WO2015087969A1

WO2015087969A1 - Method for producing triazine ring-containing hyperbranched polymer

Info

Publication number: WO2015087969A1
Application number: PCT/JP2014/082830
Authority: WO
Inventors: 泰之小出; 秀樹武蔵
Original assignee: 日産化学工業株式会社
Priority date: 2013-12-13
Filing date: 2014-12-11
Publication date: 2015-06-18
Also published as: JP6544241B2; JPWO2015087969A1

Abstract

Provided is a method for producing a triazine ring-containing hyperbranched polymer, which includes: a first step of obtaining a reaction product, that is a 1:1 (molar ratio) mixture of a diaminoaryl compound and a cyanuric halide compound, by adding the cyanuric halide compound dropwise to a diaminoaryl compound-containing solution obtained by dissolving a diaminoaryl compound in an organic solvent, and carrying out a reaction while maintaining a temperature of -20ºC to 5ºC; and a second step of carrying out polymerization by heating the reaction product obtained in the first step at a temperature of 60-150ºC. According to the method, it is possible to obtain a triazine ring-containing polymer that can suppress the formation of sublimates and that exhibits good solubility in PGME, or the like, which is used as a resist solvent.

Description

Process for producing hyperbranched polymer containing triazine ring

The present invention relates to a method for producing a triazine ring-containing hyperbranched polymer.

A triazine ring-containing polymer having a branched structure is synthesized from cyanuric chloride and diamines, and has been reported to exhibit high refractive index, high heat resistance, and high transparency (Patent Document 1).
The reason why the triazine ring-containing polymer exhibits a high refractive index is that the density becomes high due to intramolecular or intermolecular hydrogen bonding.
In one of the methods for producing the triazine ring-containing polymer, as shown in the following scheme 1, a 1: 1 (molar ratio) reaction product of cyanuric chloride and diamine (hereinafter referred to as AB2 type monomer) was used. There is a method of polymerizing this later.

In Patent Document 1, a method of adding m-phenylenediamine to a cooling solution of cyanuric chloride is preferred as the order of addition of reagents in the above reaction, and such a method has been adopted so far.
However, recently, it has been found that the triazine ring-containing polymer obtained by the above method is not sufficiently soluble in a safety solvent such as propylene glycol monomethyl ether (hereinafter, PGME).

In Patent Document 1, the solubility is improved by suppressing intramolecular and intermolecular hydrogen bonds by slowing the degree of branching of the polymer by adding a monofunctional amine (aniline) to the reaction during polymerization. However, in the triazine ring-containing polymer obtained by this method, the heat resistance (Tg, Td) may be lowered, and a thermal process at 250 to 300 ° C. after film formation ( In some cases, contamination of the apparatus and generation of foreign matter in the film may occur during the steps of baking, soldering, and the like.

International Publication No. 2010/128661

This invention is made | formed in view of such a situation, The solubility to PGME etc. which are used as a resist solvent is favorable, and the manufacturing method of the triazine ring containing hyperbranched polymer which can suppress the production | generation of a sublimate is provided. It is intended.

As a result of intensive studies to achieve the above object, the present inventors have found that the order that is preferred in Patent Document 1 described above, that is, when a diamine (solution) is dropped into a cyanuric acid chloride solution, the temperature is low. It is not the AB2 type monomer described above that is mainly produced by the reaction product (hereinafter referred to as B4 type monomer) of 2: 1 (molar ratio) of cyanuric chloride and diamine represented by the following formula. And the hyperbranched polymer obtained by polymerizing the reaction solution mainly produced from this B4 type monomer under heating was found to have poor solubility in a safety solvent such as PGME.

Furthermore, when the present inventors react by adding aniline at the time of polymerization, an aniline trisubstituted product of cyanuric chloride represented by the following formula is generated, and this causes the heat resistance of the hyperbranched polymer to be reduced. At the same time, since this compound has sublimation properties, it was also found out that contamination of the apparatus and generation of foreign matter in the film occur in the subsequent heating step.

And the present inventors preferentially produce the above-mentioned AB2 type monomer in the reaction at a low temperature, and polymerize the monomer under heating, so that the solubility in a safety solvent such as PGME is good. In order to obtain a hyperbranched polymer and efficiently produce the AB2-type monomer during the low-temperature reaction step, cyanuric acid chloride (solution) is added to the diamine solution cooled to a predetermined temperature so as to maintain the predetermined temperature range. In addition, in the low-temperature reaction step, after adding cyanuric chloride (solution) and reacting in a solution containing only diamine, the monoamine is added dropwise to produce the above-described compound having sublimation properties. The present invention has been completed.
In addition, when cyanuric acid chloride is dripped in the mixed solution of a diamine and a monoamine in a low temperature reaction process, the compound which has the said sublimation property will produce | generate (refer the below-mentioned comparative example 2).

That is, the present invention
1. Cyanuric halide is added to a diaminoaryl compound-containing solution in which a diaminoaryl compound is dissolved in an organic solvent, and the mixture is allowed to react while maintaining -20 to 5 ° C. to obtain 1: 1 (moles) of the diaminoaryl compound and the cyanuric halide compound. A triazine ring-containing hyperbranched polymer comprising: a first step of obtaining a reaction product; and a second step of polymerizing the reaction product obtained in this step by heating to 60 to 150 ° C. Production method,
2. A method for producing a triazine ring-containing hyperbranched polymer according to 1 including a step of reacting by adding monoamine to the reaction solution while maintaining −20 to 5 ° C. after the first step;
3. A method for producing one or two triazine ring-containing hyperbranched polymers, wherein a cyanuric halide-containing solution obtained by dissolving the cyanuric halide in an organic solvent is cooled to −15 to 5 ° C. and then dropped into the diaminoaryl compound-containing solution;
4). The method for producing a hyperbranched polymer containing a triazine ring according to any one of 1 to 3 represented by the formula (1):

{Wherein R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar is selected from the group represented by formulas (2) to (13) Represents at least one kind.

[Wherein R ¹ to R ⁹² are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of ˜10, R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms, W ¹ and W ² is independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group optionally having a branched structure of 1 to 10 carbon atoms ( However, these may be combined to form a ring.))), C═O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or a carbon number of 1). have a branched structure to 10 represent also alkyl groups.) represents, X ¹ Contact Fine X ² are independently of each other a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or the formula, (14)

(Wherein R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of ˜10, and Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents a group represented by: ]}
I will provide a.

According to the production method of the present invention, a triazine ring-containing hyperbranched polymer having good solubility in PGME or the like used as a resist solvent can be obtained.
Further, since the generation of sublimates can be suppressed, not only the heat resistance of the resulting polymer can be prevented, but also contamination of the apparatus and generation of foreign matter in the film can be prevented in the heating process during film formation.

It is a figure which shows the gel permeation chromatography measurement result of the high molecular compound [3] obtained by Example 1 and the comparative example 2.

Hereinafter, the present invention will be described in more detail.
In the method for producing a triazine ring-containing hyperbranched polymer according to the present invention, cyanuric halide is added to a diaminoaryl compound-containing solution obtained by dissolving a diaminoaryl compound in an organic solvent, and the reaction is performed while maintaining -20 to 5 ° C. A first step of obtaining a 1: 1 (molar ratio) reaction product (AB2 type monomer) of an aryl compound and a cyanuric halide compound, and the AB2 type monomer obtained in this step is heated to 60 to 150 ° C. for polymerization. And a second step.

In the reaction of the first step, from the viewpoint of mainly producing AB2 type monomer, the reaction temperature is set to −20 to 5 ° C., preferably −15 to 5 ° C., more preferably −5 to 5 ° C.
The cyanuric halide may be added as a solid or dropped as a solution, but since the operation is simple and the reaction temperature is easy to control, there is a technique in which it is dissolved in an organic solvent and dropped as a cyanuric halide-containing solution. preferable.
In particular, in order to easily maintain the reaction temperature within the above range, it is preferable that the diaminoaryl compound-containing solution is cooled to the above temperature range, and the cyanuric halide-containing solution added dropwise thereto is also cooled to the above temperature range.

As the organic solvent used for the preparation of the diaminoaryl compound-containing solution and the cyanuric halide-containing solution, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethyl sulfoxide; N, N -Dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ', N'-tetramethylmalonic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethyl Isobutyramide, N-methylformamide, N, N ′ Amide solvents such as dimethyl propylene urea, and mixed solvents thereof.
Among these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixed system thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.
Moreover, the organic solvent used for preparation of both containing solutions may be the same or different, but the same is preferable.

In the reaction of the first step of the present invention, it is preferable to use a diamino compound in an amount of less than 3 equivalents relative to 2 equivalents of cyanuric halide from the viewpoint of efficiently producing an AB2 type monomer. When it is intended to obtain a hyperbranched polymer having an amine terminal with a molecular weight, cyanuric halide may be used in an amount of less than 2 equivalents relative to 3 equivalents of the diamino compound.

In the production method of the present invention, monoamine can be added to the reaction solution after the first step for the purpose of improving the solubility in an organic solvent by reducing the degree of branching of the resulting hyperbranched polymer.
At this time, it is preferable to carry out the reaction while maintaining the temperature of the reaction solution at the time of adding aniline at −20 to 5 ° C., particularly at −5 to 5 ° C., in order to suppress the formation of the above-described sublimable substance.

As the monoamine, any of alkyl monoamine, aralkyl monoamine, and aryl monoamine can be used.
Specific examples of the alkyl monoamine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, 1-methyl-n-butylamine, 2 -Methyl-n-butylamine, 3-methyl-n-butylamine, 1,1-dimethyl-n-propylamine, 1,2-dimethyl-n-propylamine, 2,2-dimethyl-n-propylamine, 1- Ethyl-n-propylamine, n-hexylamine, 1-methyl-n-pentylamine, 2-methyl-n-pentylamine, 3-methyl-n-pentylamine, 4-methyl-n-pentylamine, 1, 1-dimethyl-n-butylamine, 1,2-dimethyl-n-butylamine, 1,3-dimethyl -N-butylamine, 2,2-dimethyl-n-butylamine, 2,3-dimethyl-n-butylamine, 3,3-dimethyl-n-butylamine, 1-ethyl-n-butylamine, 2-ethyl-n-

butylamine

1,1,2-trimethyl-n-propylamine, 1,2,2-trimethyl-n-propylamine, 1-ethyl-1-methyl-n-propylamine, 1-ethyl-2-methyl-n- Examples thereof include propylamine and 2-ethylhexylamine.

Specific examples of aralkyl monoamines include benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine and the like.
Specific examples of the aryl monoamine include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- And phenylaniline, 4-amino-p-terphenyl, 2-aminofluorene, and the like.
In this case, the amount of the organic monoamine used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents based on the halogenated cyanuric compound.

In the reaction of the second step, the reaction temperature is 60 to 150 ° C., but 70 to 100 ° C. is preferable from the viewpoint that the polymerization reaction proceeds efficiently.
Moreover, you may add the various bases normally used at the time of superposition | polymerization or after superposition | polymerization.
Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6 , 6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
The amount of the base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents per 1 equivalent of cyanuric halide. These bases may be used as an aqueous solution.
In the obtained hyperbranched polymer, it is preferable that no raw material components remain, but a part of the raw materials may remain as long as the effects of the present invention are not impaired.
After completion of the reaction, the produced polymer can be easily purified by a reprecipitation method or the like.

The production method of the present invention can be applied to the production of an arbitrary triazine ring-containing hyperbranched polymer in which a cyanuric halide and a diamine are reacted. Among them, a triazine ring containing a repeating unit structure represented by the following formula (1) It can be suitably applied to the production of hyperbranched polymers.

In the above formula, R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms in view of further improving the heat resistance of the polymer. Is even more preferable. Further, the structure may be any of a chain, a branch, and a ring.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl. N-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pe Til, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3- Dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n- Butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, Cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclyl Butyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl Groups and the like.

The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms in view of further improving the heat resistance of the polymer. preferable. Further, the structure of the alkyl moiety may be any of a chain, a branch, and a ring.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n -Butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n -Hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n- Examples include propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy group.

The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40. In view of further improving the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 are even more preferable. preferable.
Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group and the like.

The number of carbon atoms of the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched or cyclic.
Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, Examples include 4-isobutylphenylmethyl, α-naphthylmethyl group and the like.

Ar represents at least one selected from the group represented by formulas (2) to (13).

R ¹ to R ⁹² are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms. Represents an alkoxy group which may have a branched structure, W ¹ and W ² are each independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or carbon; An alkyl group which may have a branched structure of 1 to 10 (note that these may be combined to form a ring), C═O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms), and R ⁹³ and R ⁹⁴ represent a hydrogen atom or a carbon number Represents an alkyl group which may have 1 to 10 branched structures;
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group and alkoxy group are the same as those described above.
X ¹ and X ² each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (14).

R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. An alkoxy group which may have a branched structure is represented, and Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
Examples of the alkylene group that may have a branched structure having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups.

In particular, Ar is preferably at least one of the formulas (2), (5) to (13), and the formulas (2), (5), (7), (8), (11) to (13) More preferably, at least one selected from Specific examples of the aryl group represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulae.

Among these, an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.

In particular, it is preferable to include a repeating unit structure represented by the formula (15) in consideration of further increasing the solubility in a highly safe solvent such as a resist solvent such as PGME.

(In the formula, R, R 'and R ¹ to R ⁴ have the same meaning as described above.)

From such a viewpoint, as a particularly preferable repeating unit structure, one represented by the following formula (16) may be mentioned.

(In the formula, R and R ′ have the same meaning as described above.)

Specific examples of the triazine ring-containing hyperbranched polymer include those represented by the following formula, but are not limited thereto.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the measuring apparatus etc. which were used in the Example are as follows.
(1) GPC (gel permeation chromatography)
Equipment: SCL-10Avp series manufactured by Shimadzu Corporation Column: Shodex K-804L + K-805L
Column temperature: 60 ° C
Solvent: N-methyl-2-pyrrolidone (1% LiCl added)
Detector: UV (280 nm)
Calibration curve: Standard polystyrene

[Example 1]

In a 200 mL four-necked flask under nitrogen, 66.1 g of dimethylacetamide (hereinafter referred to as DMAc) was cooled to −15 ° C. with an acetone / dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1 ] 18.44 g (0.1 mol, manufactured by Eponic Degussa) was added and dissolved. Thereafter, 13.52 g (0.125 mol, manufactured by DuPont) of m-phenylenediamine [2] dissolved in 99.14 g of DMAc was cooled to −15 ° C. in a 300 mL four-necked flask and previously cooled to −15 ° C. A DMAc solution of 4,6-trichloro-1,3,5-triazine was added dropwise over 120 minutes, and the mixture was further stirred for 30 minutes (at this time, the temperature of the reaction solution was kept at −15 to 5 ° C.). Thereafter, 3.17 g (0.034 mol) of aniline was added dropwise over 15 minutes, and the mixture was further stirred for 30 minutes (at this time, the temperature of the reaction solution was kept at −15 to 5 ° C.).
Subsequently, 35.18 g of DMAc was added to a 500 mL four-necked flask in advance, and the reaction solution was added dropwise over 30 minutes using a dropping pump to a tank heated to 90 ° C. in an oil bath, and further stirred for 2 hours. And polymerized.
Thereafter, 24.77 g (0.266 mol) of aniline was added and stirred for 3 hours to stop the reaction. After allowing to cool to room temperature, the reaction solution was added to a mixed solution of 28.71 g of 28% aqueous ammonia and 922.1 g of ion-exchanged water to cause reprecipitation. The precipitate was filtered, and the crude product was stirred at 40 ° C. for 30 minutes in a mixed solution of 258.2 g of tetrahydrofuran (hereinafter referred to as THF) and 60.71 g of 28% aqueous ammonia solution. After stirring, the mixture was allowed to stand for 30 minutes for liquid separation, and the organic layer was taken out. After adjusting the concentration of the extracted organic layer with THF, 60.71 g of 28% ammonia aqueous solution was added again and stirred at 40 ° C., followed by liquid separation to extract the organic layer. The concentration of the organic layer was adjusted, and this solution was reprecipitated in a mixed solution of 94.11 g of 28% aqueous ammonia solution and 1383 g of ion-exchanged water. The precipitate was filtered and dried in a vacuum dryer at 150 ° C. for 20 hours to obtain 25.7 g of the target polymer [3].

[Comparative Example 1]
In a 300 mL four-necked flask under nitrogen, 99.14 g of DMAc was cooled to −15 ° C. with an acetone / dry ice bath, and 18.44 g (0.24) of 2,4,6-trichloro-1,3,5-triazine [1]. 1 mol, manufactured by Eponic Degussa) was added and dissolved. Thereafter, 13.52 g (0.125 mol, manufactured by DuPont) of m-phenylenediamine dissolved in 66.1 g of DMAc was dropped into the dropping funnel over 240 minutes, and the mixture was further stirred for 30 minutes. Then, aniline (3.17g, 0.034mol) was dripped over 15 minutes, and also stirred for 30 minutes. To this reaction solution, 135.18 g of DMAc was added in advance to a 500 mL four-necked flask and dropped into a tank heated to 90 ° C. in an oil bath over 30 minutes using a dropping pump, and further stirred for 2 hours for polymerization. .
Thereafter, 24.77 g (0.266 mol) of aniline was added and stirred for 3 hours to stop the reaction. After cooling to room temperature, it was reprecipitated in a mixed solution of 60.71 g of 28% aqueous ammonia solution and 922.1 g of ion-exchanged water. The precipitate was filtered, and the crude product was stirred at 40 ° C. for 30 minutes in a mixed solution of 258.2 g of THF and 60.71 g of 28% aqueous ammonia solution. After stirring, the mixture was allowed to stand for 30 minutes for liquid separation, and the organic layer was taken out. After adjusting the concentration of the extracted organic layer with THF, 60.71 g of 28% ammonia aqueous solution was added again and stirred at 40 ° C., followed by liquid separation to extract the organic layer. The concentration of the organic layer was adjusted, and this solution was reprecipitated in a mixed solution of 94.11 g of 28% aqueous ammonia solution and 1383 g of ion-exchanged water. The precipitate was filtered and dried in a vacuum dryer at 150 ° C. for 20 hours to obtain 25.5 g of the target polymer compound [3].

1.0 g of the polymer compound [3] obtained in Example 1 and Comparative Example 1 was dissolved in a mixed solution of 4.373 g of cyclohexanone and 0.182 g of water, respectively, and 0.100 g of this solution was added to propylene glycol monomethyl ether ( (PGME) / propylene glycol monomethyl ether acetate (PGMEA) when diluted with a mixed solution of 70/30 (mass ratio), it was evaluated to what extent the solution was uniform (no precipitation or scattering) When the polymer compound [3] obtained in Example 1 was diluted with 316 parts, the solution was uniform, but when the polymer compound [3] obtained in Comparative Example 1 was diluted with 5 parts, Precipitation of solid content was observed.

[Comparative Example 2]
In a 300 mL four-necked flask under nitrogen, 99.14 g of DMAc was cooled to −15 ° C. with an acetone / dry ice bath, and 18.44 g (0.24) of 2,4,6-trichloro-1,3,5-triazine [1]. 1 mol, manufactured by Eponic Degussa) was added and dissolved. Thereafter, 13.52 g (0.125 mol, manufactured by DuPont) of m-phenylenediamine and 3.17 g (0.034 mol) of aniline dissolved in 66.1 g of DMAc were dropped into the dropping funnel over 120 minutes, and further stirred for 30 minutes. did. To this reaction solution, 135.18 g of DMAc was added in advance to a 500 mL four-necked flask and dropped into a tank heated to 90 ° C. in an oil bath over 30 minutes using a dropping pump, and further stirred for 2 hours for polymerization. .
Thereafter, 24.77 g (0.266 mol) of aniline was added and stirred for 3 hours to stop the reaction. After cooling to room temperature, it was reprecipitated in a mixed solution of 60.71 g of 28% aqueous ammonia solution and 922.1 g of ion-exchanged water. The precipitate was filtered, and the crude product was stirred at 40 ° C. for 30 minutes in a mixed solution of 258.2 g of THF and 60.71 g of 28% aqueous ammonia solution. After stirring, the mixture was allowed to stand for 30 minutes for liquid separation, and the organic layer was taken out. After adjusting the concentration of the extracted organic layer with THF, 60.71 g of 28% ammonia aqueous solution was added again and stirred at 40 ° C., followed by liquid separation to extract the organic layer. The concentration of the organic layer was adjusted, and this solution was reprecipitated in a mixed solution of 94.11 g of 28% aqueous ammonia solution and 1383 g of ion-exchanged water. The precipitate was filtered and dried in a vacuum dryer at 150 ° C. for 20 hours to obtain 26.1 g of the target polymer compound [3].

For each polymer compound [3] obtained in Example 1 and Comparative Example 2, GPC measurement was performed. In Comparative Example 2, the peak of the aniline trisubstituted product of cyanuric chloride that becomes a sublimate (arrow in the figure). However, in Example 1, the peak could not be confirmed, indicating that the production of sublimates could be suppressed.

Claims

Cyanuric halide is added to a diaminoaryl compound-containing solution in which a diaminoaryl compound is dissolved in an organic solvent, and the mixture is allowed to react while maintaining -20 to 5 ° C. to obtain 1: 1 (moles) of the diaminoaryl compound and the cyanuric halide compound. A triazine ring-containing hyperbranched polymer comprising: a first step of obtaining a reaction product; and a second step of polymerizing the reaction product obtained in this step by heating to 60 to 150 ° C. Production method.
2. The method for producing a triazine ring-containing hyperbranched polymer according to claim 1, further comprising a step of reacting by adding monoamine to the reaction solution while maintaining −20 to 5 ° C. after the first step.
3. The production of a triazine ring-containing hyperbranched polymer according to claim 1 or 2, wherein a cyanuric halide-containing solution in which the cyanuric halide is dissolved in an organic solvent is cooled to −15 to 5 ° C. and then dropped into the diaminoaryl compound-containing solution. Method.
The method for producing a triazine ring-containing hyperbranched polymer according to any one of claims 1 to 3, wherein the triazine ring-containing hyperbranched polymer is represented by the formula (1).

{Wherein R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar is selected from the group represented by formulas (2) to (13) Represents at least one kind.

[Wherein R 1 to R 92 are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of ˜10, R 93 and R 94 represent a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms, W 1 and W 2 is independently a single bond, CR 95 R 96 (R 95 and R 96 are each independently a hydrogen atom or an alkyl group optionally having a branched structure of 1 to 10 carbon atoms ( However, these may be combined to form a ring.))), C═O, O, S, SO, SO 2 , or NR 97 (R 97 is a hydrogen atom or a carbon number of 1). have a branched structure to 10 represent also alkyl groups.) represents, X 1 Contact Fine X 2 are independently of each other a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or the formula, (14)

(Wherein R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of ˜10, and Y 1 and Y 2 each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents a group represented by: ]}