CN101544754A - Polyimide and synthetic method thereof - Google Patents
Polyimide and synthetic method thereof Download PDFInfo
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- CN101544754A CN101544754A CN200810060915A CN200810060915A CN101544754A CN 101544754 A CN101544754 A CN 101544754A CN 200810060915 A CN200810060915 A CN 200810060915A CN 200810060915 A CN200810060915 A CN 200810060915A CN 101544754 A CN101544754 A CN 101544754A
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Abstract
The invention discloses polyimide and a synthetic method thereof. The method is characterized in that the synthesis of a polyimide polymer is finished by two steps, namely a first step of preparation of 2,5-di (p-hydroxyl)-1,3,4-furodiazole monomer, and a second step of synthesis of the polyimide. Compared with the prior art, the method has the advantages that the synthetic method is simple and effective by firstly synthesizing the 2,5-di (p-hydroxyl)-1,3,4-furodiazole monomer and then synthesizing the novel polyimide polymer, the synthesis cost is comparatively low, and a catalyst KI is used. The furodiazole radical in the 2,5-di (p-hydroxyl)-1,3,4-furodiazole monomer is influenced by electron-withdrawing action, the electron density of benzene-oxygen negative ions is relatively reduced, and the nucleophilic property is relatively weakened, so the process of the reaction is quickened by adding the catalyst KI in the reaction; and simultaneously, the polyimide polymer contains furodiazole nitrogen heterocycle, so the polyimide polymer represents good optical performance besides good heat resisting performance.
Description
Technical field
The present invention relates to a kind of novel De Han oxadiazole nitrogen heterocyclic polyimide polymer, the invention still further relates to the synthetic method of this polymkeric substance.
Background technology
Polyimide (PI) has excellent thermotolerance, anti-irradiation and electric property as a class high-performance polymer, has been widely used in technical fields such as Aeronautics and Astronautics and microelectronics.In main polymer chain, introduce various heterocycle structures unit in recent years and become one of high performance polymer material research focus.Heterocyclic is introduced the mechanical property that not only can significantly improve polymkeric substance under the prerequisite of the processing characteristics that keeps polymkeric substance, adhesiveproperties etc.As for improving the thermotolerance of polyimide, contain sulphur, nitrogen, the equiatomic heterocycle of oxygen to the polyimide introducing by the synthetic method.With reference to Chinese invention patent: ZL200610010286.7, (Granted publication number: 100335810C), Yin Ru oxazole ring makes the thermotolerance of product and acid resistance significantly increase to disclose " a kind of Han polyimide containing oxazole cycle and synthetic method thereof ".Can introduce fluorine-containing heterocycle in this patent with reference to Chinese invention patent: ZL03127427.7 again, improve The comprehensive performance.
Introducing heterocycle simultaneously makes product increase at aspect of performances such as light and electricity.Heterocycle structure is introduced polyimide, and in conjunction with its synthetic route cheaply, the novel polyimide of heterocyclic of exploring the preparation novel structure is the trend of current scientific research development, this work has certain Research Significance.
Summary of the invention
Inventing first technical problem to be solved is to provide a kind of novel polyimide with luminescent properties at the above-mentioned state of the art.
The technical scheme that invention solves first technical problem is such, and a kind of polyimide is characterized in that the repeated structural unit of polymkeric substance is:
The present invention will solve above-mentioned second technical problem and provide the synthetic method that simple effectively, the synthetic cost of a kind of synthetic method is lower, prepare above-mentioned polyimide.
The technical scheme that the present invention solves above-mentioned second technical problem is such, and its synthetic circuit and concrete principle are such:
A, 2,5-two (to hydroxyl)-1,3, the monomeric preparation of 4-oxadiazole:
A1, be raw material, add catalyzer, in aceticanhydride solution, stir, reaction solution is poured into be stirred to white precipitate in the deionized water and occur, filter with the P-hydroxybenzoic acid, washing, dry must be to acetoxy-benzoic acid;
A2, will place sulfur oxychloride solution back flow reaction, obtain the acetoxyl group Benzoyl chloride to acetoxy-benzoic acid;
A3, will be dissolved in the tetrahydrofuran solution the acetoxyl group Benzoyl chloride, ice-water bath slowly drips hydrazine hydrate down, and the adularescent precipitation occurs gradually, stir, suction filtration, washing, dry must be to acetoxyl group phenmethyl two hydrazides;
A4, will be to the acetoxyl group phenmethyl two hydrazides ring closure reaction that in sulfur oxychloride solution, refluxes;
A5, reaction product washing obtain 2,5-two (to acetoxyl group)-1,3,4-oxadiazole;
A6, with 2,5-two (to acetoxyl group)-1,3, the 4-oxadiazole is sloughed acetoxyl group under alkaline condition, obtain monomer 2,5-two (to hydroxyl)-1,3,4-oxadiazole;
Synthesizing of b, polyimide:
Under the condition of b1, anhydrous and oxygen-free, feed nitrogen or rare gas element, with 2,5-two (to hydroxyl)-1,3,4-oxadiazole monomer is dissolved in the polar aprotic solvent, adds the KOH of about 2 times of mole numbers, the KI of catalytic amount and band aqua toluene;
B2, band water finish, and steam the toluene in the system, add the two chloro phthalimide phenyl ether monomers that wait mole number substantially, reaction, and with the polymers soln sedimentation, washing, extracting obtains polyimide after the drying.
As preferably, it is catalyzer that described step a1 adds 98～99% vitriol oils, is preferably 98.3% mass percent,
Being 5～10 times of P-hydroxybenzoic acid, mass percent in quality is stirring at room in greater than the solution of 99% aceticanhydride 15～20 hours;
Among the step a2, will place 5～10 times of quality, mass percent for more than or equal to 99% sulfur oxychloride solution back flow reaction 6～8 hours to acetoxy-benzoic acid;
Among the step a3, the tetrahydrofuran solution mass percent is more than or equal to 99%, and the hydrazine hydrate of dropping is about 0.5 times of acetoxyl group Benzoyl chloride mole number, and the mass percent of hydrazine hydrate is more than or equal to 85%, filter cake CHCl
3Washing;
Among the step a4, sulfur oxychloride solution quality per-cent is more than or equal to 99%, refluxes 6～8 hours;
Among the step a5, the product mass percent is the tetrahydrofuran solution washing more than or equal to 99%;
Among the step a6, in ethanolic soln, add 9～11%NaOH aqueous solution, preferred 10% mass percent is sloughed acetoxyl group, is neutralized to neutrality with the hydrochloric acid of mass percent 36～38%.
Among the described step b1, the aprotic solvent quality is 2,5-two (to hydroxyl)-1,3, and monomeric 10～12 times of 4-oxadiazole refluxes under 150 ℃ of conditions and was with water 15～20 hours;
Reacted 15～40 hours at 170～200 ℃ among the step b2.
Two chloro phthalimide phenyl ether monomer chemical structural formulas described in the step b1 are:
Polar aprotic solvent described in the step b1 is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or sulfobenzide.
At last, the polyimide limiting viscosity number of acquisition is 0.17～0.50dL/g.
Compared with prior art, the invention has the advantages that: adopt first Synthetic 2,5-two (to hydroxyl)-1,3,4-oxadiazole monomer, the polyimide polymer that resynthesis is novel, synthetic method is simply effective, and synthetic cost is lower; Use catalyzer KI.Since 2,5-two (to hydroxyl)-1,3, the influence of oxadiazole group electrophilic effect reduces the electron density of benzene negative oxygen ion relatively in the 4-oxadiazole monomer, and nucleophilicity weakens relatively, so in the reaction, add the process of fast response by adding catalyzer KI.
This polyimide polymer Nei Han You oxadiazole nitrogen heterocyclic makes it except having excellent heat resisting simultaneously, also shows the good optical performance.Polymkeric substance of the present invention is adapted at using on electroluminescent material, nonlinear optical material or the liquid-crystal display orientation mold materials.
Description of drawings
Fig. 1 is the fluorescence spectrum figure of embodiment 1 resulting polymers.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
The present invention is independent synthon 2 earlier, 5-two (to hydroxyl)-1,3, and the 4-oxadiazole carries out high-temperature polycondensation with this monomer and two chloro phthalimide phenyl ether then under the condition of anhydrous and oxygen-free, obtain polyimide.
Technical scheme of the present invention is as follows:
Monomer of the present invention is two chloro phthalimide phenyl ether, and homemade 2,5-two (to hydroxyl)-1,3, and the 4-oxadiazole, its chemical structural formula is as follows:
Polar aprotic solvent of the present invention is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or sulfobenzide.
Preparation of the present invention mainly divided for two steps carried out, and its synthetic route is as follows:
Expansion is described and is particularly:
(1) 2,5-two (to hydroxyl)-1,3, the monomeric preparation of 4-oxadiazole:
With the P-hydroxybenzoic acid is raw material, 98.3% the vitriol oil is a catalyzer, in its quality 5-10 aceticanhydride solution (content is greater than 99%) doubly behind the stirring at room 15-20h, pouring reaction solution into a large amount of deionized water for stirring to white precipitate occurs, filter, filter cake is with distillation washing, dry must be to acetoxy-benzoic acid.To place its quality 5-10 sulfur oxychloride solution (content is more than or equal to 99%) back flow reaction 6-8h doubly to acetoxy-benzoic acid, underpressure distillation goes out remaining sulfur oxychloride, obtains the acetoxyl group Benzoyl chloride.To be dissolved in content more than or equal in 99% the tetrahydrofuran solution to the acetoxyl group Benzoyl chloride, and under ice-water bath, slowly dripping the hydrazine hydrate of the content 85% of 1/2 times of its mole number to this reaction solution, stirring at room 10-15h appears in the adularescent precipitation gradually, suction filtration, filter cake CHCl
3Wash, dry must be to acetoxyl group phenmethyl two hydrazides.To finish ring closure reaction to acetoxyl group phenmethyl two hydrazides backflow 6-10h in its quality 5-10 sulfur oxychloride solution (content is more than or equal to 99%) doubly, underpressure distillation goes out excessive sulfur oxychloride again, the cancellation of reaction water.Reaction product wash more than or equal to 99% tetrahydrofuran solution with content, with the washings that obtains be spin-dried for remove tetrahydrofuran (THF) obtain white purified 2,5-two (to acetoxyl group)-1,3,4-oxadiazole.At last, with 2,5-two (to acetoxyl group)-1,3, the 4-oxadiazole is dissolved in the ethanolic soln, adds the 10%NaOH aqueous solution, sloughs acetoxyl group under alkaline condition, and (36-38%) is neutralized to neutrality with reaction solution with hydrochloric acid, obtain purified 2,5-two (to hydroxyl)-1,3,4-oxadiazole monomer.
(2) polyimide is synthetic
System is under the condition of anhydrous and oxygen-free, feed nitrogen, with 2,5-two (to hydroxyl)-1,3,4-oxadiazole monomer are dissolved in its quality 10-12 aprotic solvent doubly, the KOH that adds 2 times of mole numbers, the KI of catalytic amount, and band aqua toluene (content is greater than 99%), band water 15-20h refluxes under 150 ℃ of conditions.Band water finishes, steam the toluene in the system, two chloro phthalimide phenyl ether monomers of mole numbers such as adding, 170-200 ℃ of reaction 15-40h, slowly pour polymers soln in methanol solution sedimentation, use hot water, methyl alcohol, hot wash successively, use the methanol solution extracting at last, 120 ℃ of dry 12h of vacuum obtain the polyimide of limiting viscosity number 0.17-0.50dL/g.
Embodiment 1:
In 50ml single port bottle, add 50.248g (380mmol) P-hydroxybenzoic acid, the 250ml diacetyl oxide, 5 vitriol oils are as catalyzer, after stirring 15h under the room temperature, pour reaction solution into 2000ml deionized water for stirring 30min, white precipitate is separated out in a large number, suction filtration, washing obtains to acetoxy-benzoic acid 50.47g (productive rate 80% calculates with P-hydroxybenzoic acid).In 100ml single port bottle, add 10g (55.6mmol) to acetoxy-benzoic acid, the 40ml sulfur oxychloride, behind the back flow reaction 7h, underpressure distillation goes out excessive sulfur oxychloride solution, obtain to acetoxyl group Benzoyl chloride 10.7g (productive rate 97% is to calculate acetoxy-benzoic acid).In 250ml single port bottle, add the 200ml tetrahydrofuran solution, 10.7g (54mmol) is all dissolved the acetoxyl group Benzoyl chloride, the ice-water bath cooling down, slowly drip the hydrazine hydrate of 1.5ml content 85% in to acetoxyl group Benzoyl chloride solution, the adularescent precipitation occurs gradually, behind the stirring at room 12h, suction filtration, filter cake CHCl
3Wash, drying obtains to acetoxyl group phenmethyl two hydrazides 6.2g (productive rate 65% is to calculate the acetoxyl group Benzoyl chloride).With 6.2g to acetoxyl group phenmethyl two hydrazides, the 25ml sulfur oxychloride, place 50ml single port bottle back flow reaction 8h after, underpressure distillation goes out excessive sulfur oxychloride, water will react cancellation.The crude product that obtains is washed with tetrahydrofuran solution, remove by filter insolubles, collect washings, washings is spin-dried for removes tetrahydrofuran (THF), obtain white cotton-shaped monomer 2,5-two (to acetoxyl group)-1,3,4-oxadiazole 2.7g (productive rate 46% is to calculate acetoxyl group phenmethyl two hydrazides).With 2.7g2,5-two (to acetoxyl group)-1,3,4-oxadiazole are dissolved in the 50ml ethanolic soln, add the 10% NaOH aqueous solution, room temperature reaction 2h is neutralized to neutrality with dilute hydrochloric acid with reaction solution, white precipitate is separated out, suction filtration, washing, drying, purified 2,5-two (to hydroxyl)-1,3, (productive rate 90% is with 2 for 4-oxadiazole monomer 1.8g, 5-two (to acetoxyl group)-1,3, the 4-oxadiazole calculates).
With 2 of 7mmol, 5-two (to hydroxyl)-1,3, the 4-oxadiazole, the 18ml dimethyl sulfoxide (DMSO) joins in the 50ml there-necked flask, and letting nitrogen in and deoxidizing treats that its dissolving back adds 14mmol KOH solid, the KI of catalytic amount and 20ml toluene, 150 ℃ of band water 20h that reflux.Band water finishes, and steams toluene, adds 7mmol 4,4 '-two (3-chloro phthalimide) phenyl ether, at 170 ℃ of reaction 15h.Pour polymers soln in methyl alcohol sedimentation, use hot water, methyl alcohol, acetone, hot wash successively, again through the methanol solution extracting, 120 ℃ of dry 12h of vacuum, gained polyimide limiting viscosity is 0.50dL/g.
With reference to shown in Figure 1, the polymkeric substance of gained presents bluish voilet fluorescence under the short wavelength, and by fluorescence spectrometry, fluorescence emission peak is respectively 413nm, 520nm.Make it except having excellent heat resisting, also show the good optical performance.
Embodiment 2:
2,5-two (to hydroxyl)-1,3, the monomeric synthetic method of 4-oxadiazole is as mentioned above.
With 2 of 7mmol, 5-two (to hydroxyl)-1,3,4-oxadiazole, 18ml N-Methyl pyrrolidone join in the 50ml there-necked flask, and letting nitrogen in and deoxidizing treats that its dissolving back adds 14mmol KOH solid, the KI of catalytic amount and 20ml toluene, 150 ℃ of band water 15h that reflux.Band water finishes, and steams toluene, adds 7mmol4, and 4 '-two (3-chloro phthalimide) phenyl ether is at 180 ℃ of reaction 30h.Pour polymers soln in methyl alcohol sedimentation, use hot water, methyl alcohol, acetone, hot wash successively, again through the methanol solution extracting, 120 ℃ of dry 12h of vacuum, gained polyimide limiting viscosity is 0.44dL/g.
Other parameter is seen before and is stated the description of embodiment part.
Embodiment 3:
2,5-two (to hydroxyl)-1,3, the monomeric synthetic method of 4-oxadiazole is as mentioned above.
With 2 of 7mmol, 5-two (to hydroxyl)-1,3,4-oxadiazole, 7mmol K
2CO
3, the 20g sulfobenzide, the KI of catalytic amount and 20ml toluene join in the 50ml there-necked flask, letting nitrogen in and deoxidizing, 150 ℃ of band water 18h that reflux.Band water finishes, and steams toluene, adds 7mmol 4,4 '-two (3-chloro phthalimide) phenyl ether, at 200 ℃ of reaction 40h.Pour polymers soln in methyl alcohol sedimentation, use hot water, methyl alcohol, acetone, hot wash successively, again through the methanol solution extracting, 120 ℃ of dry 12h of vacuum, gained polyimide limiting viscosity is 0.17dL/g.
Other parameter is seen before and is stated the description of embodiment part.
Polymkeric substance of the present invention is adapted at using on electroluminescent material, nonlinear optical material or the liquid-crystal display orientation mold materials.
There is not the per-cent of specified otherwise all to refer to mass percent in the present specification, consider that the reaction of chemical reaction equivalent is the most rational, reach the perfect purpose of reaction, certainly, allow that proportioning has certain leeway between them, being controlled at 5～the 10% excessive or amounts of owing, also is to obtain similar effect substantially.
Claims (7)
1, a kind of polyimide is characterized in that the repeated structural unit of polymkeric substance is:
2, the synthetic method of the described polyimide of a kind of claim 1 is characterized in that in turn including the following steps:
A, 2,5-two (to hydroxyl)-1,3, the monomeric preparation of 4-oxadiazole:
A1, be raw material, add catalyzer, in aceticanhydride solution, stir, reaction solution is poured into be stirred to white precipitate in the deionized water and occur, filter with the P-hydroxybenzoic acid, washing, dry must be to acetoxy-benzoic acid;
A2, will place sulfur oxychloride solution back flow reaction, obtain the acetoxyl group Benzoyl chloride to acetoxy-benzoic acid;
A3, will be dissolved in the tetrahydrofuran solution the acetoxyl group Benzoyl chloride, ice-water bath slowly drips hydrazine hydrate down, and the adularescent precipitation occurs gradually, stir, suction filtration, washing, dry must be to acetoxyl group phenmethyl two hydrazides;
A4, will be to the acetoxyl group phenmethyl two hydrazides ring closure reaction that in sulfur oxychloride solution, refluxes;
A5, reaction product washing obtain 2,5-two (to acetoxyl group)-1,3,4-oxadiazole;
A6, with 2,5-two (to acetoxyl group)-1,3, the 4-oxadiazole is sloughed acetoxyl group under alkaline condition, obtain monomer 2,5-two (to hydroxyl)-1,3,4-oxadiazole;
Synthesizing of b, polyimide:
Under the condition of b1, anhydrous and oxygen-free, feed nitrogen or rare gas element, with 2,5-two (to hydroxyl)-1,3,4-oxadiazole monomer is dissolved in the polar aprotic solvent, adds the KOH of about 2 times of mole numbers, the KI of catalytic amount and band aqua toluene;
B2, band water finish, and steam the toluene in the system, add the two chloro phthalimide phenyl ether monomers that wait mole number substantially, reaction, and with the polymers soln sedimentation, washing, extracting obtains polyimide after the drying.
3, synthetic method according to claim 2 is characterized in that
It is catalyzer that step a1 adds 98～99% vitriol oils, and being 5～10 times of P-hydroxybenzoic acid, mass percent in quality is stirring at room in greater than 99% aceticanhydride solution 15～20 hours;
Among the step a2, will place 5～10 times of quality, mass percent for more than or equal to 99% sulfur oxychloride solution back flow reaction 6～8 hours to acetoxy-benzoic acid;
Among the step a3, the tetrahydrofuran solution mass percent is more than or equal to 99%, and the hydrazine hydrate of dropping is about 0.5 times of acetoxyl group Benzoyl chloride mole number, and the mass percent of hydrazine hydrate is more than or equal to 85%, and filter cake CHCl
3Washing;
Among the step a4, sulfur oxychloride solution quality per-cent is more than or equal to 99%, refluxes 6～8 hours;
Among the step a5, the product mass percent is the tetrahydrofuran solution washing more than or equal to 99%;
Among the step a6, in ethanolic soln, add 9～11%NaOH aqueous solution, slough acetoxyl group, be neutralized to neutrality with 36～38% hydrochloric acid.
4, synthetic method according to claim 2 is characterized in that
Among the step b1, the aprotic solvent quality is 2,5-two (to hydroxyl)-1,3, and monomeric 10～12 times of 4-oxadiazole refluxes under 150 ℃ of conditions and was with water 15～20 hours;
Reacted 15-40 hour at 170～200 ℃ among the step b2.
5, synthetic method according to claim 2 is characterized in that the two chloro phthalimide phenyl ether monomer chemical structural formulas described in the step b1 are:
6, synthetic method according to claim 2 is characterized in that the polar aprotic solvent described in the step b1 is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or sulfobenzide.
7, synthetic method according to claim 2 is characterized in that the polyimide limiting viscosity number that makes among the step b2 is 0.17～0.50dL/g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554497A (en) * | 2013-10-30 | 2014-02-05 | 宏威高新材料有限公司 | Method for preparing flame-retardant thermoplastic polyimide resin |
| CN107987277A (en) * | 2017-11-27 | 2018-05-04 | 长沙新材料产业研究院有限公司 | A kind of X-ray luminescence composite polyimide material and preparation method thereof |
| 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 |
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| JP2002327060A (en) * | 2001-05-07 | 2002-11-15 | Central Glass Co Ltd | Polybenzoxazol and its production method |
| CN100341942C (en) * | 2005-12-29 | 2007-10-10 | 上海交通大学 | Method for preparing poly(p-phenylene benzobisoxazole)/polyimide composite material |
| CN100355810C (en) * | 2006-07-14 | 2007-12-19 | 哈尔滨工业大学 | Polyimide containing oxazole cycle and its synthesis |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554497A (en) * | 2013-10-30 | 2014-02-05 | 宏威高新材料有限公司 | Method for preparing flame-retardant thermoplastic polyimide resin |
| CN103554497B (en) * | 2013-10-30 | 2016-05-04 | 宏威高新材料有限公司 | A kind of preparation method of flame retardant type thermoplastic polyimide resin |
| CN107987277A (en) * | 2017-11-27 | 2018-05-04 | 长沙新材料产业研究院有限公司 | A kind of X-ray luminescence composite polyimide material and preparation method thereof |
| 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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Application publication date: 20090930 Assignee: Qingdao Zhong Ke Hao Tai New Material Science & Technology Co., Ltd. Assignor: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien Contract record no.: 2012370000200 Denomination of invention: Polyimide and synthetic method thereof Granted publication date: 20110413 License type: Exclusive License Record date: 20120820 |
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