JP6544240B2 - Purification method of triazine ring-containing hyperbranched polymer - Google Patents

Description

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

It is reported that a triazine ring-containing hyperbranched polymer having a branched structure is synthesized by cyanuric acid chloride and the like and diamines, and exhibits high refractive index, high heat resistance, and high transparency (Patent Document 1).
The high refractive index of the triazine ring-containing hyperbranched polymer is due to the high density due to the intramolecular or intermolecular hydrogen bond.
On the other hand, a polymer compound having an aromatic ring or a triazine ring introduced therein or a polymer compound having high hydrogen bonding property has poor solubility in a solvent and is often insoluble in a resist solvent which is a safety solvent.

In the above triazine ring-containing hyperbranched polymer, a monofunctional amine (aniline) is added at the time of polymerization to be reacted to form a polymer having a moderate degree of branching, thereby suppressing intramolecular and intermolecular hydrogen bonding, and solubility Improve.
In the above Patent Document 1, purification of the triazine ring-containing hyperbranched polymer is carried out by a reprecipitation operation in which a polymer solution is added to a poor solvent, but the particle size of the resulting polymer solid is small, There is a problem that the filterability is extremely bad.
Due to this poor filterability, there are problems such as a significant decrease in purification efficiency due to an increase in the liquid content, and 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 volume 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 this amine addition solution into a heated poor solvent to reprecipitate. The present invention has been completed by finding that excellent purification effects can be obtained with high operability such as good filterability and volumetric efficiency.

That is, the present invention
1. An organic amine is added to the triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction, and then the solution is added dropwise to a heated poor solvent, and the amount of the organic amine added is the reprecipitation treatment. The method for purifying a triazine ring-containing hyperbranched polymer, wherein the pH of the filtrate after filtration of the precipitate formed in the step is 7.0 or more,
2. A method of purifying a triazine ring-containing hyperbranched polymer according to 1, wherein the organic amine is a monoalkylamine,
3. A purification method of the triazine ring-containing hyperbranched polymer of 2, wherein the monoalkylamine is n-propylamine;
4. The purification method of 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. 4. The method for purifying a triazine ring-containing hyperbranched polymer of 4, wherein the pH of the filtrate is 10.0 or more,
6. The purification method for 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 purification method of 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 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 re-react the product. A process for producing a triazine ring-containing hyperbranched polymer characterized by precipitation;
10. Provided is a method for producing a triazine ring-containing hyperbranched polymer of 9, wherein the amount of the organic amine added is such that the pH of the filtrate after filtration of the precipitate formed by the reprecipitation becomes 7.0 or more. .

In the purification method of the present invention, since the pH is controlled by adding the organic amine to the polymer solution after polymerization, the filterability of the precipitate is improved.
That is, the polymer solution after reaction is in an acidic state (about pH 3.0) by hydrogen halide such as by-product 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 hydrogen atoms present in the periphery is suppressed, as a result, the interaction between molecules is weakened and aggregation does not occur, and the particle size of the solid is It becomes 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 a neutral to a basic range, thereby promoting the formation of hydrogen bonds between polymer molecules and causing reprecipitation. The formed solid is coagulated to form a large particle size polymer, and the precipitate has good filterability.
In addition, since it is also a method of adding the polymer solution after amine addition to the heated poor solvent, operability such as filterability is improved.
Further, since the filterability is good as described above, the amount of use of the poor solvent can be reduced, and not only the volumetric efficiency can be improved, but also the effect of reducing the residual halogen is excellent.
In addition, since the purification method of the present invention gives a polymer having the same molecular weight and molecular weight distribution as in the purification method in which the amine is not added and the poor solvent is not heated, the polymer physical properties are hardly affected by the heating.

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

  The triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction to which the purification method of the present invention is applied is a reaction solution after the polymerization reaction of cyanuric halide and a diaminoaryl compound in an organic solvent, in particular There is no limitation, and for example, a solution obtained by reacting cyanuric halide and a diaminoaryl compound in an organic solvent, which is described in Patent Document 1 above, and the like can be mentioned.

The organic solvent is not particularly limited as long as it is generally used for the above-mentioned polymerization reaction, and examples thereof include tetrahydrofuran, dioxane, dimethylsulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ', N'-tetramethylmalonamide, N-methylcaprolactam, N-acetyl pyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methyl formamide, N, N'-dimethylpropylene urea And amide solvents such as C.I., and mixed solvents thereof.
Among them, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixture thereof are preferable, and in particular, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Is preferred.

  The organic amine to be 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 and the like, among which monoamines Are preferred, and in particular, primary monoamines are preferred.

  As the alkylamine, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-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 ester 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; Dialkylamines such as dimethylamine, diethylamine, di n-propylamine, diisopropylamine, pyrrolidine, piperidine and morpholine; and alicyclic amines; trialkylamines such as trimethylamine and triethylamine Can be mentioned.

Specific examples of the aralkylamine include monoaralkyl such as benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine, naphthylmethylamine and the like Examples thereof include amines, diaralkylamines such as 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- Monoarylamines such as phenylaniline, 4-amino-p-terphenyl and 2-aminofluorene; Diarylamines such as diphenylamine; Triarylamines such as triphenylamine and the like.
Specific examples of the nitrogen-containing heterocyclic aromatic amine include pyridine, pyrimidine and the like.

Among them, alkylamines are preferred, linear alkylamines are more preferred, and linear monoalkylamines are even more preferred, in consideration of the filterability of the precipitate and the reduction effect of the halogen contained in the purified polymer.
In addition, in the case of an amine from which a salt precipitates, it is necessary to filter the amine-added solution before the reprecipitation treatment. Therefore, considering simplification of the purification step, it is preferable to use an amine which does not precipitate a salt. Such amines include various primary amines such as monoalkylamines, monoaralkylamines and monoarylamines, and nitrogen-containing heterocyclic aromatic amines.
In consideration of both of them, linear monoalkylamines are more preferable, and in particular, n-propylamine and n-butylamine are more preferable, and n-propylamine is optimum.

  From the viewpoint of enhancing the filterability of the precipitate, the amount of the organic amine added is preferably such that the pH of the filtrate after filtering the precipitate formed in the reprecipitation treatment step is 7.0 or more. An amount of 5 or more is more preferable, an amount of 10.0 or more is even more preferable, and an amount of 11.0 or more is optimum.

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, methanol and the like. In the invention, in particular, an aqueous solvent mainly composed of water (more than 50% by mass) is preferable, and a single solvent of water is preferable.
In the poor solvent, a base such as aqueous ammonia may be added as necessary.
Although the heating temperature of the poor solvent is not particularly limited, the operation during purification such as the flocculation of precipitate and filterability, the reduction effect of residual halogen, and the reduction of coloring of the polymer after purification, etc. When it considers, 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 usually be 10 to 200 times by mass the cyanuric halide used for the polymerization, but as described above, the purification method of the present invention has good filterability. Because of this, it is possible to increase the volumetric efficiency by reducing the amount of poor solvent used compared to the case of normal temperature. In the above heating temperature range, in view 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, further 15 to 60 times by mass Preferably, 15 to 40 times by mass is optimum.

  The rate of addition of the polymer solution into the poor solvent in the reprecipitation treatment step is not particularly limited, but in consideration of the aggregation property of the polymer at the time of reprecipitation and the reduction effect of the residual halogen, etc. 0 mL / min is preferred, and 1.5 to 2.2 mL / min is more preferred.

After the re-precipitation treatment step, the precipitate is filtered, and the filtrate is washed with water or the like as necessary, and the polymer can be dried to obtain the target polymer.
The filtration equipment is not particularly limited, and a known suction filtration equipment or the like may be used.
The drying temperature and time can not be generally defined because they vary depending on the type of the organic solvent, the heat resistance of the polymer, etc., but the temperature is about 100 to 200 ° C., preferably about 120 to 180 ° C., 1 to 200 hours It is an extent. At the time of drying, the pressure may be reduced to about -10 to -100 kPa.
The precipitate formed by the re-precipitation process is stirred for a predetermined time while heated to the same temperature as the poor solvent for the purpose of reducing the 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, a second reprecipitation treatment step may be performed in order to further increase the degree of purification.
In this case, even if a solution obtained by re-dissolving the precipitate obtained in the first reprecipitation treatment step in an organic solvent is used, a solution obtained by filtering and drying it is used again. Although the method may be used, the former method is preferable in terms of simplification of the operation.
Also in the second reprecipitation treatment step, as in the first reprecipitation treatment step, a method may be used in which an organic amine is added to the above solution and this is dropped into a heated poor solvent; By doing this, 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 as those described above, but as the organic solvent, particularly from the viewpoint of reducing the residual solvent in the purified polymer, And N, N-dimethylacetamide are preferred.
When organic amines are used, the same ones as described above can be used, again with n-propylamine being the best.
Further, the heating temperature of the poor solvent, the rate of addition of the polymer solution, and the filtration / drying after reprecipitation are also the same as described above.
Also in this case, the precipitate formed in the re-precipitation treatment step is stirred for a predetermined time while heating to the same temperature as the poor solvent for the purpose of reducing the residual halogen, etc., and cooled to about 25 ° C. It may be filtered and dried.

  By carrying out the purification method of the present invention, the residual halogen in the triazine ring-containing hyperbranched polymer can be reduced to about 10000 ppm or less, or about 5000 ppm or less in some cases.

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

In each of 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. In addition, the structure may be linear, branched or cyclic.

  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, 1-methyl group -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-ethy -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, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 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- -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 Propyl, 2-ethyl-3-methyl-cyclopropyl and the like can be mentioned.

The carbon number of the above alkoxy group is not particularly limited, but is preferably 1 to 20, and in view of further enhancing the heat resistance of the polymer, the carbon number is preferably 1 to 10, more preferably 1 to 3 preferable. In addition, the structure of the alkyl moiety may be linear, branched or cyclic.
Specific examples of the alkoxy group are 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 group -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-dime 1, 2, 3-dimethyl-n-butoxy, 3, 3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 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. It can be mentioned.

The carbon number of the above aryl group is not particularly limited, but is preferably 6 to 40, and in view of further enhancing the heat resistance of the polymer, the carbon number is preferably 6 to 16 and more preferably 6 to 13 preferable.
Specific examples of the aryl group include phenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxy 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, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group etc. are mentioned.

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

  Ar in the formula (1) represents at least one selected from the group represented by the formulas (2) to (18), and particularly preferably one of the formulas (5) to (18), 5) to (12) and (14) to (18) are more preferably two selected from the group represented by formulas (7), (11), (12), (14) and (15) Two types selected from the group are more preferred.

The R ^{1 to} R ¹²⁸ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having a carbon number of 1 to 10 and which may have a branched structure, or a carbon number of 1 to 10 R ¹ represents an alkoxy group which may have a branched structure, and W ¹ and W ² each independently represent a single bond, — (CR ¹²⁹ R ¹³⁰ ) _m — (R ¹²⁹ and R ¹³⁰ independently of each other) And a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms, provided that they may together 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 optionally having a carbon number of 1 to 10). Represents
Examples of the alkyl group and the alkoxy group include the same as described above.
The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Moreover, X ¹ and X ² each independently represent a single bond, an alkylene group optionally having a carbon number of 1 to 10, and a group represented by the formula (19).

The R ^{132 to} R ¹³⁵ are, independently of one another, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group optionally having a carbon number of 1 to 10, or a carbon number of 1 to 10 Y represents an alkoxy group which may have a branched structure, and Y ¹ and Y ² each independently represent a single bond or an alkylene group which may have a C 1-10 branched structure.
Examples of the halogen atom, the alkyl group and the alkoxy group include the same as described above.
As an alkylene group which may have a C1-C10 branched structure, a methylene group, ethylene group, a propylene group, trimethylene group, tetramethylene group, pentamethylene group etc. are mentioned.

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

EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. 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)
Device: Shimadzu Corporation SCL-10Avp series Column: Shodex K-804L + K-805L
Column temperature: 60 ° C
Solvent: N-methyl-2-pyrrolidone (added 1% LiCl)
Detector: UV (280 nm)
Calibration curve: Standard polystyrene (2) Chlorine content Combustion ion chromatography system (combustion): IGF-100 manufactured by Mitsubishi Analytech Co., Ltd.
Device (ion chromatograph): Nippon Dionex Co., Ltd. ICS-1500
A sample of 40 mg is burnt in the combustion unit, absorbed into a 20 mL absorption trap, and then measured by ion chromatography

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

In a 300 mL four-necked flask under nitrogen, 128.9 g of N, N-dimethylacetamide (hereinafter abbreviated as DMAc) is cooled to -5 ° C or less with an acetone / dry ice bath, and 2,4,6-trichloro-1,3 A 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 less in a 500 mL four-necked flask and cooled to −5 ° C. or less in advance 2, 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. Stir for a further 30 minutes, add this reaction solution to a 1 L four-necked flask with DMAc 263.88 g added beforehand, and add dropwise to the tank heated to 90 ° C. with an oil bath using a dropping pump over 30 minutes. The mixture was stirred at 88 ° C. for 2 hours for polymerization.
Thereafter, aniline (48.36 g, 0.519 mol) is added dropwise over 10 minutes, and after stirring for 3 hours at 88 to 90 ° C., the reaction is stopped, and allowed to cool to room temperature, a polymer-containing solution (hereinafter HB-) 700.0 g of TmDA / DMAc solution was obtained.

[2] Purification n-Propylamine (6.41 g, 0.108 mol) was added dropwise over 38 minutes to 38.89 g of the HB-TmDA / DMAc solution, and the solution was stirred for 10 minutes. The resultant was dropwise added to ion-exchanged water (60.0 g) heated to 62 to 64 ° C. over 40 minutes to be reprecipitated. After stirring for 30 minutes at 64 ° C., the mixture was cooled to room temperature, and the precipitate was suction-filtered under reduced pressure using a Kiriyama funnel (40φ) and filter paper (5B). This is cake-washed 4 times with 20.0 g of ion-exchanged water, and dried at 150 ° C. for 5 hours in a vacuum dryer to obtain 2.78 g of the target polymer compound (hereinafter abbreviated as HB-TmDA). The

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

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

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

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

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

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

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

Comparative Example 2
To 87.50 g of the HB-TmDA / DMAc solution prepared in Example 1, n-propylamine (14.42 g, 0.244 mol) was added dropwise over 5 minutes and stirred for 10 minutes. The resultant was dropwise added to ion exchange water (60.0 g) at 26 to 28 ° C. over 40 minutes to be reprecipitated. After stirring at 24-28 ° C. for 30 minutes, it was cooled to room temperature, and the precipitate was suction-filtered under reduced pressure using a Kiriyama funnel (60φ) and filter paper (5B). The cake was washed with 45.0 g of deionized water 12 times.
Furthermore, 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 with 45.0 g of deionized water 12 times. The obtained wet product was dried at 150 ° C. for 43 hours in a vacuum drier to obtain 6.17 g of HB-TmDA.

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

Comparative Example 4
39.60 g of the HB-TmDA / DMAc solution prepared in Example 1 was dropped into ion-exchanged water (60.0 g) at 62 to 65 ° C. over 40 minutes to cause reprecipitation. After stirring at 65 ° C for 30 minutes, it was cooled to room temperature, and the precipitate was tried to be suction filtered under reduced pressure using a Kiriyama funnel (40φ) and filter paper (5B), but filtration could not be performed even if suction was continued for 20 minutes or longer. The

The filtration time of the precipitate formed 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 are summarized in Table 1.
As shown in Table 1, it can be seen that when the amine is added to the polymer solution, the filtration time is short and the residual chlorine is also reduced.

Moreover, the comparison of the filtration time by the temperature at the time of reprecipitation is shown in Table 2.
As shown in Table 2, in Comparative Example 2 in which the poor solvent is not heated, the filtration time of the precipitate formed by reprecipitation is significantly longer than that in Example 2 in which the poor solvent is heated. I understand.

Furthermore, the filtration time and the pH of the filtrate according to the difference in the equivalent of n-propylamine are shown in Table 3.
As shown in Table 3, in Comparative Example 3 in which the addition amount of n-propylamine is small and the filtrate pH is low, Examples 1 to 5 in which n-propylamine was added until the filtrate pH became basic It turns out that the filtration time of the precipitate which arose in reprecipitation compared with 7 is long. Moreover, it turns out that filtration can not be performed in the comparative example 4 which does not add n-propylamine.

[Example 8]
[1] Preparation of Triazine Ring-Containing Hyperbranched Polymer m-phenylenediamine (26.39 g, 0.244 mol, manufactured by AminoChem Inc.) dissolved in 322.6 g of dimethylacetamide in a 500 mL four-necked flask under nitrogen and cooled to 5 ° C. or less Then, 2,4,6-trichloro-1,3,5-triazine (36.00 g, 0.195 mol, manufactured by Evonik Degussa) was added in 10 portions in the form of a solid over 1 hour and 30 minutes. After stirring for 30 minutes, aniline (6.18 g, 0.0664 mol) was added dropwise over 1 minute. Stir for 30 minutes after dropping, add this reaction solution to a tank which has been previously heated to 90 ° C. by adding 263.9 g of dimethylacetamide to a 1 L four-necked flask and dropping it over 1 hour using a dropping pump. The mixture was polymerized by stirring at 85 to 87 ° C. for 2 hours.
Thereafter, aniline (48.36 g, 0.519 mol) is added dropwise over 5 minutes, and the reaction is stopped by stirring at 85 ° C. for 3 hours, and cooled to room temperature to obtain 698.3 g of a HB-TmDA / DMAc solution. The

[2] Purification n-Propylamine (14.42 g, 0.244 mol) was added dropwise to 87.29 g of the HB-TmDA / DMAc solution over 1 minute, and stirred for 10 minutes. The resultant was dropwise added to ion-exchanged water (135.0 g) at 74 ° C. over 35 minutes to be reprecipitated. After stirring for 30 minutes at 74 ° C., the solution was cooled to room temperature and the precipitate was filtered (filtration time 40 seconds). This was cake-washed 4 times with 45.0 g of ion-exchanged water to obtain 12.81 g of crudely purified product (residual chlorine concentration 4400 ppm).
The crude product is dissolved in tetrahydrofuran (54.00 g), a solution of 1.65 g of ammonium acetate dissolved in 28% aqueous ammonia (60.71 g) is added, and the mixture is stirred at room temperature for 30 minutes and then at 61 ° C. for 30 minutes did. The mixture was allowed to stand for 30 minutes to separate the organic layer.
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), cake-washed 4 times with 20.0 g of ion-exchanged water, and dried in a vacuum drier at 150 ° C. for 25 hours to obtain 6.03 g of HB-TmDA (residue Chlorine concentration 150 ppm).

Claims (9)

An organic amine is added to the triazine ring-containing hyperbranched polymer-containing solution after the polymerization reaction, and then the solution is added dropwise to a heated poor solvent, and the amount of the organic amine added is the reprecipitation treatment. the amount der the pH of the filtrate after the filtration of the resulting precipitate in step is 7.0 or more is,
The method for purifying a triazine ring-containing hyperbranched polymer, wherein the organic amine is a monoamine .   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 pH of the filtrate is 9.0 or more.   The method for purifying a triazine ring-containing hyperbranched polymer according to claim 4, wherein the pH of the filtrate is 10.0 or more.   The method for purifying a triazine ring-containing hyperbranched polymer according to any one of claims 1 to 5, wherein the heating temperature is 40 to 75 ° C.   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 hyper according to any one of claims 1 to 7, wherein the triazine ring-containing hyperbranched polymer-containing solution is obtained by reacting cyanuric halide and a diaminoaryl compound in an organic solvent. Purification method of branch polymer. 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 re-react the product. a method of manufacturing a triazine ring-containing hyperbranched polymers Ru precipitated,
The amount of the organic amine added is such that the pH of the filtrate after filtering the precipitate formed by the reprecipitation is 7.0 or more,
A method for producing a triazine ring-containing hyperbranched polymer in which the organic amine is a monoamine .