JP5669174B2 - Crystals of dicarboxylic acid triazine active ester - Google Patents

Description

  The present invention relates to a dicarboxylic acid triazine active ester and a polyamide resin obtained by reacting the dicarboxylic acid triazine active ester with a diamine compound.

  The polycondensation reaction between dicarboxylic acid compounds and diamine compounds is widely performed, but condensing agents, catalysts, additives, by-products, etc. added to advance this reaction are ionic impurities derived from them. Often occurs. For example, in the method in which dicarboxylic acid and diamine are polycondensed in the presence of an aromatic phosphite ester and a pyridine derivative, phosphorus-based ionic impurities derived from the aromatic phosphite ester remain in the obtained polyamide resin. Often to do. Since this electrical property deteriorates, the use of this impurity in applications requiring electrical insulation is limited.

  Thus, for example, Patent Document 1 proposes a technique for reducing impurities by reducing the phosphorus content in the aromatic polyamide resin, but this still uses the polyamide resin for electric and electronic parts. In that case, the remaining ionic impurities may cause a decrease in electrical characteristics.

Recently, as a condensing agent for peptide synthesis, a triazine condensing agent of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, which is a non-phosphorus compound. Was developed.
This triazine-based condensing agent can be synthesized at low cost, and since the by-product is a water-soluble hydroxytriazine compound, it is attracting attention because of its advantages such as easy post-treatment after reaction and recyclability. For example, in Patent Document 2 and Non-Patent Document 1, application to the synthesis of an aromatic polyamide resin is also being studied.

  However, the synthesized aromatic polyamide resin described above cannot obtain the target molecular weight due to decomposition of the condensing agent during the reaction, or the chloride ion or hydroxytriazine compound derived from the condensing agent remains in the polyamide resin. It is easy to use, and when used for electric / electronic parts, there is a possibility of causing a decrease in electric characteristics.

JP 2006-28367 A JP 2009-74038 A

Takatoshi Kudo, Yoshiyuki Oishi, Orabetzyan, Kunio Mori, Kobunshi Shigshu, Vol. 64, 231 (2007)

  It is an object of the present invention to reduce a dicarboxylic acid triazine active ester, which is a monomer useful for the production of a polymer that is particularly useful for electric / electronic component applications by reducing the content of ionic impurities, and the dicarboxylic acid triazine active ester. It is to provide a polyamide resin obtained by reacting with a diamine compound.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific dicarboxylic acid triazine active ester is useful as a monomer for a polymer that satisfies high performance requirements in electric and electronic parts. The invention has been completed.

（式（Ａ）中、Ｒ₁は、下記式（１）

［式（１）中、Ｒ ₄ は、Ｈ、Ｏ、Ｎ、Ｓ、Ｆ若しくはＳｉ、又は構造中にＯ、Ｎ、Ｓ、Ｆ及びＳｉからなる群から選ばれる１種以上の元素を含む炭素数１〜６の置換基を示す。Ｘは、直接結合、Ｏ、Ｎ、Ｓ、Ｆ若しくはＳｉ、又は構造中にＯ、Ｎ、Ｓ、Ｆ及びＳｉからなる群から選ばれる元素を含む炭素数１〜６の２価の結合基を示す。ａ、ｂ、ｃ及びｄは平均置換基数であって、ａ、ｂ及びｃはそれぞれ０〜４の正数を、ｄは０〜６の正数を示す。］で表される群から選ばれる２価の芳香族残基を示す。Ｒ₂は炭素数１〜４のアルキル基または、炭素数６〜８の芳香族残基を示す。）で表されるジカルボン酸トリアジン活性エステルの結晶である。 That is, the crystal of the dicarboxylic acid triazine active ester of the present invention has the following formula (A):

(In the formula (A), R ₁ represents the following formula (1)

[In formula (1), R ₄ is carbon containing one or more elements selected from the group consisting of H, O, N, S, F or Si, or O, N, S, F and Si in the structure. The substituent of number 1-6 is shown. X represents a direct bond, O, N, S, F or Si, or a divalent linking group having 1 to 6 carbon atoms containing an element selected from the group consisting of O, N, S, F and Si in the structure. Show. a, b, c and d are the average number of substituents, a, b and c each represent a positive number from 0 to 4, and d represents a positive number from 0 to 6. ] The bivalent aromatic residue chosen from the group represented by this is shown. R ₂ represents an alkyl group having 1 to 4 carbon atoms or an aromatic residue having 6 to 8 carbon atoms. ) Crystal of dicarboxylic acid triazine active ester represented by

In such a dicarboxylic acid triazine active ester, R ₂ is more preferably an alkyl group having 1 to 4 carbon atoms.

Also preferably, in formula (1), R ₄ is a hydrogen atom and X is a direct bond, O, SO ₂ or CO.

  The dicarboxylic acid triazine active ester of the present invention is particularly useful as a monomer that can reduce the content of ionic impurities and can produce a polymer suitable for use in electrical and electronic parts.

The dicarboxylic acid triazine active ester of the present invention is characterized by having a structure represented by the following formula (A).

R _{1 in the} formula (A) can be a divalent aromatic residue containing one or more elements selected from O, N, S, F and Si in the structure.
Here, the divalent aromatic residue means a residue obtained by removing two hydrogen atoms from an aromatic ring. For example, in a compound having a plurality of aromatic rings such as biphenyl ether, different aromatic rings. Residues obtained by removing two hydrogen atoms from can also be included in the category of divalent aromatic residues.
Specifically, examples of the divalent aromatic residue include residues of benzene, biphenyl, biphenyl ether, biphenyl sulfone, biphenyl ketone, and naphthalene.

In addition, R _{1 in the} formula (A) can be a C 1-12 divalent organic group.
Specific examples include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, dodecylene group, and xylylene group.

Preferably, R ₁ in the formula (A) can be a divalent aromatic residue selected from the group represented by the following formula (1).

R _{4 in} formula (1) is H, O, N, S, F, or Si, or a carbon number that includes one or more elements selected from the group consisting of O, N, S, F, and Si in the structure. A, b, c and d are the average number of substituents, a, b and c are each an integer of 0 to 4, d is an integer of 0 to 6, Includes an alkyl group having 1 to 6 carbon atoms and an alkoxy group, and more preferably a hydrogen atom.

X in the formula (1) is a direct bond, O, N, S, F or Si, or 2 having 1 to 6 carbon atoms containing an element selected from the group consisting of O, N, S, F and Si in the structure A valent linking group is shown. Specific examples include O, S, CO, SO ₂ , an alkylene group having 1 to 6 carbon atoms, an alkylene oxide having 1 to 6 carbon atoms, and more preferably a direct bond, O, SO ₂ or CO. Yes, more preferably O.

R _{1 in} formula (A) is more preferably a residue obtained by removing two hydrogen atoms from benzene, biphenyl, biphenyl ether, biphenyl sulfone, biphenyl ketone and naphthalene, and more preferably a residue of benzene and biphenyl ether. Particularly preferred are residues obtained by removing a hydrogen atom from positions 1 and 3 of benzene and positions 4 and 4 'of biphenyl ether.

R ₂ in the formula (A) can be an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and the like. Is mentioned.

R _{2 in the} formula (A) can be an aromatic residue having 6 to 8 carbon atoms, and specific examples thereof include residues such as benzene, toluene and xylene.
Here, an aromatic residue having 6 to 8 carbon atoms means a residue obtained by removing one hydrogen atom from an aromatic aromatic ring having 6 to 8 carbon atoms.

R _{2 in} formula (A) is preferably a residue of a methyl group, an ethyl group and benzene, more preferably a methyl group and an ethyl group, and further preferably a methyl group.

  The production method of the dicarboxylic acid triazine active ester of the present invention is not particularly limited. For example, after adding a chlorotriazine compound, a tertiary amine compound and a dicarboxylic acid compound to an organic solvent and reacting them, purification is performed by recrystallization or the like. Can be obtained.

  Examples of the chlorotriazine compound include 2-chloro-4,6-dimethoxy-1,3,5-triazine, 2-chloro-4,6-diethoxy-1,3,5-triazine, and 2-chloro-4. , 6-dipropoxy-1,3,5-triazine, 2-chloro-4,6-diisopropoxymethoxy-1,3,5-triazine, 2-chloro-4,6-dibutoxy-1,3,5- Examples include triazine, 2-chloro-4,6-diphenoxy-1,3,5-triazine, and the like. Among them, 2-chloro-4,6-dimethoxy-1,3,5-triazine, 2-chloro-4,6 -Diethoxy-1,3,5-triazine, 2-chloro-4,6-diphenoxy-1,3,5-triazine and the like are preferable. The amount of its use is 2-4 mol normally with respect to 1 mol of dicarboxylic acid compounds used for reaction, Preferably it is 2-2.6 mol.

  Examples of the tertiary amine compound include triethylamine, N-methylmorpholine, N-ethylmorpholine, N-isobutylmorpholine, pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 1,8- Examples thereof include diazabicyclo [5.4.0] -7-undencene, and triethylamine, N-methylmorpholine, pyridine and the like are preferable. The amount of its use is 1-6 mol normally with respect to 1 mol of dicarboxylic acid compounds used for reaction, Preferably it is 2-5 mol.

  Examples of the dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, thiodibenzoic acid, dithiodibenzoic acid, carbonyldibenzoic acid, sulfonyldibenzoic acid, and methylenedibenzoic acid. , Isopropylidenedibenzoic acid, hexafluoroisopropylidenedibenzoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, etc. Examples thereof include isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, oxydibenzoic acid, carbonyldibenzoic acid, sulfonyldibenzoic acid, and naphthalenedicarboxylic acid.

  The organic solvent that can be used for this synthesis reaction is preferably a good solvent for the dicarboxylic acid. Examples of such solvents include, but are not limited to, alcohols such as water, methanol, ethanol, isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide. N, N-dimethylformamide, N-methylcaprolactam, N, N-dimethylimidazolidone, dimethyl sulfoxide, tetramethylurea, N-methylmorpholine, pyridine, aprotic polar solvent such as γ-butyrolactone, toluene, hexane And nonpolar solvents such as heptane, ether solvents such as tetrahydrofuran, diglyme, dioxane and trioxane, or a mixed solvent thereof.

A specific method for producing a dicarboxylic acid triazine active ester is, for example, first by stirring and dissolving a dicarboxylic acid compound in an organic solvent, adding a triazine compound and a tertiary amine compound, reacting them, A dicarboxylic acid triazine active ester can be obtained by crystal or the like. The reaction temperature is usually −10 ° C. to 80 ° C., preferably 0 to 30 ° C. The reaction time is 5 minutes to 24 hours, preferably 15 minutes to 3 hours.
After completion of the reaction, the reaction mixture is poured into a poor solvent such as water or methanol to separate the product, and then purified by recrystallization or the like to remove by-products, thereby increasing the dicarboxylic acid triazine active ester. Can be obtained in purity.

  The dicarboxylic acid triazine active ester of the present invention can be obtained, for example, by adding a hydroxytriazine compound, a tertiary amine compound and a dicarboxylic acid dichloride compound in an organic solvent, reacting them, and then purifying them by recrystallization or the like. it can.

  Examples of the hydroxytriazine compound include 2-hydroxy-4,6-dimethoxy-1,3,5-triazine, 2-hydroxy-4,6-diethoxy-1,3,5-triazine, and 2-hydroxy-4. , 6-dipropoxy-1,3,5-triazine, 2-hydroxy-4,6-diisopropoxy-1,3,5-triazine, 2-hydroxy-4,6-dibutoxy-1,3,5-triazine 2-hydroxy-4,6-diphenoxy-1,3,5-triazine, etc., among which 2-hydroxy-4,6-dimethoxy-1,3,5-triazine, 2-hydroxy-4,6- Diethoxy-1,3,5-triazine, 2-hydroxy-4,6-diphenoxy-1,3,5-triazine and the like are preferable. The amount of its use is 2-4 mol normally with respect to 1 mol of dicarboxylic acid dichloride compounds used for reaction, Preferably it is 2-2.6 mol.

  Examples of the tertiary amine compound include triethylamine, N-methylmorpholine, N-ethylmorpholine, N-isobutylmorpholine, pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 1,8 -Diazabicyclo [5.4.0] -7-undenecene and the like, among which triethylamine, N-methylmorpholine, pyridine and the like are preferable. The usage-amount is 1-6 mol normally with respect to 1 mol of dicarboxylic acid dichloride compounds used for reaction, Preferably it is 2-5 mol.

  Examples of the dicarboxylic acid dichloride compound include phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, oxydibenzoic acid dichloride, thiodibenzoic acid dichloride, dithiodibenzoic acid dichloride, and carbonyl dibenzoic acid. Acid dichloride, sulfonyldibenzoic acid dichloride, methylenedibenzoic acid dichloride, isopropylidene dibenzoic acid dichloride, hexafluoroisopropylidene dibenzoic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, pimelic acid dichloride Suberic acid dichloride, azelaic acid dichloride, sebacic acid dichloride, undecane dicarboxylic acid dichloride, dodeca Examples include dicarboxylic acid dichlorides such as dicarboxylic acid dichloride, among which isophthalic acid dichloride, terephthalic acid dichloride, biphenyldicarboxylic acid dichloride, oxydibenzoic acid dichloride, carbonyldibenzoic acid dichloride, sulfonyldibenzoic acid dichloride, naphthalenedicarboxylic acid dichloride, and the like. preferable.

  The organic solvent that can be used for this reaction is preferably an inert solvent for dicarboxylic acid dichloride. Examples of such solvents include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylcaprolactam, and N, N-dimethylimidazo. Aprotic polar solvents such as lidone, tetramethylurea, pyridine, γ-butyrolactone, nonpolar solvents such as toluene, hexane, heptane, ether solvents such as tetrahydrofuran, diglyme, dioxane, trioxane, etc., or a mixed solvent thereof Etc.

  By the way, the above-mentioned dicarboxylic acid triazine active ester and a diamine compound can be polymerized to obtain a polyamide resin.

The diamine compound that can be used for the synthesis reaction of the polyamide resin is not particularly limited as long as it is a compound having two amino groups in one molecule, and is, for example, a compound represented by the following formula (B).
_{H 2 N-R 3 -NH 2} (B)
In the formula (B), R ₃ is a divalent aromatic residue containing one or more elements selected from the group consisting of O, N, S, F and Si in the structure, or having 1 to 12 carbon atoms. A divalent organic group is shown.
Examples of the divalent aromatic residue and divalent organic group are the same as those described above for R ₁ .

  Specific examples of the diamine compound include phenylenediamine, diaminotoluene, diaminoxylene, diaminomesitylene, diaminodurene, diaminoazobenzene, diaminonaphthalene and other benzene or naphthalene diamine, diaminobiphenyl, diaminodimethoxybiphenyl and other biphenyl diamine, diaminodiphenyl ether , Phenyl ether diamines such as diaminodimethyldiphenyl ether, methylene dianiline, methylene bis (methylaniline), methylene bis (dimethylaniline), methylene bis (methoxyaniline), methylene bis (dimethoxyaniline), methylene bis (ethylaniline), methylene bis (diethylaniline) , Methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), Phenylmethane diamine such as propylidene dianiline, hexafluoroisopropylidene dianiline, benzophenone diamine such as diaminobenzophenone, diaminodimethylbenzophenone, diaminoanthraquinone, diaminodiphenylthioether, diaminodimethyldiphenylthioether, diaminodiphenylsulfone, diaminodiphenylsulfoxide, , Diaminofluorene, ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undeca Methylenediamine, dodecamethylenediamine, cyclopentanediamine, Cyclohexane diamine, diaminodicyclohexylmethane, bis aminomethyl cyclopentane, bis aminomethyl cyclohexane, bis aminomethyl norbornane, and the like bis aminomethyl tricyclodecane. Among these, methylene dianiline and diaminodiphenyl ether are preferable, and 3,4'-methylene dianiline, 4,4'-methylene dianiline, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether are more preferable. These diamine compounds can be used alone or in combination of two or more. The amount used is usually 0.5 to 2 mol, preferably 0.9 to 1.1 mol, per 1 mol of the dicarboxylic acid triazine active ester component.

The reaction between the dicarboxylic acid triazine active ester and the diamine compound is generally carried out in an inert solvent.
The inert solvent is preferably a good solvent for the reaction product polyamide, in addition to having the property of not reacting substantially with the dicarboxylic acid triazine active ester and satisfactorily dissolving the diamine compound. .

  Such an inert solvent is not particularly limited, but N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylcaprolactam, N, N-dimethylimidazolidone, dimethyl Aprotic polar solvents such as sulfoxide, tetramethylurea, N-methylmorpholine, pyridine, γ-butyrolactone, sulfolane, nonpolar solvents such as toluene, hexane, heptane, ethers such as tetrahydrofuran, diglyme, dioxane, and trioxane Examples thereof include a solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, or a mixed solvent thereof. The usage-amount of these solvents is 0-1000 mL normally with respect to 0.1 mol of diamine compounds to be used, Preferably it is 50-800 mL.

  In order to obtain a polyamide resin having a high degree of polymerization, inorganic salts such as lithium chloride and calcium chloride may be added. The usage-amount of these inorganic salts is 0-10 mass% normally with respect to the usage-amount of solvent, Preferably it is 0-5 mass%.

As a specific method for producing a polyamide resin using a dicarboxylic acid triazine active ester, for example, a diamine compound is dissolved in an inert solvent, and the dicarboxylic acid triazine active ester component 0.5 is added to 1 mol of the diamine compound. A polyamide resin can be obtained by adding ~ 2.2 mol and then reacting with heating and stirring under an inert atmosphere such as nitrogen. The reaction temperature is usually −10 to 80 ° C., preferably 20 to 60 ° C. The reaction time is usually 5 minutes to 24 hours, preferably 30 minutes to 10 hours.
After completion of the reaction, the reaction mixture is poured into a poor solvent such as water or methanol to separate the polymer, and then purified by a reprecipitation method or the like to remove by-products or inorganic salts, thereby removing ionic impurities. A polyamide resin having a content of 10 ppm or less can be obtained.

The weight average molecular weight of the polyamide resin is preferably 10,000 to 1,000,000.
When the weight average molecular weight is less than 10,000, the film formability is poor and the appearance of properties as polyamide is insufficient. On the other hand, when the weight average molecular weight exceeds 1,000,000, the molecular weight is too high and the solvent solubility is deteriorated, and the moldability is poor. There is a risk.
As a simple method for adjusting the molecular weight of the polyamide resin, there may be mentioned a method in which either one of the dicarboxylic acid triazine active ester component or the diamine compound component is used in excess.

  Since such polyamide resin has a low content of ionic impurities of 10 ppm or less, there is no deterioration in electrical characteristics when used for electrical and electronic parts, and the semiconductor field such as electrical and electronic parts and heat resistant bag filters It can be applied to secondary battery separators, heat insulating materials, various filters, food packaging and clothes.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

で表されるジカルボン酸トリアジン活性エステルの反応液を得た。この反応液を１０００部のイオン交換水に投入し、析出した生成物を濾別し、酢酸エチルとｎ−ヘキサンの混合溶媒で再結晶を行い、乾燥させて、ジカルボン酸トリアジン活性エステルの白色の粉末状結晶の樹脂粉末１を得た（収率２３％）。 <Resin powder 1 of dicarboxylic acid triazine active ester>
In a flask equipped with a thermometer, nitrogen inlet tube, and stirrer, 4.2 parts of isophthalic acid, 9.7 parts of 2-chloro-4,6-dimethoxy-1,3,5-triazine, and N-methyl-2- 100 parts of pyrrolidone was added and cooled to 0 ° C. Thereafter, 7.6 parts of N-methylmorpholine was added dropwise with stirring and allowed to react for 15 minutes.

The reaction liquid of the dicarboxylic acid triazine active ester represented by these was obtained. The reaction solution was poured into 1000 parts of ion-exchanged water, and the precipitated product was filtered off, recrystallized with a mixed solvent of ethyl acetate and n-hexane, dried, and dried with a white dicarboxylic acid triazine active ester. A powdery resin powder 1 was obtained (23% yield).

で表されるジカルボン酸トリアジン活性エステルの反応液を得た。この反応液を１０００部のイオン交換水に投入し、析出した生成物を濾別し、酢酸エチルとｎ−ヘキサンの混合溶媒で再結晶を行い、乾燥させてジカルボン酸トリアジン活性エステルの白色粉末状結晶の樹脂粉末２を得た（収率４３％）。 <Resin powder 2 of dicarboxylic acid triazine active ester>
In a flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, 6.5 parts of diphenyl ether-4,4′-dicarboxylic acid, 9.7 parts of 2-chloro-4,6-dimethoxy-1,3,5-triazine And 100 parts of N-methyl-2-pyrrolidone was added and it cooled at 0 degreeC. Thereafter, 7.6 parts of N-methylmorpholine was added dropwise with stirring and allowed to react for 15 minutes.

The reaction liquid of the dicarboxylic acid triazine active ester represented by these was obtained. The reaction solution was poured into 1000 parts of ion-exchanged water, and the precipitated product was filtered off, recrystallized with a mixed solvent of ethyl acetate and n-hexane, and dried to obtain a white powder of dicarboxylic acid triazine active ester. Crystalline resin powder 2 was obtained (43% yield).

で表される本発明のジカルボン酸トリアジン活性エステルの反応液を得た。この反応液を５００部のイオン交換水に投入し、析出した生成物を濾別し、酢酸エチルとｎ−ヘキサンの混合溶媒で再結晶を行い、乾燥させてジカルボン酸トリアジン活性エステルの白色粉末状結晶の樹脂粉末３を得た（収率６０％）。 <Resin powder 3 of dicarboxylic acid triazine active ester>
To a flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, 3.1 parts of 2-hydroxy-4,6-dimethoxy-1,3,5-triazine, 50 parts of N-methyl-2-pyrrolidone and 2. 0 parts were added and cooled to 0 ° C. Thereafter, 2.0 parts of isophthalic acid dichloride was added and reacted for 20 minutes to obtain the following formula (3).

The reaction liquid of the dicarboxylic acid triazine active ester of this invention represented by these was obtained. The reaction solution was poured into 500 parts of ion-exchanged water, and the precipitated product was filtered off, recrystallized with a mixed solvent of ethyl acetate and n-hexane, and dried to obtain a white powder of dicarboxylic acid triazine active ester. Crystalline resin powder 3 was obtained (yield 60%).

<Polyamide resin powder 1>
A flask equipped with a thermometer, a nitrogen inlet tube and a stirrer is purged with nitrogen gas, 20 parts of 4,4′-diaminodiphenyl ether and 200 parts of N-methylpyrrolidone are stirred and dissolved, and the didicarboxylic acid triazine active ester obtained above is obtained. 44 parts of the above resin powder 1 was added and reacted at 20 ° C. for 6 hours to obtain a polyamide resin reaction solution. The resin deposited in 2000 parts of methanol was separated by filtration, further washed with 200 parts of methanol, and purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the polyamide resin powder 1 was obtained (yield 96%). The molecular weight (Mw) and molecular weight distribution (Mw / Mn) determined from gel conversion using gel permeation chromatography (hereinafter referred to as GPC) were 69,000 and 1.7, respectively. Further, 4 g of this resin powder and 40 g of Millipore water were treated at 121 ° C. for 20 hours, and the extracted water was analyzed for ionic impurities (P-based ions, Cl ions) by ion chromatogram. The results are shown in Table 1.

<Polyamide resin powder 2>
A flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer was purged with nitrogen gas, and 20 parts of 4,4′-diaminodiphenyl ether and 200 parts of N-methylpyrrolidone were stirred and dissolved. The dicarboxylic acid triazine active ester obtained above 54 parts of resin powder 2 was added and reacted at 20 ° C. for 6 hours to obtain a polyamide resin reaction solution. The resin deposited in 2000 parts of methanol was separated by filtration, further washed with 200 parts of methanol, and purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the polyamide resin powder 2 was obtained (yield 98%). The molecular weight (Mw) and molecular weight distribution (Mw / Mn) determined by polystyrene conversion using GPC were 59,000 and 1.8, respectively. Further, 4 g of this resin powder and 40 g of Millipore water were treated at 121 ° C. for 20 hours, and the extracted water was analyzed for ionic impurities (P-based ions, Cl ions) by ion chromatogram. The results are shown in Table 1.

<Comparative Example Resin Powder 1>
A flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer was purged with nitrogen gas, and 16.0 parts of isophthalic acid, 20.0 parts of 4,4′-diaminodiphenyl ether, 1.0 part of lithium chloride, N-methylpyrrolidone 108 0.02 parts and 23.0 parts of pyridine were added and dissolved by stirring, and then 50.0 parts of triphenyl phosphite was added and reacted at 90 ° C. for 8 hours to obtain a polyamide resin reaction solution. The resin deposited in 1000 parts of methanol was filtered off, washed with 200 parts of methanol, and purified by refluxing with methanol. Subsequently, after cooling to room temperature, it filtered, and the filtrate was dried and the comparative example resin powder 1 was obtained (yield 96%). The molecular weight (Mw) and molecular weight distribution (Mw / Mn) determined by polystyrene conversion using GPC were 71,000 and 2.1, respectively. 4 g of this resin powder and 40 g of Millipore water were treated at 121 ° C. for 20 hours, and the extracted water was analyzed for ionic impurities (P-based ions and Cl ions) by an ion chromatogram. The results are shown in Table 1.

<Comparative Example Resin Powder 2>
A reaction solution of polyamide resin and comparative resin powder 2 were obtained in the same manner except that 4,4′-diaminodiphenyl ether in comparative resin powder 1 was changed to 3,4′-diaminodiphenyl ether (yield 98%). . The molecular weight (Mw) and molecular weight distribution (Mw / Mn) determined by polystyrene conversion using GPC were 63,000 and 1.9, respectively. 4 g of this resin powder and 40 g of Millipore water were treated at 121 ° C. for 20 hours, and the extracted water was analyzed for ionic impurities (P-based ions and Cl ions) by an ion chromatogram. The results are shown in Table 1.

  The dicarboxylic acid triazine active ester of the present invention is particularly useful as a monomer useful for the production of polymers that are useful for electrical and electronic component applications by reducing the content of ionic impurities. The polyamide resin obtained by using it has a low content of ionic impurities, so it can be used in semiconductor fields such as electrical and electronic parts, heat-resistant bag filters, secondary battery separators, heat insulating materials, various filters, food packaging, clothes, etc. Adaptation to is possible.

Claims (3)

The following formula (A)

(In the formula (A), R ₁ represents the following formula (1)

[In formula (1), R ₄ is carbon containing one or more elements selected from the group consisting of H, O, N, S, F or Si, or O, N, S, F and Si in the structure. The substituent of number 1-6 is shown. X represents a direct bond, O, N, S, F or Si, or a divalent linking group having 1 to 6 carbon atoms containing an element selected from the group consisting of O, N, S, F and Si in the structure. Show. a, b, c and d are the average number of substituents, a, b and c each represent a positive number from 0 to 4, and d represents a positive number from 0 to 6. ] The bivalent aromatic residue chosen from the group represented by this is shown. R ₂ represents an alkyl group having 1 to 4 carbon atoms or an aromatic residue having 6 to 8 carbon atoms. )
The crystal | crystallization of the dicarboxylic acid triazine active ester characterized by these. The crystal of dicarboxylic acid triazine active ester according to claim 1, wherein R ₂ is an alkyl group having 1 to 4 carbon atoms. The crystal of dicarboxylic acid triazine active ester according to claim 1 or 2, wherein R _{4 in} formula (1) is a hydrogen atom, X is a direct bond, O, SO ₂ or CO.