CN101367937A - Preparation method for synthesizing soluble polyimide in polyphosphoric acids - Google Patents
Preparation method for synthesizing soluble polyimide in polyphosphoric acids Download PDFInfo
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- CN101367937A CN101367937A CNA2008102011950A CN200810201195A CN101367937A CN 101367937 A CN101367937 A CN 101367937A CN A2008102011950 A CNA2008102011950 A CN A2008102011950A CN 200810201195 A CN200810201195 A CN 200810201195A CN 101367937 A CN101367937 A CN 101367937A
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- polyphosphoric acid
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Abstract
The invention relates to a method for preparing soluble polyimide synthesized in polyphosphoric acid, including the following steps: (1) P2O5 powder is mixed with polyphosphoric acid (PPA) under nitrogen protection, stirred sufficiently under 100-150 DEG C to achieve polyphosphoric acid (PPA) solution with different P2O5 contents, and cooled to 40-60 DEG C for standby use; (2) dianhydride monomer and diamine monomer (mole ratio: 1:0.8-1:1.4) are added into the prepared polyphosphoric acid; the mass fraction of the reaction monomer is 5-40 percent of polyphosphoric acid solution, a polycondensation is conducted under inert gas protection, thermal imidization is conducted sufficiently, and then the material is washed by deionized water to achieve polyimide resin powder. The polyimide prepared by the method can effectively solve the problem of the poor solubility of the traditional polyimide materials, and the preparation process is simple, the cost is low and the environmental pollution is small.
Description
Technical field
The invention belongs to the preparation field of aromatic polyimide, particularly relate to a kind of in polyphosphoric acid the preparation method of synthesizing soluble polyimide.
Background technology
Since polyimide in 1908 is synthetic first, because polyimide has good electrical property and mechanical property, higher thermostability, thermal oxidation and chemical stability, thermal expansivity is little, good solvent resistance, dimensional stability and processing fluidity, be easy to many good performances such as forming shape complexity and high precision product, be used widely in high-tech sectors such as space flight and aviation, electrical equipment, machinery, chemical industry, microelectronics.
Formed system, ladder and the half ladder chain structure of gripping altogether of fragrant heterocycle structure in the polyimide molecule, it is higher to make its molecular chain have an energy barrier that very strong rigidity, molecule segment rotate freely, and makes polyimide have very high second-order transition temperature, very high thermal stability and stable unreactiveness; But these characteristics make also that polyimide is difficult to fusion, more indissoluble is separated, thereby have influenced its processing characteristics, thereby have limited its application.Therefore, when keeping polyimide inherent resistance toheat and other good characteristic, seek the good solvent that directly can dissolve polyimide, become one of focus of high-performance polyimide material development.
Two-step approach and the employed solvent of single stage method polycondensating process synthesis of polyimides are generally aprotic polar solvent and phenol solvent at present: aprotic polar solvent comprises N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP) etc., these aprotic polar solvents generally all have higher boiling point, even more noteworthy, these solvents can both form molecular complex with polyamic acid, even it can not removed (once have to be reported in and still have the residual solvent of finding trace under 300 ℃) under the very high temperature, this situation brings difficulty for research and development and application; And phenol solvent (as meta-cresol, para-chlorophenol etc.) toxicity is very big, be unfavorable for environmental protection, cause the industrialization difficulty, for example, United States Patent (USP) 5378420 uses meta-cresol to synthesize polyimide as solvent by the single stage method polycondensation, and spins polyimide fiber, but phenol solvent toxicity is bigger, environment is caused severe contamination, be unfavorable for industrialization.
Polyphosphoric acid has good solubility property, and some have the indissoluble high-performance polymer of rigid chain segment once to be used as synthetic PBI, PBZT, PBO etc.United States Patent (USP) 5296185 discloses the dissolving of polyparaphenylene's benzo-dioxazole in polyphosphoric acid and the method for spinning technique, and wherein PBO is at P
2O
5Content is to have formed the solution with mesomorphic phase in the polyphosphoric acid of 84.3% (massfraction).Chinese patent 200810032640.5 discloses a kind of preparation method of fluorine-containing hetero-aromatic ring liquid crystal polymer, this method is with 4,6-diamino resorcin hydrochlorate, terephthalic acid carry out copolyreaction with two (phenylformic acid) HFC-236fa in polyphosphoric acid in inert atmosphere, generated a kind of fluorine-containing liquid crystal PBO.Have again, Chinese patent 200510028891.2 discloses a kind of preparation method of cross-linked polyimide membrane, after wherein sulfonated polyimide film being handled with polyphosphoric acid, can obtain cross-linked polyimide membrane, improve the water tolerance of this film greatly and can keep mechanical property preferably.In addition, Chinese patent 200710071751.2 discloses a kind of polybenzoxazole-imide and fiber preparation method thereof, at first be preparation benzoxazole diamines in polyphosphoric acid, need not separate, directly aggregate into polybenzoxazole-imide as reaction monomers and aromatics dibasic acid anhydride.This provides certain theoretical basis for the method invention of synthesizing soluble polyimide in polyphosphoric acid.
Summary of the invention
Technical problem to be solved by this invention provide a kind of in polyphosphoric acid the preparation method of synthesizing soluble polyimide, polyimide of the present invention has higher molecular weight and good heat endurance energy, and solved the problem of the solubility of traditional polyimide material effectively, enlarged the range of application of polyimide, the preparation technology of this invention is simple, cost is low, and environmental pollution is little.
Of the present invention a kind of in polyphosphoric acid the preparation method of synthesizing soluble polyimide, comprising:
(1) preparation of polyphosphoric acid: with P
2O
5Powder mixes with polyphosphoric acid PPA under nitrogen protection, is 100-150 ℃ in temperature and fully stirs down, can obtain P
2O
5Massfraction content is 80%-90% polyphosphoric acid PPA solution, is cooled to 40-60 ℃, with standby.
(2) polyimide solution is synthetic: be in the dianhydride monomer and the above polyphosphoric acid for preparing of diamine monomer adding of 1:0.8-1:1.4 with mol ratio; the massfraction of reaction monomers is the poly phosphoric acid solution of 5-40%; protection of inert gas; carry out polycondensation, reaction system is warming up to 180-200 ℃ of reaction 3-5 hour, reacts 1-2 hour down at 220-250 ℃ again; carry out sufficient hot-imide; obtain polyimide solution,, obtain the polyimide resin powder through deionized water wash.
Dianhydride monomer in the described step (2) is pyromellitic acid anhydride, equal diphenyl disulfide acid anhydride, bibenzene tetracarboxylic dianhydride, triphen bis ether tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride or 4,4 '-oxidation, two O-phthalic acid dianhydrides;
Diamine monomer in the described step (2) is 4,4 '-diaminodiphenyl oxide, diamino-diphenyl ethane, 3,3 '-diaminodiphenyl sulfide or mphenylenediamine or 4,4 '-diaminodiphenyl sulfide.
Polyimide of the present invention has higher molecular weight and good heat endurance energy, and has solved the solubility problem of polyimide material effectively, for polyimide synthetic provides a kind of new reaction medium, has enlarged the range of application of polyimide; Compare with the method for single stage method synthesis of polyimides in phenol solvent, this preparation technology is simple, and cost is low, and environmental pollution is little, and it is bigger to have solved phenol solvent toxicity, and environment is caused great pollution, is unfavorable for problems such as industrialization; Expanded the solvent system of preparation polyimide material effectively, and for seeking better solvent has established new theoretical basis from now on; In addition, will guide the synthesis technique direction into, break the traditional research mode that is confined to polyimide structures the research of polyimide synthetic.
Beneficial effect
(1) polyimide of the present invention has solved the problem of the solubility of traditional polyimide material effectively, and has enlarged its range of application;
(2) this preparation technology is simple, and cost is low, and environmental pollution is little, and it is bigger to have solved phenol solvent toxicity, is unfavorable for problems such as industrialization.
Description of drawings
Fig. 1 is the infrared spectrogram of institute's synthesis of polyimides in polyphosphoric acid:
Curve (a) BAPE-BTDA type polyimide;
Curve (b) DDS-BTDA type polyimide;
Curve (c) ODA-BTDA type polyimide.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) in the 100ml flask with three necks,round bottom, adds P
2O
5Content is 80% polyphosphoric acid 40ml, and logical nitrogen deoxidation is protected, and adds the diamino-diphenyl ethane BAPE of 2.92g (0.012mol), is warming up to 100 ℃, and quick mechanical stirring dissolving formation concentration extremely fully is the solution of 0.3mol/L, is cooled to room temperature; Add 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride BTDA3.86g (0.012mol) is 180 ℃ of reaction 4hours down in temperature, is warming up to 220 ℃ then and continues reaction 4hours, carries out sufficient hot-imide, obtains brown xanchromatic polyimide solution.
(2) above-mentioned prepared polyimide slurries were soaked in 60 ℃ deionized water 48 hours, then carry out the several washing with 60 ℃ deionized water again, with abundant removal reaction medium polyphosphoric acid PPA.Pass through vacuum filtration again, product is dried in 80 ℃ of vacuum drying ovens, obtain brown pressed powder 6.23g, productive rate is 91.9%.25 ℃ of limiting viscosities that record is 0.285dLg
-1(vitriol oil is a solvent).
Fig. 1 curve (a) is for being the infrared spectrogram of reaction medium institute synthetic polyimide with the polyphosphoric acid among the embodiment 1,1720cm
-1, 1778cm
-1And 725cm
-1The place is the characteristic peak of imide group.
Embodiment 2
(1) in the flask with three necks,round bottom of 100ml, adds polyphosphoric acid 40ml, with the P of 21g
2O
5Under nitrogen protection, mix, be 120 ℃ in temperature and fully stir 2h down, can obtain clarifying its P with above polyphosphoric acid PPA
2O
5Content is 84% polyphosphoric acid PPA solution, is cooled to 40-60 ℃, with standby.
(2) in a new 100ml flask with three necks,round bottom, add above 84% the polyphosphoric acid 40ml for preparing, logical nitrogen deoxidation protection, the diamino-diphenyl ethane BAPE that adds 2.92g (0.012mol), be warming up to 100 ℃, mechanical stirring is the solution of 0.3mol/L to dissolving formation concentration fully fast, is cooled to room temperature; Add 3,3 ', 4 again, 4 '-benzophenone tetracarboxylic acid dianhydride BTDA 3.86g (0.012mol) is 180 ℃ of reaction 4hours down in temperature, is warming up to 220 ℃ then and continues reaction 4hours, carry out sufficient hot-imide, obtain brown xanchromatic polyimide slurries.
(3) with step (2) among the embodiment 1, obtain tan polyimide pressed powder 6.23g, productive rate is 91.9%.Adopting Ubbelohde viscometer to record its limiting viscosity at 25 ℃ is 0.447dL.g
-1(vitriol oil is a solvent).
Embodiment 3
The difference of present embodiment and embodiment 2 is: in the step (1), add the P of 36g
2O
5, can obtain P
2O
5Content is 86% polyphosphoric acid PPA solution, and other implementation steps are identical with embodiment 2.
Present embodiment obtains tan polyimide pressed powder 5.85g, and productive rate is 86.3%.Adopting Ubbelohde viscometer to record its limiting viscosity at 25 ℃ is 0.568dLg
-1(vitriol oil is a solvent).
Embodiment 4
The difference of present embodiment and embodiment 2 is: in the step (1), add the P of 71g
2O
5, can obtain P
2O
5Content is 90% polyphosphoric acid PPA solution, and other implementation steps are identical with embodiment 2.
Present embodiment obtains tan polyimide pressed powder 3.49g, and productive rate is 54.9%.Adopting Ubbelohde viscometer to record its limiting viscosity at 25 ℃ is 0.216dLg
-1(vitriol oil is a solvent).
Embodiment 5
The difference of present embodiment and embodiment 2 is: reaction monomers diamino-diphenyl ethane and 3 in the step (2), 3 ', 4, the add-on of 4 '-benzophenone tetracarboxylic acid dianhydride is respectively 1.46g and 1.93g, and forming concentration with the reaction solvent polyphosphoric acid is the solution of 0.15mol/L.Other implementation steps are identical with embodiment 2.
Present embodiment obtains tan polyimide pressed powder 2.96g, and productive rate is 87.5%.Adopting Ubbelohde viscometer to record its limiting viscosity at 25 ℃ is 0.215dLg
-1(vitriol oil is a solvent).
Embodiment 6
The difference of present embodiment and embodiment 2 is: reaction monomers diamino-diphenyl ethane and 3 in the step (2), 3 ', 4, the add-on of 4 '-benzophenone tetracarboxylic acid dianhydride is respectively 4.38g and 5.8g, and forming concentration with the reaction solvent polyphosphoric acid is the solution of 0.45mol/L.Other implementation steps are identical with embodiment 2.
Present embodiment obtains tan polyimide pressed powder 9.1g, and productive rate is 89.4%.Adopting Ubbelohde viscometer to record its limiting viscosity at 25 ℃ is 0.463dLg
-1(vitriol oil is a solvent).
Embodiment 7
The difference of present embodiment and embodiment 2 is: the diamine monomer in the step (2) is 4,4 '-diaminodiphenyl oxide (ODA), and other implementation steps are identical with embodiment 2.
Present embodiment obtains tan polyimide pressed powder 5.68g, and productive rate is 83.8%.Adopting Ubbelohde viscometer to record its limiting viscosity at 25 ℃ is 0.593dLg
-1(vitriol oil is a solvent).
Embodiment 8
The difference of present embodiment and embodiment 2 is: the diamine monomer in the step (2) is 4,4 '-diaminodiphenylsulfone(DDS) (DDS), and other implementation steps are identical with embodiment 2.
Present embodiment obtains tan polyimide pressed powder 6.1g, and productive rate is 90.2%.Adopting Ubbelohde viscometer to record its limiting viscosity at 25 ℃ is 0.54dLg
-1(vitriol oil is a solvent).
Claims (3)
1. the preparation method of a synthesizing soluble polyimide in polyphosphoric acid comprises:
(1) preparation of polyphosphoric acid: with P
2O
5Powder mixes with polyphosphoric acid PPA under nitrogen protection, is 100-150 ℃ in temperature and fully stirs down, obtains P
2O
5Massfraction content is 80%-90% polyphosphoric acid PPA solution, is cooled to 40-60 ℃, with standby.
(2) polyimide solution is synthetic: be in the dianhydride monomer and the above polyphosphoric acid for preparing of diamine monomer adding of 1:0.8-1:1.4 with mol ratio; the massfraction of reaction monomers is the poly phosphoric acid solution of 5-40%; protection of inert gas; carry out polycondensation, reaction system is warming up to 180-200 ℃ of reaction 3-5 hour, reacts 1-2 hour down at 220-250 ℃ again; carry out sufficient hot-imide; obtain polyimide solution,, obtain the polyimide resin powder through deionized water wash.
2. according to claim 1 a kind of in polyphosphoric acid the preparation method of synthesizing soluble polyimide, it is characterized in that: the dianhydride monomer in the described step (2) is pyromellitic acid anhydride, equal diphenyl disulfide acid anhydride, bibenzene tetracarboxylic dianhydride, triphen bis ether tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride or 4,4 '-oxidation, two O-phthalic acid dianhydrides.
3. according to claim 1 a kind of in polyphosphoric acid the preparation method of synthesizing soluble polyimide, it is characterized in that: the diamine monomer in the described step (2) is 4,4 '-diaminodiphenyl oxide, diamino-diphenyl ethane, 3,3 '-diaminodiphenyl sulfide or mphenylenediamine or 4,4 '-diaminodiphenyl sulfide.
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| CN2008102011950A CN101367937B (en) | 2008-10-15 | 2008-10-15 | Preparation method for synthesizing soluble polyimide in polyphosphoric acids |
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| CN101367937B CN101367937B (en) | 2010-11-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108113A (en) * | 2011-01-20 | 2011-06-29 | 中科院广州化学有限公司 | Polyimide with phosphoric acid side chain-containing long chain and preparation method and application thereof |
| CN102532498A (en) * | 2012-02-10 | 2012-07-04 | 四川大学 | Thioether-containing self-flame-retardant polyester and preparation method thereof |
| CN102586931A (en) * | 2012-01-09 | 2012-07-18 | 东华大学 | Method for preparing polyimide fibers by using polyphosphoric acid as solvent |
| CN102604090A (en) * | 2012-01-09 | 2012-07-25 | 东华大学 | Preparation method of liquid crystalline polyimide solution |
| CN111710840A (en) * | 2020-06-04 | 2020-09-25 | 东华大学 | Preparation method of polyimide composite electrode material containing ketone carbonyl bond chain structure |
| CN113896890A (en) * | 2021-09-13 | 2022-01-07 | 苏州尊尔光电科技有限公司 | Polyimide slurry and polyimide film |
-
2008
- 2008-10-15 CN CN2008102011950A patent/CN101367937B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108113A (en) * | 2011-01-20 | 2011-06-29 | 中科院广州化学有限公司 | Polyimide with phosphoric acid side chain-containing long chain and preparation method and application thereof |
| CN102108113B (en) * | 2011-01-20 | 2012-08-22 | 中科院广州化学有限公司 | Polyimide with phosphoric acid side chain-containing long chain and preparation method and application thereof |
| CN102586931A (en) * | 2012-01-09 | 2012-07-18 | 东华大学 | Method for preparing polyimide fibers by using polyphosphoric acid as solvent |
| CN102604090A (en) * | 2012-01-09 | 2012-07-25 | 东华大学 | Preparation method of liquid crystalline polyimide solution |
| CN102604090B (en) * | 2012-01-09 | 2013-10-23 | 东华大学 | Preparation method of liquid crystalline polyimide solution |
| CN102586931B (en) * | 2012-01-09 | 2014-02-26 | 东华大学 | Method for preparing polyimide fibers by using polyphosphoric acid as solvent |
| CN102532498A (en) * | 2012-02-10 | 2012-07-04 | 四川大学 | Thioether-containing self-flame-retardant polyester and preparation method thereof |
| CN102532498B (en) * | 2012-02-10 | 2013-06-12 | 四川大学 | Thioether-containing self-flame-retardant polyester and preparation method thereof |
| CN111710840A (en) * | 2020-06-04 | 2020-09-25 | 东华大学 | Preparation method of polyimide composite electrode material containing ketone carbonyl bond chain structure |
| CN111710840B (en) * | 2020-06-04 | 2022-08-12 | 东华大学 | Preparation method of polyimide composite electrode material containing ketone carbonyl bond chain structure |
| CN113896890A (en) * | 2021-09-13 | 2022-01-07 | 苏州尊尔光电科技有限公司 | Polyimide slurry and polyimide film |
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| CN101367937B (en) | 2010-11-17 |
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