CN107057063A - A kind of polyimides and its synthetic method - Google Patents
A kind of polyimides and its synthetic method Download PDFInfo
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- CN107057063A CN107057063A CN201611268187.9A CN201611268187A CN107057063A CN 107057063 A CN107057063 A CN 107057063A CN 201611268187 A CN201611268187 A CN 201611268187A CN 107057063 A CN107057063 A CN 107057063A
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- KBCHYISUSVYHLF-DVOJEQBISA-O CC(C([C@@H](CCC1)C(C)[OH2+])C1I)O Chemical compound CC(C([C@@H](CCC1)C(C)[OH2+])C1I)O KBCHYISUSVYHLF-DVOJEQBISA-O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention discloses a kind of polyimides and its synthetic method, and the synthesis of its polyimide polymer is divided into the completion of two steps, the first step：Synthesis is to the oxadiazole monomer of (hydroxyphenoxy of 3 fluorine 4) benzene 1,3,4；Second step：The monomer of first step synthesis prepares polyimides with double chloro phthalimide diphenyl ether reactions.The present invention is to use first to synthesize to the oxadiazole monomer of (hydroxyphenoxy of 3 fluorine 4) benzene 1,3,4, then synthesis of polyimides, and synthetic method is effective stronger, and the cost of synthesis is low.Due to the influence to oxadiazole group electron attraction in the oxadiazole of (hydroxyphenoxy of 3 fluorine 4) benzene 1,3,4, make the electron density relative reduction of benzene negative oxygen ion, nucleophilicity is relative to be weakened；Ether is introduced in polyimides, increases intermolecular distance, makes the increase of molecule chain flexibility, reduces the crystallinity and rigidity of polyimides；Polyimides introduces fluorine-containing strong hydrophobic group, reduces the polarity of polyimides, improves its dissolubility and water absorption rate.
Description
Technical field
The present invention relates to a kind of polyimides and its conjunction method.
Background technology
Polyimides (PI) is as a class high-performance polymer, with excellent heat resistance, resistance to irradiation and electric property,
It is widely used in the technical fields such as Aeronautics and Astronautics and microelectronics.And continuing to develop in industry technologies such as aviation, microelectronics,
Heat resistance, mechanical property to material etc. have larger requirement.It is current require high polymer material can high temperature resistant, and can be again
Used for a long time in high temperature.In the research to fire resistant polyimide, the heat resistance for improving polyimides mainly must be from its point
Substructure Analysis, introduces heterocyclic group in polyimides, can significantly improve the heat resistance of polyimides.The introducing of heterocycle is not
Only it is the heat resistance for improving polyimides, the mechanical property of polyimides is also improved simultaneously and causes product in light and electricity etc.
Aspect of performance increases.Because the strand intensity of aromatic polyimide is larger, ether group is introduced in polyimides
The length of strand can be increased, increase its compliance.The disadvantage of polyimides is that its water imbibition is larger, makes polyamides
The hydraulic performance decline of imines, introduces among polyimide structures and its hydrophobicity is had greatly improved containing groups such as chlorine, fluorine.
Heterocycle structure, halogen atom are introduced among polyimide structures, and combine its inexpensive synthetic route, is explored
The novel heterocyclic new type polyimide of preparation structure, so as to adapt to the requirement of era development trend.
The content of the invention
Contain polyimide polymer and its synthetic method it is an object of the invention to provide one kind, the polyamides of this method synthesis is sub-
Amine has heat resistance, mechanical property better than traditional polyimides performance, and overcomes the water imbibition of traditional polyimides larger
Shortcoming.The polyimides of Han oxazole rings also increases in terms of light and electrical property, is conducive to its application on microelectronics.
The present invention polyimide structures formula be：
The polyimides synthetic method of the present invention is obtained by following steps：
A1, using the chloro- 2- fluorophenols of 4- as raw material, under acid anhydrides and catalyst action formed the chloro- 2- fluorophenoxies second of 4-
Acyl；
The chloro- 2- fluorophenoxies acetyl of a2,4- and P-hydroxybenzoic acid react, under the effect of catalyst Anhydrous potassium carbonate and pole
Under property solvent, reaction solution is poured into deionized water and stirs to white precipitate by system after being reacted through oil bath heating
It is existing, filter, washing is dried to obtain 4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzoic acid；
A3,4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzoic acid heating reflux reaction in the presence of thionyl chloride, is obtained
4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) chlorobenzoyl chloride；
A4,4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) chlorobenzoyl chloride is dissolved in THF, and hydration is slowly added dropwise under ice-water bath
Hydrazine, gradually there is white precipitate appearance, stirring, suction filtration, washing, it is dry must be to (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzyl two
Hydrazides；
A5, the hydrazides of (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzyl two is heated to reflux obtaining in thionyl chloride solution
To (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzene -1,3,4- oxadiazoles；A6, to (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzene -1,3,
In the basic conditions, the acetyloxy group in removal system obtains monomer to (the fluoro- 4- hydroxyphenoxies of 3-) to 4- oxadiazoles
Benzene -1,3,4- oxadiazoles；
A7, reaction unit is washed, drying process is passed through inert gas to reaction unit, by monomer to (3- is fluoro-
4- hydroxyphenoxies) benzene -1,3,4- oxadiazoles are dissolved in polar non-solute, add catalyst KI and water entrainer toluene；
A8, after reaction a period of time until band water is finished, water entrainer toluene is distilled out of, and adds double chlorine of substantially equimolar number
For phthalimide hexichol ether monomer, polymer solution is settled, washed by reaction, and extracting obtains polyimides after drying.
Acid anhydrides wherein described in step a1 is acetic anhydride
The concentrated sulfuric acid that catalyst wherein described in step a1 is 98%；
Polar solvent wherein described in step a2：N,N-dimethylformamide；DMAC N,N' dimethyl acetamide；N, N- diethyl
Formamide；N, N- diethyl acetamide；Dimethyl sulfoxide (DMSO)；Dimethyl sulfone；1-METHYLPYRROLIDONE；Trimethyl urea；Hexamethyl
Phosphamide；Pyridine；Picoline；The one kind such as CHP；
Wherein step a2 oil bath heating temperature is 160-180 DEG C, constant temperature time length 18 to 24 hours；
4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzoic acid is heated back in thionyl chloride solution described in wherein step a3
Stream 8 to 10 hours, mass percent >=99.9% of thionyl chloride solution；
THF solution mass percent >=99% wherein described in step a4, mass percent >=85% of hydrazine hydrate；
Thionyl chloride solution quality percentage >=99% wherein described in step a5, was heated to reflux the time for 5 to 7 hours；
10% sodium hydroxide solution is added described in wherein step a6 in propanol solution, deviates from acetoxyl group；
Inert gas wherein described in step a7：Nitrogen, argon gas；Catalyst KI and water entrainer toluene；
Polar non-solute wherein described in step a7 is：Dimethyl sulfoxide (DMSO), N monomethyls pyrrolidones or diphenyl sulphone (DPS).
The double chloro phthalimide diphenyl ether monomer chemistries structural formulas of raw material are:
Polymeric reaction temperature is 160 DEG C to 180 DEG C wherein described in step a8, and the reaction time is 10 to 12 hours；
Synthetic reaction equation is as follows：
Advantage of the present invention：
1st, it is of the invention to introducing ether (C-O-C), ether in (the fluoro- 4- hydroxyphenoxies of 3-) benzene -1,3,4- oxadiazoles
The polarity of group is weaker, and C-O-C keys bond distance increases, Chain Flexibility increase, so as to reduce polyimides prepared therefrom
Polarity, introduce fluoro-containing group in Tong Shi oxadiazoles, fluoro-containing group is as strong hydrophobic group, therefore to reducing the water suction of polyimides
Rate effect is obvious；
2nd, it is of the invention to polymerize gathering of obtaining with dianhydride monomer to (the fluoro- 4- hydroxyphenoxies of 3-) benzene -1,3,4- oxadiazoles
Acid imide contains aromatic structure and azepine ring structure, and the heat resistance and mechanical property to polyimides are greatly improved；
3rd, it is of the invention to oxadiazole group electron attraction in (the fluoro- 4- hydroxyphenoxies of 3-) benzene -1,3,4- oxadiazoles
Influence make the electron density relative reduction of benzene negative oxygen ion, nucleophilicity is relative to be weakened；
4th, the introducing of heterocycle is not merely the heat resistance for improving polyimides in polyimides of the invention, also carries simultaneously
The mechanical property of high polyimides and cause product increased in the aspect of performance such as light and electricity；
Embodiment
The polyimides synthetic method of the present invention is obtained by following steps：
A1, using the chloro- 2- fluorophenols of 4- as raw material, under acid anhydrides and catalyst action formed the chloro- 2- fluorophenoxies second of 4-
Acyl；
The chloro- 2- fluorophenoxies acetyl of a2,4- and P-hydroxybenzoic acid react, under the effect of catalyst Anhydrous potassium carbonate and pole
Under property solvent, reaction solution is poured into deionized water and stirs to white precipitate by system after being reacted through oil bath heating
It is existing, filter, washing is dried to obtain 4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzoic acid；
A3,4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzoic acid heating reflux reaction in the presence of thionyl chloride, is obtained
4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) chlorobenzoyl chloride；
A4,4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) chlorobenzoyl chloride is dissolved in THF, and hydration is slowly added dropwise under ice-water bath
Hydrazine, gradually there is white precipitate appearance, stirring, suction filtration, washing, it is dry must be to (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzyl two
Hydrazides；
A5, the hydrazides of (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzyl two is heated to reflux obtaining in thionyl chloride solution
To (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzene -1,3,4- oxadiazoles；A6, to (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzene -1,3,
In the basic conditions, the acetyloxy group in removal system obtains monomer to (the fluoro- 4- hydroxyphenoxies of 3-) to 4- oxadiazoles
Benzene -1,3,4- oxadiazoles；
A7, reaction unit is washed, drying process is passed through inert gas to reaction unit, by monomer to (3- is fluoro-
4- hydroxyphenoxies) benzene -1,3,4- oxadiazoles are dissolved in polar non-solute, add catalyst KI and water entrainer toluene；
A8, after reaction a period of time until band water is finished, water entrainer toluene is distilled out of, and adds double chlorine of substantially equimolar number
For phthalimide hexichol ether monomer, polymer solution is settled, washed by reaction, and extracting obtains polyimides after drying.
Claims (8)
1. a kind of polyimides, the constitutional repeating unit of its polymer is：
。
2. according to claim 1, a kind of synthetic method of polyimides, it is characterised in that methods described includes：
A1, using the chloro- 2- fluorophenols of 4- as raw material, under acid anhydrides and catalyst action formed the chloro- 2- fluorophenoxies acetyl of 4-；
A2, reacted by the chloro- 2- fluorophenoxies acetyl of 4- obtained by a1 and P-hydroxybenzoic acid, made in catalyst Anhydrous potassium carbonate
With under lower and polar solvent, reaction solution is poured into deionized water and stirred to white by system after being reacted through oil bath heating
Color precipitation occurs, and filters, and washing is dried to obtain 4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzoic acid；
A3, it is heated to reflux in the presence of thionyl chloride by 4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzoic acid obtained by a2
Reaction, obtains 4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) chlorobenzoyl chloride；
A4, it is dissolved in THF by 4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) chlorobenzoyl chloride obtained by a3, it is slow under ice-water bath
Be added dropwise hydrazine hydrate, gradually have white precipitate appearance, stir, suction filtration, washing, it is dry must be to (the fluoro- 4- acetoxyl groups phenoxy groups of 3-)
The hydrazides of benzyl two；
A5, by being heated obtained by a4 to the hydrazides of (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzyl two in thionyl chloride solution
Backflow is obtained to (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzene -1,3,4- oxadiazoles；
A6, by obtained by a5 to (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzene -1,3,4- oxadiazoles in the basic conditions, remove
Acetyloxy group in system, obtains monomer to (the fluoro- 4- hydroxyphenoxies of 3-) benzene -1,3,4- oxadiazoles；
A7, reaction unit is washed, drying process is passed through inert gas to reaction unit, by monomer to (the fluoro- 4- hydroxyls of 3-
Phenoxyl) benzene -1,3,4- oxadiazoles are dissolved in polar non-solute, add catalyst KI and water entrainer toluene；
A8, after reaction a period of time until band water is finished, water entrainer toluene is distilled out of, and adds double chloro phthaleins of substantially equimolar number
Acid imide hexichol ether monomer, reaction, polymer solution is settled, and is washed, and extracting obtains polyimides after drying.
3. synthetic method according to claim 2, the wherein acid anhydrides described in step a1 are acetic anhydride, catalyst is 98%
The concentrated sulfuric acid.
4. synthetic method according to claim 2, the wherein polar solvent described in step a2：N,N-dimethylformamide；
DMAC N,N' dimethyl acetamide；N, N- diethylformamide；N, N- diethyl acetamide；Dimethyl sulfoxide (DMSO)；Dimethyl sulfone；N- methyl
Pyrrolidones；Trimethyl urea；Hexamethyl phosphoramide；Pyridine；Picoline；The one kind such as CHP；Oil bath
Heating-up temperature is 160-180 DEG C, constant temperature time length 18 to 24 hours.
5. by 4- (the fluoro- 4- acetoxyl groups phenoxy groups of 3-) benzene described in synthetic method according to claim 2, wherein step a3
Formic acid is heated to reflux 8 to 10 hours in thionyl chloride solution, mass percent >=99.9% of thionyl chloride solution；Wherein walk
THF solution mass percent >=99%, mass percent >=85% of hydrazine hydrate described in rapid a4；Protochloride wherein described in step a5
Sulfolane solution mass percent >=99%, was heated to reflux the time for 5 to 7 hours.
6. 10% sodium hydroxide is added in propanol solution described in synthetic method according to claim 2, wherein step a6
Solution, deviates from acetoxyl group；Inert gas wherein described in step a7：Nitrogen, argon gas；Catalyst KI and water entrainer toluene；Its
Polymeric reaction temperature described in middle step a8 is 160 DEG C to 180 DEG C, and the reaction time is 10 to 12 hours.
7. according to claim 2, double chloro phthalimide diphenyl ether monomer chemistries structural formulas are:
8. synthetic method according to claim 2, described polar non-solute is：Dimethyl sulfoxide (DMSO), N monomethyl pyrroles
Pyrrolidone or diphenyl sulphone (DPS).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417916A (en) * | 2017-09-13 | 2017-12-01 | 长沙新材料产业研究院有限公司 | A kind of polyimide resin and preparation method thereof |
| CN110563606A (en) * | 2019-09-16 | 2019-12-13 | 湖南速博生物技术有限公司 | Synthesis method of (R) -2- [4- (4-cyano-2-fluorophenoxy) phenoxy ] propionic acid |
| CN115260491A (en) * | 2022-08-18 | 2022-11-01 | 江西同益高分子材料科技有限公司 | Alkali-degradation-resistant polyimide engineering plastic and preparation method thereof |
-
2016
- 2016-12-31 CN CN201611268187.9A patent/CN107057063A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417916A (en) * | 2017-09-13 | 2017-12-01 | 长沙新材料产业研究院有限公司 | A kind of polyimide resin and preparation method thereof |
| CN107417916B (en) * | 2017-09-13 | 2020-02-07 | 长沙新材料产业研究院有限公司 | Polyimide resin and preparation method thereof |
| CN110563606A (en) * | 2019-09-16 | 2019-12-13 | 湖南速博生物技术有限公司 | Synthesis method of (R) -2- [4- (4-cyano-2-fluorophenoxy) phenoxy ] propionic acid |
| CN115260491A (en) * | 2022-08-18 | 2022-11-01 | 江西同益高分子材料科技有限公司 | Alkali-degradation-resistant polyimide engineering plastic and preparation method thereof |
| CN115260491B (en) * | 2022-08-18 | 2023-08-08 | 江西同益高分子材料科技有限公司 | Alkali-resistant hydrolysis-resistant polyimide engineering plastic and preparation method thereof |
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