WO2016117531A1 - Method for purifying triazine-ring-containing polymer - Google Patents

Method for purifying triazine-ring-containing polymer Download PDF

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WO2016117531A1
WO2016117531A1 PCT/JP2016/051371 JP2016051371W WO2016117531A1 WO 2016117531 A1 WO2016117531 A1 WO 2016117531A1 JP 2016051371 W JP2016051371 W JP 2016051371W WO 2016117531 A1 WO2016117531 A1 WO 2016117531A1
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containing polymer
group
triazine ring
propanol
organic solvent
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PCT/JP2016/051371
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French (fr)
Japanese (ja)
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仁宏 西村
陽介 大竹
武明 庄子
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日産化学工業株式会社
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Priority to JP2016570639A priority Critical patent/JP6766653B2/en
Publication of WO2016117531A1 publication Critical patent/WO2016117531A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

Definitions

  • the present invention relates to a method for purifying a triazine ring-containing polymer.
  • the triazine ring-containing polymer is synthesized by polymerization of cyanuric chloride and the like with diamines, and has been reported to exhibit high refractive index, high heat resistance, and high transparency (Patent Document 1).
  • Patent Document 1 a triazine ring-containing polymer is purified by a reprecipitation operation in which a polymer solution is added to a poor solvent.
  • the triazine ring-containing polymer has a hydrophilic group, there is a problem that the filterability of the subsequent precipitate is extremely poor because it is water-soluble. Due to the poor filterability, there has been a problem that the purification efficiency is greatly reduced due to an increase in the liquid content, and the operability of the purification process is deteriorated.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a method for purifying a triazine ring-containing polymer with high operability and volumetric efficiency.
  • the present inventors have re-precipitated the polymer after polymerization, and then adding a predetermined organic solvent, the polymer is agglomerated and the filterability is improved.
  • the present invention has been completed.
  • this invention provides the manufacturing method of the following triazine ring containing polymer.
  • a first reprecipitation treatment step in which the triazine ring-containing polymer-containing solution after the polymerization reaction is dropped into a poor solvent; and tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1-methoxy-2- (2-methoxyethoxy) ethane Dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol and A method for purifying a triazine ring-containing polymer comprising a first filtration step of adding an organic solvent selected from ethylene glycol and filtering.
  • a method for producing a triazine ring-containing polymer comprising a step of adding a solvent selected from 1-butanol, 1-methoxy-2-propanol and ethylene glycol and filtering.
  • the purification method of the present invention agglomeration of the polymer after reprecipitation occurs, and the operability such as filterability of the precipitate is improved. Moreover, since filterability is favorable, the usage-amount of a poor solvent can be decreased, and not only can volume efficiency be improved, but it is excellent also in the residual halogen amount reduction effect.
  • the method for purifying a triazine ring-containing polymer according to the present invention includes a first reprecipitation treatment step in which the triazine ring-containing polymer-containing solution after the polymerization reaction is dropped into a poor solvent, and addition of a predetermined organic solvent for filtration. 1 filtration process is included.
  • the triazine ring-containing polymer-containing solution after the polymerization reaction is not particularly limited as long as it is a reaction solution obtained by polymerizing a cyanuric halide and a diaminoaryl compound in an organic solvent.
  • the reaction solution etc. after carrying out the polymerization reaction of the cyanuric halide and the diaminoaryl compound described in patent document 1 in the organic solvent are mentioned.
  • the organic solvent is not particularly limited as long as it is widely used in the polymerization reaction, and examples thereof include 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 such as these, and mixed solvents thereof.
  • N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and mixed solvents thereof are preferred, and in particular, N, N-dimethylacetamide, N-methyl- 2-pyrrolidone is preferred.
  • the basic organic compound is not particularly limited, but is preferably an alkylamine or pyridine, more preferably a linear alkylamine, and even more preferably a linear monoalkylamine. Specific examples thereof include methylamine, ethylamine, n-propylamine, n-butylamine and the like, and n-propylamine is particularly preferable.
  • the amount of the organic amine added is preferably 0.1 to 1.6, more preferably 0.5, in terms of a molar ratio with respect to the total amount of hydrogen chloride produced (theoretical amount).
  • the amount is 5 to 1.6, more preferably 0.8 to 1.2, and still more preferably 1.0.
  • the poor solvent used in the first reprecipitation treatment step is not particularly limited as long as the target polymer is precipitated, and examples thereof include water, hexane, heptane, toluene, acetonitrile, methanol and the like.
  • an aqueous solvent mainly containing water (more than 50% by mass) is particularly preferable, and a water-only solvent is preferable.
  • bases such as aqueous ammonia, in a poor solvent as needed.
  • the heating temperature of the poor solvent is not particularly limited, but considering the operability at the time of purification such as agglomeration and filterability of precipitates, the effect of reducing residual halogen, and the reduction in coloring of the polymer after purification, About 35 to 80 ° C. is preferable, 40 to 75 ° C. is more preferable, and 50 to 70 ° C. is optimal.
  • the amount of the poor solvent used in the first reprecipitation treatment step can usually be 10 to 200 times by mass with respect to the cyanuric halide used for the polymerization.
  • the purification method of the present invention is filtered. Therefore, the volumetric efficiency can be increased by reducing the amount of the poor solvent used compared to the case of normal temperature.
  • the amount of the poor solvent used is preferably 10 to 100 times by mass, more preferably 15 to 70 times by mass, and further 30 to 60 times by mass. 30 to 50 times by mass is preferable.
  • the rate at which the polymer solution is added to the poor solvent is not particularly limited. However, in consideration of the cohesiveness of the polymer during reprecipitation and the effect of reducing the residual halogen, 0.1 to 24 mL / min. Is preferable, and 0.5 to 12 mL / min is more preferable.
  • filtration is performed by adding a predetermined organic solvent (referred to as a first filtration step). This improves the filterability because the precipitated polymer aggregates.
  • the organic solvent added at this time is tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1-methoxy-2- (2-methoxyethoxy) ethane, dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone.
  • N, N-dimethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, ethylene glycol and the like are preferable.
  • tetrahydrofuran dioxane, 1,2-dimethoxyethane, and 1-methoxy-2- (2-methoxyethoxy) ethane are more preferable, and tetrahydrofuran is even more preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • the amount of the organic solvent used is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the poor solvent used for reprecipitation. From the viewpoint of promoting aggregation of the polymer and improving filterability, 6 to 13 parts by mass is more preferable, and 8 to 11 parts by mass is even more preferable.
  • the heating temperature is preferably about 35 to 80 ° C. in consideration of operability during purification such as coagulation and filterability of precipitates, reduction effect of residual halogen, and reduction in coloring of the polymer after purification. ⁇ 75 ° C. is more preferable, and 50 to 70 ° C. is optimal.
  • filtration may be performed using a known suction filtration facility or the like.
  • the filtrate can be washed with water or the like as necessary, and dried to obtain the desired polymer.
  • the drying temperature and time vary depending on the kind of the organic solvent and the heat resistance of the polymer, and thus cannot be defined unconditionally. However, the drying temperature and time are about 100 to 200 ° C., preferably about 120 to 180 ° C. and about 1 to 200 hours. is there. During drying, the pressure may be reduced to about ⁇ 10 to ⁇ 100 kPa.
  • 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 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 preferably about 0.1 to 5 hours, more preferably about 0.1 to 2 hours.
  • a second reprecipitation treatment step may be performed for the purpose of further increasing the degree of purification.
  • 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.
  • the former method is preferable from the viewpoint of simplifying the operation.
  • 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.
  • Tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1-methoxy-2- (2-methoxyethoxy) ethane and the like are preferable.
  • the heating temperature of the poor solvent, the rate at which the polymer solution is added, and the filtration and drying after reprecipitation are the same as described above.
  • filtration is performed by adding a predetermined organic solvent as in the first filtration step (referred to as the second filtration step).
  • organic solvent used at this time include the same solvents that can be used in the first filtration step.
  • the amount of the organic solvent used in the second filtration step is preferably 0.1 to 16 parts by mass with respect to 100 parts by mass of the poor solvent used for reprecipitation. From the viewpoint of improvement, 3 to 13 parts by mass is more preferable, and 5 to 11 parts by mass is even more preferable.
  • the solution may or may not be heated.
  • heating it is preferable that the temperature is the same as the temperature in a 1st filtration process.
  • filtration may be performed using a known suction filtration facility or the like.
  • 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 the purification method without heating the poor solvent, so that there is almost no influence on the polymer physical properties by heating.
  • the purification method of the present invention can be applied to a triazine ring-containing polymer.
  • the triazine ring-containing polymer include those described in JP2012-092611A, International Publication No. 2010/128661, International Publication No. 2012/057104, International Publication No. 2012/060268, and the like.
  • the purification method of the present invention is suitable for purification of a triazine ring-containing polymer having a hydrophilic group, and in particular, a triazine ring-containing polymer containing a repeating unit represented by the following formula (1) or (2) It is suitable for purification.
  • each of R 1 to R 9 independently represents a hydrogen atom, a halogen atom, a C 1-10 carbon atom, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, a C 1-10 carbon atom, Preferably, it represents a linear or branched alkoxy group having 1 to 3 carbon atoms or a hydrophilic group, and at least one of R 1 to R 9 is a hydrophilic group.
  • at least one of R 6 to R 9 is preferably a hydrophilic group
  • R 8 is more preferably a hydrophilic group.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl 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 group -N-propyl group, 1-ethyl-n-propyl 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
  • alkoxy group examples 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 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 group -N-butoxy group, 2,3-
  • hydrophilic group examples include a carboxyl group, a sulfone group, a phosphate group, a hydroxy group, and an amino group.
  • a carboxyl group and a hydroxy group are preferable, and a carboxyl group is more preferable.
  • the end of the triazine ring-containing polymer may be sealed with a terminal blocking agent.
  • the end-capping agent include acrylic acid chloride, methacrylic acid chloride, acetyl chloride, propionic acid chloride, methanesulfonic acid chloride, benzyl chloroformate, acrylic anhydride, methacrylic anhydride, acetic anhydride, propionic anhydride, maleic anhydride. And di-t-butyl dicarbonate.
  • the weight average molecular weight of the triazine ring-containing polymer is not particularly limited, but is preferably 500 to 100,000, more preferably 1,000 or more from the viewpoint of further improving heat resistance and reducing the shrinkage rate. 10,000 or less are preferable from the viewpoint of increasing the properties and reducing the viscosity of the resulting solution.
  • the weight average molecular weight is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.
  • the said triazine ring containing polymer contains the repeating unit represented by Formula (1) or (2), it may contain the repeating unit which does not contain a hydrophilic group.
  • the repeating unit represented by the formula (1) or (2) is preferably 1 to 90 mol%, more preferably 5 to 50 mol% in all repeating units.
  • Example 1 Under a nitrogen atmosphere, 40,56 g of N, N-dimethylacetamide was cooled to 0 ° C. or lower with an acetone / dry ice bath, and 2,4,6-trichloro-1,3,5-triazine (8.00 g, 0.0434 mol) was cooled. ) was added and dissolved. Thereafter, 2,6-xylidine (5.26 g, 0.0434 mol) was added dropwise at ⁇ 6 to ⁇ 4 ° C. over 30 minutes, and the mixture was stirred for 30 minutes, heated to 15 ° C. and stirred for 1 hour.
  • n-propylamine (9.74 g, 0.165 mol) was added dropwise over 5 minutes and stirred at 25 ° C. for 30 minutes to obtain a polymer-containing solution.
  • the polymer-containing solution was added dropwise to 608.0 g of ion-exchanged water heated to 56 ° C. over 30 minutes for reprecipitation. After stirring at 56 ° C. for 30 minutes, 52.00 g of tetrahydrofuran was added, and the mixture was stirred at 56 ° C. for 30 minutes. After cooling to room temperature, the precipitate was suction filtered under reduced pressure using a Kiriyama funnel (95 ⁇ ) and filter paper (5B) (filtration time: 1 minute 10 seconds).
  • the cake was washed four times with 80.00 g of ion-exchanged water to obtain 30.37 g of a crude product.
  • the crude product was dissolved in 76.00 g of tetrahydrofuran, 32.00 g of 10 mass% ammonium acetate aqueous solution and 41.63 g of ion-exchanged water were added, the temperature was raised to 55 ° C., and the mixture was stirred at 55-60 ° C. for 30 minutes.
  • the solution was separated by allowing to stand, and the organic layer was taken out.
  • the organic layer was added dropwise to 608.0 g of ion-exchanged water heated to 30 ° C. over 30 minutes for reprecipitation. After stirring at 30 to 33 ° C.
  • Example 2 Under a nitrogen atmosphere, 40,57 g of N, N-dimethylacetamide was cooled to 0 ° C. or lower with an acetone / dry ice bath, and 2,4,6-trichloro-1,3,5-triazine (8.00 g, 0.0434 mol) was obtained. ) Was added and dissolved. Thereafter, 2,6-xylidine (5.26 g, 0.0434 mol) was added dropwise at ⁇ 8 to ⁇ 5 ° C. over 30 minutes, and the mixture was stirred for 30 minutes, heated to 15 ° C. and stirred for 1 hour.
  • pyridine (15.43 g, 0.195 mol) was added dropwise over 6 minutes, and the mixture was stirred at 26 to 28 ° C. for 30 minutes to obtain a polymer-containing solution.
  • the polymer-containing solution was added dropwise to 608.0 g of ion-exchanged water heated to 58 ° C. over 30 minutes for reprecipitation. After stirring at 59 ° C. for 30 minutes, 52.00 g of tetrahydrofuran was added, and the mixture was stirred at 59-60 ° C. for 30 minutes. After cooling to room temperature, the precipitate was suction filtered using a Kiriyama funnel (95 ⁇ ) and filter paper (5B) under reduced pressure.
  • Example 3 A triazine ring-containing polymer was synthesized according to the following scheme.
  • the crude product was dissolved in 76.02 g of tetrahydrofuran, 32.03 g of 10 mass% ammonium acetate aqueous solution and 26.60 g of ion-exchanged water were added, the temperature was raised to 59 ° C., and the mixture was stirred at 59 ° C. for 30 minutes. The solution was separated by allowing to stand, and the organic layer was taken out. The organic layer was added dropwise to 360.0 g of ion-exchanged water heated to 28-30 ° C. over 30 minutes for reprecipitation. After stirring at 30 to 31 ° C. for 30 minutes, 15.97 g of tetrahydrofuran was added, and the mixture was stirred at 31 ° C. for 30 minutes.
  • the precipitate was filtered with suction using a Kiriyama funnel (95 ⁇ ) and filter paper (5A) under reduced pressure.
  • the cake was washed with 80.00 g of ion-exchanged water, dried in a vacuum dryer at 90 ° C. for 62 hours, and a triazine ring. 12.84 g of the containing polymer was obtained.
  • the structure of the triazine ring-containing polymer was confirmed by 1 H-NMR and 13 C-NMR.
  • the weight average molecular weight of the triazine ring-containing polymer was 1,100, and the degree of dispersion was 1.2.

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Abstract

Provided is a method for purifying a triazine-ring-containing polymer, the method including a first reprecipitation step for dripping a solution containing a triazine-ring-containing polymer into a poor solvent, and a first filtration step for adding an organic solvent selected from tetrahydrofuran, dioxane, 1,2-diemthoxyethane, 1-methoxy-2-(2-methoxyethoxy)ethane, dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N,N-diemethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, and ethylene glycol and performing filtration.

Description

トリアジン環含有ポリマーの精製方法Method for purifying triazine ring-containing polymer
　本発明は、トリアジン環含有ポリマーの精製方法に関する。 The present invention relates to a method for purifying a triazine ring-containing polymer.
　トリアジン環含有ポリマーは、シアヌル酸クロリド等とジアミン類との重合により合成され、高屈折率、高耐熱性、高透明性を示すことが報告されている（特許文献１）。特許文献１において、トリアジン環含有ポリマーは、ポリマー溶液を貧溶媒へと添加する再沈殿操作によって精製が行われている。しかし、特にトリアジン環含有ポリマーが親水性基を有する場合、水溶性があるため、その後の沈殿物のろ過性が極めて悪いという問題があった。このろ過性の悪さのため、含液率の増加による精製効率の大幅な低下や、精製工程の操作性の悪化という問題が生じていた。 The triazine ring-containing polymer is synthesized by polymerization of cyanuric chloride and the like with diamines, and has been reported to exhibit high refractive index, high heat resistance, and high transparency (Patent Document 1). In Patent Document 1, a triazine ring-containing polymer is purified by a reprecipitation operation in which a polymer solution is added to a poor solvent. However, particularly when the triazine ring-containing polymer has a hydrophilic group, there is a problem that the filterability of the subsequent precipitate is extremely poor because it is water-soluble. Due to the poor filterability, there has been a problem that the purification efficiency is greatly reduced due to an increase in the liquid content, and the operability of the purification process is deteriorated.
国際公開第２０１０／１２８６６１号International Publication No. 2010/128661
　本発明は、前記問題に鑑みなされたもので、トリアジン環含有ポリマーを、高い操作性及び容積効率にて精製する方法を提供することを目的とする。 The present invention has been made in view of the above problems, and an object thereof is to provide a method for purifying a triazine ring-containing polymer with high operability and volumetric efficiency.
　本発明者らは、前記目的を達成するために鋭意検討した結果、重合後のポリマーを再沈殿した後所定の有機溶媒を添加することで、ポリマーが凝集してろ過性が向上し、操作性が改善されることを見出し、本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventors have re-precipitated the polymer after polymerization, and then adding a predetermined organic solvent, the polymer is agglomerated and the filterability is improved. The present invention has been completed.
　すなわち、本発明は、下記トリアジン環含有ポリマーの製造方法を提供する。
１．重合反応後のトリアジン環含有ポリマー含有溶液を貧溶媒中へ滴下する第１の再沈殿処理工程、及びテトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン、１－メトキシ－２－(２－メトキシエトキシ)エタン、ジメチルスルホキシド、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、Ｎ,Ｎ－ジメチルアセトアミド、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、１－メトキシ－２－プロパノール及びエチレングリコールから選ばれる有機溶媒を添加してろ過をする第１のろ過工程を含むことを特徴とするトリアジン環含有ポリマーの精製方法。
２．前記トリアジン環含有ポリマーが、カルボキシル基、スルホン基、リン酸基、ヒドロキシ基及びアミノ基から選ばれる少なくとも１つの親水性基を有するものである１のトリアジン環含有ポリマーの精製方法。
３．前記貧溶媒が、水系溶媒である１又は２のトリアジン環含有ポリマーの精製方法。
４．前記有機溶媒が、テトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン及び１－メトキシ－２－(２－メトキシエトキシ)エタンから選ばれる１～３のいずれかのトリアジン環含有ポリマーの精製方法。
５．前記有機溶媒が、テトラヒドロフランである４のトリアジン環含有ポリマーの精製方法。
６．前記トリアジン環含有ポリマー含有溶液が、有機溶媒中、ハロゲン化シアヌルと、ジアミノアリール化合物とを反応させて得られたものである１～５のいずれかのトリアジン環含有ポリマーの精製方法。
７．ハロゲン化シアヌルとジアミノアリール化合物とを有機溶媒中で反応させる工程、反応後の溶液を貧溶媒中へ滴下して生成物を再沈殿させる工程、及びテトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン、１－メトキシ－２－(２－メトキシエトキシ)エタン、ジメチルスルホキシド、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、Ｎ,Ｎ－ジメチルアセトアミド、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、１－メトキシ－２－プロパノール及びエチレングリコールから選ばれる溶媒を添加してろ過をする工程を含むことを特徴とするトリアジン環含有ポリマーの製造方法。 That is, this invention provides the manufacturing method of the following triazine ring containing polymer.
1. A first reprecipitation treatment step in which the triazine ring-containing polymer-containing solution after the polymerization reaction is dropped into a poor solvent; and tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1-methoxy-2- (2-methoxyethoxy) ethane Dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol and A method for purifying a triazine ring-containing polymer comprising a first filtration step of adding an organic solvent selected from ethylene glycol and filtering.
2. The method for purifying a triazine ring-containing polymer according to 1, wherein the triazine ring-containing polymer has at least one hydrophilic group selected from a carboxyl group, a sulfone group, a phosphate group, a hydroxy group, and an amino group.
3. The purification method of the 1 or 2 triazine ring containing polymer whose said poor solvent is an aqueous solvent.
4). A method for purifying a triazine ring-containing polymer according to any one of 1 to 3, wherein the organic solvent is selected from tetrahydrofuran, dioxane, 1,2-dimethoxyethane, and 1-methoxy-2- (2-methoxyethoxy) ethane.
5. 4. A method for purifying a triazine ring-containing polymer, wherein the organic solvent is tetrahydrofuran.
6). The method for purifying a triazine ring-containing polymer according to any one of 1 to 5, wherein the triazine ring-containing polymer-containing solution is obtained by reacting cyanuric halide with a diaminoaryl compound in an organic solvent.
7). Reacting cyanuric halide with diaminoaryl compound in an organic solvent, dropping the solution after the reaction into a poor solvent to reprecipitate the product, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1 -Methoxy-2- (2-methoxyethoxy) ethane, dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, A method for producing a triazine ring-containing polymer, comprising a step of adding a solvent selected from 1-butanol, 1-methoxy-2-propanol and ethylene glycol and filtering.
　本発明の精製方法によれば、再沈殿後のポリマーの凝集が生じて沈殿物のろ過性等の操作性が良好になる。また、ろ過性が良好であるため、貧溶媒の使用量を少なくでき、容積効率を向上できるのみならず、残留ハロゲン量の低減効果にも優れる。 According to the purification method of the present invention, agglomeration of the polymer after reprecipitation occurs, and the operability such as filterability of the precipitate is improved. Moreover, since filterability is favorable, the usage-amount of a poor solvent can be decreased, and not only can volume efficiency be improved, but it is excellent also in the residual halogen amount reduction effect.
　本発明のトリアジン環含有ポリマーの精製方法は、重合反応後のトリアジン環含有ポリマー含有溶液を貧溶媒中へ滴下する第１の再沈殿処理工程、及び所定の有機溶媒を添加してろ過をする第１のろ過工程を含むものである。 The method for purifying a triazine ring-containing polymer according to the present invention includes a first reprecipitation treatment step in which the triazine ring-containing polymer-containing solution after the polymerization reaction is dropped into a poor solvent, and addition of a predetermined organic solvent for filtration. 1 filtration process is included.
　前記重合反応後のトリアジン環含有ポリマー含有溶液は、ハロゲン化シアヌルとジアミノアリール化合物とを有機溶媒中で重合反応させた後の反応溶液であれば特に限定されない。例えば、特許文献１に記載された、ハロゲン化シアヌルとジアミノアリール化合物とを有機溶媒中で重合反応させた後の反応溶液等が挙げられる。 The triazine ring-containing polymer-containing solution after the polymerization reaction is not particularly limited as long as it is a reaction solution obtained by polymerizing a cyanuric halide and a diaminoaryl compound in an organic solvent. For example, the reaction solution etc. after carrying out the polymerization reaction of the cyanuric halide and the diaminoaryl compound described in patent document 1 in the organic solvent are mentioned.
　前記有機溶媒としては、前記重合反応に汎用されるものであれば特に限定されず、例えば、テトラヒドロフラン、ジオキサン、ジメチルスルホキシド；Ｎ,Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、テトラメチル尿素、ヘキサメチルホスホルアミド、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピペリドン、Ｎ,Ｎ－ジメチルエチレン尿素、Ｎ,Ｎ,Ｎ',Ｎ'－テトラメチルマロン酸アミド、Ｎ－メチルカプロラクタム、Ｎ－アセチルピロリジン、Ｎ,Ｎ－ジエチルアセトアミド、Ｎ－エチル－２－ピロリドン、Ｎ,Ｎ－ジメチルプロピオン酸アミド、Ｎ,Ｎ－ジメチルイソブチルアミド、Ｎ－メチルホルムアミド、Ｎ,Ｎ'－ジメチルプロピレン尿素等のアミド系溶媒、及びこれらの混合溶媒が挙げられる。これらのうち、Ｎ,Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチル－２－ピロリドン、Ｎ,Ｎ－ジメチルアセトアミド、及びこれらの混合溶媒が好ましく、特に、Ｎ,Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドンが好適である。 The organic solvent is not particularly limited as long as it is widely used in the polymerization reaction, and examples thereof include 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 such as these, and mixed solvents thereof. Of these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and mixed solvents thereof are preferred, and in particular, N, N-dimethylacetamide, N-methyl- 2-pyrrolidone is preferred.
　前記重合反応後には、反応溶液に塩基性有機化合物を添加してもよい。これによって、沈殿物のろ過性がより良好になる。前記塩基性有機化合物としては、特に限定されないが、アルキルアミン又はピリジンが好ましく、直鎖状アルキルアミンがより好ましく、直鎖状モノアルキルアミンがより一層好ましい。その具体例としては、メチルアミン、エチルアミン、ｎ－プロピルアミン、ｎ－ブチルアミン等が挙げられるが、特にｎ－プロピルアミンが好ましい。 After the polymerization reaction, a basic organic compound may be added to the reaction solution. Thereby, the filterability of the precipitate becomes better. The basic organic compound is not particularly limited, but is preferably an alkylamine or pyridine, more preferably a linear alkylamine, and even more preferably a linear monoalkylamine. Specific examples thereof include methylamine, ethylamine, n-propylamine, n-butylamine and the like, and n-propylamine is particularly preferable.
　有機アミンの添加量は、沈殿物のろ過性を高めるという観点から、生成する塩化水素の全量（理論量）に対して、モル比で、好ましくは０.１～１.６、より好ましく０.５～１.６、より一層好ましくは０.８～１.２、更に好ましくは１.０となる量である。 From the viewpoint of improving the filterability of the precipitate, the amount of the organic amine added is preferably 0.1 to 1.6, more preferably 0.5, in terms of a molar ratio with respect to the total amount of hydrogen chloride produced (theoretical amount). The amount is 5 to 1.6, more preferably 0.8 to 1.2, and still more preferably 1.0.
　第１の再沈殿処理工程に用いられる貧溶媒としては、目的のポリマーが沈殿するものであれば特に限定されず、例えば、水、ヘキサン、ヘプタン、トルエン、アセトニトリル、メタノール等が挙げられるが、本発明では、特に、水を主体（５０質量％超）とする水系溶媒が好ましく、水単独溶媒が好適である。なお、貧溶媒中には、必要に応じてアンモニア水等の塩基を添加してもよい。 The poor solvent used in the first reprecipitation treatment step is not particularly limited as long as the target polymer is precipitated, and examples thereof include water, hexane, heptane, toluene, acetonitrile, methanol and the like. 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.
　前記貧溶媒の加熱温度は、特に限定されないが、沈殿物の凝集性やろ過性等の精製時の操作性、残留ハロゲンの低減化効果、及び精製後のポリマーの着色の低減等を考慮すると、３５～８０℃程度が好ましく、４０～７５℃がより好ましく、５０～７０℃が最適である。 The heating temperature of the poor solvent is not particularly limited, but considering the operability at the time of purification such as agglomeration and filterability of precipitates, the effect of reducing residual halogen, and the reduction in coloring of the polymer after purification, About 35 to 80 ° C. is preferable, 40 to 75 ° C. is more preferable, and 50 to 70 ° C. is optimal.
　第１の再沈殿処理工程における貧溶媒の使用量は、通常、重合に用いたハロゲン化シアヌルに対して１０～２００質量倍とすることができるが、前述のとおり、本発明の精製方法はろ過性が良好であるため、常温の場合よりも貧溶媒の使用量を少なくして容積効率を高めることができる。前記加熱温度範囲において、容積効率および沈殿物のろ過性等を考慮すると、貧溶媒の使用量は、１０～１００質量倍が好ましく、１５～７０質量倍がより好ましく、３０～６０質量倍がさらに好ましく、３０～５０質量倍が最適である。 The amount of the poor solvent used in the first reprecipitation treatment step can usually be 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 is filtered. Therefore, the volumetric efficiency can be increased by reducing the amount of the poor solvent used compared to the case of normal temperature. In consideration of volumetric efficiency and filterability of precipitates in the heating temperature range, the amount of the poor solvent used is preferably 10 to 100 times by mass, more preferably 15 to 70 times by mass, and further 30 to 60 times by mass. 30 to 50 times by mass is preferable.
　第１の再沈殿処理工程において、ポリマー溶液を貧溶媒中へ加える速度は特に限定されないが、再沈殿時のポリマーの凝集性や残留ハロゲンの低減効果等を考慮すると、０.１～２４ｍＬ／分が好ましく、０.５～１２ｍＬ／分がより好ましい。 In the first reprecipitation treatment step, the rate at which the polymer solution is added to the poor solvent is not particularly limited. However, in consideration of the cohesiveness of the polymer during reprecipitation and the effect of reducing the residual halogen, 0.1 to 24 mL / min. Is preferable, and 0.5 to 12 mL / min is more preferable.
　再沈殿処理後は、所定の有機溶媒を添加してろ過を行う（第１のろ過工程という。）。これによって、沈殿したポリマーが凝集するためろ過性が向上する。 After the reprecipitation treatment, filtration is performed by adding a predetermined organic solvent (referred to as a first filtration step). This improves the filterability because the precipitated polymer aggregates.
　このとき添加する有機溶媒は、テトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン、１－メトキシ－２－(２－メトキシエトキシ)エタン、ジメチルスルホキシド、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、Ｎ,Ｎ－ジメチルアセトアミド、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、１－メトキシ－２－プロパノール、エチレングリコール等が好ましい。これらのうち、テトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン及び１－メトキシ－２－(２－メトキシエトキシ)エタンから選ばれるものであることがより好ましく、テトラヒドロフランであることがより一層好ましい。前記有機溶媒は、１種単独でも２種以上を混合して使用してもよい。 The organic solvent added at this time is tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1-methoxy-2- (2-methoxyethoxy) ethane, dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone. N, N-dimethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, ethylene glycol and the like are preferable. Of these, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, and 1-methoxy-2- (2-methoxyethoxy) ethane are more preferable, and tetrahydrofuran is even more preferable. The organic solvent may be used alone or in combination of two or more.
　前記有機溶媒の使用量は、通常、再沈殿に用いた貧溶媒１００質量部に対して０.１～１５質量部とすることが好ましいが、ポリマーの凝集促進、及びろ過性向上の観点から、６～１３質量部がより好ましく、８～１１質量部がより一層好ましい。 Usually, the amount of the organic solvent used is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the poor solvent used for reprecipitation. From the viewpoint of promoting aggregation of the polymer and improving filterability, 6 to 13 parts by mass is more preferable, and 8 to 11 parts by mass is even more preferable.
　前記有機溶媒を添加した後、溶液を加熱することが好ましい。加熱温度は、沈殿物の凝集性やろ過性等の精製時の操作性、残留ハロゲンの低減化効果、及び精製後のポリマーの着色の低減等を考慮すると、３５～８０℃程度が好ましく、４０～７５℃がより好ましく、５０～７０℃が最適である。 It is preferable to heat the solution after adding the organic solvent. The heating temperature is preferably about 35 to 80 ° C. in consideration of operability during purification such as coagulation and filterability of precipitates, reduction effect of residual halogen, and reduction in coloring of the polymer after purification. ˜75 ° C. is more preferable, and 50 to 70 ° C. is optimal.
　この後、公知の吸引ろ過設備等を用いてろ過を行えばよい。 Thereafter, filtration may be performed using a known suction filtration facility or the like.
　ろ過後、ろ物を必要に応じて水等で洗浄し、これを乾燥することで目的のポリマーを得ることができる。乾燥温度及び時間は、前記有機溶媒の種類やポリマーの耐熱性等によって異なるため一概に規定することはできないが、１００～２００℃程度、好ましくは１２０～１８０℃程度で、１～２００時間程度である。なお、乾燥時、－１０～－１００ｋＰａ程度に減圧してもよい。なお、再沈殿処理工程により生じた沈殿物は、残留ハロゲンをより低減させる目的等で貧溶媒と同じ温度に加熱した状態で所定時間攪拌し、２５℃程度まで冷却してから前記ろ過・乾燥を行ってもよい。この場合、攪拌時間は特に限定されないが、好ましくは０.１～５時間程度、より好ましくは０.１～２時間程度である。 After filtration, the filtrate can be washed with water or the like as necessary, and dried to obtain the desired polymer. The drying temperature and time vary depending on the kind of the organic solvent and the heat resistance of the polymer, and thus cannot be defined unconditionally. However, the drying temperature and time are about 100 to 200 ° C., preferably about 120 to 180 ° C. and about 1 to 200 hours. is there. During drying, the pressure may be reduced to about −10 to −100 kPa. 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 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 preferably about 0.1 to 5 hours, more preferably about 0.1 to 2 hours.
　本発明の精製方法では、更に精製度を高める目的で第２の再沈殿処理工程を行ってもよい。この場合、１回目の再沈殿処理工程で得られた沈殿物を再度有機溶媒に溶かした溶液を用いても、それをろ過・乾燥して得られたポリマーを再度有機溶媒に溶かした溶液を用いてもよいが、操作の簡便化を図るという点から前者の方法が好ましい。 In the purification method of the present invention, a 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.
　第２の再沈殿処理工程で用いる有機溶媒及び貧溶媒としては、先に説明したものと同様のものが挙げられるが、有機溶媒としては、精製ポリマー中の残留溶媒を低減するという観点から、特に、テトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン及び１－メトキシ－２－(２－メトキシエトキシ)エタン等が好適である。 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. , Tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1-methoxy-2- (2-methoxyethoxy) ethane and the like are preferable.
　また、貧溶媒の加熱温度やポリマー溶液を加える速度、再沈殿後のろ過・乾燥も先に説明したものと同様である。 Also, the heating temperature of the poor solvent, the rate at which the polymer solution is added, and the filtration and drying after reprecipitation are the same as described above.
　第２の再沈殿処理工程後は、第１のろ過工程と同様に所定の有機溶媒を添加してろ過を行う（第２のろ過工程という。）。このときに用いる有機溶媒は、第１のろ過工程において使用できるものと同様のものが挙げられる。 After the second reprecipitation treatment step, filtration is performed by adding a predetermined organic solvent as in the first filtration step (referred to as the second filtration step). Examples of the organic solvent used at this time include the same solvents that can be used in the first filtration step.
　第２のろ過工程における有機溶媒の使用量は、通常、再沈殿に用いた貧溶媒１００質量部に対して０.１～１６質量部とすることが好ましいが、ポリマーの凝集促進、及びろ過性向上の観点から、３～１３質量部がより好ましく、５～１１質量部がより一層好ましい。 In general, the amount of the organic solvent used in the second filtration step is preferably 0.1 to 16 parts by mass with respect to 100 parts by mass of the poor solvent used for reprecipitation. From the viewpoint of improvement, 3 to 13 parts by mass is more preferable, and 5 to 11 parts by mass is even more preferable.
　前記有機溶媒を添加した後は、溶液を加熱してもよいし、しなくてもよい。加熱する場合、その温度は、第１のろ過工程における温度と同様であることが好ましい。この後、公知の吸引ろ過設備等を用いてろ過を行えばよい。 After adding the organic solvent, the solution may or may not be heated. When heating, it is preferable that the temperature is the same as the temperature in a 1st filtration process. Thereafter, filtration may be performed using a known suction filtration facility or the like.
　なお、本発明の精製方法は、貧溶媒を加熱しない精製方法の場合と同等の分子量及び分子量分布を有するポリマーを与えることから、加熱によるポリマー物性への影響はほとんどない。 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 the purification method without heating the poor solvent, so that there is almost no influence on the polymer physical properties by heating.
　本発明の精製方法は、トリアジン環含有ポリマーに適用し得る。前記トリアジン環含有ポリマーとしては、特開２０１２－０９２２６１号公報、国際公開第２０１０／１２８６６１号、国際公開第２０１２／０５７１０４号、国際公開第２０１２／０６０２６８号等に記載のものが挙げられる。 The purification method of the present invention can be applied to a triazine ring-containing polymer. Examples of the triazine ring-containing polymer include those described in JP2012-092611A, International Publication No. 2010/128661, International Publication No. 2012/057104, International Publication No. 2012/060268, and the like.
　本発明の精製方法は、これらのうち、親水性基を有するトリアジン環含有ポリマーの精製に好適であり、特に、下記式（１）又は（２）で表される繰り返し単位を含むトリアジン環含有ポリマーの精製に好適である。 Among these, the purification method of the present invention is suitable for purification of a triazine ring-containing polymer having a hydrophilic group, and in particular, a triazine ring-containing polymer containing a repeating unit represented by the following formula (1) or (2) It is suitable for purification.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式中、Ｒ1～Ｒ9は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１～１０、好ましくは炭素数１～３の直鎖状若しくは分岐状のアルキル基、炭素数１～１０、好ましくは炭素数１～３の直鎖状若しくは分岐状のアルコキシ基、又は親水性基を表すが、Ｒ1～Ｒ9のうち少なくとも１つは親水性基である。特に、Ｒ6～Ｒ9の少なくとも１つが親水性基であることが好ましく、Ｒ8が親水性基であることがより好ましい。 In the formula, each of R 1 to R 9 independently represents a hydrogen atom, a halogen atom, a C 1-10 carbon atom, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, a C 1-10 carbon atom, Preferably, it represents a linear or branched alkoxy group having 1 to 3 carbon atoms or a hydrophilic group, and at least one of R 1 to R 9 is a hydrophilic group. In particular, at least one of R 6 to R 9 is preferably a hydrophilic group, and R 8 is more preferably a hydrophilic group.
　前記アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１,１－ジメチル－ｎ－プロピル基、１,２－ジメチル－ｎ－プロピル基、２,２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１,１－ジメチル－ｎ－ブチル基、１,２－ジメチル－ｎ－ブチル基、１,３－ジメチル－ｎ－ブチル基、２,２－ジメチル－ｎ－ブチル基、２,３－ジメチル－ｎ－ブチル基、３,３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１,１,２－トリメチル－ｎ－プロピル基、１,２,２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基、１－エチル－２－メチル－ｎ－プロピル基等が挙げられる。 Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl 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 group -N-propyl group, 1-ethyl-n-propyl 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 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 Examples include a 1-methyl-n-propyl group and a 1-ethyl-2-methyl-n-propyl group.
　前記アルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基、ｎ－ペントキシ基、１－メチル－ｎ－ブトキシ基、２－メチル－ｎ－ブトキシ基、３－メチル－ｎ－ブトキシ基、１,１－ジメチル－ｎ－プロポキシ基、１,２－ジメチル－ｎ－プロポキシ基、２,２－ジメチル－ｎ－プロポキシ基、１－エチル－ｎ－プロポキシ基、ｎ－ヘキシルオキシ基、１－メチル－ｎ－ペンチルオキシ基、２－メチル－ｎ－ペンチルオキシ基、３－メチル－ｎ－ペンチルオキシ基、４－メチル－ｎ－ペンチルオキシ基、１,１－ジメチル－ｎ－ブトキシ基、１,２－ジメチル－ｎ－ブトキシ基、１,３－ジメチル－ｎ－ブトキシ基、２,２－ジメチル－ｎ－ブトキシ基、２,３－ジメチル－ｎ－ブトキシ基、３,３－ジメチル－ｎ－ブトキシ基、１－エチル－ｎ－ブトキシ基、２－エチル－ｎ－ブトキシ基、１,１,２－トリメチル－ｎ－プロポキシ基、１,２,２－トリメチル－ｎ－プロポキシ基、１－エチル－１－メチル－ｎ－プロポキシ基、１－エチル－２－メチル－ｎ－プロポキシ基等が挙げられる。 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 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 group -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. It is done.
　前記親水性基としては、カルボキシル基、スルホン基、リン酸基、ヒドロキシ基、アミノ基等が挙げられる。これらのうち、カルボキシル基、ヒドロキシ基が好ましく、カルボキシル基がより好ましい。 Examples of the hydrophilic group include a carboxyl group, a sulfone group, a phosphate group, a hydroxy group, and an amino group. Among these, a carboxyl group and a hydroxy group are preferable, and a carboxyl group is more preferable.
　前記トリアジン環含有ポリマーは、その末端が末端封止剤によって封止されていてもよい。前記末端封止剤としては、アクリル酸クロライド、メタクリル酸クロライド、アセチルクロライド、プロピオン酸クロライド、メタンスルホン酸クロライド、クロロギ酸ベンジル、無水アクリル酸、無水メタクリル酸、無水酢酸、無水プロピオン酸、無水マレイン酸、二炭酸ジ－ｔ－ブチル等が挙げられる。 The end of the triazine ring-containing polymer may be sealed with a terminal blocking agent. Examples of the end-capping agent include acrylic acid chloride, methacrylic acid chloride, acetyl chloride, propionic acid chloride, methanesulfonic acid chloride, benzyl chloroformate, acrylic anhydride, methacrylic anhydride, acetic anhydride, propionic anhydride, maleic anhydride. And di-t-butyl dicarbonate.
　前記トリアジン環含有ポリマーの重量平均分子量は、特に限定されないが、５００～１００,０００が好ましく、より耐熱性を向上させるとともに、収縮率を低くするという点から、１,０００以上が好ましく、より溶解性を高め、得られた溶液の粘度を低下させるという点から、１０,０００以下が好ましい。なお、本発明において重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析による標準ポリスチレン換算で得られる平均分子量である。 The weight average molecular weight of the triazine ring-containing polymer is not particularly limited, but is preferably 500 to 100,000, more preferably 1,000 or more from the viewpoint of further improving heat resistance and reducing the shrinkage rate. 10,000 or less are preferable from the viewpoint of increasing the properties and reducing the viscosity of the resulting solution. In the present invention, the weight average molecular weight is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.
　なお、前記トリアジン環含有ポリマーは、式（１）又は（２）で表される繰り返し単位を含むものであれば、親水性基を含まない繰り返し単位を含んでもよい。この場合、式（１）又は（２）で表される繰り返し単位は、全繰り返し単位中１～９０モル％であることが好ましく、５～５０モル％であることがより好ましい。 In addition, as long as the said triazine ring containing polymer contains the repeating unit represented by Formula (1) or (2), it may contain the repeating unit which does not contain a hydrophilic group. In this case, the repeating unit represented by the formula (1) or (2) is preferably 1 to 90 mol%, more preferably 5 to 50 mol% in all repeating units.
　以下、実施例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されない。なお、実施例で用いた各測定装置は以下のとおりである。
［1Ｈ－ＮＭＲ］
　装置：Bruker社製、AVANCE III 600
　測定溶媒：ＤＭＳＯ－ｄ６
　基準物質：テトラメチルシラン（ＴＭＳ）（δ０.０ｐｐｍ）
［13Ｃ－ＮＭＲ］
　装置：Bruker社製、AVANCE III 600
　測定溶媒：ＤＭＳＯ－ｄ６
　基準物質：テトラメチルシラン（ＴＭＳ）（δ０.０ｐｐｍ）
［ＧＰＣ］
　装置：東ソー(株)製、HLC-8320GPC
　カラム：東ソー(株)製、TSKgelα-3000、TSKgelα-2000、TSKgel guardcolumn α
　カラム温度：６０℃
　溶媒：１質量％ＬｉＣｌ／ＮＭＰ溶液
　検出器：ＵＶ（２７１ｎｍ）
　検量線：標準ポリスチレン EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
[ 1 H-NMR]
Equipment: Bruker AVANCE III 600
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm)
[ 13 C-NMR]
Equipment: Bruker AVANCE III 600
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm)
[GPC]
Equipment: Tosoh Corporation, HLC-8320GPC
Column: manufactured by Tosoh Corporation, TSKgelα-3000, TSKgelα-2000, TSKgel guardcolumn α
Column temperature: 60 ° C
Solvent: 1% by mass LiCl / NMP solution Detector: UV (271 nm)
Calibration curve: Standard polystyrene
［実施例］
　下記スキームに従って、トリアジン環含有ポリマーを合成した。
Figure JPOXMLDOC01-appb-C000002
 [Example]
A triazine ring-containing polymer was synthesized according to the following scheme.
Figure JPOXMLDOC01-appb-C000002
［実施例１］
　窒素雰囲気下、Ｎ,Ｎ－ジメチルアセトアミド４０.５６ｇをアセトン／ドライアイス浴で０℃以下に冷却し、２,４,６－トリクロロ－１,３,５－トリアジン（８.００ｇ、０.０４３４ｍｏｌ）を加えて溶解した。その後、２,６－キシリジン（５.２６ｇ、０.０４３４ｍｏｌ）を－６～－４℃にて３０分かけて滴下後、３０分攪拌し、１５℃まで昇温後１時間攪拌した。これを３℃に冷却後、３,５－ジアミノ安息香酸（６.６０ｇ、０.０４３４ｍｏｌ）とｍ－フェニレンジアミン（２.３５ｇ、０.０２１７ｍｏｌ）をＮ－メチル－２－ピロリドン６０.８０ｇに室温にてあらかじめ溶解させた溶液を３０分かけて滴下し、８３℃まで１時間かけて昇温後、２時間攪拌して重合した。その後、２８℃に冷却し、アクリル酸クロライド（３.１４ｇ、０.０３４７ｍｏｌ）を５分かけて滴下し、２５～２６℃で３０分攪拌した。更に、ｎ－プロピルアミン（９.７４ｇ、０.１６５ｍｏｌ）を５分かけて滴下し、２５℃にて３０分攪拌し、ポリマー含有溶液を得た。
　ポリマー含有溶液を５６℃に加熱したイオン交換水６０８.０ｇに３０分かけて滴下し、再沈殿させた。５６℃にて３０分攪拌後、テトラヒドロフラン５２.００ｇを加え、５６℃にて３０分攪拌した。室温まで冷却し、沈殿物を桐山ロート（９５φ）及びろ紙（５Ｂ）を用いて減圧下で吸引ろ過した（ろ過時間１分１０秒）。これをイオン交換水８０.００ｇで４回ケーキ洗浄し、粗精製物３０.３７ｇを得た。
　粗精製物をテトラヒドロフラン７６.００ｇに溶解し、１０質量％酢酸アンモニウム水溶液３２.００ｇ、イオン交換水４１.６３ｇを加え、５５℃に昇温後、５５～６０℃にて３０分攪拌した。これを静置することで分液し、有機層を取り出した。
　有機層を３０℃に加熱したイオン交換水６０８.０ｇに３０分かけて滴下し、再沈殿させた。３０～３３℃にて３０分攪拌後、テトラヒドロフラン４８.００ｇを加え、３０～３１℃にて３０分攪拌した。沈殿物を桐山ロート（９５φ）及びろ紙（５Ａ）を用いて減圧下で吸引ろ過し（ろ過時間１分）、これをイオン交換水８０.００ｇでケーキ洗浄し、減圧乾燥機で１２０℃、１９時間乾燥し、トリアジン環含有ポリマー１４.５２ｇを得た。
　トリアジン環含有ポリマーの構造は、1Ｈ－ＮＭＲ、13Ｃ－ＮＭＲによって確認した。各繰り返し単位の組成比は、ａ：ｂ＝０.３３：０.６７であった。また、ＧＰＣ測定の結果、トリアジン環含有ポリマーの重量平均分子量は１,５００、分散度は１.６であった。 [Example 1]
Under a nitrogen atmosphere, 40,56 g of N, N-dimethylacetamide was cooled to 0 ° C. or lower with an acetone / dry ice bath, and 2,4,6-trichloro-1,3,5-triazine (8.00 g, 0.0434 mol) was cooled. ) Was added and dissolved. Thereafter, 2,6-xylidine (5.26 g, 0.0434 mol) was added dropwise at −6 to −4 ° C. over 30 minutes, and the mixture was stirred for 30 minutes, heated to 15 ° C. and stirred for 1 hour. After cooling to 3 ° C., 3,5-diaminobenzoic acid (6.60 g, 0.0434 mol) and m-phenylenediamine (2.35 g, 0.0217 mol) were added to 60.80 g of N-methyl-2-pyrrolidone. A solution previously dissolved at room temperature was added dropwise over 30 minutes, the temperature was raised to 83 ° C. over 1 hour, and the mixture was stirred for 2 hours for polymerization. Thereafter, the mixture was cooled to 28 ° C., acrylic acid chloride (3.14 g, 0.0347 mol) was added dropwise over 5 minutes, and the mixture was stirred at 25 to 26 ° C. for 30 minutes. Further, n-propylamine (9.74 g, 0.165 mol) was added dropwise over 5 minutes and stirred at 25 ° C. for 30 minutes to obtain a polymer-containing solution.
The polymer-containing solution was added dropwise to 608.0 g of ion-exchanged water heated to 56 ° C. over 30 minutes for reprecipitation. After stirring at 56 ° C. for 30 minutes, 52.00 g of tetrahydrofuran was added, and the mixture was stirred at 56 ° C. for 30 minutes. After cooling to room temperature, the precipitate was suction filtered under reduced pressure using a Kiriyama funnel (95φ) and filter paper (5B) (filtration time: 1 minute 10 seconds). The cake was washed four times with 80.00 g of ion-exchanged water to obtain 30.37 g of a crude product.
The crude product was dissolved in 76.00 g of tetrahydrofuran, 32.00 g of 10 mass% ammonium acetate aqueous solution and 41.63 g of ion-exchanged water were added, the temperature was raised to 55 ° C., and the mixture was stirred at 55-60 ° C. for 30 minutes. The solution was separated by allowing to stand, and the organic layer was taken out.
The organic layer was added dropwise to 608.0 g of ion-exchanged water heated to 30 ° C. over 30 minutes for reprecipitation. After stirring at 30 to 33 ° C. for 30 minutes, 48.00 g of tetrahydrofuran was added, and the mixture was stirred at 30 to 31 ° C. for 30 minutes. The precipitate was suction filtered using Kiriyama funnel (95φ) and filter paper (5A) under reduced pressure (filtration time: 1 minute), and the cake was washed with 80.00 g of ion-exchanged water. After drying for a while, 14.52 g of triazine ring-containing polymer was obtained.
The structure of the triazine ring-containing polymer was confirmed by 1 H-NMR and 13 C-NMR. The composition ratio of each repeating unit was a: b = 0.33: 0.67. As a result of GPC measurement, the weight average molecular weight of the triazine ring-containing polymer was 1,500, and the degree of dispersion was 1.6.
［実施例２］
　窒素雰囲気下、Ｎ,Ｎ－ジメチルアセトアミド４０.５７ｇをアセトン／ドライアイス浴で０℃以下に冷却し、２,４,６－トリクロロ－１,３,５－トリアジン（８.００ｇ、０.０４３４ｍｏｌ）を加えて溶解した。その後、２,６－キシリジン（５.２６ｇ、０.０４３４ｍｏｌ）を－８～－５℃にて３０分かけて滴下後、３０分攪拌し、１５℃まで昇温後１時間攪拌した。これを５℃に冷却後、３,５－ジアミノ安息香酸（６.６０ｇ、０.０４３４ｍｏｌ）とｍ－フェニレンジアミン（２.３５ｇ、０.０２１７ｍｏｌ）をＮ－メチル－２－ピロリドン６０.８１ｇに室温にてあらかじめ溶解させた溶液を３０分かけて滴下し、８３℃まで１時間かけて昇温後、２時間攪拌して重合した。その後、２７℃に冷却し、アクリル酸クロライド（５.８８ｇ、０.０６５０ｍｏｌ）を４分かけて滴下し、２４～２５℃で３０分攪拌した。更に、ピリジン（１５.４３ｇ、０.１９５ｍｏｌ）を６分かけて滴下し、２６～２８℃にて３０分攪拌し、ポリマー含有溶液を得た。
　ポリマー含有溶液を５８℃に加熱したイオン交換水６０８.０ｇに３０分かけて滴下し、再沈殿させた。５９℃にて３０分攪拌後、テトラヒドロフラン５２.００ｇを加え、５９～６０℃にて３０分攪拌した。室温まで冷却し、沈殿物を桐山ロート（９５φ）及びろ紙（５Ｂ）を用いて減圧下で吸引ろ過した。これをイオン交換水８０.００ｇで４回ケーキ洗浄し、粗精製物３５.４３ｇを得た。
　粗精製物をテトラヒドロフラン７６.０４ｇに溶解し、１０質量％酢酸アンモニウム水溶液３２.０４ｇ、イオン交換水３６.５８ｇを加え、５７℃に昇温後、５７～６０℃にて３０分攪拌した。これを静置することで分液し、有機層を取り出した。
　有機層を３０℃に加熱したイオン交換水６０８.１ｇに３０分かけて滴下し、再沈殿させた。３１～３３℃にて３０分攪拌後、テトラヒドロフラン３２.０４ｇを加え、２９～３３℃にて３０分攪拌した。沈殿物を桐山ロート（９５φ）及びろ紙（５Ａ）を用いて減圧下で吸引ろ過し、これをイオン交換水８０.００ｇでケーキ洗浄し、減圧乾燥機で１２０℃、１９時間乾燥し、トリアジン環含有ポリマー１６.１２ｇを得た。
　トリアジン環含有ポリマーの構造は、1Ｈ－ＮＭＲ、13Ｃ－ＮＭＲによって確認した。各繰り返し単位の組成比は、ａ：ｂ＝０.３８：０.６２であった。また、ＧＰＣ測定の結果、トリアジン環含有ポリマーの重量平均分子量は１,６００、分散度は１.５であった。 [Example 2]
Under a nitrogen atmosphere, 40,57 g of N, N-dimethylacetamide was cooled to 0 ° C. or lower with an acetone / dry ice bath, and 2,4,6-trichloro-1,3,5-triazine (8.00 g, 0.0434 mol) was obtained. ) Was added and dissolved. Thereafter, 2,6-xylidine (5.26 g, 0.0434 mol) was added dropwise at −8 to −5 ° C. over 30 minutes, and the mixture was stirred for 30 minutes, heated to 15 ° C. and stirred for 1 hour. After cooling to 5 ° C., 3,5-diaminobenzoic acid (6.60 g, 0.0434 mol) and m-phenylenediamine (2.35 g, 0.0217 mol) were added to 60.81 g of N-methyl-2-pyrrolidone. A solution previously dissolved at room temperature was added dropwise over 30 minutes, the temperature was raised to 83 ° C. over 1 hour, and the mixture was stirred for 2 hours for polymerization. Thereafter, the mixture was cooled to 27 ° C., acrylic acid chloride (5.88 g, 0.0650 mol) was added dropwise over 4 minutes, and the mixture was stirred at 24 to 25 ° C. for 30 minutes. Further, pyridine (15.43 g, 0.195 mol) was added dropwise over 6 minutes, and the mixture was stirred at 26 to 28 ° C. for 30 minutes to obtain a polymer-containing solution.
The polymer-containing solution was added dropwise to 608.0 g of ion-exchanged water heated to 58 ° C. over 30 minutes for reprecipitation. After stirring at 59 ° C. for 30 minutes, 52.00 g of tetrahydrofuran was added, and the mixture was stirred at 59-60 ° C. for 30 minutes. After cooling to room temperature, the precipitate was suction filtered using a Kiriyama funnel (95φ) and filter paper (5B) under reduced pressure. This was washed with cake four times with 80.00 g of ion-exchanged water to obtain 35.43 g of a crude product.
The crude product was dissolved in 76.04 g of tetrahydrofuran, 32.04 g of 10 mass% ammonium acetate aqueous solution and 36.58 g of ion-exchanged water were added, the temperature was raised to 57 ° C., and the mixture was stirred at 57-60 ° C. for 30 minutes. The solution was separated by allowing to stand, and the organic layer was taken out.
The organic layer was added dropwise to 608.1 g of ion-exchanged water heated to 30 ° C. over 30 minutes for reprecipitation. After stirring at 31-33 ° C. for 30 minutes, 32.04 g of tetrahydrofuran was added, and the mixture was stirred at 29-33 ° C. for 30 minutes. The precipitate was filtered with suction using a Kiriyama funnel (95φ) and filter paper (5A) under reduced pressure, washed with cake with 80.00 g of ion-exchanged water, dried in a vacuum dryer at 120 ° C. for 19 hours, and triazine ring. 16.12 g of the containing polymer was obtained.
The structure of the triazine ring-containing polymer was confirmed by 1 H-NMR and 13 C-NMR. The composition ratio of each repeating unit was a: b = 0.38: 0.62. As a result of GPC measurement, the weight average molecular weight of the triazine ring-containing polymer was 1,600, and the degree of dispersion was 1.5.
［実施例３］
　下記スキームに従って、トリアジン環含有ポリマーを合成した。
Figure JPOXMLDOC01-appb-C000003
 [Example 3]
A triazine ring-containing polymer was synthesized according to the following scheme.
Figure JPOXMLDOC01-appb-C000003
　窒素雰囲気下、Ｎ－メチル－２－ピロリドン１８４.６ｇに溶解した３,５－ジアミノ安息香酸（６.６０ｇ、０.０４３４ｍｏｌ）、ｍ－フェニレンジアミン（２.３５ｇ、０.０２１７ｍｏｌ）、２,６－キシリジン（２.６３ｇ、０.０２１７ｍｏｌ）をアセトン／ドライアイス浴で０℃以下に冷却し、２,４,６－トリクロロ－１,３,５－トリアジン（２０.００ｇ、０.１０９ｍｏｌ）を１０分割して１時間３０分かけて加えた。この反応溶液を、あらかじめＮ－メチル－２－ピロリドン９９.４２ｇを加えて７６℃に加熱してある槽へ１時間かけて滴下し、７５～７６℃で２時間攪拌して重合した。
　その後、アニリン（２５.２６ｇ、０.２７１ｍｏｌ）を１７分かけて滴下し、７５℃で２時間攪拌して反応を停止した。２３℃まで冷却してｎ－プロピルアミン（１９.２５ｇ、０.３２６ｍｏｌ）を５分かけて滴下後、２３～２７℃にて４５分攪拌し、ポリマー含有溶液３５８.２ｇを得た。
　ポリマー含有溶液１４３.３ｇを６５℃に加熱したイオン交換水６０８.１ｇに３０分かけて滴下し、再沈殿させた。６５～６６℃にて３０分攪拌後、テトラヒドロフラン２３.９９ｇを加え、６６～６７℃にて３０分攪拌した。室温まで冷却し、沈殿物を桐山ロート（９５φ）及びろ紙（５Ｂ）を用いて減圧下で吸引ろ過した。これをイオン交換水８０.００ｇで４回ケーキ洗浄し、粗精製物４５.４４ｇを得た。
　粗精製物をテトラヒドロフラン７６.０２ｇに溶解し、１０質量％酢酸アンモニウム水溶液３２.０３ｇ、イオン交換水２６.６０ｇを加え、５９℃に昇温後、５９℃にて３０分攪拌した。これを静置することで分液し、有機層を取り出した。
　有機層を２８～３０℃に加熱したイオン交換水３６０.０ｇに３０分かけて滴下し、再沈殿させた。３０～３１℃にて３０分攪拌後、テトラヒドロフラン１５.９７ｇを加え、３１℃にて３０分攪拌した。沈殿物を桐山ロート（９５φ）及びろ紙（５Ａ）を用いて減圧下で吸引ろ過し、これをイオン交換水８０.００ｇでケーキ洗浄し、減圧乾燥機で９０℃、６２時間乾燥し、トリアジン環含有ポリマー１２.８４ｇを得た。
　トリアジン環含有ポリマーの構造は、1Ｈ－ＮＭＲ、13Ｃ－ＮＭＲによって確認した。各繰り返し単位の組成比は、ａ：ｂ＝０.３７：０.６３であった。また、ＧＰＣ測定の結果、トリアジン環含有ポリマーの重量平均分子量は１,１００、分散度は１.２であった。 Under a nitrogen atmosphere, 3,5-diaminobenzoic acid (6.60 g, 0.0434 mol), m-phenylenediamine (2.35 g, 0.0217 mol) dissolved in 184.6 g of N-methyl-2-pyrrolidone, 2, 6-Xylidine (2.63 g, 0.0217 mol) was cooled to below 0 ° C. in an acetone / dry ice bath and 2,4,6-trichloro-1,3,5-triazine (20.00 g, 0.109 mol) Was added in 10 portions over 1 hour 30 minutes. This reaction solution was added dropwise to a tank that had been previously heated to 76 ° C. with 99.42 g of N-methyl-2-pyrrolidone added thereto, and polymerized by stirring at 75 to 76 ° C. for 2 hours.
Thereafter, aniline (25.26 g, 0.271 mol) was added dropwise over 17 minutes, and the reaction was stopped by stirring at 75 ° C. for 2 hours. After cooling to 23 ° C., n-propylamine (19.25 g, 0.326 mol) was added dropwise over 5 minutes, and the mixture was stirred at 23 to 27 ° C. for 45 minutes to obtain 358.2 g of a polymer-containing solution.
143.3 g of the polymer-containing solution was added dropwise to 608.1 g of ion-exchanged water heated to 65 ° C. over 30 minutes for reprecipitation. After stirring at 65 to 66 ° C. for 30 minutes, 23.99 g of tetrahydrofuran was added, and the mixture was stirred at 66 to 67 ° C. for 30 minutes. After cooling to room temperature, the precipitate was suction filtered using a Kiriyama funnel (95φ) and filter paper (5B) under reduced pressure. The cake was washed four times with 80.00 g of ion-exchanged water to obtain 45.44 g of a crude product.
The crude product was dissolved in 76.02 g of tetrahydrofuran, 32.03 g of 10 mass% ammonium acetate aqueous solution and 26.60 g of ion-exchanged water were added, the temperature was raised to 59 ° C., and the mixture was stirred at 59 ° C. for 30 minutes. The solution was separated by allowing to stand, and the organic layer was taken out.
The organic layer was added dropwise to 360.0 g of ion-exchanged water heated to 28-30 ° C. over 30 minutes for reprecipitation. After stirring at 30 to 31 ° C. for 30 minutes, 15.97 g of tetrahydrofuran was added, and the mixture was stirred at 31 ° C. for 30 minutes. The precipitate was filtered with suction using a Kiriyama funnel (95φ) and filter paper (5A) under reduced pressure. The cake was washed with 80.00 g of ion-exchanged water, dried in a vacuum dryer at 90 ° C. for 62 hours, and a triazine ring. 12.84 g of the containing polymer was obtained.
The structure of the triazine ring-containing polymer was confirmed by 1 H-NMR and 13 C-NMR. The composition ratio of each repeating unit was a: b = 0.37: 0.63. As a result of GPC measurement, the weight average molecular weight of the triazine ring-containing polymer was 1,100, and the degree of dispersion was 1.2.

Claims (7)

  1. 　重合反応後の、トリアジン環含有ポリマー含有溶液を貧溶媒中へ滴下する第１の再沈殿処理工程、及びテトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン、１－メトキシ－２－(２－メトキシエトキシ)エタン、ジメチルスルホキシド、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、Ｎ,Ｎ－ジメチルアセトアミド、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、１－メトキシ－２－プロパノール及びエチレングリコールから選ばれる有機溶媒を添加してろ過をする第１のろ過工程を含むことを特徴とするトリアジン環含有ポリマーの精製方法。 A first reprecipitation treatment step in which a triazine ring-containing polymer-containing solution is dropped into a poor solvent after the polymerization reaction; and tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1-methoxy-2- (2-methoxyethoxy) Ethane, dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol And a method for purifying a triazine ring-containing polymer, comprising a first filtration step of adding an organic solvent selected from ethylene glycol and filtering.
  2. 　前記トリアジン環含有ポリマーが、カルボキシル基、スルホン基、リン酸基、ヒドロキシ基及びアミノ基から選ばれる少なくとも１つの親水性基を有するものである請求項１記載のトリアジン環含有ポリマーの精製方法。 The method for purifying a triazine ring-containing polymer according to claim 1, wherein the triazine ring-containing polymer has at least one hydrophilic group selected from a carboxyl group, a sulfone group, a phosphate group, a hydroxy group and an amino group.
  3. 　前記貧溶媒が、水系溶媒である請求項１又は２記載のトリアジン環含有ポリマーの精製方法。 The method for purifying a triazine ring-containing polymer according to claim 1 or 2, wherein the poor solvent is an aqueous solvent.
  4. 　前記有機溶媒が、テトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン及び１－メトキシ－２－(２－メトキシエトキシ)エタンから選ばれる請求項１～３のいずれか１項記載のトリアジン環含有ポリマーの精製方法。 The purification of a triazine ring-containing polymer according to any one of claims 1 to 3, wherein the organic solvent is selected from tetrahydrofuran, dioxane, 1,2-dimethoxyethane, and 1-methoxy-2- (2-methoxyethoxy) ethane. Method.
  5. 　前記有機溶媒が、テトラヒドロフランである請求項４記載のトリアジン環含有ポリマーの精製方法。 The method for purifying a triazine ring-containing polymer according to claim 4, wherein the organic solvent is tetrahydrofuran.
  6. 　前記トリアジン環含有ポリマー含有溶液が、有機溶媒中、ハロゲン化シアヌルと、ジアミノアリール化合物とを反応させて得られたものである請求項１～５のいずれか１項記載のトリアジン環含有ポリマーの精製方法。 The purification of a triazine ring-containing polymer according to any one of claims 1 to 5, wherein the triazine ring-containing polymer-containing solution is obtained by reacting cyanuric halide with a diaminoaryl compound in an organic solvent. Method.
  7. 　ハロゲン化シアヌルとジアミノアリール化合物とを有機溶媒中で反応させる工程、反応後の溶液を貧溶媒中へ滴下して生成物を再沈殿させる工程、及びテトラヒドロフラン、ジオキサン、１,２－ジメトキシエタン、１－メトキシ－２－(２－メトキシエトキシ)エタン、ジメチルスルホキシド、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、Ｎ,Ｎ－ジメチルアセトアミド、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、１－メトキシ－２－プロパノール及びエチレングリコールから選ばれる溶媒を添加してろ過をする工程を含むことを特徴とするトリアジン環含有ポリマーの製造方法。 A step of reacting cyanuric halide with a diaminoaryl compound in an organic solvent, a step of dropping the solution after the reaction into a poor solvent to reprecipitate the product, and tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1 -Methoxy-2- (2-methoxyethoxy) ethane, dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, methanol, ethanol, 1-propanol, 2-propanol, A method for producing a triazine ring-containing polymer, comprising a step of adding a solvent selected from 1-butanol, 1-methoxy-2-propanol and ethylene glycol and filtering.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018097000A1 (en) * 2016-11-22 2018-05-31 出光興産株式会社 Triazine-ring-containing polymer and composition in which same is used
WO2019054301A1 (en) * 2017-09-15 2019-03-21 日産化学株式会社 Method for purifying sulfo group-containing hyperbranched polymer and method for producing same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS323145B1 (en) * 1954-10-12 1957-05-27
WO2010128660A1 (en) * 2009-05-07 2010-11-11 日産化学工業株式会社 Carbon nanotube dispersing/solubilizing agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS323145B1 (en) * 1954-10-12 1957-05-27
WO2010128660A1 (en) * 2009-05-07 2010-11-11 日産化学工業株式会社 Carbon nanotube dispersing/solubilizing agent

Cited By (9)

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Publication number Priority date Publication date Assignee Title
WO2018097000A1 (en) * 2016-11-22 2018-05-31 出光興産株式会社 Triazine-ring-containing polymer and composition in which same is used
CN109937227A (en) * 2016-11-22 2019-06-25 出光兴产株式会社 Triazine ring-containing polymer and composition using same
JPWO2018097000A1 (en) * 2016-11-22 2019-10-17 出光興産株式会社 Triazine ring-containing polymer and composition using the same
CN109937227B (en) * 2016-11-22 2021-12-21 出光兴产株式会社 Triazine ring-containing polymer and composition using same
TWI769192B (en) * 2016-11-22 2022-07-01 日商出光興產股份有限公司 Tri-ring-containing polymers and compositions using the same
US11673998B2 (en) 2016-11-22 2023-06-13 Idemitsu Kosan Co., Ltd. Triazine-ring-containing polymer and composition in which same is used
WO2019054301A1 (en) * 2017-09-15 2019-03-21 日産化学株式会社 Method for purifying sulfo group-containing hyperbranched polymer and method for producing same
JPWO2019054301A1 (en) * 2017-09-15 2020-10-15 日産化学株式会社 A method for purifying a highly branched polymer containing a sulfo group and a method for producing the same.
JP7099466B2 (en) 2017-09-15 2022-07-12 日産化学株式会社 A method for purifying a highly branched polymer containing a sulfo group and a method for producing the same.

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