JP2016210845A - Method for producing polyester amide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of producing polyester amide of high quality having high purity even if reaction is performed under relatively warm conditions.SOLUTION: Provided is a method for producing polyester amide obtained by mixing a condensed matter (A) with diamine (B) and reacting them: the condensed matter (A) reacted with the diamine (B) satisfies the following requirements (1) to (3): (1) that the condensed matter (A) being the one between aromatic dicarboxylic acid (A1) and at least one kind of alcohol (A2) selected from 2C or more diol, 2-4C aliphatic monoalcohol and 6-9C aromatic monoalcohol; (2) that the molar ratio between the structural unit derived from alcohol (A2) to the structural unit derived from the aromatic dicarboxylic acid (A1) in all the condensed matters (A), (A2/A1) is higher than 1; and (3) that the melting temperature of the condensed matter (A) being below the boiling point of the diamine (B).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polyesteramide.

  Polyesteramide is a resin that has an ester unit and an amide unit, and has excellent performance such as thermal stability, heat resistance, chemical resistance, mechanical properties, barrier properties, etc., and can be used in textile materials, packaging materials, engineering plastics, etc. Expected. However, polyester amide is not widely spread industrially, and one of the causes is difficulty in industrial production of polyester amide.

Conventionally, methods for synthesizing polyester amides include a method of chemically bonding polyester and polyamide, and a method of obtaining a polymer from various raw materials by controlling polymerization while controlling esterification reaction and amidation reaction.
In the former case, thermal degradation is likely to proceed during the reaction, and it is difficult to obtain a high-purity polyester amide. Also, since a large amount of energy is required by combining the polymers once synthesized, it is preferable in terms of economy and environmental load. It's not a method.

  In the latter case, in order to synthesize polyesteramide in high yield, high purity and economically, it is necessary to control the esterification reaction and the amidation reaction which are greatly different in reaction rate and reaction equilibrium. For example, when trying to react diamine, dicarboxylic acid and diol at the same time, the diamine neutralizes the acid and the polyesterification does not proceed sufficiently, or the diamine having a relatively low boiling point is distilled out of the system. Therefore, it is difficult to control the material balance. Therefore, conventionally, a method of obtaining a polyesteramide by sealing a terminal amine by adding a diamine to a derivative obtained by diesterifying a dicarboxylic acid in advance and performing esteramide exchange is known.

  Specifically, Patent Documents 1 to 3 show a method of synthesizing a polyester amide by adding a diamine to dimethyl terephthalate (hereinafter sometimes referred to as “DMT”). However, when diamine is added to DMT, there may be a large amount of side reactions such as methylation of amine, and an extreme decrease in molecular weight may occur. Patent Documents 2 and 3 also show a method of promoting a milder reaction by using a solvent and a dispersion medium. However, it is costly to remove the solvent and the dispersion medium, and is not economically advantageous. It is not preferable as a general manufacturing method.

  Furthermore, Patent Documents 4 and 5 show a method of adding diamine to polyethylene terephthalate or a hydrolyzate thereof. However, since this method uses polyethylene terephthalate having a high melting point, it requires a reaction at a high temperature or a high temperature and high pressure. For this reason, by-products are generated, the diamine is distilled off and the material balance is likely to be lost, and it is necessary to use special equipment such as pressure-resistant equipment, which is disadvantageous economically.

JP-A-8-311199 Japanese Patent Laid-Open No. 10-273531 JP-A-10-287807 Japanese Patent Laid-Open No. 9-324037 JP 2001-011175 A

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to produce a high-purity and high-quality polyester amide even if the reaction is performed under relatively mild conditions that do not require special equipment. It is providing the manufacturing method of the polyesteramide which can be manufactured.

As a result of intensive studies, the inventors of the present invention use a condensate having predetermined characteristics in a production method in which diamine is amidated by transesterification with a condensate and then further esterified to obtain a polyesteramide. Thus, it was found that even if the reaction was carried out under relatively mild conditions, it was possible to synthesize high-purity and high-quality polyester amide, and the present invention was completed. The present invention provides the following [1] to [15].
[1] The aromatic dicarboxylic acid ester condensate (A) is mixed with the diamine (B) to react them,
The manufacturing method of the polyesteramide which the aromatic dicarboxylic acid ester condensate (A) made to react with diamine (B) satisfy | fills the following requirements (1)-(3).
(1) The aromatic dicarboxylic acid ester condensate (A) is an aromatic dicarboxylic acid (A1), a diol having 2 or more carbon atoms, an aliphatic monoalcohol having 2 to 4 carbon atoms, and an aromatic having 6 to 9 carbon atoms. It is a condensate with at least one alcohol (A2) selected from the group monoalcohols.
(2) The molar ratio (A2 / A1) of the structural unit derived from the alcohol (A2) to the structural unit derived from the aromatic dicarboxylic acid (A1) in the total condensate (A) is greater than 1.
(3) The melting temperature of the aromatic dicarboxylic acid ester condensate (A) is lower than the boiling point of the diamine (B).
[2] The aromatic dicarboxylic acid ester condensate (A) is a condensate of an alkanediol having 2 to 4 carbon atoms and an aromatic dicarboxylic acid represented by the following general formula [1], and the following general The method for producing a polyesteramide according to the above [1], which is at least one selected from compounds represented by the formula [2].

(In General Formula [1], X ¹ represents an arylene group having 6 to 14 carbon atoms or a heteroarylene group having 3 to 14 carbon atoms.)

(In General Formula [2], X ² represents an arylene group having 6 to 14 carbon atoms or a heteroarylene group having 3 to 14 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom or a fatty acid having 2 to 4 carbon atoms. Selected from an aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 9 carbon atoms, and a hydroxyalkyl group having 2 to 4 carbon atoms, and at least one of R ¹ and R ² is either a hydrocarbon group or a hydroxyalkyl group .)
[3] After producing a reaction product of the aromatic dicarboxylic acid ester condensate (A) and the diamine (B), the reaction product is further mixed with the post-addition diol compound (X), and the post-addition diol compound (X ) With the reaction product,
The post-addition diol compound (X) is a condensate of a diol having 2 or more carbon atoms and an aromatic dicarboxylic acid, and is at least selected from a compound having both ends being hydroxyl groups and an aliphatic diol having 2 to 4 carbon atoms. The method for producing a polyesteramide according to [1] or [2], which is one type.
[4] Maintaining the aromatic dicarboxylic acid ester condensate (A) at a temperature not lower than its melting temperature and lower than the boiling point of the diamine (B), the molten aromatic dicarboxylic acid ester condensate (A) is converted into a diamine (B ) Is added, The manufacturing method of the polyesteramide of any one of said [1]-[3].
[5] The process for producing a polyesteramide as described in any one of [1] to [4] above, wherein the reaction is carried out by heating at a temperature equal to or higher than the melting point of the resulting polyesteramide or at least 10 ° C. higher than the glass transition temperature.
[6] A by-product formed as a by-product by the amidation reaction performed by reacting the diamine (B) with the aromatic dicarboxylic acid ester condensate (A), and a by-product generated by an esterification reaction further performed after the amidation. The method for producing a polyesteramide according to any one of [1] to [5], wherein at least one of the by-products is distilled off under reduced pressure.
[7] Said [1]-[6] whose diamine (B) is 1-99 mol% to 100 mol% of structural units derived from aromatic dicarboxylic acid contained in aromatic dicarboxylic acid ester condensate (A). ] The manufacturing method of the polyesteramide of any one of.
[8] The above-described [1] to [1], wherein the diamine (B) is reacted with the aromatic dicarboxylic acid ester condensate (A) to perform an amidation reaction, and then the esterification reaction further performed in the presence of a transition metal catalyst. [7] The process for producing a polyesteramide according to any one of [7].
[9] At least one of an amidation reaction performed by reacting the diamine (B) with the aromatic dicarboxylic acid ester condensate (A) and an esterification reaction further performed after the amidation is performed in the presence of an antioxidant. The manufacturing method of the polyesteramide of any one of said [1]-[8] performed.
[10] The method for producing a polyesteramide according to any one of [1] to [9], wherein the solvent and the dispersion medium are reacted with substantially no addition.
[11] The above-mentioned [1], in which the diamine (B) is reacted with the aromatic dicarboxylic acid ester condensate (A) to perform an amidation reaction, and then the polyesteramide obtained through the further esterification reaction is further solid-phase polymerized. ] The manufacturing method of the polyesteramide of any one of [10].
[12] The aromatic dicarboxylic acid ester condensate (A) is diethyl terephthalate, diisopropyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dibenzyl terephthalate, condensate of terephthalic acid and ethylene glycol, terephthalic acid and 1,3 -Production of polyester amide according to any one of [1] to [11], which is at least one selected from a condensate of trimethylene glycol and a condensate of terephthalic acid and 1,4-butanediol. Method.
[13] The process for producing a polyesteramide according to [12], wherein the condensate of terephthalic acid and ethylene glycol contains bis (2-hydroxyethyl) terephthalate.
[14] The diamine (B) is at least one selected from an aliphatic diamine having 2 to 12 carbon atoms, an alicyclic diamine having 2 to 15 carbon atoms, and an aromatic diamine having 6 to 27 carbon atoms. [1] The method for producing a polyesteramide according to any one of [13].
[15] Diamine (B) is xylylenediamine, 1,3- (bisaminomethyl) cyclohexane, 1,4- (bisaminomethyl) cyclohexane, 1,6-hexamethylenediamine, 1,9-nonamethylenediamine , A method for producing a polyesteramide according to any one of [1] to [14], which is at least one selected from decamethylenediamine and 1,4-phenylenediamine.

  In the present invention, it is possible to produce a high-purity and high-quality polyester amide even if the reaction is carried out under relatively mild conditions that do not require special equipment.

1 shows a ¹ H NMR chart of the polyesteramide obtained in Example 1. The ¹ H NMR chart of the polyesteramide obtained in Example 2 is shown.

Hereinafter, the present invention will be described using embodiments.
The method for producing a polyesteramide of the present invention is a method for producing a polyesteramide by mixing the diamine (B) with the aromatic dicarboxylic acid ester condensate (A) and reacting them at least. Hereinafter, the aromatic dicarboxylic acid ester condensate (A) and the diamine (B) used in the present invention will be described first.

[Aromatic dicarboxylic acid ester condensate (A)]
The aromatic dicarboxylic acid ester condensate (A) (hereinafter also simply referred to as “condensate (A)”) satisfies the following requirements (1) to (3).
(1) The condensate (A) is selected from an aromatic dicarboxylic acid (A1), a diol having 2 or more carbon atoms, an aliphatic monoalcohol having 2 to 4 carbon atoms, and an aromatic monoalcohol having 6 to 9 carbon atoms. A condensate with at least one alcohol (A2).
(2) The molar ratio (A2 / A1) of the structural unit derived from the alcohol (A2) to the structural unit derived from the aromatic dicarboxylic acid (A1) in the total condensate (A) is greater than 1.
(3) The melting temperature of the condensate (A) is less than the boiling point of the diamine (B).

In the present invention, it is possible to proceed with amidation with high selectivity by using a specific alcohol (A2) constituting the condensate (A) as in the requirement (1). The reason why amidation proceeds with high selectivity by using various alcohols shown in requirement (1) is not clear, but is estimated as follows.
That is, in the reaction of the condensate (A) and the diamine (B), the main side reaction is that the nucleophilic reaction of the diamine (B) is a constituent unit at the terminal of the condensate derived from the alkoxy group (ie, the alcohol (A2)). ) Of the carbon atom bonded to the oxygen atom, the use of the specific alcohol (A2) described above suppresses such a nucleophilic reaction and improves the selectivity. Presumed.

On the other hand, when the alcohol (A2) has, for example, 1 carbon atom (that is, when it is methanol), the alkoxy group of the condensate (A) is not bulky and carbon bonded to the oxygen atom of the alkoxy group. A nucleophilic reaction of diamine occurs with respect to atoms, and a by-product tends to be generated. As a result, secondary or tertiary amines are produced, resulting in problems such as changes in physical properties, amidation and inhibition of molecular weight. Further, among the alcohols (A2), the monoalcohol is eliminated from the aromatic dicarboxylic acid (A1) and becomes a by-product in the amidation reaction and esterification reaction described later. If it is an aliphatic monoalcohol with a carbon number greater than 4, or an aromatic monoalcohol with a carbon number greater than 10, it will be difficult to remove in the distillation step described later, and foaming and odor generation during molding, or from molded products May cause problems such as elution.
On the other hand, some diols are incorporated into the polyesteramide skeleton and others are by-products. As in the case of the aliphatic monoalcohol, when a diol having a carbon number greater than 4 becomes a by-product, a problem similar to the above may occur. It is preferable to adjust so that it hardly occurs as a product.

  As shown in the requirement (2), the condensate (A) is a molar ratio of the structural unit derived from the alcohol (A2) to the structural unit derived from the aromatic dicarboxylic acid (A1) in the total condensate (A) (A2 / A1) is greater than 1. When the molar ratio (A2 / A1) is 1 or less, a considerable amount of the carboxyl group of the component (A1) is not esterified, and the amidation of the condensate (A) is difficult to proceed under mild conditions. Become. Further, the melting temperature of the condensate (A) is not lowered, and it is difficult to satisfy the requirement (3).

  The molar ratio (A2 / A1) shown in the requirement (2) is preferably 1.2 to 2, more preferably 1.5 to 2, and particularly preferably 1.8 to 2. Thus, when the molar ratio (A2 / A1) is set to 2 or a value close to 2, the condensate (A) is almost esterified at both terminal carboxyl groups. The diamine (B) can be amidated easily by transesterification. Therefore, it is possible to proceed with amidation at a higher selectivity without generating much by-products. Furthermore, the melting temperature of the condensate (A) can be easily lowered.

  The condensate (A) has a melting temperature lower than the boiling point of the diamine (B) as shown in the requirement (3). If the melting temperature is not lower than the boiling point of the diamine, the condensate (A) is brought to the vicinity of the boiling point of the diamine (B) in order to bring the condensate (A) into a uniform fluid state without using a solvent or a dispersion medium. It is necessary to heat. Under such heating conditions, the diamine (B) is distilled off from the reaction system and the material balance of the raw material is lost, or a side reaction occurs, making it difficult to produce a polyester amide with good quality.

The melting temperature of the condensate (A) is preferably 5 ° C. or more lower than the boiling point of the diamine (B), more preferably 10 ° C. or more lower than the boiling point of the diamine (B), and 20 ° C. lower than the boiling point of the diamine (B). It is particularly preferable that the value is lower. Thus, when the melting temperature of the condensate (A) is lowered, the amidation reaction of the condensate (A) and the diamine (B) can be performed at a lower temperature, and it becomes easier to produce a high-quality polyamide. . The specific melting temperature of the condensate (A) is, for example, 240 ° C. or lower, preferably 220 ° C. or lower, more preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower.
The lower limit of the melting temperature of the condensate (A) is not particularly limited, but the melting temperature is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 30 ° C. or higher, particularly preferably 40 ° C. or higher. is there.

Specific examples of the aromatic dicarboxylic acid (A1) used in the condensate (A) include those represented by the following general formula [1].

However, in the general formula [1], X ¹ represents an arylene group having 6 to 14 carbon atoms or a heteroarylene group having 3 to 14 carbon atoms.

  Here, examples of the arylene group having 6 to 14 carbon atoms include a phenylene group, a naphthalene group, and an anthrylene group. Further, as the heteroarylene group having 3 to 14 carbon atoms, a furanylene group, a thiophenylene group, an imidazolylene group, a pyrazolylene group, an oxazolylene group, an isoxazolylene group, a thiazolylene group, an isothiazolylene group, a triazolylene group, a tetrazolylene group, a pyridinylene group , Pyrazinylene group, pyrimidinylene group, pyridaminylene group, thiazinylene group, indonylene group, isoindonylene group, benzofuranylene group, benzothiazonylylene group, pynylene group, quinolinylene group, isoquinolinylene group, quinoxalinylene group, phthalazinylene group, pteridinylene group Group and carbazonylene group. Among these, a phenylene group and a naphthalene group are preferable, and a phenylene group is more preferable, and terephthalic acid is most preferable as the aromatic dicarboxylic acid (A1).

Examples of the aliphatic monoalcohol having 2 to 4 carbon atoms used as the alcohol (A2) include alkane monools such as ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, 2-methylpropanol, and tert-butanol. Is mentioned. Examples of the aromatic monoalcohol having 6 to 9 carbon atoms include phenol, cresol, ethylphenol, propylphenol, benzyl alcohol, phenylethanol, and phenylpropanol.
Preferred examples of the diol having 2 or more carbon atoms used as the alcohol (A2) include aliphatic diols having 2 to 4 carbon atoms. Some diols having 2 or more carbon atoms are incorporated into the polyesteramide skeleton, and some diols are produced as side reactions like monoalcohols. However, aliphatic diols having 4 or less carbon atoms are used as side reactions. Even if it is formed, it can be easily removed from the reaction system.
Specific examples of the aliphatic diol having 2 to 4 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol (1,3-trimethylene glycol), diethylene glycol, 1,2-butylene glycol, Examples include 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butanediol, and among these, alkanediol having 2 to 4 carbon atoms is preferable. Among these, ethylene glycol, 1,3-butanediol are preferable. Examples include propanediol and 1,4-butanediol.

  Among the above alcohols (A2), alkane monools having 2 to 4 carbon atoms and alkane diols having 2 to 4 carbon atoms are preferable, and among these, the reactivity is good and the condensate (A) can be easily formed. From the viewpoint of availability, ethanol, ethylene glycol, and 1,4-butanediol are more preferable, and ethylene glycol is most preferable.

In addition, as the diol having 2 or more carbon atoms used for the alcohol (A2), a diol other than the aliphatic diol having 2 to 4 carbon atoms may be used. However, such a diol is usually used as a part of the alcohol (A2) in an amount that does not impair the purpose of the present application.
In view of the fact that these diols are less likely to be distilled off from the polyester amide in the present production method and can be finally contained in the polyester amide skeleton, the aliphatic diols having 2 to 4 carbon atoms and carbon numbers shown above The blending amount is adjusted and added together with 2 to 4 aliphatic monoalcohol or C6 to C9 aromatic monoalcohol.
Examples of the diol other than the aliphatic diol having 2 to 4 carbon atoms include cyclohexanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, methylpentanediol, and 1,2-cyclohexane. Diol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, norbornenedimethanol , Tricyclodecane dimethanol, 1,10-decamethylene glycol, 2-butene-1,4-diol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc. Rhoquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (P-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol, isosorbide, 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol, glycols obtained by adding ethylene oxide to these glycols, and the like. Among these, 1,4-cyclohexanedimethanol and neopentyl glycol are particularly preferably used.
When these diols other than aliphatic diols having 2 to 4 carbon atoms are contained in alcohol (A2), they are usually contained in a small amount with respect to the total amount of alcohol (A2). That is, in the condensate (A), an alcohol selected from an aliphatic diol having 2 to 4 carbon atoms, an aliphatic monoalcohol having 2 to 4 carbon atoms, and an aromatic monoalcohol having 6 to 9 carbon atoms is an alcohol ( It is a main component of A2) and is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more with respect to the total amount of alcohol (A2).
In addition, although the upper limit of the carbon number of diol is not specifically limited, Usually, it is about 50 or less.

The condensate (A) may be a monomer having an aromatic dicarboxylic acid repeating number of 1 in the molecule, an oligomer having an aromatic dicarboxylic acid repeating number of 2 or more, and A mixture thereof may be used, but a monomer is preferable. When an aliphatic diol is used as the alcohol (A2), the condensate (A) can be converted into an oligomer by polycondensation with the aromatic dicarboxylic acid (A1).
When an oligomer is contained in the condensate (A), the number average molecular weight (Mn) may be lower than that of the polyester amide to be produced. Specifically, the condensate (A) is preferably 300 to 3000, more preferably 500 to 2000. .

The condensate (A) is more specifically a condensate of an alkanediol having 2 to 4 carbon atoms and the aromatic dicarboxylic acid represented by the above formula [1], and the following formula [2]: It is preferable that it is at least 1 sort (s) selected from the condensate represented by these.

However, in the general formula [2], X ² represents an arylene group having 6 to 14 carbon atoms or a heteroarylene group having 3 to 14 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 2 to 4 carbon atoms. It is selected from an aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 9 carbon atoms, and a hydroxyalkyl group having 2 to 4 carbon atoms, and at least one of R ¹ and R ² is any of a hydrocarbon group and a hydroxyalkyl group It is.

The condensate of the alkanediol having 2 to 4 carbon atoms and the aromatic dicarboxylic acid represented by the formula [1] may be a monomer, an oligomer, or a mixture of a monomer and an oligomer. There may be. In addition, when this condensate contains an oligomer, the number average molecular weight of a condensate (A) is as above-mentioned.
In addition, a condensate of an alkanediol having 2 to 4 carbon atoms and an aromatic dicarboxylic acid represented by the formula [1] includes an aromatic dicarboxylic acid in which X ¹ is a phenylene group, ethylene glycol, 1,3- A condensate with any alcohol selected from propanediol and 1,4-butanediol is preferred, and among them, a condensate of aromatic dicarboxylic acid wherein X ¹ is a phenylene group and ethylene glycol is more preferred.

In the formula [2], specific examples of the aliphatic hydrocarbon group having 2 to 4 carbon atoms include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert group. -A butyl group is mentioned. Examples of the aromatic hydrocarbon group having 6 to 9 carbon atoms include phenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, benzyl group, phenylethyl group, and phenylpropyl group. Moreover, as a C2-C4 hydroxyalkyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group is mentioned.
Among these, an alkyl group having 2 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and a benzyl group are preferable, and an ethyl group and a hydroxyalkyl group having 2 to 4 carbon atoms are more preferable, and in particular, 2-hydroxy Most preferred is an ethyl group.
Further, specific examples and preferred examples of X ² in the formula [2] is the same as X ¹ in the formula [1] described above, a description thereof will be omitted.

Preferred compounds of the condensate (A) include diethyl terephthalate, diisopropyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dibenzyl terephthalate, condensates of terephthalic acid and ethylene glycol, terephthalic acid and 1,3-trimethylene. Examples include a condensate of glycol and a condensate of terephthalic acid and 1,4-butanediol. Among these, diethyl terephthalate, a condensate of terephthalic acid and ethylene glycol, and a condensate of terephthalic acid and 1,4-butanediol are preferable, and among these, a condensate of terephthalic acid and ethylene glycol is more preferable. .
The condensate of terephthalic acid and ethylene glycol may be an oligomer or a monomer or a mixture thereof, but bis (2-hydroxyethyl) terephthalate which is a monomer is still more preferable.
Similarly, the condensate of terephthalic acid and 1,3-propanediol or the condensate of terephthalic acid and 1,4-butanediol may be an oligomer or a monomer, or a mixture thereof.

The condensate (A) may or may not contain the diol (a). In addition, as a specific example of diol (a), it is a condensate of aromatic dicarboxylic acid (A1) and a diol with 2 or more carbon atoms among the condensates (A) exemplified above, and both ends are hydroxyl groups. The condensate may be an oligomer or a monomer, or a mixture thereof.
Preferable specific examples of the diol (a) include a condensate of terephthalic acid and ethylene glycol, a condensate of terephthalic acid and 1,3-propanediol, and a condensate of terephthalic acid and 1,4-butanediol. Among these, a condensate of terephthalic acid and ethylene glycol, a condensate of terephthalic acid and 1,4-butanediol are preferable, and a condensate of terephthalic acid and ethylene glycol is more preferable, and bis (2-hydroxyethyl) ) Terephthalate is most preferred.

In the present invention, if the condensate (A) to be mixed with the diamine contains the diol (a), an amidation reaction can be performed without adding the post-addition diol compound (X) to the reaction system in a diol post-addition step described later. The esterification reaction performed later can be appropriately advanced.
On the other hand, when the condensate (A) mixed with the diamine (B) does not contain the diol (a), the post-addition diol compound (X) is added to the reaction system in the diol post-addition step described later, or the diol The esterification reaction can be carried out by adding a diol compound (C) described later to the reaction system in a process other than the post-addition process.

Various condensates (A) of the present invention can be produced by a conventionally known production method. For example, an aromatic carboxylic acid (A1) and an alcohol (A2) can be synthesized by a known polycondensation reaction. It is. It can also be produced by a transesterification method, a reaction between an acid halide and an alcohol, or the like. Furthermore, the condensate (A) may be obtained by decomposing polyester such as polyethylene terephthalate.
In the case where the alcohol (A2) contains an aliphatic diol, by using the alcohol (A2) more than twice as much as the aromatic dicarboxylic acid (A2) at the time of synthesis, the monomer (substantially from the monomer alone). Although it is possible to produce the condensate which becomes, it is good also as a mixture of a monomer and an oligomer by using more than 1 time and 2 times or less.
In addition, the condensate (A) includes aromatic dicarboxylic acid (A1), alcohol (A2), etc. that remain without reacting when the condensate (A) is produced, as long as the effects of the present invention are not impaired. It may be mixed.

[Diamine (B)]
As the diamine (B), various diamines conventionally used for producing polyamides can be used. For example, an aliphatic diamine having 2 to 12 carbon atoms, an alicyclic diamine having 2 to 15 carbon atoms, and carbon. It is preferable that it is at least 1 sort (s) selected from several 6-27 aromatic diamine.
Examples of the aliphatic diamine having 2 to 12 carbon atoms include 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, , 7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine and the like.
Examples of the alicyclic diamine having 2 to 15 carbon atoms include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane. Bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane, isophoronediamine, norbornenediamine and the like.

  Examples of the aromatic diamine having 6 to 27 carbon atoms include metaxylylenediamine, paraxylylenediamine, orthoxylylenediamine, bis (4-aminophenyl) ether, 1,4-phenylenediamine, bis (aminomethyl) naphthalene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, diaminodiphenyl ether, diaminodiphenyl sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone Bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4 ′-[p-phenylenediisopropylidene] dianiline, 4,4 ′-[m-phenylenediisopropylidene] dianiline, 4,4′- Diaminobenzanilide, aminobenzylamine, diethylto Enjiamin, dimethylthiotoluenediamine, and the like.

Among these, diamine (B) is various xylylenediamine, 1,3- (bisaminomethyl) cyclohexane, 1,4- (bisaminomethyl) cyclohexane, 1,6-hexamethylenediamine, 1,9. -More preferably, it is at least one selected from nonamethylenediamine, decamethylenediamine, and 1,4-phenylenediamine.
In addition, the boiling point of diamine (B) is 100-350 degreeC normally, Preferably it is 150-280 degreeC.

[Production method of polyester amide]
In the present invention, the mixed condensate (A) and the diamine (B) are reacted to perform amidation, and then further esterified to obtain a polyesteramide. Here, esterification is performed by further reacting the reaction product obtained by amidation with at least one of a condensate (A), a diol compound (C) described later, or a post-addition diol compound (X). It is. Amidation and esterification may be carried out, for example, continuously in one pot. Alternatively, the reaction product obtained by amidation may be once taken out without carrying out in one pot, and then the post-addition diol compound (X) may be added to the reaction product for esterification.
Hereinafter, the manufacturing method of the polyesteramide of this invention is demonstrated in detail.

(Mixing process)
In the production method of the present invention, first, the diamine (B) is mixed with the aromatic dicarboxylic acid ester condensate (A).
As a method of mixing the diamine (B) with the condensate (A), the condensate (A) is heated so as to be maintained at a temperature equal to or higher than the melting temperature and lower than the boiling point of the diamine (B). The method of adding diamine (B) to (A) is mentioned. The diamine (B) is added by, for example, dropping the diamine (B) intermittently or continuously into the condensate (A) charged and melted in the reaction kettle. As described above, when the condensate (A) is preheated to the melting temperature or higher, the reaction system including the mixture of the condensate (A) and the diamine (B) becomes a uniform fluidized state. It is possible to appropriately proceed the reaction in one reaction step.

  The condensate (A) and the diamine (B) may be mixed by mixing the diamine (B) with the solid condensate (A). In such a mixing method, for example, after the solid condensate (A) and the liquid diamine (B) are charged into the reaction kettle, the reaction system is heated to melt the condensate (A), and the condensate ( What is necessary is just to make the reaction system containing A) and diamine (B) into a uniform fluid state. In this method, since the solid condensate (A) is dissolved or compatible with the liquid diamine (B) at a temperature lower than its melting temperature, the reaction system can be used even at a temperature lower than the melting temperature of the condensate (A). Can be made into a uniform flow state.

  The diamine (B) is preferably 1 to 99 mol%, more preferably 3 to 70 mol%, based on 100 mol% of the structural unit derived from the aromatic dicarboxylic acid contained in the condensate (A). 5 to 50 mol% is more preferable. In the present invention, by reducing the amount of the diamine (B) used relative to the condensate (A), the amino group of the diamine (B) can be easily blocked by the amidation reaction. The esterification reaction that occurs is likely to proceed. Moreover, by setting it as 50 mol% or less, it becomes possible to seal the amino group of diamine (B) reliably irrespective of the structure of a condensate (A).

Moreover, in this mixing process, in addition to the condensate (A) and the diamine (B), a diol compound (C) other than the condensate (A) may be mixed.
Examples of the diol compound (C) other than the condensate (A) include diols having 2 or more carbon atoms, among which aliphatic diols having 2 to 4 carbon atoms are preferable. Specific examples of the aliphatic diol having 2 to 4 carbon atoms used in the diol compound (C) include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, diethylene glycol, 1,2 -Butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butanediol and the like. Among these, a C 1-4 alkanediol is preferable, and ethylene glycol is more preferable.
In addition, the diol having 2 or more carbon atoms may contain a diol other than the aliphatic diol having 2 to 4 carbon atoms in an amount that does not impair the purpose of the present application. Specifically, cyclohexanediol, triethylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, methylpentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1, 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, norbornene dimethanol, tricyclodecane dimethanol, 1,10- Hydroquinone such as decamethylene glycol, 2-butene-1,4-diol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, 4,4′-dihydroxybi Sphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (P-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol, isosorbide, 2,2,4,4-tetramethyl-1,3 -Cyclobutanediol, glycols obtained by adding ethylene oxide to these glycols, and the like. Among these, 1,4-cyclohexanedimethanol and neopentyl glycol are particularly preferably used.
Although the upper limit of carbon number of a diol compound (C) is not specifically limited, For example, it is 50.
The diol compound (C) reacts with the reaction product obtained by amidating the condensate (A) and the diamine (B) in the second reaction step described later, for example, in the same manner as the diol (a). It is possible to proceed with esterification.

  In addition, although the mixing process demonstrated above was demonstrated as a process separate from the 1st reaction process mentioned later for convenience of explanation, these may be implemented integrally and a condensate (A) and diamine (B) And the diol compound (C) to be added as necessary, the amidation reaction may be allowed to proceed.

(Amidation reaction: first reaction step)
The mixture (reaction system) obtained by mixing in the mixing step is preferably heated to advance the amidation reaction (this heating step is referred to as “first reaction step”). In the mixing step, as described above, the reaction system containing the condensate (A) and the diamine (B) is heated so as to be in a uniform fluid state, and by this heating, (A) and (B) The amidation reaction of the component may proceed, but usually the amidation does not proceed sufficiently. For this reason, in the first reaction step, it is preferable to further raise the system temperature after mixing the condensate (A) and the diamine (B) to obtain a fluid state.

The first reaction step is preferably performed by raising the temperature of the reaction system to a temperature lower than the boiling point of the diamine (B). In this way, by performing the first reaction step below the boiling point of the diamine (B), it is possible to proceed with the amidation reaction while preventing the outflow of the diamine (B) and maintaining the material balance. Become. Furthermore, the use of excessive heat energy can also be suppressed. In the first reaction step, the reaction system is heated to a temperature that is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, higher than the melting temperature of component (A) in order to allow the amidation reaction to proceed more appropriately. Do it.
The temperature of the reaction system in the first reaction step is usually 0 to 280 ° C, preferably 40 to 250 ° C. The first reaction step may be performed by raising the temperature of the reaction system to a predetermined temperature within the above range and then maintaining the temperature, or by gradually raising the temperature of the reaction system within the above range.
By performing the first reaction step as described above, the diamine (B) is surely amidated, and the amino group of the diamine (B) is appropriately sealed. Therefore, in the following 2nd reaction process, it becomes possible to advance polyesterification smoothly, suppressing generation | occurrence | production of a side reaction.

(Esterification reaction: second reaction step)
In the present invention, when the condensate (A) contains the diol (a), it is preferable to heat the reaction system subsequent to the first reaction step (hereinafter, this heating step is referred to as “second reaction step”). Also called).
In this second reaction step, the reaction product (usually an oligomer) obtained by the amidation reaction between the component (A) and the component (B) is further esterified with the diol (a), and the polyester amide Is generated. According to such a technique, an amidation reaction and an esterification reaction can be sequentially performed in one pot, and efficient polyester amide production can be realized. However, when the condensate (A) contains the diol (a), esterification may proceed in part not only in the second reaction step but also in the first reaction step.

  The esterification reaction performed in the second reaction step is preferably performed in the presence of a transition metal catalyst. That is, when the condensate (A) contains the diol (a) as described above, it is preferable to add the transition metal catalyst to the reaction system after the first reaction step and then perform the second reaction step.

Examples of the transition metal catalyst used in the second reaction step include germanium compounds, antimony compounds, titanium compounds, aluminum compounds and the like, and among these, antimony compounds are preferable. Specific examples of the antimony compound include antimony trioxide, antimony pentoxide, antimony tartrate, antimony potassium tartrate, antimony oxychloride, antimony glycolate, and triphenylantimony, and antimony trioxide is particularly preferable. A transition metal catalyst is 0.001-0.1 mol% normally with respect to 100 mol% of structural units derived from the aromatic dicarboxylic acid contained in a reaction system in a 2nd reaction process, Preferably it is 0.01-0. 05 mol% is used.
The transition metal catalyst may be diluted and then added to the reaction system, or may be added to the reaction system as it is without being diluted. The transition metal catalyst is diluted with, for example, a diol compound. Here, the diol compound used as the diluent can be appropriately selected from the various diols exemplified in the above-mentioned diol compound (C).

In the production of polyester amide, as polyesterification proceeds, the melting point and glass transition temperature of the reaction product (polyester amide) in the reaction system gradually increase. Therefore, in the second reaction step, the reaction system is equal to or higher than the melting point of the reaction product in the reaction system, or when no melting point is detected, so that the reaction system can maintain a uniform flow state. It is preferable that the glass transition temperature is 10 ° C. or more higher than the glass transition temperature. Then, at the end of the second reaction step, the reaction system is higher than the melting point of the obtained polyesteramide (that is, extracted from the reaction kettle) or higher than the glass transition temperature by 10 ° C. or higher if the melting point is not detected. Is preferably heated.
For example, the melting point of polyesteramide is detected when it is in a crystalline state, but the melting point is not normally detected when it is in an amorphous state.

In the second reaction step, the reaction system is usually heated to a temperature equal to or higher than the temperature of the first reaction step. In the second reaction step, the temperature of the reaction system may be gradually raised, or may be maintained at the last temperature of the first reaction step. The temperature of a 2nd reaction process is 100-300 degreeC normally, Preferably it is 200-280 degreeC.
In the second reaction step, the esterification reaction is carried out by proceeding the reaction under the above temperature conditions in the presence of a predetermined catalyst (for example, in the presence of a transition metal catalyst or in the presence of a transition metal catalyst and an antioxidant described later). It is possible to proceed smoothly. In the first reaction step, the diamine (B) is amidated and is not substantially present in the reaction system. Therefore, in the second reaction step, even if the reaction system is heated to the boiling point of the diamine (B) or more, there is little influence that the diamine (B) flows out of the system and the material balance is lost.

  In the above description, for convenience of explanation, the first stage of the reaction process is described as being divided into the first reaction process and the latter stage is divided into the second reaction process. However, in the case where these processes are performed continuously, actually, Although these reaction steps may not be clearly separated, it goes without saying that such a step is within the scope of the present invention as long as the effects of the present invention are obtained.

(Distillation step)
In the present invention, it is preferable that the by-product by-produced by at least one of the amidation reaction and the subsequent esterification reaction is distilled off under reduced pressure. Specifically, after the second reaction step, it is preferable to depressurize the reaction system and distill off the by-product. In the amidation reaction and esterification reaction, the alcohol (A2) described above is generated as a by-product. Therefore, in the distillation step, alcohol (A2) is removed from the reaction system.
However, when the by-product (alcohol (A)) has already been separated and removed in the separation step described later, the by-product (alcohol generated in the esterification reaction (second reaction step) is removed in the distillation step. (A)) is mainly removed.

The distillation step is preferably performed by adjusting the temperature of the reaction mixture inside the reaction kettle to 100 to 300 ° C. and reducing the pressure to 50 torr or less, and 200 to 280 ° C. and reducing the pressure to 10 torr or less. More preferred. The lower limit value of the pressure in the distillation step is not particularly limited, but is usually 0.1 torr or more, preferably 0.01 torr or more, due to restrictions of the decompression device.
In the distillation step, by reducing the pressure while being heated as described above, esterification usually proceeds further while removing by-products. Even in the distillation step, the inside of the reaction system is heated to a temperature higher than the melting point of the polyesteramide obtained (that is, extracted from the reaction kettle) or 10 ° C. higher than the glass transition temperature when the melting point is not detected. It is preferable.
After completion of the distillation step, the inside of the reaction kettle is returned to normal pressure, and then the polyesteramide remaining in the reaction kettle is extracted from the reaction kettle.

(Drying and solid phase polymerization process)
After the distillation step, the polyesteramide extracted from the reaction kettle may be dried after being pelletized, for example. Further, the polyesteramide extracted from the reaction kettle may be subjected to solid-phase polymerization in order to further increase the degree of polymerization after being pelletized, for example.
As a heating device used in drying or solid-phase polymerization, a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum heating device called a rotary dryer, or a rotary blade inside a nauta mixer is used. A conical heating device and a vibratory dryer equipped with the above can be suitably used, but a known method and apparatus can be used without being limited thereto.

(Separation process)
In the above description, an example in which the second reaction step is continuously performed in the same reaction vessel without removing the reaction product obtained in the first reaction step from the reaction vessel has been described. The reaction product obtained in the step may be subjected to separation treatment, and then the second reaction step may be performed.
As a separation treatment method, for example, a method of precipitating and separating a reaction product by crystallization or the like, or a method of distilling at least a part of by-products and raw materials under reduced pressure or heating, By-products (for example, alcohol (A1)) by-produced in the first reaction step, and a method of separating at least a part of the condensate (A) and diamine (B) as raw materials from the reaction product can be mentioned. . When the reaction product is thus separated, the polyesterification in the second reaction step is performed as a by-product alcohol (A1) (particularly, a monoalcohol), a raw material condensate (A), or a diamine (B). It progresses without being inhibited.
The separated reaction product is returned to a different reaction kettle or the same reaction kettle, and usually after a diol post-addition step described later, the second reaction step is performed.

  The separation step is preferably carried out when the alcohol (A2) constituting the condensate (A) as a raw material contains a monoalcohol. When the alcohol (A2) is a monoalcohol, a byproduct produced as a by-product from the condensate (A) is also a monoalcohol, which tends to inhibit polyesterification. Therefore, such a byproduct is removed in advance in the separation step. By doing so, side reactions are prevented from occurring in the second reaction step.

(Diol post-addition process)
As described above, in the first reaction step, a reaction product of the condensate (A) and the diamine (B) is generated by an amidation reaction, and then the added diol compound (X) is further mixed with the reaction product. (Diol post-addition step). Thus, it becomes easy to adjust the copolymerization ratio of diamine and aromatic dicarboxylic acid by adding the post-diol addition step.
The reaction product and the post-addition diol compound (X) can be mixed, for example, after the first reaction step, without adding the reaction product from the reaction kettle to the reaction kettle (reaction system). The diol compound (X) may be added. Alternatively, the reaction product may be extracted from the reaction kettle, and the reaction product may be charged again in the same or different reaction kettle as that in which the first reaction step has been performed and mixed with the post-addition diol compound (X). In this case, the post-addition diol compound (X) may be previously charged in the reaction kettle, and then the reaction product may be added to the post-addition diol compound (X), or the reaction product may be added to the reaction kettle first. Then, the post-addition diol compound (X) may be added to the reaction product, or the reaction product and the post-addition diol compound (X) may be simultaneously added to the reaction kettle. The reaction product extracted from the reaction kettle is preferably charged again into the reaction kettle after the above-described separation step.

In the diol post-addition step, the post-addition diol compound (X) mixed with the reaction product is a condensate of an aliphatic diol having 2 or more carbon atoms and an aromatic dicarboxylic acid, and a compound in which both ends are hydroxyl groups ( And at least one selected from aliphatic diols having 2 or more carbon atoms (also referred to as “diol (XC)”).
Here, a compound (diol (XA)), which is a condensate of an aliphatic diol having 2 or more carbon atoms and an aromatic dicarboxylic acid, and both ends are hydroxyl groups, is a compound listed in the above-mentioned condensate (A). Among these, it can be used by appropriately selecting from diols.
The diol (XA) is a condensate of an aliphatic diol having 2 to 4 carbon atoms (more preferably an alkanediol) and the aromatic dicarboxylic acid (A1) represented by the above general formula [1]. In addition, the compound is preferably a compound in which both ends are hydroxyl groups, and may be a monomer or an oligomer, or a mixture thereof.
In addition, since other description and preferable aspects of this compound (diol (XA)) are the same as the above-mentioned condensate (A) and the diol (a) contained in the condensate (A), the description thereof Omitted. The amount of the diol (XA) charged is such that the mol% of the structural unit derived from the diamine with respect to the structural unit derived from the aromatic dicarboxylic acid in the reaction system of the second reaction step falls within the range described later. You only have to set it.
Further, the diol having 2 or more carbon atoms (diol (XC)) can be appropriately selected from the compounds exemplified as the diol compound (C) and can be used.

  In the diol post-addition step, one or both of the diol (XA) and diol (XC) described above may be mixed with the reaction product, but at least the diol (XA) is mixed with the reaction product. It is preferable. By using diol (XA), it is possible to advance esterification more appropriately.

In addition, when diol (XC) is added in the diol post-addition step, the amount of diol present in the reaction system increases, and thus the esterification reaction rate tends to increase. On the other hand, since the unreacted diol needs to be removed from the reaction system in the above distillation step, if it is excessively charged, the time for the distillation step becomes long.
Therefore, in order to make the time of the distillation step moderately long while the esterification proceeds moderately, the amount of diol (XC) charged is derived from the diol present in the reaction system in the second reaction step. The structural unit is preferably set to 5 to 250 mol%, more preferably 10 to 200 mol%, based on 100 mol% of the structural unit derived from the aromatic dicarboxylic acid (A1) present in the reaction system. The

In addition, as mentioned above, when the condensate (A) mixed with the diamine (B) in the mixing step contains the diol (a), the diol post-addition step is a step that is not so necessary and is performed. Or may not be implemented. On the other hand, when the diol (a) is not contained in the condensate (A) mixed with the diamine (B), it is appropriate to carry out the diol post-addition step. This is because when the condensate (A) does not contain the diol (a), an ester bond is not formed only with the condensate (A) and the diamine (B).
However, even if the diol (a) is not contained in the condensate (A), in the mixing step as described above, in addition to the condensate (A) and the diamine (B), other diol compounds (C ) May be mixed with the reaction system, the diol post-addition step may not be performed. This is because the esterification reaction can also proceed with the diol compound (C).

When the diol post-addition step is performed, the second reaction step is performed after the diol post-addition step. That is, after the diol post-addition step, the reaction system is heated to cause the reaction product to react with the post-addition diol compound (X), and an esterification reaction is performed to generate a polyesteramide.
The second reaction step performed after the diol post-addition step is also preferably performed in the presence of a transition metal catalyst. That is, it is preferable to mix the post-addition diol compound (X) and the transition metal catalyst into the reaction product, and then perform the second reaction step.
Also when it is performed after the diol post-addition step, the other features of the second reaction step are as described above, and thus the description thereof is omitted. And after a 2nd reaction process, it is preferable to implement a distillation process etc. continuously as mentioned above.

  In addition, although the diol post-addition process demonstrated above was demonstrated as a process isolate | separated from the 1st and 2nd reaction heating process for convenience of explanation, it may be implemented, advancing amidation reaction and esterification reaction. At least a part of the post-addition step may be performed in parallel with the second reaction heating step, for example. That is, for example, the esterification reaction may be advanced by heating the reaction system while adding the post-addition diol compound (X) to the reaction product.

Moreover, in said 2nd reaction process, each raw material is used so that the structural unit derived from a diamine may be 1-99 mol% with respect to 100 mol% of all the structural units derived from aromatic dicarboxylic acid contained in a reaction system. (That is, the condensate (A), the diamine (B), and the post-addition diol compound (X)) are preferably charged, and the mol% is more preferably 3 to 75 mol%, and more preferably 10 to 50 mol. % Is more preferable.
In the case where the diol post-addition step is not performed, the ratio of the structural unit derived from diamine to the total structural unit derived from aromatic dicarboxylic acid contained in the reaction system is 100% by mole. What is necessary is just to adjust suitably the addition amount of the diamine (B) with which a structural unit derived from a group dicarboxylic acid is 100 mol%, and is prepared by a mixing process.

On the other hand, when performing a diol post-addition process, it is necessary to add diol (XA) so that it may become the said mol% range in this process. For example, the diol post-addition step is performed after the first reaction step and the separation step. The separation step removes the condensate (A) from the reaction system, and the aromatic dicarboxylic acid (A) contained in the reaction system ( A part of the structural unit derived from A1) is removed from the reaction system. Therefore, in such a case, after confirming the molar amount of the structural unit derived from the aromatic dicarboxylic acid (A1) and the structural unit derived from the diamine (B) contained in the reaction product by, for example, ¹ H NMR. The amount of diol (XA) charged may be set.

In the present invention, the amidation reaction and esterification reaction can be performed under normal pressure. That is, the first and second reaction steps are preferably performed under normal pressure. Moreover, after mixing a condensate (A) and a diamine by a mixing process, a reaction system can also be maintained under a normal pressure until the distillation process is started.
In this way, by performing the amidation reaction and the esterification reaction under normal pressure, it is not necessary to set the equipment such as the reaction kettle to withstand pressure specifications. In addition, as described above, by using a condensate (A) that satisfies the requirements (1) to (3), it is possible to appropriately advance the amidation reaction and the esterification reaction even under normal pressure. It is.

In the present invention, the reaction is preferably carried out without substantially adding a solvent and a dispersion medium. That is, from the mixing step to the end of the second reaction step, the solvent and the dispersion medium are not substantially added to the reaction system, and the amidation reaction and the esterification reaction are performed without substantially adding the solvent and the dispersion medium. Is preferred.
Here, the solvent and the dispersion medium are not reactive to the raw material of the present invention (diamine (B) and condensate (A)) or reaction product and are liquid at room temperature (23 ° C.). A typical example is water or a monoalcohol having 1 to 7 carbon atoms. The various alcohols (A2) by-produced in the amidation reaction or esterification reaction, the diol compound (C) added to the reaction system, and the post-addition diol compound (X) are included in the solvent and the dispersion medium. Absent.
In addition, “solvent and dispersion medium substantially not added” means that a small amount of solvent and dispersion medium is added to the reaction system to such an extent that the fluidity of the reaction system is not substantially improved, as well as when no solvent and dispersion medium are added. Means that it may be added. In addition, the addition amount of such a solvent and a dispersion medium is normally less than 20 mass% with respect to the total amount of the condensate (A) and diamine (B) with which a reaction system is prepared, for example, Preferably it is 10 mass% Less than, more preferably less than 3% by mass.

(Antioxidant)
In the present invention, it is preferable to perform at least one of an amidation reaction performed by reacting the condensate (A) with the diamine (B) and an esterification reaction further performed after the amidation in the presence of an antioxidant. . In the present invention, by performing the reaction in the presence of an antioxidant, it is possible to improve the thermal stability of the reaction mixture in the reaction system and improve the quality of the obtained polyesteramide. The timing at which the antioxidant is added to the reaction system is not particularly limited. For example, it may be added in the mixing step or the diol post-addition step.

  The antioxidant is more preferably present in the reaction system in the esterification reaction (that is, the second reaction step). The esterification reaction is usually carried out in a higher temperature environment than the amidation reaction (that is, the first reaction step), so that the reaction mixture in the reaction system is likely to be thermally deteriorated, but by adding an antioxidant, Such thermal degradation can be effectively prevented. In the present invention, the esterification reaction is preferably performed in the presence of a transition metal catalyst as described above, that is, the esterification reaction is preferably performed in the presence of a transition metal catalyst and an antioxidant. .

However, it is effective that the antioxidant is present in the reaction system also in the amidation reaction (first reaction step). Therefore, when there is no separation step between the first and second reaction steps, the antioxidant is preferably added to the reaction system before the first reaction step, for example, in the mixing step. When there is no separation step, the antioxidant added before the first reaction step is present not only in the first reaction step but also in the second reaction step. It can be used effectively.
On the other hand, if an antioxidant is added to the reaction system in the first reaction step, the antioxidant may partially deactivate due to its thermal history, and may not be sufficiently effective in the subsequent steps. There is. Therefore, the antioxidant may be added to the reaction system during the first and second reaction steps (when there is a separation step, between the separation step and the second reaction step), for example, in the diol post-addition step. It is mentioned as a preferred embodiment.

  Furthermore, in order to obtain the condensate (A) before the mixing step, the aromatic dicarboxylic acid (A1) and the alcohol (A2) may be subjected to a polycondensation reaction. And may be added to the reaction system. In that case, the antioxidant added in the polycondensation reaction can be allowed to exist as it is in either of the reaction systems of the first and second reaction steps, and thus is used more effectively.

Examples of the antioxidant include phosphorus compounds and phenol compounds. Among these, phosphorus compounds are preferable.
Specific examples of the phosphorus compound include phosphoric acid, phosphorous acid, phosphoric acid ester, phosphorous acid ester and the like. Examples of phosphate esters include methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, And triphenyl phosphate. Phosphites include methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphite, phosphorous acid Examples include trimethyl, triethyl phosphite, tributyl phosphite, triphenyl phosphite, and the like. Among these, triethyl phosphate (triethyl phosphate) is preferable.

  Moreover, a hindered phenol type compound is mentioned as a phenol type compound. Specific examples of the hindered phenol compound include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4′-butylidenebis (3-methyl-6). -T-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6 (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-1-butylphenol), N, N′-hexamethylenebis (3,5-di-t-butyl) -4-hydroxy-hydroxycinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzyl sulfonate) calcium, tris- (3,5-di-t-butyl-4-hydroxy) Benzyl) -isocyanurate, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylpheno , Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 2,2′-methylene- Bis- (4-ethyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O -Cresol, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetra Oxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, bis [3,3′-bis- (4′-hydroxy-3′-T-butylphenyl) butyric acid] glycol ester, 1,3, 5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, d-α-tocopherol, etc. It is done.

The antioxidant is usually used in an amount of 0.001 to 0.5 mol%, preferably 0.005 to 0.05 mol%, based on 100 mol% of the structural unit derived from the aromatic dicarboxylic acid contained in the reaction system. The
The antioxidant may be diluted and then added to the reaction system, or may be added to the reaction system as it is without being diluted. The antioxidant is diluted with, for example, a diol compound. Here, as the diol compound used as the diluent, various diols exemplified in the above-mentioned diol compound (C) can be used.

The polyesteramide obtained in the present invention is a polymer having an ester bond and an amide bond, and the molar ratio (E: A) of the ester bond (E) to the amide bond (A) is, for example, 1: 0.01. ˜1: 20, preferably 1: 0.03 to 1: 2.5, more preferably 1: 0.05 to 1: 1. The ratio of such an ester bond to an amide bond is detected by an integral ratio of ¹ H NMR. As a specific example, it can be determined by a ratio of an integral value derived from a proton on an aromatic dicarboxylic acid bonded to a diol and an integral value derived from a proton on an aromatic dicarboxylic acid bonded to a diamine. If it is difficult to discriminate between the two peaks, or if the peaks overlap, a peak that can be appropriately compared is selected, such as another proton integral value derived from diamine.

  As described above, in the present invention, the condensate (A) and the diamine (B) may be amidated under relatively mild conditions and without losing the material balance, and then esterified subsequently. Is possible. Therefore, it is possible to obtain a high-purity and high-quality polyester amide without generating many by-products without using industrially special equipment.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to a following example.

In addition, the measuring method and evaluation method of various physical properties in the present invention are as follows.
[Melting temperature]
The melting temperature of the aromatic dicarboxylic acid ester condensate (A) was measured by differential scanning calorimetry (DSC) using DSC-60 manufactured by Shimadzu Corporation. As measurement conditions, about 5 mg of a sample was charged in a DSC measurement pan and heated at 10 ° C./min under a nitrogen atmosphere.
[Thermal properties evaluation]
The glass transition point (Tg), melting point (Tm), and temperature drop crystallization temperature (Tcc) of polyesteramide were measured by differential scanning calorimetry (DSC) using DSC-60 manufactured by Shimadzu Corporation. As measurement conditions, a sample of about 5 mg was charged in a DSC measurement pan, heated at 10 ° C./min under a nitrogen atmosphere, rapidly cooled when it reached 300 ° C., and again at 10 ° C./min. The temperature was raised.
[Number average molecular weight]
The number average molecular weight (Mn) of the polyesteramide was measured by the gel permeation chromatograph (GPC) method under the following conditions.
The number average molecular weight (Mn) of the polyesteramide was determined by GPC measurement using HLC-8320GPC manufactured by Tosoh Corporation. TSKgel SuperHM-H was used as the measurement column, hexafluoroisopropanol (HFIP) in which 10 mmol / l sodium trifluoroacetate was dissolved was used as the solvent, and the measurement temperature was 40 ° C. In addition, the number average molecular weight of the polyesteramide was calculated | required as a molecular weight of PMMA conversion. A calibration curve was prepared by dissolving 6 levels of PMMA in HFIP.
[NMR]
¹ H NMR was measured at 400 MHz using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., trade name: JNM-AL400) as a measuring apparatus. As a solvent, d-trifluoroacetic acid was used, and tetramethylsilane was measured as an internal standard.
[Amount of impurities]
^In the measurement result of ¹ H NMR, components other than those that could be identified as the peak derived from the polyesteramide were defined as contaminants, and the amount of the contaminants was evaluated. In addition, it was determined that there were few impurities when the total peak integrated value of impurities was less than 20% with respect to the total integrated value of proton peaks on terephthalic acid derived from polyesteramide. Further, when the total peak integrated value of the contaminants was 20% or more, it was determined that there were many contaminants.

<Example 1>
In a 500 mL reaction kettle, 331.6 g (1.304 mol, molar ratio (A2 / A1) = 2, melting temperature: 106 ° C.) of bis (2-hydroxyethyl) terephthalate (BHET) and 10% by weight of triethyl phosphate were dissolved. 475 mg of ethylene glycol solution (261 μmol as triethyl phosphate, 0.020 mol% with respect to BHET) was added, and after nitrogen substitution, the mixture was heated to 140 ° C. at normal pressure. After 35.5 g (0.261 mol, boiling point: 248 ° C.) of metaxylylenediamine was added dropwise to the molten BHET over 10 minutes, the temperature was raised to 240 ° C. over 90 minutes.
Thereafter, 5.70 g of an ethylene glycol solution in which 2% by weight of antimony trioxide was dissolved (391 μmol as antimony trioxide, 0.030 mol% with respect to BHET) was added and stirred at 240 ° C. for 10 minutes. Next, while maintaining the temperature at 240 ° C., the pressure was reduced to 1.05 torr over 90 minutes to distill off ethylene glycol, and after the torque became a constant value, nitrogen was fed into the reaction kettle to normal pressure. Then, the polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1. Further, FIG. 1 shows a ¹ H NMR chart of the polyesteramide obtained in Example 1.

<Example 2>
In a 500 mL reaction kettle, 343.9 g (1.353 mol) of bis (2-hydroxyethyl) terephthalate (BHET) and 493 mg of ethylene glycol solution in which 10% by weight of triethyl phosphate was dissolved (271 μmol as triethyl phosphate, 0 with respect to BHET) 0.020 mol%) was added and nitrogen substitution was performed, followed by heating to 140 ° C. at normal pressure. After 18.4 g (0.135 mol) of metaxylylenediamine was added dropwise to the molten BHET over 10 minutes, the temperature was raised to 240 ° C. over 90 minutes.
Thereafter, 5.92 g of an ethylene glycol solution in which 2 wt% of antimony trioxide was dissolved (406 μmol as antimony trioxide, 0.030 mol% with respect to BHET) was added and stirred at 240 ° C. for 10 minutes. Next, while maintaining the temperature at 240 ° C., the pressure was reduced to 1.03 torr over 90 minutes to distill off ethylene glycol, and after the torque became a constant value, nitrogen was fed into the reaction kettle and normal pressure was reached. The polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1. Further, FIG. 2 shows a ¹ H NMR chart of the polyesteramide obtained in Example 2.

<Example 3>
In a 500-mL reaction kettle, 320.2 g (1.259 mol) of bis (2-hydroxyethyl) terephthalate (BHET) and 459 mg of ethylene glycol solution in which 10 wt% of triethyl phosphate was dissolved (252 μmol as triethyl phosphate, 0 with respect to BHET) 0.020 mol%) was added and nitrogen substitution was performed, followed by heating to 140 ° C. at normal pressure. After 51.5 g (0.378 mol) of metaxylylenediamine was added dropwise to BHET in a molten state over 10 minutes, the temperature was raised to 240 ° C. over 90 minutes.
Thereafter, 5.51 g of ethylene glycol solution in which 2% by weight of antimony trioxide was dissolved (378 μmol as antimony trioxide, 0.030 mol% with respect to BHET) was added and stirred at 240 ° C. for 10 minutes. Next, while maintaining the temperature at 240 ° C., the pressure was reduced to 1.10 torr over 90 minutes to distill off ethylene glycol, and after the torque became a constant value, nitrogen was fed into the reaction kettle and normal pressure was reached. The polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1.

<Example 4>
In a 500 mL reaction vessel, 299.5 g (1.178 mol) of bis (2-hydroxyethyl) terephthalate (BHET) and 429 mg of ethylene glycol solution in which 10% by weight of triethyl phosphate was dissolved (236 μmol as triethyl phosphate, 0 with respect to BHET) 0.020 mol%) was added and nitrogen substitution was performed, followed by heating to 140 ° C. at normal pressure. After 80.2 g (0.589 mol) of metaxylylenediamine was added dropwise to the molten BHET over 10 minutes, the temperature was raised to 240 ° C. over 90 minutes.
Thereafter, 5.15 g of an ethylene glycol solution in which 2 wt% of antimony trioxide was dissolved (353 μmol as antimony trioxide, 0.030 mol% with respect to BHET) was added and stirred at 240 ° C. for 10 minutes. Next, while maintaining the temperature at 240 ° C., the pressure was reduced to 1.10 torr over 90 minutes to distill off ethylene glycol, and after the torque became a constant value, nitrogen was fed into the reaction kettle and normal pressure was reached. The polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1.

<Example 5>
762.7 g (3.000 mol) of bis (2-hydroxyethyl) terephthalate (BHET) was charged into a 3 L reaction kettle, and after nitrogen substitution, it was heated to 140 ° C. at normal pressure. After 204.29 g (1.500 mol) of metaxylylenediamine (MXDA) was added dropwise to BHET in a molten state over 10 minutes, the temperature was raised to 180 ° C. over 20 minutes and stirred for 10 minutes. Thereafter, the reaction mixture was cooled to room temperature, methanol was added, and the precipitated white solid was collected by filtration and dried in a vacuum dryer to obtain a reaction product composed of a condensate of BHET and MXDA. When this reaction product was measured by ¹ H NMR, the constituent unit derived from MXDA in the condensate was 37 mol%, and the constituent unit derived from TPA was 41 mol%.
Subsequently, 258.1 g (1.015 mol) of bis (2-hydroxyethyl) terephthalate (BHET), 475 mg of ethylene glycol solution in which 10% by weight of triethyl phosphate was dissolved (261 μmol as triethyl phosphate) in a 500 mL reaction kettle, and Then, 87.88 g of reaction product (containing 0.261 mol as MXDA and 0.289 mol as terephthalic acid) was added, and after replacing with nitrogen, the mixture was heated to 240 ° C. over 90 minutes.
Then, 5.70 g (391 μmol as antimony trioxide) of an ethylene glycol solution in which 2% by weight of antimony trioxide was dissolved was added and stirred at 240 ° C. for 10 minutes. Next, while maintaining the temperature at 240 ° C., the pressure was reduced to 1.05 torr over 90 minutes to distill off ethylene glycol, and after the torque became a constant value, nitrogen was fed into the reaction kettle to return to normal pressure, Polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1.

<Example 6>
Ethylene glycol in which 389.0 g (2.342 mol) of terephthalic acid (TPA), 290.7 g (4.683 mol) of ethylene glycol (EG), and 10% by weight of triethyl phosphate were dissolved in a 1 L reaction kettle equipped with a partial condenser 853 mg of the solution (468 μmol as triethyl phosphate, 0.020 mol% with respect to terephthalic acid) was added, and after nitrogen substitution, the solution was heated to 240 ° C. at 0.3 MPa. After the generated water was distilled off, the pressure was returned to normal pressure, a part was taken out and the melting temperature was measured. Further, the TPA content ratio was measured by ¹ H NMR. The melting temperature of the obtained condensate (A) was 104 ° C., and the content of structural units derived from TPA was 50 mol% with respect to 100 mol% of EG (molar ratio (A2 / A1) = 2). The number average molecular weight of the product (A) was 1600.
Subsequently, 331.6 g of the obtained condensate (A) was transferred to another 500 mL reaction kettle, purged with nitrogen, and then kept at 140 ° C. at normal pressure. After 35.5 g (0.261 mol) of metaxylylenediamine was added dropwise over 10 minutes to the molten condensate (A), the temperature was raised to 240 ° C. over 90 minutes. Thereafter, 5.70 g of ethylene glycol solution in which 2% by weight of antimony trioxide was dissolved (391 μmol as antimony trioxide, 0.030 mol% with respect to the molar amount of the structural unit derived from TPA in the condensate (A)) was added. After stirring at 240 ° C. for 10 minutes, while maintaining at 240 ° C., the pressure was reduced to 1.05 torr over 90 minutes to distill off ethylene glycol, and after the torque became a constant value, nitrogen was sent to the reaction kettle. The pressure was returned to normal pressure, and the polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1.

<Example 7>
A 3 L reactor was charged with 880.1 g of polyethylene terephthalate (including 4.584 mol as a polyethylene terephthalate unit structure) and 284.5 g (4.584 mol) of ethylene glycol (EG), and after nitrogen substitution, 220 MPa at 0.3 MPa. Heated to ° C. After 120 minutes, the temperature was returned to room temperature and normal pressure, the resulting condensate (A) was taken out, and the melting point was measured. Further, the TPA content ratio was measured by ¹ H NMR. The melting point of the condensate (A) was 110 ° C., and the content of the structural unit derived from TPA with respect to 100 mol% of the structural unit derived from EG in the condensate (A) was 51 mol% (molar ratio (A2 / A1) = 100 / 51). The number average molecular weight of the condensate (A) was 1800.
Subsequently, 331.6 g of the condensate (A) obtained was transferred to another 500 mL reaction kettle, and 853 mg of ethylene glycol solution in which 10% by weight of triethyl phosphate was dissolved (468 μmol as triethyl phosphate, TPA in the condensate (A)). After replacing with nitrogen by adding 0.020 mol% to the unit molar amount, the mixture was heated to 140 ° C. at normal pressure. After 35.5 g (0.261 mol) of metaxylylenediamine was added dropwise over 10 minutes to the molten condensate (A), the temperature was raised to 240 ° C. over 90 minutes. Thereafter, 5.70 g of ethylene glycol solution in which 2% by weight of antimony trioxide was dissolved (391 μmol as antimony trioxide, 0.030 mol% with respect to the molar amount of TPA unit in the condensate (A)) was added at 240 ° C. After stirring for 10 minutes, while maintaining the temperature at 240 ° C., the pressure was reduced to 1.05 torr over 90 minutes and the ethylene glycol was distilled off. After the torque reached a constant value, nitrogen was fed into the reaction kettle. The pressure was restored and the polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1.

<Example 8>
37.1 g (0.261 mol) of 1,3- (bisaminomethyl) cyclohexane (1,3-BAC, cis isomer / trans isomer = 7/3, boiling point: 220 ° C.) instead of metaxylylenediamine as diamine A polyesteramide was obtained by synthesizing in the same manner as in Example 1 except that.

<Example 9>
As a diamine, 37.1 g (0.261 mol) of 1,4- (bisaminomethyl) cyclohexane (cis isomer / trans isomer = 6/4; 1,4-BAC, boiling point: 241 ° C.) was added instead of metaxylylenediamine. A polyesteramide was obtained by synthesizing in the same manner as in Example 1 except that.

<Example 10>
Polyesteramide was obtained by synthesizing in the same manner as in Example 1 except that 30.3 g (0.261 mol) of 1,6-hexamethylenediamine (HMDA, boiling point: 204 ° C.) was added in place of metaxylylenediamine as diamine.

<Example 11>
666.7 g (3.000 mol) of diethyl terephthalate (melting temperature: 42 ° C., molar ratio (A2 / A1) = 2/1) was charged into a 3 L reactor, and after nitrogen substitution, 80 ° C. at normal pressure. Until heated. After adding 204.3 g (1.500 mol) of metaxylylenediamine over 10 minutes to diethyl terephthalate in a molten state, the mixture was heated to 100 ° C. over 10 minutes and stirred for 30 minutes. Thereafter, the mixture was cooled to room temperature, methanol was added, and the precipitated white solid was collected by filtration and dried in a vacuum dryer to obtain a reaction product. The MXDA content in the reaction product was 33 mol%, and the TPA content was 45 mol%.
Subsequently, 241.2 g (0.949 mol) of bis (2-hydroxyethyl) terephthalate (BHET) in a 500 mL reaction kettle and 475 mg of ethylene glycol solution (261 μmol as triethyl phosphate) in which 10% by weight of triethyl phosphate was dissolved, and 99.0 g (containing 0.261 mol as MXDA and 0.356 mol as terephthalic acid) was added to the above reaction product, and the mixture was purged with nitrogen, and then heated to 240 ° C. over 90 minutes. Thereafter, 5.70 g of ethylene glycol solution in which 2% by weight of antimony trioxide was dissolved (391 μmol as antimony trioxide) was added, stirred at 240 ° C. for 10 minutes, and maintained at 240 ° C. for 90 minutes to 1.05 torr. The pressure was reduced and ethylene glycol was distilled off, and after the torque became a constant value, nitrogen was fed into the reaction kettle to return to normal pressure, and the polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1.

<Comparative Example 1>
Into a 3 L reactor, 582.6 g (3.000 mol) of dimethyl terephthalate (melting temperature: 140 ° C.) was added, and after nitrogen substitution, it was heated to 140 ° C. at normal pressure. After 204.3 g (1.500 mol) of metaxylylenediamine was added dropwise to molten dimethyl terephthalate over 10 minutes, the temperature was raised to 180 ° C. over 20 minutes and stirred for 10 minutes. Thereafter, the mixture was cooled to room temperature, methanol was added, and the precipitated white solid was collected by filtration and dried in a vacuum dryer to obtain a reaction product. The MXDA content in the reaction product was 33 mol%, and the TPA content was 45 mol%.
Subsequently, 241.2 g (0.949 mol) of bis (2-hydroxyethyl) terephthalate (BHET), 475 mg of ethylene glycol solution in which 10% by weight of triethyl phosphate was dissolved in a 500 mL reaction kettle (261 μmol as triethyl phosphate), and the above 99.0 g of reaction product (containing 0.261 mol as MXDA, containing 0.356 mol as terephthalic acid) was added, and after replacing with nitrogen, the mixture was heated to 240 ° C. over 90 minutes. Thereafter, 5.70 g of ethylene glycol solution containing 2% by weight of antimony trioxide (391 μmol as antimony trioxide) was added and stirred at 240 ° C. for 10 minutes, and then the pressure was reduced to 1.05 torr over 90 minutes. While distilling off, after the torque became a constant value, nitrogen was fed into the reaction kettle to return to normal pressure, and the polyesteramide was extracted. The evaluation results of the obtained polyesteramide are shown in Table 1.

<Comparative example 2>
In a 500 mL reaction kettle, 237.6 g of polyethylene terephthalate (melting temperature: 255 ° C.) pulverized product (containing 1.238 mol of ethylene terephthalate unit) and 5.41 g of ethylene glycol solution containing 2% by weight of antimony trioxide (antimony trioxide) 371 μmol, 0.030 mol% with respect to the ethylene terephthalate unit mol amount), and 33.7 g (0.248 mol) of metaxylylenediamine were further mixed. Thereafter, the temperature was increased to 280 ° C. and 3 MPa over 90 minutes. Thereafter, 5.41 g of an ethylene glycol solution in which 2% by weight of antimony trioxide was dissolved (371 μmol as antimony trioxide, 0.030 mol% with respect to the mol amount of ethylene terephthalate unit) was added and stirred at 280 ° C. and 3 MPa for 10 minutes. After that, the pressure was reduced to 1.05 torr over 90 minutes, but the torque did not increase. Thereafter, nitrogen was introduced into the reaction kettle to return to normal pressure, and the polyesteramide was extracted.

As is apparent from the results of Examples 1 to 11, by using the predetermined alcohol (A2) and aromatic dicarboxylic acid condensate (A) as a raw material, amidation and reaction can be performed under mild reaction conditions at normal pressure. Esterification proceeded appropriately, and polyester amides with good thermophysical properties and few by-products could be synthesized.
On the other hand, in Comparative Examples 1 and 2, since a condensate of methanol and aromatic dicarboxylic acid (dimethyl terephthalate) or polyester having a high melting temperature was used as a raw material, the reaction was appropriate when the reaction was performed under mild conditions. Thus, a polyester amide with many by-products and a low molecular weight was obtained. In addition, the polyesteramides of Comparative Examples 1 and 2 had lower glass transition temperatures and inferior thermophysical properties than Examples 1, 5, 6, and 11 synthesized at the same diamine ratio.

Claims (15)

The aromatic dicarboxylic acid ester condensate (A) is mixed with the diamine (B) to react them,
The manufacturing method of the polyesteramide which the aromatic dicarboxylic acid ester condensate (A) made to react with diamine (B) satisfy | fills the following requirements (1)-(3).
(1) The aromatic dicarboxylic acid ester condensate (A) is an aromatic dicarboxylic acid (A1), a diol having 2 or more carbon atoms, an aliphatic monoalcohol having 2 to 4 carbon atoms, and an aromatic having 6 to 9 carbon atoms. It is a condensate with at least one alcohol (A2) selected from the group monoalcohols.
(2) The molar ratio (A2 / A1) of the structural unit derived from the alcohol (A2) to the structural unit derived from the aromatic dicarboxylic acid (A1) in the total condensate (A) is greater than 1.
(3) The melting temperature of the aromatic dicarboxylic acid ester condensate (A) is lower than the boiling point of the diamine (B). The aromatic dicarboxylic acid ester condensate (A) is a condensate of an alkanediol having 2 to 4 carbon atoms with an aromatic dicarboxylic acid represented by the following general formula [1], and the following general formula [2 The method for producing a polyesteramide according to claim 1, wherein the method is at least one selected from the compounds represented by the formula:

(In General Formula [1], X ¹ represents an arylene group having 6 to 14 carbon atoms or a heteroarylene group having 3 to 14 carbon atoms.)

(In General Formula [2], X ² represents an arylene group having 6 to 14 carbon atoms or a heteroarylene group having 3 to 14 carbon atoms, and R ¹ and R ² are each independently a hydrogen atom or a fatty acid having 2 to 4 carbon atoms. Selected from an aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 9 carbon atoms, and a hydroxyalkyl group having 2 to 4 carbon atoms, and at least one of R ¹ and R ² is either a hydrocarbon group or a hydroxyalkyl group .) After the reaction product of the aromatic dicarboxylic acid ester condensate (A) and the diamine (B) is formed, the post-addition diol compound (X) is further mixed with the reaction product, React with the reaction product,
The post-addition diol compound (X) is a condensate of a diol having 2 or more carbon atoms and an aromatic dicarboxylic acid, and is at least selected from a compound having both ends being hydroxyl groups and an aliphatic diol having 2 to 4 carbon atoms. The method for producing a polyesteramide according to claim 1 or 2, wherein the polyesteramide is one type.   Maintain the aromatic dicarboxylic acid ester condensate (A) at a temperature not lower than its melting temperature and lower than the boiling point of the diamine (B), and add the diamine (B) to the molten aromatic dicarboxylic acid ester condensate (A). The manufacturing method of the polyesteramide of any one of Claims 1-3 to do.   The method for producing a polyesteramide according to any one of claims 1 to 4, wherein the reaction is carried out by heating at a temperature equal to or higher than the melting point of the obtained polyesteramide or 10 ° C or higher than the glass transition temperature.   A by-product by-produced by the amidation reaction performed by reacting the diamine (B) with the aromatic dicarboxylic acid ester condensate (A), and a by-product by-produced by the esterification reaction further performed after the amidation The method for producing a polyesteramide according to any one of claims 1 to 5, wherein at least one of the above is distilled off under reduced pressure.   The diamine (B) is 1 to 99 mol% with respect to 100 mol% of the structural unit derived from the aromatic dicarboxylic acid contained in the aromatic dicarboxylic acid ester condensate (A). A process for producing a polyesteramide as described in 1.   The diamine (B) is reacted with the aromatic dicarboxylic acid ester condensate (A) to perform an amidation reaction, and then an esterification reaction further performed in the presence of a transition metal catalyst. The manufacturing method of the polyesteramide as described in a term.   The amidation reaction performed by reacting the diamine (B) with the aromatic dicarboxylic acid ester condensate (A) and the esterification reaction further performed after the amidation are performed in the presence of an antioxidant. The manufacturing method of the polyesteramide of any one of 1-8.   The method for producing a polyesteramide according to any one of claims 1 to 9, wherein the solvent and the dispersion medium are reacted with substantially no addition.   The amide (B) is reacted with the aromatic dicarboxylic acid ester condensate (A) to carry out an amidation reaction, and then the polyester amide obtained through the further esterification reaction is further subjected to solid phase polymerization. The manufacturing method of the polyesteramide of any one.   Aromatic dicarboxylic acid ester condensate (A) is diethyl terephthalate, diisopropyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dibenzyl terephthalate, condensate of terephthalic acid and ethylene glycol, terephthalic acid and 1,3-trimethylene The method for producing a polyesteramide according to any one of claims 1 to 11, which is at least one selected from a condensate of glycol and a condensate of terephthalic acid and 1,4-butanediol.   The method for producing a polyesteramide according to claim 12, wherein the condensate of terephthalic acid and ethylene glycol contains bis (2-hydroxyethyl) terephthalate.   The diamine (B) is at least one selected from an aliphatic diamine having 2 to 12 carbon atoms, an alicyclic diamine having 2 to 15 carbon atoms, and an aromatic diamine having 6 to 27 carbon atoms. 14. A process for producing a polyesteramide as set forth in any one of 13 above.   Diamine (B) is xylylenediamine, 1,3- (bisaminomethyl) cyclohexane, 1,4- (bisaminomethyl) cyclohexane, 1,6-hexamethylenediamine, 1,9-nonamethylenediamine, decamethylene. It is at least 1 sort (s) selected from diamine and 1, 4- phenylenediamine, The manufacturing method of the polyesteramide of any one of Claims 1-14.