the pressure-reducing line.

The antioxidant can be added to one or more types of well-known hindered phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

Further, in order to reduce the content of tetrahydrofuran, one or more of the above stabilizers may be added before the polymerization reaction as a thermal stabilizer in the polymerization reaction.

The antioxidant is added in an amount of 0.01 to 5 wt%, preferably 0.05 to 3 wt%, more preferably 0.1 to 2 wt%, based on 100 wt% of the polyester elastomer. add When the amount is 0.01% or more, not only odor, heat resistance or hydrolysis resistance, but also the mechanical strength of the polymer is improved. When the amount of addition is 5% by weight or less, an effect commensurate with an increase in the amount of addition cannot be obtained. The content of the antioxidant in the polyester elastomer composition is also the same as the above-mentioned addition amount.

Further, it is possible to add a known light stabilizer such as a hindered amine-based, triazole-based, diphenylketone-based, benzoic acid-based, nickel-based, or citric acid-based, antistatic agent, a lubricant, a peroxide, or the like. Molecular modifiers, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent whitening agents, fillers, flame retardants, and flame retardant auxiliaries.

Hindered Phenolic Antioxidant The hindered phenol antioxidant in the present invention may, for example, be 3,5-di-t-butyl-4-hydroxy-toluene or n-octadecyl-β-(4'-hydroxy-3'. 5'-di-t-butylphenyl)propionate, neopentyl pentoxide [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], sulphur diene Ethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecylbis[3-(3,5-di-t-butyl-4- Hydroxyphenyl)propionate, hydrazine [methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, 1,3,5-three Methyl-2,4,6'-paraxyl (3,5-di-t-butyl-4-hydroxybenzyl)benzene, (3,5-di-t-butyl-4-hydroxy-benzyl- Monoethyl-phosphoric acid) calcium, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-bis[1,1 -Dimethyl-2-{ β- (3-tert-butyl-4-hydroxy-5-methylphenyl)propenyloxy}ethyl]2,4,8,10-tetraoxaspiro[ 5,5]undecane, bis[3,3-bis(4'-hydroxy-3'-tert-butylphenyl)butyric acid] glycolate, tocopherol, 2,2'-Asia Bis(4,6-di-tert-butylphenol), N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propylamine), 1,3,5-bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl phosphite, hydrazine (2,4-di- Tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphinate, bis(2,4-di-t-butylphenyl)neopentanol Phosphite, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene, 2,2'-oxalylamine bis[ethyl -3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,1,3-parade (2-methyl-4-hydroxy-5-t-butylbenzene) Butane, 1,3,5-gin (3',5'-di-t-butyl-4'-hydroxybenzyl)-S-three -2,4,6(1H,3H,5H)-trione, trimer isocyanate 1,3,5-gin (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl ) ester, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate and (with)-1,3,5-gino(2-hydroxyethyl)-S-three -2, 4, 6 (1H, 3H, 5H) and the like.

Sulfur-based antioxidants The sulfur-based antioxidants of the present invention include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and second hard. Lipidinyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, di-octadecyl sulfide, neopentyl alcohol-肆( β -lauryl-thiopropionate) and the like.

Phosphorus antioxidant Examples of the phosphorus-based antioxidants include ginseng (mixed, mono- and di-phenylene ether phenyl) phosphites, ginseng (2,3-di-tert-butylphenyl) phosphite, and 4,4'-butylene. Base-bis(3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-gin (2-methyl-4-di-tridecyl) Phosphite-5-t-butylphenyl)butane, bis(2,4-di-t-butylphenyl)neopentanol-di-phosphite, ruthenium (2,4-di- Tert-butylphenyl)-4,4'-extended biphenylphosphonate, bis(2,6-di-t-butyl-4-methylphenyl)neopentanol-di-phosphite Ester, 2,2'-ethylidene-bis(4,6-di-t-butylphenyl)-2-ethylhexyl-phosphite, bis(2,4,6-di-third Phenyl) pentaerythritol-di-phosphite, Triphenyl phosphite, diphenyl decyl phosphite, didecyl phenyl phosphite, tridecyl phosphite, trioctyl phosphite, tri-dodecyl phosphite, tri-octade phosphite An alkyl ester, tridecyl phosphite, tri-dodecyl trithiophosphate, and the like.

Hindered Amine Light Stabilizers The hindered amines of the present invention may include dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperididine ( Piperodine) polycondensate, poly[[6-(1,1,3,3-tetramethyl)imido-1,3,5-three -2,4-diyl]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imide]], 2-n-butylmalonic acid double (1,2 , 2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, sebacic acid bis(2,2,6,6-tetramethyl- Polycondensate of 4-piperidinyl)ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1,2-dibromoethane , poly[(N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine)-(4-sodium sulphate-1,3,5-three -2,6-diyl)-bis(3,3,5,5-tetramethylperidine Ketone), ginseng (2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl-1,2,3,4-butane tetracarboxylate, ginseng (1,2, 2,6,6-pentamethyl-4-piperidinyl)-dodecyl-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-five Methyl-4-piperidinyl) sebacate, 1,6,11-paran [{4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl) Piperidin-4-yl)amino-1,3,5-three -2-yl}amino]dodecane, 1-[2-[3-5-di-t-butyl-4-hydroxyphenyl)propenyloxy]-2,2,6,6-tetra Methylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triaziro[4,5]undecane-2,4-di Ketone, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(3-aminophenyl)ethylenediamine-2,4-bis[N -butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-three Condensate, etc.

In the third aspect of the invention Examples of the photostabilizer such as a diphenylketone, a benzoate, a nickel or a salicylic acid include 2,2'-dihydroxy-4-methoxydiphenyl ketone and 2-hydroxyl group. 4-n-octyloxydiphenyl ketone, p-tert-butylphenyl lysate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxyl Benzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-third-pentyl-phenyl) Benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5 '-Di-t-butylphenyl)-5-chlorobenzotriazole, 2,5-bis-[5'-tert-butylbenzo Azyl-(2)]-thiophene, [bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel salt, 2-ethoxy-5-t-butyl group -2'-ethyl oxalic acid-bis-indoleaniline 85~90% with 2-ethoxy-5-t-butyl-2'-ethyl-4'-tert-butyl oxalic acid-bis-hydrazine 10~15% mixture of aniline, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α- Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-ethoxy-2'-ethyloxalic acid-bisguanidine, 2-[2'-hydroxy-5'-methyl-3 '-(3",4",5",6"-tetrahydrofurfurimide-methyl)phenyl]benzotriazole, bis(5-benzylidene-4-hydroxy-2-methoxy Phenyl)methane, 2-(2'-hydroxy-5'-th-octylphenyl)benzotriazole, 2-hydroxy-4-isooctyloxydiphenyl ketone, 2-hydroxy-4- Dodecyloxydiphenyl ketone and 2-hydroxy-octadecyloxydiphenyl ketone and the like.

Antistatic agent Examples of the antistatic agent of the present invention include glycerin fatty acid (C8-C22) ester, sorbitan fatty acid (C8-C22) ester, propylene glycol fatty acid (C8-C22) ester, and sucrose fatty acid (C8-C22) ester. , citric acid one (two or three) stearate, neopentyl alcohol fatty acid (C8~C18) ester, trimethylolpropane fatty acid (C8~C18) ester, polyglycerol fatty acid (C8~C22) ester, poly Oxyethylene (20 mol) glycerol fatty acid (C12~C18) ester, polyoxyethylene (20 mol) sorbitol lipid Fatty acid (C12~C18) ester, polyethylene glycol fatty acid (C8~C22) ester, polyoxyethylene fatty alcohol (C12~C20) ether, polyoxyethylene (4~50 mol) alkyl (C4 or higher) benzene Ether, N,N-bis(2-hydroxyethyl) fat (C8~C18) amine, condensation product of fatty acid and diethanolamine, polyoxypropylene polyoxyethylene block polymer, polyethylene glycol, polypropylene glycol Nonionic surfactants; alkyl (C10 ~ C20) sulfonate (Na, K, NH4), alkyl naphthalene sulfonate (Na), dialkyl (C4 ~ C16) sodium succinate, Anionic surfactants such as alkyl (C8~C20) sulfate (Na, K, NH4), fatty acid (C8~C22) salts (Na, K, NH4); N-thiol (C8~C18) sarcosine An amphoteric surfactant such as an ester; other auxiliary agents such as polyacrylic acid and a sodium salt thereof.

Slide agent The slip agent which can be formulated in the resin composition of the present invention may, for example, be hexamethyleneamine, octylamine, stearylamine, decylamine, cis-docosa carbamide, ethyl bis-stearylamine a saturated or unsaturated aliphatic decylamine having a carbon number of 3 to 30, such as laurylamine, behenylamine, methylenebisstearylamine or ricinoleamine; and a derivative thereof; a saturated or unsaturated aliphatic ester having a carbon number of 3 to 30, such as an ester or isobutyl stearate, and a derivative thereof; a commercially available antimony compound such as an antimony release agent such as eucalyptus oil or silicone; a commercially available fluorine-based mold release A fluorine-based compound such as a tetrafluoroethylene or the like.

Metal passivator The metal deactivator which can be formulated in the resin composition of the present invention is exemplified by 3-N'-cannonylamino-1,2,4-triazole, salicylaldehyde, salicylate, N,N'-bis-[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene, oxalyl-bis[benzylidene fluorene], 9,10-dihydro-9-oxygen Hetero-10-phosphaphenanthrene-10-oxide, 3,4,5,6-dibenzo-1,2-oxaindole-2-oxide, ginseng [2-t-butyl 4-Sulphur (2'-methyl-4'-hydroxy-5-t-butyl)phenyl-5-methyl]phenylphosphite, 2,2'-oxalylamine-bis-[B Base-3 (3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like.

Nuclear agent The nucleating agent which can be formulated in the resin composition of the present invention may, for example, be 1,3,2,4-di-benzylidene-sorbitol or 1,3,2,4-di-di-(p-methyl) - bis-benzylidene) sorbitol, 1,3,2,4-di-(p-ethyl-benzylidene) sorbitol, 1,3,2,4-di-(2',4' - bis-methyl-benzylidene) sorbitol, 1,3-p-chloro-benzylidene-2,4-p-methyl-benzylidene-sorbitol, 1,3,2,4-di -(p-propyl-benzylidene) sorbitol, monohydroxy-di-p-butyl butyl benzoate, sodium bis(4-t-butylphenyl)phosphate, 2,2'-methylene - bis-(4,6-di-tert-butyl-phenyl)phosphate, talc, sodium benzoate and 2,2'-methylene-bis-(4,6-di-t-butylphenyl) Lithium phosphate and the like.

Neutralizer and antacid Examples of the neutralizing agent and the antacid which can be formulated in the resin composition of the present invention include lithium stearate, 1,2-hydroxylithium stearate, sodium stearate, sodium stearate, and potassium stearate. Lithium citrate, lithium octadecanoate, sodium citrate, sodium octadecanoate, calcium sulphate, calcium citrate, calcium octadecanoate, cadmium lactate, cadmium laurate, ricinole Cadmium acid, barium naphthenate, barium 2-ethylhexanoate, barium stearate, barium 2-ethylhexanoate, calcium stearate, calcium laurate, calcium ricinoleate, barium stearate , zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexanoate, zinc stearate, lead dibasic stearate, lead naphthenate, tin stearate, stearic acid Higher fatty acids such as aluminum and magnesium stearate, alkyl lactic acid or alkaline earth metal salts; basic magnesium-aluminum-hydroxy-carbonate-hydrotaleite, basic zeolite, epichlorohydrin and bisphenol A polymer Class, ring Oxidized soybean oils, epoxidized fatified monoesters, epoxidized lipid cyclic fatty acids, polycarbodiimides, and isocyanate compounds.

filler The filler which can be formulated in the resin composition of the present invention may, for example, be magnesium oxide, aluminum oxide, cerium oxide, calcium oxide, titanium oxide, chromium oxide (trivalent), iron oxide, zinc oxide, cerium oxide or diatomaceous earth. , oxides of alumina fiber, cerium oxide, cerium ferrite, cerium ferrite, cerium oxide, pumice, pumice balloon, etc.; alkali or hydroxide of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, etc. Carbonate of magnesium carbonate, calcium carbonate, barium sulfate, ammonium sulfate, calcium sulfite, dolomite, Dawsonite, etc.; calcium sulfate, barium sulfate, ammonium thiocyanate, calcium sulfite, basic sulfuric acid (Sub)sulfate such as magnesium; sodium citrate, magnesium citrate, aluminum citrate, potassium citrate, calcium citrate, talc, clay, mica, asbestos, fiberglass, montmorillonite, glass balloons, glass beads, Citrate such as bentonite; kaolin (ceramic), bead iron, iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, boron fiber, tantalum carbide fiber, brass fiber, potassium titanate, zirconium titanate Lead acid, zinc borate, aluminum borate, metaboric acid, calcium borate and sodium borate.

Flame retardant The flame retardant of the present invention is not limited, and examples thereof include a halogen-based type, and a non-halogen-based polyphosphoric acid or metal hydroxide system.

Specifically, the antimony compound is exemplified by antimony trioxide, antimony tetroxide, and antimony pentoxide.

Halogen is a bromine-based flame retardant or a chlorine-based flame retardant. Specific examples of the bromine-based flame retardant include decabromodiphenyl ether, hexabromobenzene, hexabromocyclododecane, and tetrabromobisphenol. A, tetrabromobisphenol A-tetrabromobisphenol A-diepoxypropyl ether copolymerization Things. Specific representative examples of the chlorine-based flame retardant include chlorinated paraffin and perchlorocyclodecane.

Specific examples of the polyphosphoric acid system include ammonium polyphosphate and melamine polyphosphate.

Examples of the metal hydroxide system (also referred to as a metal hydrate) include magnesium hydroxide and aluminum hydroxide.

The polyester elastomer thus obtained has less free matter, does not impair odor, heat resistance, and has a small amount of by-produced tetrahydrofuran, as compared with the polymer obtained by the conventional transesterification polymerization method or the esterification polymerization method. Moreover, the productivity is better when compared with the previous transesterification polymerization method and the esterification polymerization method, and it is advantageous in terms of production cost.

The polyester elastomer produced by the present invention can be used in various applications such as fibers, films, sheets, electric and electronic components, automobile components, and home electric appliances, as a monomer or a resin composition.

Example

Hereinafter, the present invention will be specifically described by way of examples.

(1) Contrast viscosity 0.05 g of the sample was dissolved in 25 ml of a mixed solvent (phenol/tetrachloroethane = 60/40), and measured at 30 ° C using an Oswald viscometer.

(2) Determination of thermal characteristics The thermal properties of the obtained polyester elastomer were DSC manufactured by TA Instruments, and the amount of the sample was 10 mg. The temperature conditions under nitrogen atmosphere were appropriately set in accordance with the obtained polyester elastomer. The temperature rise and the temperature drop rate conditions were raised from room temperature to 250 ° C or less at 20 ° C /min, cooled to room temperature at 20 ° C / min, and repeated twice, and the melting point (Tm) obtained at the second temperature rise was repeated. As a result of the measurement.

(3) Free matter content, linear oligomer content The sample was dissolved in a solvent (hexafluoroisopropanol / chloroform = 2 / 3 (v / v)) 3 ml of a mixture, and diluted with 20 ml of chloroform. After adding 10 ml of methanol and allowing the polymer to precipitate, it was filtered. The filtrate was evaporated to dryness and redissolved using 10 mL of dimethylformamide. The centrifugally filtered solution was supplied to a liquid chromatography mass spectrometer (LC-MS) to quantify each component. The measurement conditions are as follows.

[LC condition] Apparatus: Agilent 1100 column: Imtakt Cadenza CD-C18 2 x 150 mm mobile phase: A 0.1% formic acid, B acetonitrile 0 min (10% B) -40 (98) - 60 (98) Flow rate: 0.2 ml / min column temperature : 40 ° C implantation volume: 5 μl detection wavelength: 258 nm

[MS condition] Device: BRUKER DALTONICS esquire 3000 Plus ionization method: ESI (positive)

(4) Heat resistance The polymer was melted in an air atmosphere at 250 ° C for 5 minutes, and was carried out by a method of color difference before and after visual melting.

○: Almost uncolored △: slightly yellow colored, or gray ×: marked yellow coloring

(5) Functional test (odor) A YAMATO Scientific Vacuum Dryer Model DP61 was used and a dry inert gas (nitrogen) was blown in a forming material hopper using a polyester elastomer chip which was dried under reduced pressure in advance to prevent moisture absorption of the chips during forming.

The plasticizing conditions of the M-150C (DM) injection molding machine are the feed screw rotation number = 70%, the screw rotation number = 120 rpm, the back pressure is 0.5 MPa, and the cylinder temperature is set to 45 ° C, 240 from the bottom of the hopper. °C, the following nozzle is 245 ° C, forming a stage forming plate and cutting a 3 mm plate, placing it in ion-exchanged water at 70 ° C for 30 minutes, cooling to room temperature and leaving it for 1 month, then flavoring, stinky Tests such as taste. Ion exchange water was used for comparison with the blank test system. The functional test was carried out by 10 participants, according to the following criteria, and compared by the average value.

0: No odor or odor was felt. 1: The feeling is slightly different from the blank test. 2: The feeling is different from the blank test. 3: The feeling is quite different from the blank test. 4: There is a big difference between the feeling and the blank test.

(6) Measurement and Calculation Method of Tetrahydrofuran Content 20 g of the cast pieces were placed in a container which can be sealed, and the pressure was replaced with nitrogen gas three times, and then sealed under a nitrogen atmosphere. After holding the sealed container in an oil bath set at 245 ° C for 30 minutes, a piece of molten resin (long diameter of 3 to 5 mm, short diameter of 2 to 4 mm, height of 2 to 4 mm, and grain weight of 20 ~) was selected. 30 mg / piece). After selecting 5 g of the chips, the sample was placed in a sample bottle within 10 minutes and 50 g of pure water was added, and the lid was closed without voids in the sample bottle and sealed in such a manner that tetrahydrofuran did not volatilize. Since it takes time to measure from the measurement of the fragments to the closing of the sample vial, the tetrahydrofuran will volatilize from the chips and will not be analyzed correctly. Next, the sealed sample bottle was placed in a warm air dryer at 50 ° C for 24 hours or more, and tetrahydrofuran in the polyester elastomer was extracted in pure water. The concentration of extracted tetrahydrofuran is determined by adding 20 μl of 1,4-two to 1 ml of the extract. An alkane standard stock solution of 5180 μg/ml was injected into a gas chromatograph (6850 Series II manufactured by Agilent). The tetrahydrofuran content was multiplied by 10 times to calculate the tetrahydrofuran content in the polyester elastomer.

Hereinafter, the present invention will be described in detail by way of examples. However, the invention is not limited to the following examples unless the gist of the invention is not exceeded.

Example 1

In the vertical reaction tank, 36.9 kg of DMT (dimethyl phthalate), 25.8 kg of BD (butanediol), 36.5 kg of PTMG (polybutane diol, number average molecular weight of 1000), and 150 g of antioxidant IRGANOX 1330 (Japan) were added. An atmospheric pressure transesterification reaction was carried out by heating 60 g of TBT (tetrahydrofuran) and heating from 130 ° C to 220 ° C for 2 hours. Subsequently, the temperature was raised from 220 ° C to 245 ° C over 1 hour, and the polymerization reaction was carried out at 245 ° C under reduced pressure to 2 hPa or less to a predetermined melt viscosity. After the polymerization reaction, 375 g of IRGANOX 1330 was added as an antioxidant for reducing the tetrahydrofuran content in the same reaction tank, and the mixture was mixed under reduced pressure to 2 hPa for 5 minutes. After mixing, the polymer is cast to fragment the polymer.

The obtained polyester elastomer had a comparative viscosity of 1.94 dl/g, Tm 187 ° C, tetrahydrofuran (THF) content of 600 ppm, free paraic acid of 9 ppm, free butanediol of 8 ppm, linear oligomer of 200 ppm, and heat resistance. The functional test was good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like. Here, the linear oligomer amount is an oligomer having a molecular weight of 606 bonded by TPA-BD-TPA-BD-TPA and The total of the oligomers having a smaller molecular weight than the smaller ones.

Example 2

The polymerization was carried out in the same manner as in Example 1 until the completion of the polymerization reaction. After the polymerization reaction, 150 g of SANDSTAB P-EPQ (manufactured by CLARIANT JAPAN Co., Ltd.) was added as an antioxidant in the same reaction vessel, and the mixture was mixed under reduced pressure to 2 hPa or less for 5 minutes. After mixing, the polymer is cast to fragment the polymer.

The obtained polyester elastomer had a comparative viscosity of 2.04 dl/g, Tm 187 ° C, a THF content of 440 ppm, a free paraic acid of 8 ppm, a free butanediol of 7 ppm, a linear oligomer of 195 ppm, heat resistance, and functionality. The test was good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 3

The polymerization was carried out in the same manner as in Example 1 until the completion of the polymerization reaction. After the polymerization reaction, 150 g of IRGANOX 1098 (manufactured by Nippon CIBA-GEIGY Co., Ltd.) was added as an antioxidant in the same reaction vessel, and the mixture was mixed under reduced pressure to 2 hPa or less for 5 minutes. After mixing, the polymer is cast to fragment the polymer.

The obtained polyester elastomer had a comparative viscosity of 2.00 dl/g, Tm 186 ° C, a THF content of 830 ppm, a free paraic acid of 8 ppm, a free butanediol of 5 ppm, a linear oligomer of 184 ppm, heat resistance, and functionality. The test was good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 4

The polymerization was carried out in the same manner as in Example 1 until the completion of the polymerization reaction. After the polymerization reaction, 375 g of IRGANOX 1010 (manufactured by CIBA-GEIGY Co., Ltd., Japan) and 150 g of IRGANOX 1098 were added as antioxidants in the same reaction tank. The mixture was decompressed to below 2 hPa and mixed for 10 minutes. After mixing, the pressure was reduced to 2 hPa or less, and polymerization was carried out until a predetermined melt viscosity, followed by casting to break the polymer.

The obtained polyester elastomer had a comparative viscosity of 1.95 dl/g, Tm 185 ° C, a THF content of 500 ppm, a free paraic acid of 9 ppm, a free butanediol of 9 ppm, a linear oligomer of 202 ppm, heat resistance, and functionality. The test was good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 5

41.8 kg of PBT, 36.5 kg of PTMG (number average molecular weight of 1000), 150 g of IRGANOX 1330, and 41 g of TBT were added to the vertical reaction tank, and the temperature was raised from 130 ° C to 245 ° C in 1 hour while reducing the pressure to 2 hPa or less. Subsequently, the polymerization reaction was carried out at 245 ° C to a prescribed melt viscosity. After the polymerization, 150 g of IRGANOX 1330, 150 g of SANDSTA BP-EPQ was added, and mixing was reduced, followed by casting to fragment the polymer.

The obtained polyester elastomer had a comparative viscosity of 2.00 dl/g, Tm 184 ° C, a THF content of 550 ppm, a free paraic acid of 7 ppm, a free butanediol of 1.0 ppm, a linear oligomer of 205 ppm, heat resistance, and functionality. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process and the like.

Example 6

PBT (number average molecular weight 20000) was continuously supplied to the twin-screw extruder at 4.2 kg/hr, PTMG (number average molecular weight 1000) at 3.7 kg/hr, IRGANOX 1330 at 15 g/hr, and TBT at 4.1 g/hr. And mixed at 245 ° C to obtain a comparative viscosity of After 0.3 dl/g of the polyester elastomer, it was transferred to a thin film evaporation reactor and decompressed at 245 ° C to 2 hPa or less. Subsequently, the polymerization reaction is carried out to a prescribed melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a twin-screw extruder in a molten state, and IRGANOX 1098 was supplied at 15 g/hr and mixed, followed by casting to pellet the polymer. The obtained polyester elastomer had a comparative viscosity of 1.90 dl/g, Tm 185 ° C, a THF content of 400 ppm, a free paraic acid of 5 ppm, a free butanediol of 0.8 ppm, a linear oligomer of 140 ppm, heat resistance, and a functional group. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 7

PBT (number average molecular weight 20000) was continuously supplied to the vertical reaction tank at 4.2 kg/hr, PTMG (number average molecular weight 1000) at 3.7 kg/hr, IRGANOX 1330 at 15 g/hr, and TBT at 4.1 g/hr. After mixing at 245 ° C, the pressure was reduced to 2 hPa or less at 245 ° C and polymerization was carried out until the comparative viscosity of the polyester elastomer was 0.4 dl / g. Subsequently, the mixture was transferred to a thin film evaporation reactor and subjected to polymerization at 245 ° C and 2 hPa to a predetermined melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1330 at 15 g/hr, supplied to SANDSTAB P-EPQ at 15 g/hr, mixed, and cast to fragment the polymer. . The obtained polyester elastomer had a comparative viscosity of 1.90 dl/g, Tm 187 ° C, a THF content of 350 ppm, a free paraic acid of 3 ppm, a free butanediol of 0.9 ppm, a linear oligomer of 130 ppm, heat resistance, and functionality. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 8

PBT (number average molecular weight 20000) was continuously supplied to the twin-screw extruder at 4.2 kg/hr, PTMG (number average molecular weight 1000) at 3.7 kg/hr, IRGANOX 1330 at 15 g/hr, and TBT at 4.1 g/hr. The mixture is heated and mixed under a barrel heater of 230 to 290 ° C, and reacted to a comparative viscosity of 0.2 to 0.5 dl / g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed to 245 ° C to 2 hPa or less, and polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1098 at 15 g/hr, and supplied to SANDSTAB P-EPQ at 15 g/hr, and mixed to cast polymer chips. Chemical. The obtained polyester elastomer had a comparative viscosity of 2.45 dl/g, Tm 190 ° C, a THF content of 150 ppm, a free paraic acid of 5 ppm, a free butanediol of 0.7 ppm, a linear oligomer of 142 ppm, heat resistance, and functionality. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 9

PBT (number average molecular weight 20000) was continuously supplied to the twin-screw extruder at 27.4 kg/hr, PTMG (number average molecular weight 1000) at 2.8 kg/hr, IRGANOX 1330 at 60 g/hr, and TBT at 12 g/hr. The mixture is heated and mixed under a barrel heater of 230 to 290 ° C, and reacted to a comparative viscosity of 0.2 to 0.5 dl / g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed to 245 ° C to 2 hPa or less, and polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1330 at 15 g/hr, IRGANOX 1098 at 15 g/hr, and SANDSTAB P-EPQ at 15 g/hr and mixed. Casting and polymer fragmentization. The obtained polyester elastomer had a comparative viscosity of 1.15 dl/g, Tm 222 ° C, a THF content of 90 ppm, a free paraic acid of 5 ppm, a free butanediol of 0.7 ppm, a linear oligomer of 165 ppm, heat resistance, and functionality. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 10

PBT (number average molecular weight 20000) at 6.9 kg / hr, PTMG (number average molecular weight 1000) at 0.7 kg / h, butanediol (BD) at 10 g / h, IRGANOX 1330 at 15 g / h, TBT at 3.0 g /hr continuously supplied to a twin-screw extruder, and heated and mixed under a barrel heater of 230 to 290 ° C, and reacted to a comparative viscosity of 0.2 to 0.5 dl / g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed to 245 ° C to 2 hPa or less, and polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a dual-axis extruder for addition of an antioxidant in a molten state, and supplied to IRGANOX 1330 at 15 g/hr, and supplied to IRGANOX 1098 at 15 g/hr, and mixed, and cast to pellet the polymer. The comparative polyester elastomer obtained had a comparative viscosity of 1.10 dl/g, Tm 223 ° C, a THF content of 50 ppm, a free paraic acid of 4 ppm, a free butanediol of 0.6 ppm, a linear oligomer of 168 ppm, heat resistance and functionality. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 11

PBT (number average molecular weight 20000) at 5.8 kg / hr, PTMG (number average molecular weight 1000) at 1.9 kg / h, butanediol (BD) at 20 g / h, IRGANOX 1330 at 15 g / h, TBT at 3.0 g /hour continuous supply to the twin-screw extruder and barrel at 230~290 °C The mixture was heated and mixed under the heater, and the reaction was carried out until the comparative viscosity was 0.2 to 0.5 dl/g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed to 245 ° C to 2 hPa or less, and polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a dual-axis extruder for antioxidant addition in a molten state, and IRGANOX 1010 was supplied at 15 g/hr, and IRGANOX 1098 was supplied at 15 g/hr, and mixed, followed by casting to pellet the polymer. The obtained polyester elastomer had a comparative viscosity of 1.60 dl/g, Tm 210 ° C, a THF content of 6 ppm, a free paraic acid of 5 ppm, a free butanediol of 0.8 ppm, a linear oligomer of 160 ppm, heat resistance, and a functional group. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 12

PBT (number average molecular weight 20000) was continuously supplied to the twin-screw extruder at 3.6 kg/hr, PTMG (number average molecular weight 2000) at 4.1 kg/hr, IRGANOX 1330 at 15 g/hr, and TBT at 5.0 g/hr. The mixture is heated and mixed under a barrel heater of 230 to 290 ° C, and reacted to a comparative viscosity of 0.2 to 0.5 dl / g. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and decompressed to 245 ° C to 2 hPa or less, and polymerization reaction was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1330 at 15 g/hr, IRGANOX 1010 at 15 g/hr, and SANDSTAB P-EPQ at 15 g/hr and mixed. Casting to fragment the polymer. The obtained polyester elastomer had a comparative viscosity of 2.30 dl/g, Tm 205 ° C, a THF content of 100 ppm, a free paraic acid of 5 ppm, a free butanediol of 0.6 ppm, a linear oligomer of 120 ppm, heat resistance, and a functional group. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 13

PBT (number average molecular weight 20000) was heated and mixed at 3.6 kg/hr, polycarbonate diol (PCD) at 1.4 kg/hr, IRGANOX 1330 at 15 g/hr, and at a barrel heater of 225-290 °C. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and depressurized to 2 hPa or less at 225 to 245 ° C, and polymerization was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, it was transferred to a dual-axis extruder for antioxidant addition in a molten state, and supplied to IRGANOX 1330 at 15 g/hr, IRGANOX 1010 at 15 g/hr, and IRGANOX 1098 at 15 g/hr at 15 g/hr. After the SANDSTAB P-EPQ was supplied and mixed, it was cast to fragment the polymer. The obtained polyester elastomer had a comparative viscosity of 1.25 dl/g, Tm 214 ° C, a THF content of 50 ppm, a free paraic acid of 6 ppm, a free butanediol of 0.9 ppm, a linear oligomer of 125 ppm, heat resistance, and functionality. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 14

PBT (number average molecular weight 20000) was heated and mixed at 3.6 kg/hr, PCD at 1.4 kg/hr, IRGANOX 1330 at 15 g/hr, and at a barrel heater of 225-290 °C. Subsequently, the mixture was continuously transferred to a horizontal twin-screw extruder and depressurized to 2 hPa or less at 225 to 245 ° C, and polymerization was carried out to a predetermined melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a dual-axis extruder for addition of an antioxidant in a molten state, and supplied to SANDSTAB P-EPQ at 15 g/hr, and mixed, and cast to pellet the polymer. The obtained polyester elastomer had a comparative viscosity of 1.15 dl/g, Tm 212 ° C, a THF content of 40 ppm, a free paraic acid of 5 ppm, a free butanediol of 0.8 ppm, a linear oligomer of 122 ppm, heat resistance, and functionality. The sex test is good. Moreover, since the content of tetrahydrofuran is small, there is no odor in the casting process. question.

Example 15

PBT (number average molecular weight 20000) was continuously supplied to the twin-screw extruder at 4.2 kg/hr, PTMG (number average molecular weight 1000) at 3.7 kg/hr, IRGANOX 1330 at 15 g/hr, and TBT at 4.1 g/hr. The mixture is heated and mixed under a barrel heater of 230 to 290 ° C, and reacted to a comparative viscosity of 0.2 to 0.5 dl / g. Then, it was continuously transferred to a horizontal twin-screw extruder and decompressed to 245 ° C to 2 hPa or less. At a later stage of the polymerization reaction in which the comparative viscosity was 0.2 dl/g lower than the specified viscosity, IRGANOX 1010 was supplied at 15 g/hr to 15 g. After IRGANOX 1098 was supplied and mixed, it was cast to fragment the polymer. The obtained polyester elastomer had a comparative viscosity of 2.05 dl/g, Tm 189 ° C, a THF content of 100 ppm, a free paraic acid of 6 ppm, a free butanediol of 0.7 ppm, a linear oligomer of 130 ppm, heat resistance, and a functional group. The sex test is good. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Example 16

PBT (number average molecular weight 20000) was continuously supplied to the twin-screw extruder at 4.2 kg/hr, PTMG (number average molecular weight 1000) at 3.7 kg/hr, IRGANOX 1330 at 15 g/hr, and TBT at 4.1 g/hr. The mixture is heated and mixed under a barrel heater of 230 to 290 ° C, and reacted to a comparative viscosity of 0.2 to 0.5 dl / g. Then, it was continuously transferred to a horizontal twin-screw extruder and decompressed to 245 ° C to 2 hPa or less. At a later stage of the polymerization reaction in which the comparative viscosity was 0.1 dl/g lower than the specified viscosity, IRGANOX 1098 was supplied at 15 g/hr and mixed. The polymerization reaction is carried out to a predetermined melt viscosity. After completion of the polymerization reaction, the mixture was transferred to a biaxial extruder for antioxidant addition, and supplied to SANDSTAB P-EPQ at 15 g/hr and mixed, and cast to pellet the polymer. The comparative viscosity of the obtained polyester elastomer is 1.90 dl/g, Tm 186 ° C, THF content: 125 ppm, free paraic acid of 6 ppm, free butanediol of 0.7 ppm, linear oligomer of 140 ppm, and good heat resistance and functionality test. Further, since the content of tetrahydrofuran is small, there is no problem of odor in the casting process or the like.

Comparative example 1

The completion of the polymerization reaction was carried out in the same manner as in Example 1. Immediately after completion of the polymerization reaction, the polymer was cast and the polymer was fragmented. The obtained polyester elastomer had a comparative viscosity of 2.04 dl/g, Tm 184 ° C, a THF content of 9000 ppm, a free paraic acid of 20 ppm, a free butanediol of 15 ppm, a linear oligomer of 255 ppm, heat resistance, and functionality. Poor test.

Comparative example 2

In a vertical reaction tank, 51.1 kg of DMT, 38.7 kg of BD, 18.7 kg of PTMG (number average molecular weight of 1000), 150 g of IRGANOX 1330, and 60 g of TBT were added, and polymerization was carried out under the same reaction conditions as in Example 1. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The obtained polyester elastomer had a comparative viscosity of 1.50 dl/g, Tm 212 ° C, a THF content of 5700 ppm, a free paraic acid of 15 ppm, a free butanediol of 20 ppm, a linear oligomer of 280 ppm, heat resistance, and functionality. Poor test.

Comparative example 3

In a vertical reaction tank, 31.7 kg of DMT, 23.2 kg of BD, 40.8 kg of PTMG (quantitative average molecular weight of 2000), 150 g of IRGANOX 1330, and 62.3 g of TBT were added, and polymerization was carried out under the same reaction conditions as in Example 1. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The comparative polyester elastomer obtained had a comparative viscosity of 2.20 dl/g, Tm 203 ° C, a THF content of 6,200 ppm, a free paraic acid of 17 ppm, a free butanediol of 16 ppm, a linear oligomer of 258 ppm, heat resistance and functionality. Poor test.

Comparative example 4

In the vertical reaction tank, 60.4 kg of DMT, 47.0 kg of BD, 7.1 kg of PTMG (quantitative average molecular weight of 1000), 150 g of IRGANOX 1330, 60 g of TBT were added, and the temperature was raised from 130 ° C to 220 ° C for 2 hours to carry out atmospheric pressure transesterification. reaction. Subsequently, the temperature was raised from 220 ° C to 245 ° C over 1 hour, and the pressure was reduced to 2 hPa or less, and the polymerization reaction was carried out at 245 ° C to a predetermined melt viscosity. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The obtained polyester elastomer had a comparative viscosity of 1.14 dl/g, Tm 223 ° C, a THF content of 5000 ppm, a free paraic acid of 20 ppm, a free butanediol of 25 ppm, a linear oligomer of 305 ppm, heat resistance, and functionality. Poor test.

Comparative Example 5

In the vertical reaction tank, add 31.6 kg of citric acid (TPA), 25.8 kg of BD, 36.5 kg of PTMG (quantitative average molecular weight of 1000), 150 g of IRGANOX 1330, 60 g of TBT, and raise the temperature from 130 ° C to 220 ° C for 2 hours. The atmospheric pressure transesterification reaction is carried out. Subsequently, the temperature was raised from 220 ° C to 245 ° C over 1 hour, and the pressure was reduced to 2 hPa or less, and the polymerization reaction was carried out at 245 ° C to a predetermined melt viscosity. Immediately after the completion of the polymerization, the polymer was cast to fragment the polymer. The obtained polyester elastomer had a comparative viscosity of 2.00 dl/g, Tm 186 ° C, a THF content of 10,000 ppm, a free paraic acid of 30 ppm, a free butanediol of 28 ppm, a linear oligomer of 260 ppm, heat resistance, and functionality. Poor test.

The above results are shown in Tables 1 and 2.

Industrial availability

In a polyester elastomer obtained from a dicarboxylic acid component, a glycol component having a molecular weight of less than 250 mainly composed of 1,4-butanediol, and a polyol having a number average molecular weight of 400 to 70,000, The antioxidant is 0.01 to 5 wt%, the tetrahydrofuran is 2000 ppm or less, the free dicarboxylic acid is 50 ppm or less, the free diol is 10 ppm or less, and the linear oligomer having a molecular weight of 650 or less is 300 ppm or less, and the odor and heat resistance can be improved. The polyester elastomer composition can be suitably used as a raw material of a fiber, a molded body, and a stretched film which are required to be strict.

Claims (9)

A polyester elastomer composition obtained by a dicarboxylic acid component, a glycol component having a molecular weight of less than 250 mainly composed of 1,4-butanediol, and a polyol having a number average molecular weight of 400 to 70,000. The polyester elastomer contains 0.01 to 5 wt% of an antioxidant, 2000 ppm or less of tetrahydrofuran, 15 ppm or less of a free dicarboxylic acid, 2 ppm or less of a free diol, and 200 ppm or less of a linear oligomer having a molecular weight of 650 or less. A polyester elastomer composition characterized in that a number average molecular weight of 5,000 to 50,000 is obtained by heating and mixing a glycol component having a molecular weight of less than 250 mainly composed of a dicarboxylic acid component and 1,4-butanediol. An ester, a polyol having a number average molecular weight of 400 to 70,000, and a polyester elastomer having a comparative viscosity of 0.2 dl/g or more is transferred to a thin film evaporator or a horizontal biaxial reaction tank at 230 to 255 The polymerization reaction is further carried out at ° C or below 2 hPa, and at least one of the late stage of the polymerization reaction and the completion of the polymerization reaction is added with 0.01 to 5 wt% of an antioxidant. A process for producing a polyester elastomer composition which is a polyester elastomer composition as claimed in claim 1 which is a melt-polymerized polyester elastomer. A method for preparing a polyester elastomer composition, which is a polyester elastomer composition as claimed in claim 1, which is transferred to a thin film evaporator or a horizontal biaxial reaction tank for polymerization, and then transferred to a double The shaft extruder is equipped with an antioxidant. A method for producing a polyester elastomer composition, which is a polyester elastomer composition according to claim 1, wherein the antioxidant is selected from the group consisting of hindered phenol, sulfur, and phosphorus. . The method for preparing a polyester elastomer composition according to claim 3 or 4, wherein the polyester is selected from the group consisting of polybutylene terephthalate, polybutylene naphthalate, and polybutylene adipate. At least one or more selected from the group consisting of at least one selected from the group consisting of polytetramethylene glycol, polycarbonate diol, polypropylene glycol, and polyethylene glycol. A fibrous material characterized by being extruded by molding a polyester elastomer composition according to claim 1 of the patent application. A sheet material characterized by being extruded by molding a polyester elastomer composition according to claim 1 of the patent application. A molded body characterized by comprising a polyester elastomer composition as claimed in claim 1. A stretched film characterized by stretching a sheet of the seventh item of the patent application in at least one direction.