CN101392055A - A kind of isomerism polythioetherimide and preparation method thereof - Google Patents

Abstract

The invention provides isomerized polythioetherimide and a preparation method thereof. Using mixed isomers of chlorinated phthalic anhydride as raw material to react with mono-substituted amines to produce N-substituted-3-chlorophthalimide and N-substituted-4-chlorophthalimide Isomers, the latter react with alkali metal sulfides in an aprotic polar solvent to generate N, N'-disubstituted thioether tetraimide isomers in different proportions, hydrolyze and acidify the tetraimide Different ratios of thioether tetraacid isomers are obtained, and different ratios of thioether tetraacid dianhydride isomers are obtained after dehydration. These dianhydride isomers can be polymerized with organic diamines to generate corresponding isomeric polythioetherimide resins, which have excellent comprehensive properties such as heat resistance, mechanical properties and melt processing properties, and can be widely used It is used in related fields such as high temperature resistant engineering plastics, films, adhesives, enameled wires, foam plastics, fibers, and advanced composite materials.

Description

A kind of isomerism polythioetherimide and preparation method thereof

technical field

The invention belongs to the technical field of preparation of thioether-type tetra-acid dianhydride isomers and corresponding isomeric polythioetherimides, and in particular relates to a method using mixed chlorinated phthalic anhydride as raw material and alkali metal sulfide as coupling agent, a technical method for preparing thioether tetraacid dianhydride isomers and corresponding isomerized polythioetherimides.

Background technique

Thioether tetraacid dianhydride is an important raw material for the synthesis of polythioetherimide. Since the flexible unit of thioether bond is introduced into the rigid polyimide main chain, the polythioether prepared from thioether tetraacid dianhydride In addition to good thermomechanical properties, imide is also characterized by good solubility, low melt viscosity and melt processability, and is a very promising thermoplastic heat-resistant polymer material. Therefore, the synthesis of thioether-type tetra-acid dianhydrides and corresponding polythioetherimides has attracted people's attention very early. For example, U.S. Patents 3989712, 4054584, and 4092297 report that 3-nitrophthalic anhydride or 4-nitrophthalic anhydride is used as a raw material, and after aniline protection, a nitro-substituted phthalimide is generated, and the latter reacts with an alkali metal sulfide such as sodium sulfide The corresponding thioetherimide is generated, and then hydrolyzed, acidified, and dehydrated to obtain 3,3'-position thioether dianhydride or 4,4'-position thioether dianhydride, which can be polymerized with diamine to obtain the corresponding polythioetherimide. U.S. Patent 4625037 reports the use of alkali metal hydrosulfide as a coupling agent to react with halogenated or nitro-substituted phthalimides to prepare 3,3'-position thioether dianhydride or 4,4'-position thioether di anhydride. The Chinese Patent No. 1038676 published by the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences in 1992 reported that sulfur was used as a coupling agent to react with chlorophthalimide in a polar aprotic solvent to prepare 3,3'-,3, 4'- and 4,4'-thioether tetraacids and dianhydrides. The Changchun Institute of Applied Chemistry of the Chinese Academy of Sciences reported in the recently published Chinese patent 1724528 that sodium hydrosulfide was used as a coupling agent to react with chlorophthalimide in a polar aprotic solvent to prepare 3,4'-position sulfur The method of ether tetraacid and dianhydride. All the above reports focus on the preparation of pure 3,3'-, 3,4'- or 4,4'-position thioether dianhydride and corresponding polyimides. Although these polyimides have excellent heat resistance and mechanical properties, on the one hand, the preparation cost is relatively high, and on the other hand, the melt processing performance needs to be further improved.

Contents of the invention

The primary technical problem to be solved by the present invention is to provide a heterogeneous polythioetherimide, which has the characteristics of low cost, good heat resistance, high toughness, and low melt viscosity. The resin is used in high temperature resistant engineering plastics, Films, adhesives, enameled wires, foam plastics, fibers, and advanced composite materials have good application prospects.

Another technical problem to be solved by the present invention is to provide a preparation method of isomeric polythioetherimide, which uses mixed chlorinated phthalic anhydride as raw material, and does not need to separate chlorinated phthalic anhydride isomers during preparation, which greatly saves the preparation of raw materials. cost, and use cheap alkali metal sulfides such as sodium sulfide as the coupling agent, no separation of isomers is required in the intermediate process, and the final obtained thioether dianhydride isomers and isomerized polythioetherimide resins have low cost , Good heat resistance, high toughness, low melt viscosity and so on.

The technical solution adopted by the present invention to solve the above-mentioned primary technical problems is: a kind of isomerized polythioetherimide, which is characterized in that it has the following structure I:

Wherein the position of thioether bond can be in 3-bond, also can be in 4-bond, wherein specified 3-bond and 4-bond mean that in this copolymer, in the structure unit that contains phthalimide The isomeric position on the phthalimide ring.

The technical solution adopted by the present invention to solve the above-mentioned another technical problem is: a preparation method of isomerized polythioetherimide, which is characterized in that the mixed isomers of chlorinated phthalic anhydride of the following structural formula II are used as raw materials, and Reaction of monosubstituted amines _R1NH2 to produce N-substituted-3 _- chlorophthalimides and isomers of N-substituted-4-chlorophthalimides, the latter and base Metal sulfide reacts in an aprotic polar solvent to generate different proportions of N, N'-disubstituted thioether tetraimide isomers, and the tetraimide is hydrolyzed and acidified to obtain different proportions of thioether tetraimide Acid isomers, after dehydration, different proportions of thioether-type tetra-acid dianhydride isomers are obtained, and these dianhydride isomers are polymerized with organic diamine NH ₂ R ₂ NH ₂ in a usual way to generate the corresponding ones as shown below The isomeric polythioetherimide resin of structure I;

where the chlorine substituent is at the 3- or 4-position.

The position of the thioether bond in the polythioetherimide can be at the 3-bond or at the 4-bond, wherein the specified 3-bond and 4-bond refer to the overall phthalate-containing The isomeric position on the phthalimide ring in the structural unit of carboximide.

The weight ratio of 3-chlorophthalic anhydride to 4-chlorophthalic anhydride in the raw material mixed chlorophthalic anhydride isomers is between about 99.9:0.1 and about 0.1:99.9.

The _R1 is a substituted or unsubstituted straight-chain or branched alkyl group containing 1-8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl or pentyl, etc., R ₁ can also be a substituted or unsubstituted aryl group containing 6-20 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, chlorophenyl, or bromomethylphenyl, etc.

The vulcanizing agent for coupling isomers of chlorinated phthalimides is an alkali metal sulfide such as lithium sulfide, potassium sulfide or sodium sulfide.

The solvent used in the reaction of the N'-disubstituted thioether tetraimide isomer is a polar aprotic solvent such as N, N'-dimethylformamide (DMF), N, N'-di Methylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), or sulfolane.

The base for the hydrolysis of N, N'-disubstituted thioether tetraimide isomers is sodium hydroxide or potassium hydroxide, and sodium hydroxide or potassium hydroxide and N, N'-disubstituted sulfur The molar ratio of ether tetraimide is 6:1-12:1.

The method for dehydrating the thioether tetraacid isomers into dianhydrides is to reflux in acetic anhydride, or to reflux in a benzene solvent with water, or to melt in vacuum. Wherein, in the method of reflux with water in the benzene solvent, the benzene solvent refers to benzene, toluene, xylene or chlorobenzene.

The R ₂ is a substituted or unsubstituted aliphatic or aromatic diamine, and R ₂ can be selected from at least one of the following diamines: p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-dimethyl Base benzidine, 2,2'-dimethylbenzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3, 4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminobis Phenylisopropane, 4,4'-diaminodiphenylsulfide, 2,2'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-di Aminodiphenylmethane, 4,4'-diamino-diphenoxy-4", 4"'biphenyl, 4,4'-diamino-diphenoxy-4", 4"'diphenyl ether, 4,4'-diamino-diphenoxy-4", 4"'diphenylsulfone, 4,4'-diamino-diphenoxy-4", 4"'diphenylisopropane, 1, 6-hexanediamine, 2,4-toluenediamine, 5-methyl-4,6-diethyl-1,3-phenylenediamine, 3,3'-dimethyl-4,4'-di Aminodiphenylmethane, 2,2'3,3'-tetramethyl-4,4'-diaminodiphenylmethane, and mixtures thereof.

When the thioether dianhydride and diamine are polymerized, the usual two-step method is to first generate polyamic acid in an aprotic polar solvent, and then generate polyimide by heating or chemical imine; Or the usual one-step method, that is, one-step high-temperature polycondensation in a phenolic solvent such as cresol, phenol or p-chlorophenol to directly generate polyimide; or one-step high-temperature polycondensation in a mixed solvent of an aprotic polar solvent and a benzene solvent Directly generate polyimide; or directly obtain polyimide by one-step high-temperature melt polymerization of dianhydride and diamine.

Moreover, substituted or unsubstituted monoanhydrides or monoamines are used as end-capping agents in the polymerization reaction to control the degree of polymerization of the reaction and the molecular weight of the final polymer. The end-blocking agent is phthalic anhydride or phthalic anhydride derivatives including phthalic anhydride, 3-chlorophthalic anhydride, 3-methylphthalic anhydride, 4-chlorophthalic anhydride, or 4-methylphthalic anhydride, or is a derivative including aniline, 3-methylaniline, 4-Chloroaniline, or aniline or aniline derivatives of 4-methylaniline.

The finally obtained polythioetherimide has an inherent viscosity of about 0.25 to about 1.95 dL/g as measured by an Ubbelohde viscometer in m-cresol at a concentration of 0.5 dL/g at 30°C, It has a weight average molecular weight of between about 8,000 and about 200,000 relative to polystyrene standards as determined by gel permeation chromatography.

Compared with the prior art, the present invention has the advantages of: using mixed chlorinated phthalic anhydride as raw material, there is no need to separate chlorinated phthalic anhydride isomers during preparation, which greatly saves the cost of raw material preparation, and uses cheap alkali metal sulfides such as sulfide Sodium is used as the coupling agent, no isomer separation is required in the intermediate process, and the final thioether dianhydride isomers and isomerized polythioetherimide resins have low cost, good heat resistance, high toughness, and low melt viscosity And other high-performance characteristics, the resin has good application prospects in related fields such as high-temperature-resistant engineering plastics, films, adhesives, enameled wires, foamed plastics, fibers, and advanced composite materials.

Description of drawings

Figure 1 Schematic diagram of the reaction process.

Detailed ways

The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.

Example 1:

Add 36.5 grams (0.2 mol) of mixed chlorinated phthalic anhydride with a mass ratio of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride in a 5:1 ratio to a 500 ml three-necked flask, 250 ml glacial acetic acid, stir and heat to 40°C, etc. After all the solids are dissolved, slowly add 30 ml of 25% methylamine aqueous solution dropwise, and after the dropwise addition, heat up to 120°C for 10 hours of reaction. After cooling the obtained reactant, filter the precipitated crystals, wash them several times with distilled water, and vacuum at 100°C. After drying in an oven, 35.60 g of N-methylchloroimide isomer mixture was obtained, with a yield of 91%. 19.55 grams (0.1mol) of the above-mentioned reactant, 3.9 grams (0.05mol) of anhydrous sodium sulfide, and 120 milliliters of N, N'-dimethylformamide were added to a dry 250 milliliter three-necked flask under a nitrogen atmosphere. , stirred and heated to 60°C for 2 hours, then heated to 140°C for 15 hours, cooled to room temperature, poured into 400 ml of 1:5 (concentrated hydrochloric acid: water = volume ratio) dilute hydrochloric acid, filtered The precipitate was removed, washed with distilled water until neutral, and dried in a vacuum oven at 130°C to obtain 15.3 g of N,N'-dimethyl diphenyl sulfide tetraimide isomer mixture, with a yield of 87%. The resulting product was heated to reflux in 90 ml of 20% aqueous sodium hydroxide solution for 17 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated sulfuric acid: water=volume ratio) sulfuric acid, stirred and placed Overnight, filter the separated precipitate, wash it with distilled water until neutral, dry the filter cake in a vacuum oven at 100°C to obtain a mixture of isomers of thioether tetraacid, continue to recrystallize with acetic anhydride to obtain 5.61 grams of isomers of thioether dianhydride , put the obtained filtrate into a 250 ml round-bottomed flask, add 120 ml of toluene, heat to reflux and separate the water in the solution, filter out the insoluble matter in the solution while hot, filter the crystals separated out after the filtrate is cooled, and dry to obtain sulfide 5.32 grams of dianhydride isomers, 10.93 grams of combined secondary thioether dianhydride isomers, yield 77%. Under a nitrogen atmosphere, add 1.0000 g (4.42 mmol) of 3,3'-dimethyl-4,4'-diaminodiphenylmethane and 15 ml of N,N'-dimethylformamide to 50 ml of three-neck Bottle, mechanically stirred, after the solid diamine was fully dissolved, 1.4422 g (4.42 mmol) of the above-mentioned thioether dianhydride isomer solid powder was added in batches within 0.5 hours, and stirred at room temperature for 24 hours to obtain a viscous polyamic acid solution . Add 3 milliliters of acetic anhydride and 1 milliliter of triethylamine to the polyamic acid solution, stir at room temperature for 24 hours, pour into 500 milliliters of methanol, filter, extract with methanol in a Soxhlet extractor for 6 hours and then vacuum-dry to obtain polyamide The imine powder is 2.03g, and the yield is 89%. The inherent viscosity measured in m-cresol at a concentration of 0.5 dL/g at 30°C is 1.25 dL/g. IR (KBr): 3475, 2292, 1775, 1717, 1605, 1376, ^{742 cm -1} .

Example 2:

In a 1000 ml three-necked flask, add 73 grams (0.4 mol) of mixed chlorophthalic anhydride with a mass ratio of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride of 1:1, 450 ml of glacial acetic acid, stir and heat to 60°C, etc. After all the solids are dissolved, slowly add 60 ml of 25% methylamine aqueous solution dropwise, and after the dropwise addition, heat up to 130°C for 15 hours of reaction. After cooling the obtained reactant, filter the precipitated crystals, wash them with distilled water for several times, and place them under vacuum at 100°C. After drying in an oven, 68.80 g of N-methylchloroimide isomer mixture was obtained, with a yield of 88%. 39.1 grams (0.2mol) of the above-mentioned reactant, 4.6 grams (0.1mol) of anhydrous lithium sulfide, and 300 milliliters of N, N'-dimethylformamide were added to a dry 500 milliliter three-necked flask under nitrogen atmosphere , stirred and heated to 40°C for 4 hours, then heated to 120°C for 24 hours, cooled to room temperature, poured into 1000 ml of dilute hydrochloric acid (concentrated hydrochloric acid: water = volume ratio) and filtered The precipitate was washed with distilled water until neutral, and dried in a vacuum oven at 130°C to obtain 29.3 g of N,N'-dimethyl diphenyl sulfide tetraimide isomer mixture, with a yield of 83%. The resulting product was heated to reflux in 250 ml of 10% potassium hydroxide aqueous solution for 47 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated hydrochloric acid: water=volume ratio) hydrochloric acid, and 300 ml of Toluene was heated to reflux and the water in the solution was separated. The insoluble matter in the solution was filtered out while it was hot. After the filtrate was cooled, the precipitated crystals were filtered and dried to obtain 24.1 g of thioether dianhydride isomers, with a yield of 89%. Under a nitrogen atmosphere, add 10.0000 g (50.5 mmol) of 4,4'-diaminodiphenylmethane and 250 ml of N,N'-dimethylacetamide into a 500 ml three-necked bottle, stir mechanically, and the solid diamine is completely After dissolving, 15.8246 grams (48.5 mmol) of the thioether dianhydride isomers obtained above and 0.2962 grams (4.0 mmol) of phthalic anhydride solid powder were added in batches within 2 hours, and stirred at room temperature for 24 hours to obtain a viscous polyamic acid solution. Add 30 ml of acetic anhydride and 15 ml of triethylamine to the polyamic acid solution, stir at room temperature for 24 hours, pour into 5000 ml of methanol, filter, extract with methanol in a Soxhlet extractor for 6 hours and then vacuum dry to obtain polyamide 22.33 g of imine powder, yield 92%. The inherent viscosity measured in m-cresol at a concentration of 0.5 dL/g at 30°C is 0.78 dL/g. IR (KBr): 3478, 2361, 1776, 1719, 1608, 1388, ^{738 cm -1} .

Example 3:

In a 500 ml three-necked flask, add 36.5 grams (0.2 mol) of mixed chlorophthalic anhydride with a mass ratio of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride of 2:3, 300 milliliters of glacial acetic acid, stir and heat to 60°C, etc. After all the solids were dissolved, slowly add 18.3 milliliters (0.2 mol) of aniline dropwise, after the dropwise addition, the temperature was raised to 120°C for 15 hours of reaction. After oven drying, 47.91 g of N-phenylchloroimide isomer mixture was obtained, with a yield of 93%. 25.76 grams (0.1mol) of the above-mentioned reactant, 3.9 grams (0.05mol) of anhydrous sodium sulfide, and 140 milliliters of N, N'-dimethylacetamide were added to a dry 250 milliliter three-necked flask under a nitrogen atmosphere. , stirred and heated to 60°C for 3 hours, then heated to 150°C for 24 hours, cooled to room temperature, poured into 400 ml of dilute hydrochloric acid (concentrated hydrochloric acid: water = volume ratio) and filtered The precipitate was washed with distilled water until neutral, and dried in a vacuum oven at 130°C to obtain 19.5 g of N,N'-diphenyldiphenylsulfide tetraimide isomer mixture, with a yield of 82%. The resulting product was heated to reflux in 200 milliliters of 13% aqueous sodium hydroxide solution for 34 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated sulfuric acid: water=volume ratio) sulfuric acid, stirred and placed Overnight, filter the separated precipitate, wash it with distilled water until neutral, dry the filter cake in a vacuum oven at 100°C to obtain a mixture of isomers of thioether tetraacid, continue to recrystallize with acetic anhydride to obtain 8.07 grams of isomers of thioether dianhydride , put the obtained filtrate into a 250 ml round bottom flask, add 80 ml of toluene, heat to reflux and separate the water in the solution, filter out the insoluble matter in the solution while hot, filter the crystals separated out after the filtrate is cooled, and dry to obtain sulfide 2.34 grams of dianhydride isomers, 10.41 grams of combined secondary thioether dianhydride isomers, yield 78%. Under a nitrogen atmosphere, 0.9980 grams (4.99 mmol) of 4,4'-diaminodiphenyl ether, 0.5389 grams (4.99 mmol) of m-phenylenediamine and 35 milliliters of NMP were added to a 100-milliliter three-necked flask, mechanically stirred, and the solid two After the amine was completely dissolved, 3.2588 g (9.98 mmmol) of the solid powder of thioether dianhydride isomer obtained above was added in batches within 1 hour, and stirred at room temperature for 24 hours to obtain a viscous polyamic acid solution. Add 5 milliliters of toluene to the polyamic acid solution, stir at 170 degrees for 17 hours, pour into 500 milliliters of methanol after cooling to room temperature, filter, extract with methanol in a Soxhlet extractor for 10 hours and then vacuum dry to obtain polyimide Powder 4.49g, yield 92%. The inherent viscosity measured in m-cresol at a concentration of 0.5 dL/g at 30°C is 0.85 dL/g. IR (KBr): 3466, 2325, 1778, 1723, 1608, 1382, 730 cm-1.

Example 4:

Add 146 grams (0.8 mol) of 3-chlorophthalic anhydride to 4-chlorophthalic anhydride in a 4:1 mass ratio, 1400 milliliters of glacial acetic acid, stir and heat to 80°C, etc. After all the solids are dissolved, slowly add 73.1 milliliters (0.8 mol) of aniline dropwise, after the dropwise addition, the temperature is raised to 130°C for 24 hours of reaction, the resulting reactant is cooled, and the separated crystals are filtered, washed several times with distilled water, and placed in vacuum at 100°C. After oven drying, 181.40 g of N-phenylchloroimide isomer mixture was obtained, with a yield of 88%. 103 grams (0.4mol) of the above-mentioned reactant, 15.6 grams (0.2mol) of anhydrous sodium sulfide, and 600 milliliters of N, N'-dimethylformamide were added to a dry 1000 milliliter three-necked flask under a nitrogen atmosphere. , stirred and heated to 80 ° C for 1 hour, then heated to 140 ° C for 24 hours, cooled to room temperature, poured it into 3000 ml of dilute hydrochloric acid (concentrated hydrochloric acid: water = volume ratio), filtered The precipitate was washed with distilled water until neutral, and dried in a vacuum oven at 100°C to obtain 72.4 g of N,N'-diphenyldiphenylsulfide tetraimide isomer mixture, with a yield of 76%. The resulting product was heated to reflux in 400 ml of 15% potassium hydroxide aqueous solution for 46 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated hydrochloric acid: water=volume ratio) hydrochloric acid, stirred and placed Overnight, add 300 milliliters of toluene, heat to reflux and separate the water in the solution, filter out the insoluble matter in the solution while hot, and dry the crystals separated out after the filtrate is cooled to obtain 39.2 grams of thioether dianhydride isomers, with a yield of 79 %. Under a nitrogen atmosphere, add 4.0000 g (19.97 mmol) of 3,4'-diaminodiphenyl ether and 65 ml of N,N'-dimethylformamide into a 100 ml three-necked bottle, stir mechanically, and the solid diamine is completely After dissolving, 6.5158 g (19.97 mmol) of the solid powder of thioether dianhydride isomers obtained above was added in batches within 1 hour, and stirred at room temperature for 24 hours to obtain a viscous polyamic acid solution. Add 30 ml of toluene to the polyamic acid solution, stir at 170 degrees for 24 hours, pour it into 1000 ml of methanol after cooling to room temperature, filter, extract with methanol in a Soxhlet extractor for 10 hours, and then vacuum dry to obtain polyimide Powder 8.42g, yield 86%. The inherent viscosity measured in m-cresol at a concentration of 0.5 dL/g at 30°C is 1.44 dL/g. IR (KBr): 3453, 2325, 1776, 1716, 1601, 1391, 728 cm-1.

Example 5:

In a 1000 ml three-necked flask, add 73 grams (0.4 mol) of mixed chlorophthalic anhydride with a mass ratio of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride of 3:1, 600 ml of glacial acetic acid, stir and heat to 80°C, etc. After all the solids are dissolved, slowly add 36.6 milliliters (0.4 mol) of aniline dropwise, and after the dropwise addition, heat up to 120°C for 18 hours of reaction. After the resulting reactant is cooled, filter the precipitated crystals, wash them several times with distilled water, and place them under vacuum at 100°C. After drying in an oven, 93.8 g of N-phenylchloroimide isomer mixture was obtained, with a yield of 91%. Add 51.50 g (0.2 mol) of the reactant obtained above, 4.6 g (0.1 mol) of anhydrous lithium sulfide, and 350 ml of N-methylpyrrolidone into a dry 500 ml three-necked flask under a nitrogen atmosphere, stir and heat React at 70°C for 5 hours, then raise the temperature to 110°C for 24 hours, after cooling to room temperature, pour it into 2000 ml of dilute hydrochloric acid of 1:6 (concentrated hydrochloric acid: water = volume ratio), filter out the precipitate, and use distilled water Wash until neutral, and dry in a vacuum oven at 120°C to obtain 41.9 g of N,N'-diphenyldiphenylsulfide tetraimide isomer mixture, with a yield of 88%. The resulting product was heated to reflux in 250 milliliters of 10% aqueous sodium hydroxide solution for 50 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated hydrochloric acid: water=volume ratio) hydrochloric acid, stirred and placed Overnight, filter the separated precipitate, wash with distilled water until neutral, dry the filter cake in a vacuum oven at 100°C to obtain a mixture of isomers of thioether tetraacid, continue to recrystallize with acetic anhydride to obtain 10.23 grams of isomers of thioether dianhydride , put the obtained filtrate into a 500 ml round bottom flask, add 150 ml of toluene, heat to reflux and separate the water in the solution, filter out the insoluble matter in the solution while hot, filter the crystals precipitated after the filtrate is cooled, and dry to obtain sulfide 13.28 grams of dianhydride isomers, 23.5 grams of combined secondary thioether dianhydride isomers, yield 82%. Under a nitrogen atmosphere, add 4.0000 g (19.97 mmol) of 4,4'-diaminodiphenyl ether, 4.0000 g (19.97 mmol) of 3,4'-diaminodiphenyl ether and 50 ml of m-cresol to 100 ml of three Neck bottle, mechanical stirring, after the solid diamine is fully dissolved, add 13.0316 g (39.94 mmmol) of the above-mentioned thioether dianhydride isomer solid powder, stir at 160 degrees for 24 hours, pour into 500 ml of methanol, filter, and Extract with methanol in the extractor for 10 hours and then vacuum dry to obtain 17.81 g of polyimide powder with a yield of 91%. The inherent viscosity measured in m-cresol with a concentration of 0.5 dL/g at 30°C is 1.58 dL/g. IR (KBr): 3469, 2309, 1779, 1726, 1611, 1386, 749 cm-1.

Embodiment 6:

Add 36.5 g (0.2 mol) of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride in a 3:2 mass ratio to a 500-ml three-necked flask, 200 ml of glacial acetic acid, stir and heat to 50°C, etc. After all the solids are dissolved, slowly add 35 ml of 25% methylamine aqueous solution dropwise, and after the dropwise addition, heat up to 120°C for 14 hours of reaction. After cooling the obtained reactant, filter the precipitated crystals, wash with distilled water for several times, and vacuum at 100°C. After drying in an oven, 32.45 g of N-methylchloroimide isomer mixture was obtained, with a yield of 83%. 19.55 grams (0.1mol) of the above-mentioned reactant, 3.9 grams (0.05mol) of anhydrous sodium sulfide, and 150 milliliters of N, N'-dimethylacetamide were added to a dry 250 milliliter three-necked flask under a nitrogen atmosphere. , stirred and heated to 50°C for 2 hours, and then heated to 140°C for 20 hours, after cooling to room temperature, pour it into 800 ml of dilute hydrochloric acid of 1:10 (concentrated hydrochloric acid: water = volume ratio), filter The precipitate was washed with distilled water until neutral, and dried in a vacuum oven at 130°C to obtain 14.1 g of N,N'-dimethyl diphenyl sulfide tetraimide isomer mixture, with a yield of 80%. The resulting product was heated to reflux in 120 ml of 12% potassium hydroxide aqueous solution for 28 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated sulfuric acid: water=volume ratio) sulfuric acid, stirred and placed Overnight, filter the separated precipitate, wash with distilled water until neutral, and dry the filter cake in a vacuum oven at 100°C to obtain a mixture of thioether tetraacid isomers, and continue to recrystallize with acetic anhydride to obtain 7.19 grams of thioether dianhydride isomers , put the obtained filtrate into a 250 ml round bottom flask, add 60 ml of toluene, heat to reflux and separate the water in the solution, filter out the insoluble matter in the solution while hot, filter the crystals separated out after the filtrate is cooled, and dry to obtain sulfide 3.89 grams of dianhydride isomers, 11.08 grams of combined secondary thioether dianhydride isomers, yield 85%. Under a nitrogen atmosphere, put 5.0000 grams (22.09 mmol) of 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 100 milliliters of m-cresol, and 7.1586 grams (21.94 mmol) of the above obtained thioether dianhydride Isomers and 0.0444 g (0.30 mmol) phthalic anhydride were added to a 250 ml three-necked flask, mechanically stirred, and heated to 50 ° C for 2 hours, then heated to 140 ° C for 20 hours, cooled to room temperature, poured into 1200 ml of methanol , filtered, extracted with methanol in a Soxhlet extractor for 24 hours and then vacuum-dried to obtain 10.03 g of polyimide powder with a yield of 88%. The inherent viscosity measured in m-cresol at a concentration of 0.5 dL/g at 30°C is 1.18 dL/g. IR (KBr): 3489, 2294, 1784, 1715, 1609, 1383, ^{759 cm -1} .

Embodiment 7:

In a 1000 ml three-necked flask, add 73 grams (0.4 mol) of mixed chlorophthalic anhydride with a mass ratio of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride of 1:4, 500 ml of glacial acetic acid, stir and heat to 60°C, etc. After all the solids are dissolved, slowly add 66 ml of 25% methylamine aqueous solution dropwise, and after the dropwise addition, heat up to 120°C for 19 hours of reaction. After cooling the obtained reactant, filter the precipitated crystals, wash with distilled water several times, and vacuum at 100°C. After drying in an oven, 67.30 g of N-methylchloroimide isomer mixture was obtained, with a yield of 86%. Add 39.1 g (0.2 mol) of the reactant obtained above, 4.6 g (0.1 mol) of anhydrous lithium sulfide, and 250 ml of N-methylpyrrolidone into a dry 500 ml three-necked flask under a nitrogen atmosphere, stir and heat React at 60°C for 1 hour, then raise the temperature to 120°C for 14 hours, after cooling to room temperature, pour it into 1000 ml of dilute hydrochloric acid 1:6 (concentrated hydrochloric acid: water = volume ratio), filter out the precipitate, and wash with distilled water Wash until neutral, and dry in a vacuum oven at 130°C to obtain 29.9 g of N,N'-dimethyldiphenylsulfide tetraimide isomer mixture, with a yield of 85%. The resulting product was heated to reflux in 200 ml of 20% aqueous sodium hydroxide solution for 10 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated hydrochloric acid: water=volume ratio) hydrochloric acid, and 100 ml of Toluene was heated to reflux and the water in the solution was separated, and the insoluble matter in the solution was filtered out while it was hot. After the filtrate was cooled, the precipitated crystals were filtered and dried to obtain 24.6 grams of thioether dianhydride isomers, with a yield of 89%. Under a nitrogen atmosphere, put 2.5000 g (11.8 mmol) of 4,4'-diaminobenzophenone, 2.5000 g (11.8 mmol) of 4,4'-diaminobenzophenone and 125 ml of N,N'-dimethyl Acetamide was added to a 250 milliliter three-necked bottle, mechanically stirred, and after the solid diamine was fully dissolved, 7.5044 grams (23.0 mmol) of the above-mentioned obtained thioether dianhydride isomers and 0.1776 grams (1.2 mmol) of phthalic anhydride solid powder were separated within 2 hours. Add in batches and stir at room temperature for 24 hours to obtain a viscous polyamic acid solution. Add 20 ml of acetic anhydride and 10 ml of triethylamine to the polyamic acid solution, stir at room temperature for 36 hours, pour into 2000 ml of methanol, filter, extract with methanol in a Soxhlet extractor for 10 hours and then vacuum dry to obtain polyamide 11.13 g of imine powder, yield 93%. The inherent viscosity measured in m-cresol at a concentration of 0.5 dL/g at 30°C is 0.35 dL/g. IR (KBr): 3468, 2386, 1786, 1725, 1665, 1601, 1379, 723 ^{cm -1} .

Embodiment 8:

Add 182.5 grams (1.0 mol) of 3-chlorophthalic anhydride to 4-chlorophthalic anhydride in a 3-necked three-necked flask with a mass ratio of 1:2, 2000 milliliters of glacial acetic acid, stir and heat to 70°C, etc. After all the solids are dissolved, slowly add 91.3 milliliters (1.0 mol) of aniline dropwise, and after the dropwise addition, heat up to 130°C for 24 hours of reaction. After cooling the obtained reactant, filter the precipitated crystals, wash them several times with distilled water, and place them under vacuum at 100°C. After drying in an oven, 244.8 g of N-phenylchloroimide isomer mixture was obtained, with a yield of 95%. 128.8 grams (0.5mol) of the reactant obtained above, 11.5 grams (0.25mol) of anhydrous lithium sulfide, and 1000 milliliters of dry dimethyl sulfoxide were added to a dry 2000 milliliter three-necked flask under a nitrogen atmosphere, stirred and Heated to 50°C for 5 hours, then raised to 160°C for 15 hours, cooled to room temperature, poured into 4000 ml of dilute hydrochloric acid (concentrated hydrochloric acid: water = volume ratio), filtered out the precipitate, and used Wash with distilled water until neutral, and dry in a vacuum oven at 120°C to obtain 100.1 g of N,N'-diphenyldiphenylsulfide tetraimide isomer mixture, with a yield of 84%. The resulting product was heated to reflux in 600 ml of 25% potassium hydroxide aqueous solution for 17 hours, and a little solid impurity was filtered out after the reaction, and the aqueous solution was acidified to pH=2 with 1:1 (concentrated sulfuric acid: water=volume ratio) sulfuric acid, and 500 ml of Toluene was heated to reflux and the water in the solution was separated. The insoluble matter in the solution was filtered out while it was hot. After the filtrate was cooled, the precipitated crystals were filtered and dried to obtain 58.9 grams of thioether dianhydride isomers, with a yield of 86%. Under a nitrogen atmosphere, add 20.0000 grams (92.5 mmol) of 4,4'-diaminodiphenyl sulfide and 500 milliliters of N-methylpyrrolidone into a 1000 milliliter three-necked bottle, stir mechanically, and after the solid diamine is fully dissolved, 30.1809 Grams (92.5 mmol) of the thioether dianhydride isomer solid powder obtained above were added in batches within 2 hours, and stirred at room temperature for 24 hours to obtain a viscous polyamic acid solution. Add 200 ml of toluene to the polyamic acid solution, stir at 160 degrees for 18 hours, pour it into 1000 ml of methanol after cooling to room temperature, filter, extract with methanol in a Soxhlet extractor for 24 hours, and then vacuum dry to obtain polyimide Powder 44.46g, yield 95%. The inherent viscosity measured in m-cresol at a concentration of 0.5 dL/g at 30°C is 1.87 dL/g. IR (KBr): 3490, 2381, 1782, 1726, 1619, 1379, 728 ^{cm -1} .

Claims (16)

1, a kind of iso-poly (sulfide-imide) is characterized in that having structure I as follows:

Wherein the position of thioether bond can be at the 3-key, also can be at the 4-key, and wherein specified 3-key and 4-key are meant the isomery position on the phthalic imidine ring in the structural unit that all contains phthalic imidine in this multipolymer.

2, a kind of preparation method of iso-poly (sulfide-imide) is characterized in that adopting the chloro-benzoic anhydride mixed isomers of structural formula II as follows is raw material, with mono-substituted amine R ₁NH ₂The isomer of N-replacement-3-chlorophthalimide and N-replacement-4-chlorophthalimide is produced in reaction, the latter and alkali metalsulphide react the N that generates different ratios in aprotic polar solvent, N '-dibasic thioether four imide isomer, this four imides hydrolysis, acidifying are obtained the thioether type tetracid isomer of different ratios, obtain the thioether type tetraacid dianhydride isomer of different ratios after the dehydration, these dianhydride isomer again with organic diamine NH ₂R ₂NH ₂Generate the iso-poly (sulfide-imide) resin of corresponding structure I as follows with the usual method polymerization;

Wherein chlorine substituent is in 3-or 4-position.

3, preparation method according to claim 2 is characterized in that thioether type tetraacid dianhydride isomer refers to 3,3 ' shown in the following structural formula-position dianhydride, 3,4 '-position dianhydride and 4, and 4 '-position any two kinds or three kinds in the dianhydride,

3,3 '-position dianhydride 3,4 '-position dianhydride 4,4 '-the position dianhydride.

4, preparation method according to claim 2, the position that it is characterized in that thioether bond in the Polythioetherimide can be at the 3-key, also can be at the 4-key, wherein specified 3-key and 4-key are meant the isomery position on the phthalic imidine ring in the structural unit that all contains phthalic imidine in this multipolymer.

5, preparation method according to claim 2, the weight ratio that it is characterized in that 3-chloro-benzoic anhydride and 4-chloro-benzoic anhydride in the raw material mixing isomers of chloro-benzoic anhydride at about 99.9:0.1 between about 0.1:99.9.

6, preparation method according to claim 2, it is characterized in that R1 be replace or unsubstituted comprise methyl, ethyl, propyl group, sec.-propyl, butyl or amyl group contain 1-8 carbon atom straight chain or branched alkyl, R1 also can be replacement or the unsubstituted aryl that contains 6-20 carbon atom that comprises phenyl, tolyl, xylyl, naphthyl, chloro-phenyl-, toluene bromide base.

7, preparation method according to claim 2, the vulcanizing agent that it is characterized in that coupling chloro phthalimide isomer is alkali metalsulphide such as lithium sulfide, potassium sulphide or sodium sulphite.

8, preparation method according to claim 2, the used solvent of reaction that it is characterized in that N '-dibasic thioether four imide isomer is polar aprotic solvent such as N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl sulfoxide (DMSO) (DMSO), HMPA (HMPA) or tetramethylene sulfone.

9, preparation method according to claim 2, it is characterized in that hydrolyzing N, the alkali of N '-dibasic thioether four imide isomer is sodium hydroxide or potassium hydroxide, and sodium hydroxide or potassium hydroxide and N, and N '-dibasic thioether four imido mol ratios are 6:1-12:1.

10, preparation method according to claim 2 is characterized in that the method employing of thioether tetracid isomer dehydration becoming dianhydride refluxes in diacetyl oxide, perhaps adopting the band water that refluxes in benzene kind solvent, perhaps adopts vacuum fusion.

11, preparation method according to claim 10 is characterized in that refluxing in the benzene kind solvent and is with in the method for water, and benzene kind solvent refers to benzene,toluene,xylene or chlorobenzene.

12, preparation method according to claim 2 is characterized in that R ₂For replacing or unsubstituted fat or aromatic diamines R ₂Can be selected from following at least a diamines: Ursol D, mphenylenediamine, p-diaminodiphenyl, 3,3 '-tolidine, 2,2 '-tolidine, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diaminodiphenylsulfone(DDS), 3,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 4, the different propane of 4 '-diamino-diphenyl, 4,4 '-diaminodiphenyl sulfide, 2,2 '-two chloro-4,4 '-diaminodiphenylmethane, 3,3 '-two chloro-4,4 '-diaminodiphenylmethane, 4,4 '-diamino-two phenoxy group-4 "; 4 " ' biphenyl, 4,4 '-diamino-two phenoxy group-4 "; 4 " ' phenyl ether, 4,4 '-diamino-two phenoxy group-4 "; 4 " ' sulfobenzide, 4,4 '-diamino-two phenoxy group-4 "; 4 " ' the different propane of phenylbenzene, 1, the 6-hexanediamine, 2,4-tolylene diamine, 5-methyl-4,6-diethyl-1,3-phenylenediamine, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 2,2 ' 3,3 '-tetramethyl--4,4 '-diaminodiphenylmethane, and composition thereof.

13, preparation method according to claim 2, when it is characterized in that thioether dianhydride and diamines polymerization reaction take place, be that common two-step approach promptly generates polyamic acid earlier in aprotic polar solvent, and then the method for heat or chemical imines generate polyimide; Or common single stage method promptly in phenol solvent such as cresols, phenol or P-Chlorophenol one the step high-temperature polycondensation directly generate polyimide; Or a step high-temperature polycondensation directly generates polyimide in the mixed solvent of aprotic polar solvent and benzene kind solvent; Or the one step high-temperature fusion polymerization of dianhydride and diamines directly obtains polyimide.

14, preparation method according to claim 2, it is characterized in that adopting replacement or unsubstituted single acid anhydride or monoamine be the polymerization degree of end-capping reagent control reaction of polyreaction and the molecular weight of final polymkeric substance.

15, preparation method according to claim 14, it is characterized in that end-capping reagent is to comprise phthalic anhydride, 3-chloro-benzoic anhydride, 3-methyl phthalic anhydride, 4-chloro-benzoic anhydride or the phthalic anhydride of 4-methyl phthalic anhydride or the derivative of phthalic anhydride, perhaps is to comprise the aniline of aniline, 3-monomethylaniline, 4-chloro aminobenzen or 4-monomethylaniline or the derivative of aniline.

16, preparation method according to claim 2, it is characterized in that Polythioetherimide, its by Ubbelohde viscometer concentration 30 ℃ the time be the logarithmic viscosity number measured in the meta-cresol of 0.5dL/g between about 0.25 to about 1.95dL/g, its pass through gel permeation chromatography with respect to the weight-average molecular weight of polystyrene standard between about 8000 to about 200000.

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