JPWO2015087968A1 - Method for purifying hyperbranched polymer containing triazine ring - Google Patents

Abstract

After adding the organic amine to the triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction, this step includes a reprecipitation treatment step in which the amine addition solution is dropped into a heated poor solvent. The triazine ring-containing hyperbranch with high operability and volumetric efficiency is obtained by the method for purifying the triazine ring-containing hyperbranched polymer in an amount that the pH of the filtrate after filtration of the precipitate generated in the process is 7.0 or more. The polymer can be purified.

Description

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

A triazine ring-containing hyperbranched polymer having a branched structure is synthesized from cyanuric chloride and the like and diamines, and has been reported to exhibit high refractive index, high heat resistance, and high transparency (Patent Document 1).
A factor that the triazine ring-containing hyperbranched polymer exhibits a high refractive index is that the density becomes high due to intramolecular or intermolecular hydrogen bonding.
On the other hand, a polymer compound into which an aromatic ring or a triazine ring is introduced or a polymer compound having high hydrogen bonding properties is poor in solubility in a solvent and is often insoluble in a resist solvent which is a safety solvent.

The above triazine ring-containing hyperbranched polymer reacts with the addition of a monofunctional amine (aniline) during the polymerization, resulting in a polymer with a moderate degree of branching, thereby suppressing the intra- and inter-molecular hydrogen bonds. Has improved.
In Patent Document 1, purification of the triazine ring-containing hyperbranched polymer is carried out by a reprecipitation operation in which the polymer solution is added to a poor solvent. There is a problem that the filterability is extremely poor.
Due to this poor filterability, there are problems such as a significant reduction in purification efficiency due to an increase in liquid content and a deterioration in the operability of the purification process.

International Publication No. 2010/128661

  The present invention has been made in view of such circumstances, and an object thereof is to provide a method for purifying a triazine ring-containing hyperbranched polymer with high operability and volumetric efficiency.

  As a result of intensive studies to achieve the above object, the present inventors added a predetermined amine to the polymer solution after polymerization, and dropped the amine-added solution into a heated poor solvent for reprecipitation. The present inventors have found that an excellent purification effect can be obtained with high operability such as good filterability and volumetric efficiency, and the present invention has been completed.

That is, the present invention
1. A reprecipitation treatment step of adding the organic amine to the triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction and then dropping the solution into a heated poor solvent, wherein the amount of the organic amine added is the reprecipitation treatment A method for purifying a triazine ring-containing hyperbranched polymer, characterized in that the pH of the filtrate after filtering the precipitate produced in the step is 7.0 or more,
2. A method for purifying a triazine ring-containing hyperbranched polymer, wherein the organic amine is a monoalkylamine,
3. A method for purifying a hyperbranched polymer containing two triazine rings, wherein the monoalkylamine is n-propylamine;
4). The method for purifying a triazine ring-containing hyperbranched polymer according to any one of 1 to 3, wherein the pH of the filtrate is 9.0 or more,
5). A method for purifying the triazine ring-containing hyperbranched polymer of 4, wherein the pH of the filtrate is 10.0 or more;
6). The method for purifying a triazine ring-containing hyperbranched polymer according to any one of 1 to 5, wherein the heating temperature is 40 to 75 ° C,
7). The method for purifying a triazine ring-containing hyperbranched polymer according to any one of 1 to 6, wherein the poor solvent used in the reprecipitation treatment step is an aqueous solvent,
8). The method for purifying a triazine ring-containing hyperbranched polymer according to any one of 1 to 7, wherein the triazine ring-containing hyperbranched polymer-containing solution is obtained by reacting a cyanuric halide and a diaminoaryl compound in an organic solvent. ,
9. After the cyanuric halide and the diaminoaryl compound are reacted in an organic solvent, an organic amine is added to the reaction solution, and the solution after the addition of the organic amine is dropped into a heated poor solvent to regenerate the product. A method of producing a triazine ring-containing hyperbranched polymer, characterized by precipitating,
10. Provided is a method for producing a triazine ring-containing hyperbranched polymer, wherein the amount of the organic amine added is such that the pH of the filtrate after filtration of the precipitate produced by the reprecipitation is 7.0 or more. .

In the purification method of the present invention, since the pH is controlled by adding an organic amine to the polymer solution after polymerization, the filterability of the precipitate is improved.
That is, the polymer solution after the reaction is in an acidic state (about pH 3.0) due to by-produced hydrogen halide such as hydrogen chloride, and forms a salt such as hydrochloride with the terminal amino group of the polymer. In the salt state, the formation of hydrogen bonds between the nitrogen atom of the terminal amino group and the surrounding hydrogen atoms is suppressed. As a result, the interaction between molecules weakens and aggregation does not occur, and the solid particle size is reduced. Get smaller.
In the purification method of the present invention, the terminal amino group is liberated by adding an organic amine to bring the pH from the neutral to the basic range, thereby promoting the formation of hydrogen bonds between the polymer molecules. Since the produced solid is agglomerated to form a polymer having a large particle size, the filterability of the precipitate is improved.
In addition, since it is also a method of adding a polymer solution after addition of amine to a heated poor solvent, operability such as filterability is improved.
In addition, since the filterability is good as described above, the amount of the poor solvent used can be reduced, the volume efficiency can be improved, and the residual halogen reduction effect is also excellent.
The purification method of the present invention gives a polymer having a molecular weight and molecular weight distribution equivalent to that in the case of a purification method in which no poor solvent is heated without addition of an amine, so that there is almost no influence on the polymer physical properties by heating.

Hereinafter, the present invention will be described in more detail.
In the method for purifying a triazine ring-containing hyperbranched polymer according to the present invention, an organic amine is added to the triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction, and then the solution after the addition of the organic amine is dropped into a heated poor solvent. A reprecipitation treatment step is included.

  The triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction to which the purification method of the present invention is applied is particularly a reaction solution after a polymerization reaction between cyanuric halide and a diaminoaryl compound in an organic solvent. It is not limited, For example, the solution after reacting cyanuric halide and the diaminoaryl compound described in the said patent document 1 in the organic solvent etc. are mentioned.

The organic solvent is not particularly limited as long as it is widely used for the polymerization reaction. 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-dimethylisobutyramide, N-methylformamide, N, N′-dimethylpropylene urea And amide solvents, 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.

  The organic amine added to the polymer-containing solution after the polymerization reaction is not particularly limited, and examples thereof include alkylamines, arylamines, aralkylamines, nitrogen-containing heterocyclic aromatic amines, etc. Are preferred, and primary monoamines are particularly preferred.

  Examples of the alkylamine 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-butyl Amine, 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-propylamine, Monoalkylamines such as 2-ethylhexylamine and ethanolamine; dialkyl or alicyclic amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, pyrrolidine, piperidine and morpholine; trialkylamines such as trimethylamine and triethylamine Is mentioned.

Specific examples of aralkylamine include monoaralkyl such as benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine, naphthylmethylamine, and the like. Examples include diaralkylamines such as amine and dibenzylamine, and triaralkylamines such as tribenzylamine.
Specific examples of the arylamine include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- And monoarylamines such as phenylaniline, 4-amino-p-terphenyl and 2-aminofluorene; diarylamines such as diphenylamine; and triarylamines such as triphenylamine.
Specific examples of the nitrogen-containing heterocyclic aromatic amine include pyridine and pyrimidine.

Among these, considering the filterability of precipitates and the effect of reducing halogen contained in the purified polymer, alkylamines are preferable, linear alkylamines are more preferable, and linear monoalkylamines are even more preferable.
Further, in the case of an amine in which a salt is precipitated, it is necessary to filter the amine-added solution before the reprecipitation treatment. Therefore, considering the simplification of the purification process, it is preferable to use an amine in which no salt is precipitated. Examples of such amines include various primary amines such as monoalkylamines, monoaralkylamines, and monoarylamines, and nitrogen-containing heterocyclic aromatic amines.
Considering both of these, linear monoalkylamine is more preferable, among which n-propylamine and n-butylamine are more preferable, and n-propylamine is most preferable.

  From the viewpoint of improving the filterability of the precipitate, the amount of the organic amine added is preferably such that the pH of the filtrate after filtration of the precipitate generated in the reprecipitation treatment step is 7.0 or more. The amount of 5 or more is more preferable, the amount of 10.0 or more is even more preferable, and the amount of 11.0 or more is optimal.

The poor solvent used in the reprecipitation treatment step is not particularly limited as long as the target polymer precipitates, and examples thereof include water, hexane, heptane, toluene, acetonitrile, and methanol. In the invention, an aqueous solvent mainly containing water (more than 50% by mass) is particularly preferable, and a water-only solvent is preferable.
In addition, you may add bases, such as aqueous ammonia, in a poor solvent as needed.
The heating temperature of the poor solvent is not particularly limited, but the operability during purification such as agglomeration and filterability of the precipitate, the effect of reducing residual halogen, and the reduction in coloring of the polymer after purification, etc. Considering, about 35-80 degreeC is preferable and 40-75 degreeC is more preferable.

  The amount of the poor solvent used in the reprecipitation treatment step can be usually 10 to 200 times by mass with respect to the cyanuric halide used for the polymerization. As described above, the purification method of the present invention has good filterability. Therefore, the volume efficiency can be increased by reducing the amount of the poor solvent used compared to the case of normal temperature. In the above heating temperature range, in consideration of volumetric efficiency and filterability of precipitates, the use amount of the poor solvent is preferably 10 to 100 times by mass, more preferably 15 to 70 times by mass, and further preferably 15 to 60 times by mass. 15 to 40 times mass is preferable.

  In the reprecipitation treatment step, the rate at which the polymer solution is added to the poor solvent is not particularly limited, but considering the aggregation property of the polymer at the time of reprecipitation, the effect of reducing residual halogen, and the like, 0.7 to 3. 0 mL / min is preferable, and 1.5 to 2.2 mL / min is more preferable.

After the reprecipitation treatment step, the target polymer can be obtained by filtering the precipitate, washing the filtrate with water or the like as necessary, and drying the precipitate.
The filtration equipment is not particularly limited, and a known suction filtration equipment or the like may be used.
Further, the drying temperature and time cannot be defined unconditionally because they vary depending on the kind of the organic solvent and the heat resistance of the polymer, but are about 100 to 200 ° C., preferably about 120 to 180 ° C. and 1 to 200 hours. Degree. During drying, the pressure may be reduced to about −10 to −100 kPa.
The precipitate generated by the reprecipitation treatment step is stirred for a predetermined time in the state heated to the same temperature as the poor solvent for the purpose of further reducing residual halogen, etc., cooled to about 25 ° C., and then filtered and dried. You may go. In this case, the stirring time is not particularly limited, but is about 0.1 to 5 hours, preferably about 0.1 to 2 hours.

In the purification method of the present invention, the second reprecipitation treatment step may be performed for the purpose of further increasing the degree of purification.
In this case, even if a solution obtained by dissolving the precipitate obtained in the first reprecipitation treatment step in an organic solvent is used again, a solution obtained by dissolving the polymer obtained by filtering and drying the solution in an organic solvent is used. However, the former method is preferable from the viewpoint of simplifying the operation.
Also, in the second reprecipitation treatment step, as in the first reprecipitation treatment step, a method of adding an organic amine to the above solution and dropping it into a heated poor solvent may be used. As a result, operability such as filterability can be improved and residual halogen can be reduced.

Examples of the organic solvent and the poor solvent used in the second reprecipitation treatment step include the same ones as described above, but the organic solvent is particularly preferable from the viewpoint of reducing the residual solvent in the purified polymer. N, N-dimethylacetamide is preferred.
In the case of using an organic amine, those similar to those described above can be used, and in this case, n-propylamine is optimal.
The heating temperature of the poor solvent, the rate at which the polymer solution is added, and filtration / drying after reprecipitation are the same as described above.
In this case as well, the precipitate produced by the reprecipitation treatment step is stirred for a predetermined time in the state heated to the same temperature as the poor solvent for the purpose of further reducing the residual halogen, etc., and cooled to about 25 ° C. Filtration and drying may be performed.

  By carrying out the purification method of the present invention, the residual halogen of the triazine ring-containing hyperbranched polymer can be reduced to usually 10,000 ppm or less, and in some cases, about 5000 ppm or less.

Although the purification method of the present invention can be applied to any triazine ring-containing hyperbranched polymer, as described above, it is particularly suitable for the post-treatment of the method for producing a hyperbranched polymer disclosed in Patent Document 1.
Specific examples of the hyperbranched polymer structure include a triazine ring-containing hyperbranched polymer including a repeating unit structure represented by the following formula (1).

In the above formulas, R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
Although it does not specifically limit as carbon number of the said alkyl group, 1-20 are preferable, 1-10 are more preferable, and 1-3 are still more preferable. Further, the structure may be any of a chain, a branch, and a ring.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, and 1-methyl. -Cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl -N-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl -Cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl -Cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1- Dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl -N-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3 -Methyl-cyclopentyl group, 1- Til-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3- Dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2 -Methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclo A propyl group, 2-ethyl-3-methyl-cyclopropyl group, etc. are mentioned.

Although it does not specifically limit as carbon number of the said alkoxy group, 1-20 are preferable, when it considers raising the heat resistance of a polymer more, C1-C10 is more preferable, and 1-3 are much more. 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 group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, 1-methyl- n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl -N-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl Ru-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1 , 2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, etc. Can be mentioned.

Although it does not specifically limit as carbon number of the said aryl group, 6-40 are preferable, and when it considers raising the heat resistance of a polymer more, 6-16 are more preferable, and 6-13 are much more preferable.
Specific examples of the aryl group include a phenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, and a p-methoxy group. Phenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, Examples include 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

Although it does not specifically limit as carbon number of an aralkyl group, C7-C20 is preferable and the linear, branched, and cyclic | annular form may be sufficient as the alkyl part.
Specific examples thereof include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenylmethyl group. 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, α-naphthylmethyl group and the like.

  Ar in Formula (1) represents at least one selected from the group represented by Formulas (2) to (18), and in particular, one type represented by Formulas (5) to (18) is preferable. Two types selected from the group represented by 5) to (12) and (14) to (18) are more preferable, and are represented by the formulas (7), (11), (12), (14) and (15). Two types selected from the group are even more preferable.

R ^{1 to} R ¹²⁸ 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 ¹²⁹ R ¹³⁰ ) _m — (R ¹²⁹ and R ¹³⁰ are each independently Represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, these may be combined to form a ring), and m is an integer of 1 to 10 ), C═O, O, S, SO, SO ₂ , or NR ¹³¹ (R ¹³¹ represents a hydrogen atom or an alkyl group that may have a branched structure having 1 to 10 carbon atoms.) Represents.
Examples of these alkyl groups and alkoxy groups are the same as those described above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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 (19).

R ^{132 to} R ¹³⁵ 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. An alkoxy group that may have a branched structure is represented, and Y ¹ and Y ² each independently represent an alkylene group that 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 which may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

  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, each measuring apparatus etc. which were used in the Example are as follows.
(1) Number average molecular weight Mn, mass average molecular weight Mw
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 (with 1% LiCl)
Detector: UV (280 nm)
Calibration curve: Standard polystyrene (2) Chlorine content combustion ion chromatography method Apparatus (combustion): IGF-100 manufactured by Mitsubishi Analytech Co., Ltd.
Apparatus (ion chromatograph): ICS-1500 manufactured by Nippon Dionex Co., Ltd.
Combustion treatment of 40mg of sample with a combustion device, absorption in a 20mL absorption trap, and measurement with an ion chromatograph

[Example 1]
[1] Production of triazine ring-containing hyperbranched polymer

Under nitrogen, 128.9 g of N, N-dimethylacetamide (hereinafter abbreviated as DMAc) was cooled to −5 ° C. or lower in an acetone / dry ice bath in a 300 mL four-necked flask, and 2,4,6-trichloro-1,3 , 5-triazine (36.00 g, 0.195 mol, manufactured by Evonik Degussa) was added and dissolved. Thereafter, m-phenylenediamine (26.39 g, 0.244 mol, manufactured by AminoChem) dissolved in 193.7 g of dimethylacetamide was cooled to 5 ° C. or lower in a 500 mL four-necked flask and previously cooled to −5 ° C. or lower. A DMAc solution of 4,6-trichloro-1,3,5-triazine was added dropwise over 120 minutes. After dropping, the mixture was stirred for 30 minutes, and aniline (6.18 g, 0.0664 mol) was added dropwise over 4 minutes. The mixture was further stirred for 30 minutes, and this reaction solution was added dropwise over 30 minutes using a dropping pump to a tank in which 263.88 g of DMAc was previously added to a 1 L four-necked flask and heated to 90 ° C. in an oil bath. The polymerization was carried out by stirring at 88 ° C. for 2 hours.
Thereafter, aniline (48.36 g, 0.519 mol) was added dropwise over 10 minutes, and after stirring at 88-90 ° C. for 3 hours, the reaction was stopped, the mixture was allowed to cool to room temperature, and a polymer-containing solution (hereinafter, HB- 700.0 g) was obtained (abbreviated as TmDA / DMAc solution).

[2] Purification To 38.89 g of HB-TmDA / DMAc solution, n-propylamine (6.41 g, 0.108 mol) was added dropwise over 5 minutes and stirred for 10 minutes. This was dropped into ion-exchanged water (60.0 g) heated to 62 to 64 ° C. over 40 minutes to cause reprecipitation. After stirring at 64 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water and dried in a vacuum dryer at 150 ° C. for 5 hours to obtain 2.78 g of a target polymer compound (hereinafter abbreviated as HB-TmDA). It was.

[Example 2]
To 87.50 g of the HB-TmDA / DMAc solution produced in Example 1, n-propylamine (14.42 g, 0.244 mol) was added dropwise over 5 minutes and stirred for 10 minutes. This was added dropwise to ion-exchanged water (60.0 g) heated to 62 to 63 ° C. over 40 minutes to cause reprecipitation. After stirring at 63-64 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (60φ) and filter paper (5B) under reduced pressure. The cake was washed 12 times with 45.0 g of ion exchange water.
Further, the obtained wet product and 135.0 g of ion-exchanged water were charged again, stirred at 60 to 61 ° C. for 3 hours, cooled to room temperature, and filtered. The cake was washed 12 times with 45.0 g of ion exchange water. The obtained wet product was dried with a vacuum dryer at 150 ° C. for 43 hours to obtain 6.17 g of HB-TmDA.

[Example 3]
Triethylamine (10.97 g, 0.108 mol) was added dropwise to 39.04 g of the HB-TmDA / DMAc solution prepared in Example 1 over 5 minutes, and the mixture was stirred for 10 minutes. Thereafter, the precipitated triethylamine hydrochloride was filtered, and the filtrate was added dropwise to ion-exchanged water (60.0 g) heated to 62 to 63 ° C. over 40 minutes for reprecipitation. After stirring at 63 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water and dried at 150 ° C. for 22 hours with a vacuum dryer to obtain 2.59 g of HB-TmDA.

[Example 4]
Ethanolamine (6.62 g, 0.108 mol) was added dropwise to 38.89 g of the HB-TmDA / DMAc solution produced in Example 1 over 2 minutes and stirred for 10 minutes. This was dropped into ion-exchanged water (60.0 g) heated to 63 to 64 ° C. over 40 minutes to cause reprecipitation. After stirring at 64-65 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water and dried at 150 ° C. for 18 hours with a vacuum dryer to obtain 3.08 g of HB-TmDA.

[Example 5]
To 38.98 g of the HB-TmDA / DMAc solution produced in Example 1, n-propylamine (4.49 g, 0.0760 mol) was added dropwise over 5 minutes and stirred for 10 minutes. This was dropped into ion-exchanged water (60.0 g) heated to 63 to 64 ° C. over 40 minutes to cause reprecipitation. After stirring at 64-65 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water, and dried at 150 ° C. for 88 hours with a vacuum dryer to obtain 2.84 g of HB-TmDA.

[Example 6]
To 38.98 g of the HB-TmDA / DMAc solution produced in Example 1, n-propylamine (3.21 g, 0.0543 mol) was added dropwise over 5 minutes and stirred for 10 minutes. This was dropped into ion-exchanged water (60.0 g) heated to 62 to 64 ° C. over 40 minutes to cause reprecipitation. After stirring at 64-65 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water and dried at 150 ° C. for 65 hours with a vacuum dryer to obtain 3.02 g of HB-TmDA.

[Example 7]
To 38.98 g of the HB-TmDA / DMAc solution produced in Example 1, n-propylamine (1.92 g, 0.0324 mol) was added dropwise over 5 minutes and stirred for 10 minutes. This was dropped into ion-exchanged water (60.0 g) heated to 63 ° C. over 40 minutes to cause reprecipitation. After stirring at 63-65 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water and dried at 150 ° C. for 65 hours with a vacuum dryer to obtain 2.98 g of HB-TmDA.

[Comparative Example 1]
To a mixed solution of 28% aqueous ammonia solution (6.58 g, 0.108 mol) and ion-exchanged water (60.0 g) heated to 62 to 64 ° C., 38.96 g of the HB-TmDA / DMAc solution prepared in Example 1 was added. The solution was dropped over a period of time and reprecipitated. After stirring at 64 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water and dried at 150 ° C. for 21 hours with a vacuum dryer to obtain 2.95 g of HB-TmDA.

[Comparative Example 2]
To 87.50 g of the HB-TmDA / DMAc solution produced in Example 1, n-propylamine (14.42 g, 0.244 mol) was added dropwise over 5 minutes and stirred for 10 minutes. This was dripped in ion-exchange water (60.0g) of 26-28 degreeC over 40 minutes, and was reprecipitated. After stirring at 24-28 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (60φ) and filter paper (5B) under reduced pressure. The cake was washed 12 times with 45.0 g of ion-exchanged water.
Further, the obtained wet product and 135.0 g of ion-exchanged water were charged again, stirred at 60 to 61 ° C. for 3 hours, cooled to room temperature, and filtered. The cake was washed 12 times with 45.0 g of ion-exchanged water. The obtained wet product was dried at 150 ° C. for 43 hours with a vacuum dryer to obtain 6.17 g of HB-TmDA.

[Comparative Example 3]
To 38.98 g of the HB-TmDA / DMAc solution produced in Example 1, n-propylamine (0.643 g, 0.0108 mol) was added dropwise over 5 minutes and stirred for 10 minutes. This was dropped into ion-exchanged water (60.0 g) at 62 to 64 ° C. over 40 minutes to cause reprecipitation. After stirring at 64 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was suction filtered using a Kiriyama funnel (40φ) and filter paper (5B) under reduced pressure. The cake was washed 4 times with 20.0 g of ion-exchanged water and dried at 150 ° C. for 65 hours with a vacuum dryer to obtain 3.20 g of HB-TmDA.

[Comparative Example 4]
39.60 g of the HB-TmDA / DMAc solution produced in Example 1 was added dropwise to ion-exchanged water (60.0 g) at 62 to 65 ° C. over 40 minutes for reprecipitation. After stirring at 65 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was subjected to suction filtration under reduced pressure using a Kiriyama funnel (40φ) and filter paper (5B). It was.

Table 1 summarizes the filtration time of the precipitate produced by reprecipitation, the residual chlorine concentration of the dried product, the presence or absence of hydrochloride precipitation, and the pH of the filtrate after reprecipitation in the above Examples and Comparative Examples.
As shown in Table 1, it can be seen that when amine is added to the polymer solution, the filtration time is short and the residual chlorine is reduced.

In addition, Table 2 shows a comparison of filtration time depending on the temperature during reprecipitation.
As shown in Table 2, in Comparative Example 2 where the poor solvent is not heated, the filtration time of the precipitate generated by reprecipitation is remarkably longer than that of Example 2 where the poor solvent is heated. I understand.

Further, Table 3 shows the filtration time and the pH of the filtrate depending on the equivalent of n-propylamine.
As shown in Table 3, in Comparative Example 3 in which the amount of n-propylamine added was small and the filtrate pH was low, Examples 1, 5 and 5 in which n-propylamine was added until the filtrate pH became basic It can be seen that the filtration time of the precipitate generated by reprecipitation is longer than that of 7. Moreover, it turns out that it cannot filter in the first place in the comparative example 4 which does not add n-propylamine.

[Example 8]
[1] Production of triazine ring-containing hyperbranched polymer Under nitrogen, m-phenylenediamine (26.39 g, 0.244 mol, manufactured by AminoChem) dissolved in 322.6 g of dimethylacetamide was cooled to 5 ° C. or lower in a 500 mL four-necked flask. Then, 2,4,6-trichloro-1,3,5-triazine (36.00 g, 0.195 mol, manufactured by Evonik Degussa) was added in 10 divided portions over 1 hour and 30 minutes. After stirring for 30 minutes, aniline (6.18 g, 0.0664 mol) was added dropwise over 1 minute. After dropping, the reaction solution was stirred for 30 minutes. The reaction solution was added dropwise to a tank in which 263.9 g of dimethylacetamide was previously added to a 1 L four-necked flask and heated to 90 ° C. in an oil bath using a dropping pump over 1 hour. The mixture was stirred at 85 to 87 ° C. for 2 hours for polymerization.
Thereafter, aniline (48.36 g, 0.519 mol) was added dropwise over 5 minutes, the reaction was stopped by stirring at 85 ° C. for 3 hours, and the mixture was allowed to cool to room temperature to obtain 698.3 g of an HB-TmDA / DMAc solution. It was.

[2] Purification To 87.29 g of the HB-TmDA / DMAc solution, n-propylamine (14.42 g, 0.244 mol) was added dropwise over 1 minute and stirred for 10 minutes. This was dripped in 74 degreeC ion-exchange water (135.0g) over 35 minutes, and was reprecipitated. After stirring at 74 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was filtered (filtration time 40 seconds). The cake was washed 4 times with 45.0 g of ion-exchanged water to obtain 12.81 g of a crude product (residual chlorine concentration: 4400 ppm).
The crude product was dissolved in tetrahydrofuran (54.00 g), a solution of 1.65 g of ammonium acetate dissolved in 28% aqueous ammonia solution (60.71 g) was added, and the mixture was stirred at room temperature for 30 minutes and then stirred at 61 ° C. for 30 minutes. did. The solution was separated by allowing to stand for 30 minutes, and the organic layer was taken out.
The organic layer heated to 60 ° C. was dropped into ion-exchanged water (90.00 g) over 40 minutes and reprecipitated at room temperature. The precipitate was filtered (filtration time: 40 seconds), washed with cake 4 times with 20.0 g of ion-exchanged water, and dried in a vacuum dryer at 150 ° C. for 25 hours to obtain 6.03 g of HB-TmDA (residual). Chlorine concentration 150 ppm).

Claims (10)

  A reprecipitation treatment step of adding the organic amine to the triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction and then dropping the solution into a heated poor solvent, wherein the amount of the organic amine added is the reprecipitation treatment A method for purifying a triazine ring-containing hyperbranched polymer, wherein the pH of the filtrate after filtering the precipitate produced in the step is 7.0 or more.   The method for purifying a triazine ring-containing hyperbranched polymer according to claim 1, wherein the organic amine is a monoalkylamine.   The method for purifying a triazine ring-containing hyperbranched polymer according to claim 2, wherein the monoalkylamine is n-propylamine.   The method for purifying a triazine ring-containing hyperbranched polymer according to any one of claims 1 to 3, wherein the filtrate has a pH of 9.0 or more.   The method for purifying a triazine ring-containing hyperbranched polymer according to claim 4, wherein the filtrate has a pH of 10.0 or more.   The said heating temperature is 40-75 degreeC, The purification method of the triazine ring containing hyperbranched polymer of any one of Claims 1-5.   The method for purifying a triazine ring-containing hyperbranched polymer according to any one of claims 1 to 6, wherein the poor solvent used in the reprecipitation treatment step is an aqueous solvent.   The triazine ring-containing hyperbranch according to any one of claims 1 to 7, wherein the triazine ring-containing hyperbranched polymer-containing solution is obtained by reacting cyanuric halide with a diaminoaryl compound in an organic solvent. Branch polymer purification method.   After the cyanuric halide and the diaminoaryl compound are reacted in an organic solvent, an organic amine is added to the reaction solution, and the solution after the addition of the organic amine is dropped into a heated poor solvent to regenerate the product. A method for producing a triazine ring-containing hyperbranched polymer, characterized by precipitating.   The method for producing a triazine ring-containing hyperbranched polymer according to claim 9, wherein the organic amine is added in an amount such that the pH of the filtrate after filtration of the precipitate produced by the reprecipitation is 7.0 or more. .