WO2016117524A1 - Method for purifying triazine-ring-containing polymer - Google Patents
Method for purifying triazine-ring-containing polymer Download PDFInfo
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- WO2016117524A1 WO2016117524A1 PCT/JP2016/051351 JP2016051351W WO2016117524A1 WO 2016117524 A1 WO2016117524 A1 WO 2016117524A1 JP 2016051351 W JP2016051351 W JP 2016051351W WO 2016117524 A1 WO2016117524 A1 WO 2016117524A1
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- the present invention relates to a method for purifying a triazine ring-containing polymer.
- Triazine ring-containing polymers are synthesized by polymerization of cyanuric chloride and the like with diamines, and are reported to exhibit high refractive index, high heat resistance, and high transparency (Patent Documents 1 and 2).
- Patent Documents 1 and 2 When the ends are sealed after the polymerization reaction, the hydrogen halide generated at that time is removed by neutralization or the like, but at that time fumes are generated or insoluble salts are generated, resulting in a decrease in operability. was there.
- 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.
- the present inventors have added a basic organic compound selected from alkylamine and pyridine to a polymer solution whose end is sealed after the polymerization reaction, thereby generating slurry and fume.
- the present invention has been completed.
- this invention provides the manufacturing method of the following triazine ring containing polymer.
- a basic organic compound selected from alkylamine and pyridine is added to a triazine ring-containing polymer-containing solution obtained by reacting cyanuric halide with a diaminoaryl compound in an organic solvent, and then the solution is dropped into a poor solvent.
- the amount of the basic organic compound added is 0.1 to 1.6 in terms of molar ratio with respect to the total amount (theoretical amount) of hydrogen chloride produced.
- a method for purifying a triazine ring-containing polymer 2.
- the manufacturing method of a triazine ring containing polymer including the process of reprecipitating a product.
- an alkylamine is added to the polymer solution after the polymerization reaction. That is, the polymer solution after the reaction is in an acidic state due to by-produced hydrogen halide such as hydrogen chloride, but the alkylamine hydrochloride purified by adding alkylamine is dissolved in the solvent used for the polymerization reaction.
- the slurry is not formed, and the operability is improved. In addition, since the generation of fumes can be suppressed, the operability is also improved.
- a basic organic compound selected from alkylamine and pyridine is added to a triazine ring-containing polymer-containing solution obtained by reacting a cyanuric halide with a diaminoaryl compound in an organic solvent.
- a reprecipitation treatment step of dropping the solution into a poor solvent is included.
- 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 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 basic organic compound is preferably an alkylamine. Although it does not specifically limit as said alkylamine, A linear alkylamine is preferable and a linear monoalkylamine is more preferable. Specific examples thereof include methylamine, ethylamine, n-propylamine, n-butylamine and the like, and n-propylamine is particularly preferable.
- the amount of the basic organic compound added is preferably 0.1 to 1.6 in terms of molar ratio with respect to the total amount (theoretical amount) of hydrogen chloride produced from the viewpoint of improving the filterability of the precipitate.
- the amount is preferably 0.5 to 1.6, more preferably 0.8 to 1.2, and still more preferably 1.0.
- the poor solvent used in the 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 preferable, and a water single 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 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 has good filterability. Therefore, the volume efficiency can be increased by reducing the amount of the poor solvent used compared to the case of normal temperature.
- 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 40 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 residual halogen, 0.1 to 24 mL / min is preferable. 0.5-12 mL / min is more preferable.
- the purified polymer may be recovered by a known method such as filtration.
- the purification method of the present invention can be applied to any 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 the purification of a triazine ring-containing polymer having a terminal end capped with the above-described end capping agent and having a hydrophilic group.
- 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 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.
- Example 4 A triazine ring-containing polymer was synthesized according to the following scheme.
- the solution was separated by allowing to stand, and the organic layer was taken out.
- the organic layer was dropped into a mixed solution of 60.00 g of ion-exchanged water and 26.00 g of methanol over 25 minutes, and reprecipitated at 21 ° C.
- the precipitate was suction filtered using Kiriyama funnel (40 ⁇ ) and filter paper (No.424, manufactured by ADVANTEC) under reduced pressure, and this was caked 4 times with 20.00 g of ion-exchanged water.
- a vacuum dryer at 120 ° C. for 17 hours, 3.17 g of a 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 weight average molecular weight of the triazine ring-containing polymer was 10,400, and the degree of dispersion was 3.0.
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Abstract
Provided is a method for purifying a triazine-ring-containing polymer, said method comprising: a re-precipitation step in which, after adding a basic organic compound selected from alkylamines and pyridines to a solution containing a triazine-ring-containing polymer, said solution being obtained by reacting a cyanuric halide and a diaminoaryl compound in an organic solvent, said solution is dripped into a poor solvent. The basic organic compound is added at a molar ratio of 0.1 to 1.6 with respect to the total amount (theoretical amount) of hydrogen chloride to be generated.
Description
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、２）。重合反応後に末端を封止した場合、その時に発生するハロゲン化水素は中和等によって除去されるが、その際にヒュームが発生したり、不溶性の塩が生じたりして操作性が低下することがあった。
Triazine ring-containing polymers are synthesized by polymerization of cyanuric chloride and the like with diamines, and are reported to exhibit high refractive index, high heat resistance, and high transparency (Patent Documents 1 and 2). When the ends are sealed after the polymerization reaction, the hydrogen halide generated at that time is removed by neutralization or the like, but at that time fumes are generated or insoluble salts are generated, resulting in a decrease in operability. was there.
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.
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、重合反応後末端を封止したポリマー溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を加えることによって、スラリーやヒュームの発生を抑制することができることを見出し、本発明を完成させた。
As a result of diligent studies to achieve the above object, the present inventors have added a basic organic compound selected from alkylamine and pyridine to a polymer solution whose end is sealed after the polymerization reaction, thereby generating slurry and fume. 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．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トリアジン環含有ポリマー含有溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を添加した後、該溶液を貧溶媒中へ滴下する再沈殿処理工程を含み、前記塩基性有機化合物の添加量が、生成する塩化水素の全量（理論量）に対して、モル比で、０.１～１.６である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．前記塩基性有機化合物がアルキルアミンである１のトリアジン環含有ポリマーの精製方法。
３．前記アルキルアミンが直鎖状モノアルキルアミンである１又は２のトリアジン環含有ポリマーの精製方法。
４．前記直鎖状モノアルキルアミンがｎ－プロピルアミンである３のトリアジン環含有ポリマーの精製方法。
５．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、得られたポリマー含有溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を添加した後、該溶液を貧溶媒中へ滴下して生成物を再沈殿させる工程を含む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 basic organic compound selected from alkylamine and pyridine is added to a triazine ring-containing polymer-containing solution obtained by reacting cyanuric halide with a diaminoaryl compound in an organic solvent, and then the solution is dropped into a poor solvent. The amount of the basic organic compound added is 0.1 to 1.6 in terms of molar ratio with respect to the total amount (theoretical amount) of hydrogen chloride produced. A method for purifying a triazine ring-containing polymer.
2. A method for purifying a triazine ring-containing polymer, wherein the basic organic compound is an alkylamine.
3. A method for purifying one or two triazine ring-containing polymers, wherein the alkylamine is a linear monoalkylamine.
4). 3. A method for purifying a triazine ring-containing polymer, wherein the linear monoalkylamine is n-propylamine.
5. The step of reacting cyanuric halide and diaminoaryl compound in an organic solvent, adding a basic organic compound selected from alkylamine and pyridine to the resulting polymer-containing solution, and then dropping the solution into a poor solvent. The manufacturing method of a triazine ring containing polymer including the process of reprecipitating a product.
１．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トリアジン環含有ポリマー含有溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を添加した後、該溶液を貧溶媒中へ滴下する再沈殿処理工程を含み、前記塩基性有機化合物の添加量が、生成する塩化水素の全量（理論量）に対して、モル比で、０.１～１.６である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．前記塩基性有機化合物がアルキルアミンである１のトリアジン環含有ポリマーの精製方法。
３．前記アルキルアミンが直鎖状モノアルキルアミンである１又は２のトリアジン環含有ポリマーの精製方法。
４．前記直鎖状モノアルキルアミンがｎ－プロピルアミンである３のトリアジン環含有ポリマーの精製方法。
５．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、得られたポリマー含有溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を添加した後、該溶液を貧溶媒中へ滴下して生成物を再沈殿させる工程を含む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 basic organic compound selected from alkylamine and pyridine is added to a triazine ring-containing polymer-containing solution obtained by reacting cyanuric halide with a diaminoaryl compound in an organic solvent, and then the solution is dropped into a poor solvent. The amount of the basic organic compound added is 0.1 to 1.6 in terms of molar ratio with respect to the total amount (theoretical amount) of hydrogen chloride produced. A method for purifying a triazine ring-containing polymer.
2. A method for purifying a triazine ring-containing polymer, wherein the basic organic compound is an alkylamine.
3. A method for purifying one or two triazine ring-containing polymers, wherein the alkylamine is a linear monoalkylamine.
4). 3. A method for purifying a triazine ring-containing polymer, wherein the linear monoalkylamine is n-propylamine.
5. The step of reacting cyanuric halide and diaminoaryl compound in an organic solvent, adding a basic organic compound selected from alkylamine and pyridine to the resulting polymer-containing solution, and then dropping the solution into a poor solvent. The manufacturing method of a triazine ring containing polymer including the process of reprecipitating a product.
本発明の精製方法では、重合反応後、ポリマー溶液にアルキルアミンを添加する。すなわち、反応後のポリマー溶液は、副生する塩化水素等のハロゲン化水素によって酸性状態であるが、アルキルアミンを添加することによって精製するアルキルアミン塩酸塩が重合反応に用いる溶媒に溶解するため、スラリーが形成されることがなく、操作性が向上する。また、ヒュームの発生を抑制することもできるため、やはり操作性が向上する。
In the purification method of the present invention, an alkylamine is added to the polymer solution after the polymerization reaction. That is, the polymer solution after the reaction is in an acidic state due to by-produced hydrogen halide such as hydrogen chloride, but the alkylamine hydrochloride purified by adding alkylamine is dissolved in the solvent used for the polymerization reaction. The slurry is not formed, and the operability is improved. In addition, since the generation of fumes can be suppressed, the operability is also improved.
本発明のトリアジン環含有ポリマーの精製方法は、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トリアジン環含有ポリマー含有溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を添加した後、該溶液を貧溶媒中へ滴下する再沈殿処理工程を含むものである。
In the method for purifying a triazine ring-containing polymer of the present invention, a basic organic compound selected from alkylamine and pyridine is added to a triazine ring-containing polymer-containing solution obtained by reacting a cyanuric halide with a diaminoaryl compound in an organic solvent. After the addition, a reprecipitation treatment step of dropping the solution into a poor solvent is included.
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.
前記塩基性有機化合物としては、アルキルアミンが好ましい。前記アルキルアミンとしては、特に限定されないが、直鎖状アルキルアミンが好ましく、直鎖状モノアルキルアミンがより好ましい。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。
The basic organic compound is preferably an alkylamine. Although it does not specifically limit as said alkylamine, A linear alkylamine is preferable and a linear monoalkylamine is more preferable. Specific examples thereof include methylamine, ethylamine, n-propylamine, n-butylamine and the like, and n-propylamine is particularly preferable.
前記塩基性有機化合物の添加量は、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、より好ましくは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。
The amount of the basic organic compound added is preferably 0.1 to 1.6 in terms of molar ratio with respect to the total amount (theoretical amount) of hydrogen chloride produced from the viewpoint of improving the filterability of the precipitate. The amount is preferably 0.5 to 1.6, more preferably 0.8 to 1.2, and still more preferably 1.0.
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 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 particular, an aqueous solvent mainly containing water (more than 50% by mass) is preferable, and a water single 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.
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質量倍が更に好ましく、３０～４０質量倍が最適である。
The amount of the poor solvent used in the 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 has good filterability. Therefore, the volume efficiency can be increased by reducing the amount of the poor solvent used compared to the case of normal temperature. In consideration of volumetric efficiency and filterability of the precipitate 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 40 times by mass is preferable.
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 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 residual halogen, 0.1 to 24 mL / min is preferable. 0.5-12 mL / min is more preferable.
再沈殿処理後、精製したポリマーは、ろ過等の公知の方法によって回収すればよい。
After the reprecipitation treatment, the purified polymer may be recovered by a known method such as filtration.
本発明の精製方法は、任意の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 any 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、末端が前述した末端封止剤によって封止され、かつ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 the purification of a triazine ring-containing polymer having a terminal end capped with the above-described end capping agent and having a hydrophilic group. In particular, the following formula (1) or ( It is suitable for purification of a triazine ring-containing polymer containing the repeating unit represented by 2).
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
［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。
[Example]
A triazine ring-containing polymer was synthesized according to the following scheme.
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。
A triazine ring-containing polymer was synthesized according to the following scheme.
［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.
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.
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。
[Example 3]
A triazine ring-containing polymer was synthesized according to the following scheme.
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。
A triazine ring-containing polymer was synthesized according to the following scheme.
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.
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.
［実施例４］
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。
[Example 4]
A triazine ring-containing polymer was synthesized according to the following scheme.
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。
A triazine ring-containing polymer was synthesized according to the following scheme.
窒素雰囲気下、Ｎ,Ｎ－ジメチルアセトアミド１７０.０ｇに溶解したｍ－フェニレンジアミン（１２.９５ｇ、０.１２０ｍｏｌ）をアセトン／ドライアイス浴で－５℃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。３０分攪拌した後、この反応溶液を、あらかじめＮ,Ｎ－ジメチルアセトアミド１３０.２ｇを加えて８５～８６℃に加熱してある槽へ１時間かけて滴下し、８５℃で２時間攪拌して重合した。
その後、４－アミノベンゾトリフルオリド（２１.００ｇ、０.１３０ｍｏｌ）を３分かけて滴下し、８５℃で３時間攪拌して反応を停止した。３２℃まで冷却してｎ－プロピルアミン（１９.４１ｇ、０.３２８ｍｏｌ）を１３分かけて滴下後、３２～４０℃にて１０分攪拌し、ポリマー含有溶液３８１.８ｇを得た。
イオン交換水６０８.０ｇ、メタノール３０.００ｇに酢酸アンモニウム１.００ｇを溶解させた溶液を５０℃に加熱した。その溶液にポリマー含有溶液３８.１８ｇを３０分かけて滴下し、再沈殿させた。５０℃にて３０分攪拌後、室温まで冷却し、沈殿物を桐山ロート（４０φ）及びろ紙（Ｎｏ.４２４、ＡＤＶＡＮＴＥＣ社製）を用いて減圧下で吸引ろ過した。これをイオン交換水２０.００ｇで４回ケーキ洗浄し、粗精製物８.１９ｇを得た。
粗精製物をテトラヒドロフラン２３.００ｇに溶解し、１０質量％アンモニア水４.００ｇ、イオン交換水１.８１ｇ、酢酸アンモニウム０.８０１ｇを加え、２４～２５℃で３０分攪拌後、６０℃に昇温した。これを静置することで分液し、有機層を取り出した。
有機層をイオン交換水６０.００ｇ、メタノール２６.００ｇの混合溶液に２５分かけて滴下し、２１℃にて再沈殿させた。２１℃にて３０分攪拌後、沈殿物を桐山ロート（４０φ）及びろ紙（Ｎｏ.４２４、ＡＤＶＡＮＴＥＣ社製）を用いて減圧下で吸引ろ過し、これをイオン交換水２０.００ｇで４回ケーキ洗浄し、減圧乾燥機で１２０℃、１７時間乾燥し、トリアジン環含有ポリマー３.１７ｇ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。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１０,４００、分散度は３.０であった。 In a nitrogen atmosphere, m-phenylenediamine (12.95 g, 0.120 mol) dissolved in 170.0 g of N, N-dimethylacetamide was cooled to −5 ° C. or lower with 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. After stirring for 30 minutes, the reaction solution was added dropwise to a tank previously heated to 85 to 86 ° C with addition of 130.2 g of N, N-dimethylacetamide and stirred at 85 ° C for 2 hours. Polymerized.
Thereafter, 4-aminobenzotrifluoride (21.00 g, 0.130 mol) was added dropwise over 3 minutes and the reaction was stopped by stirring at 85 ° C. for 3 hours. After cooling to 32 ° C., n-propylamine (19.41 g, 0.328 mol) was added dropwise over 13 minutes and then stirred at 32 to 40 ° C. for 10 minutes to obtain 381.8 g of a polymer-containing solution.
A solution prepared by dissolving 1.00 g of ammonium acetate in 608.0 g of ion-exchanged water and 30.00 g of methanol was heated to 50 ° C. To the solution, 38.18 g of the polymer-containing solution was dropped over 30 minutes to cause reprecipitation. After stirring at 50 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was subjected to suction filtration under reduced pressure using a Kiriyama funnel (40φ) and filter paper (No. 424, manufactured by ADVANTEC). The cake was washed 4 times with 20.00 g of ion-exchanged water to obtain 8.19 g of a crude product.
The crude product was dissolved in 23.00 g of tetrahydrofuran, 4.00 g of 10% by mass ammonia water, 1.81 g of ion exchange water and 0.801 g of ammonium acetate were added, and the mixture was stirred at 24 to 25 ° C. for 30 minutes and then raised to 60 ° C. Warm up. The solution was separated by allowing to stand, and the organic layer was taken out.
The organic layer was dropped into a mixed solution of 60.00 g of ion-exchanged water and 26.00 g of methanol over 25 minutes, and reprecipitated at 21 ° C. After stirring at 21 ° C. for 30 minutes, the precipitate was suction filtered using Kiriyama funnel (40φ) and filter paper (No.424, manufactured by ADVANTEC) under reduced pressure, and this was caked 4 times with 20.00 g of ion-exchanged water. After washing and drying with a vacuum dryer at 120 ° C. for 17 hours, 3.17 g of a triazine ring-containing polymer was obtained.
The structure of the triazine ring-containing polymer was confirmed by 1 H-NMR and 13 C-NMR. As a result of GPC measurement, the weight average molecular weight of the triazine ring-containing polymer was 10,400, and the degree of dispersion was 3.0.
その後、４－アミノベンゾトリフルオリド（２１.００ｇ、０.１３０ｍｏｌ）を３分かけて滴下し、８５℃で３時間攪拌して反応を停止した。３２℃まで冷却してｎ－プロピルアミン（１９.４１ｇ、０.３２８ｍｏｌ）を１３分かけて滴下後、３２～４０℃にて１０分攪拌し、ポリマー含有溶液３８１.８ｇを得た。
イオン交換水６０８.０ｇ、メタノール３０.００ｇに酢酸アンモニウム１.００ｇを溶解させた溶液を５０℃に加熱した。その溶液にポリマー含有溶液３８.１８ｇを３０分かけて滴下し、再沈殿させた。５０℃にて３０分攪拌後、室温まで冷却し、沈殿物を桐山ロート（４０φ）及びろ紙（Ｎｏ.４２４、ＡＤＶＡＮＴＥＣ社製）を用いて減圧下で吸引ろ過した。これをイオン交換水２０.００ｇで４回ケーキ洗浄し、粗精製物８.１９ｇを得た。
粗精製物をテトラヒドロフラン２３.００ｇに溶解し、１０質量％アンモニア水４.００ｇ、イオン交換水１.８１ｇ、酢酸アンモニウム０.８０１ｇを加え、２４～２５℃で３０分攪拌後、６０℃に昇温した。これを静置することで分液し、有機層を取り出した。
有機層をイオン交換水６０.００ｇ、メタノール２６.００ｇの混合溶液に２５分かけて滴下し、２１℃にて再沈殿させた。２１℃にて３０分攪拌後、沈殿物を桐山ロート（４０φ）及びろ紙（Ｎｏ.４２４、ＡＤＶＡＮＴＥＣ社製）を用いて減圧下で吸引ろ過し、これをイオン交換水２０.００ｇで４回ケーキ洗浄し、減圧乾燥機で１２０℃、１７時間乾燥し、トリアジン環含有ポリマー３.１７ｇ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。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１０,４００、分散度は３.０であった。 In a nitrogen atmosphere, m-phenylenediamine (12.95 g, 0.120 mol) dissolved in 170.0 g of N, N-dimethylacetamide was cooled to −5 ° C. or lower with 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. After stirring for 30 minutes, the reaction solution was added dropwise to a tank previously heated to 85 to 86 ° C with addition of 130.2 g of N, N-dimethylacetamide and stirred at 85 ° C for 2 hours. Polymerized.
Thereafter, 4-aminobenzotrifluoride (21.00 g, 0.130 mol) was added dropwise over 3 minutes and the reaction was stopped by stirring at 85 ° C. for 3 hours. After cooling to 32 ° C., n-propylamine (19.41 g, 0.328 mol) was added dropwise over 13 minutes and then stirred at 32 to 40 ° C. for 10 minutes to obtain 381.8 g of a polymer-containing solution.
A solution prepared by dissolving 1.00 g of ammonium acetate in 608.0 g of ion-exchanged water and 30.00 g of methanol was heated to 50 ° C. To the solution, 38.18 g of the polymer-containing solution was dropped over 30 minutes to cause reprecipitation. After stirring at 50 ° C. for 30 minutes, the mixture was cooled to room temperature, and the precipitate was subjected to suction filtration under reduced pressure using a Kiriyama funnel (40φ) and filter paper (No. 424, manufactured by ADVANTEC). The cake was washed 4 times with 20.00 g of ion-exchanged water to obtain 8.19 g of a crude product.
The crude product was dissolved in 23.00 g of tetrahydrofuran, 4.00 g of 10% by mass ammonia water, 1.81 g of ion exchange water and 0.801 g of ammonium acetate were added, and the mixture was stirred at 24 to 25 ° C. for 30 minutes and then raised to 60 ° C. Warm up. The solution was separated by allowing to stand, and the organic layer was taken out.
The organic layer was dropped into a mixed solution of 60.00 g of ion-exchanged water and 26.00 g of methanol over 25 minutes, and reprecipitated at 21 ° C. After stirring at 21 ° C. for 30 minutes, the precipitate was suction filtered using Kiriyama funnel (40φ) and filter paper (No.424, manufactured by ADVANTEC) under reduced pressure, and this was caked 4 times with 20.00 g of ion-exchanged water. After washing and drying with a vacuum dryer at 120 ° C. for 17 hours, 3.17 g of a triazine ring-containing polymer was obtained.
The structure of the triazine ring-containing polymer was confirmed by 1 H-NMR and 13 C-NMR. As a result of GPC measurement, the weight average molecular weight of the triazine ring-containing polymer was 10,400, and the degree of dispersion was 3.0.
Claims (5)
- 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トリアジン環含有ポリマー含有溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を添加した後、該溶液を貧溶媒中へ滴下する再沈殿処理工程を含み、前記塩基性有機化合物の添加量が、生成する塩化水素の全量（理論量）に対して、モル比で、０.１～１.６である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 basic organic compound selected from alkylamine and pyridine is added to a triazine ring-containing polymer-containing solution obtained by reacting cyanuric halide with a diaminoaryl compound in an organic solvent, and then the solution is dropped into a poor solvent. The amount of the basic organic compound added is 0.1 to 1.6 in terms of molar ratio with respect to the total amount (theoretical amount) of hydrogen chloride produced. A method for purifying a triazine ring-containing polymer.
- 前記塩基性有機化合物がアルキルアミンである請求項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 basic organic compound is an alkylamine.
- 前記アルキルアミンが直鎖状モノアルキルアミンである請求項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 alkylamine is a linear monoalkylamine.
- 前記直鎖状モノアルキルアミンがｎ－プロピルアミンである請求項３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 3, wherein the linear monoalkylamine is n-propylamine.
- 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、得られたポリマー含有溶液にアルキルアミン及びピリジンから選ばれる塩基性有機化合物を添加した後、該溶液を貧溶媒中へ滴下して生成物を再沈殿させる工程を含むトリアジン環含有ポリマーの製造方法。 The step of reacting cyanuric halide and diaminoaryl compound in an organic solvent, adding a basic organic compound selected from alkylamine and pyridine to the resulting polymer-containing solution, and then dropping the solution into a poor solvent. The manufacturing method of a triazine ring containing polymer including the process of reprecipitating a product.
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| 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 |
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| JP2012092261A (en) * | 2010-10-28 | 2012-05-17 | Nissan Chem Ind Ltd | Polymer containing triazine ring, and film-forming composition including the same |
| WO2015087968A1 (en) * | 2013-12-13 | 2015-06-18 | 日産化学工業株式会社 | Purification method for triazine ring-containing hyperbranched polymer |
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| WO2015087968A1 (en) * | 2013-12-13 | 2015-06-18 | 日産化学工業株式会社 | Purification method for triazine ring-containing hyperbranched polymer |
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| 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 |
| 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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