CN102604090A - Preparation method of liquid crystalline polyimide solution - Google Patents
Preparation method of liquid crystalline polyimide solution Download PDFInfo
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- CN102604090A CN102604090A CN2012100054002A CN201210005400A CN102604090A CN 102604090 A CN102604090 A CN 102604090A CN 2012100054002 A CN2012100054002 A CN 2012100054002A CN 201210005400 A CN201210005400 A CN 201210005400A CN 102604090 A CN102604090 A CN 102604090A
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- polyphosphoric acid
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Abstract
The invention relates to a preparation method of a liquid crystalline polyimide solution. The preparation method comprises the following steps of: mixing P2O5 and polyphosphoric acid under the protection of nitrogen gas at 100-150 DEG C, stirring to obtain a polyphosphoric acid solution of P2O5, and cooling the polyphosphoric acid solution to 100-120 DEG C; and (2) adding a diamine monomer containing heterocyclic rings and a dianhydride monomer into the polyphosphoric acid solution to obtain a reactant with the solid content of 5-20wt%, raising the temperature to 120-220 DEG C under the protection of nitrogen gas and reacting for 4-6h to obtain the liquid crystalline polyimide solution. The liquid crystalline polyimide solution is prepared on the basis of realizing the solubility of polyimide, which lays the technological basis for further preparing high-performance polyimide fiber or film; and the preparation method is simple in process, low in cost, capable of solving the problem that a phenol solvent has great influence to the environment and favorable in application prospect.
Description
Technical field
The invention belongs to the preparation field of polyimide, particularly a kind of preparation method of polyimide liquid crystal solution.
Background technology
Polyimide has good electrical property and mechanical property, and higher thermostability and chemicalstability, dimensional stability wait excellent performance well, and in aerospace, fields such as electronics are widely used.Virtue in the polyimide molecule, the formed conjugated system of heterocycle structure, ladder and half hierarchic structure; Make its molecular chain have very high rigidity; Thereby make when polyimide has the good characteristics of very high second-order transition temperature, thermostability height and unreactiveness indissoluble infusibility again, influenced its processing characteristics.Therefore, seeking to make polyimide dissolved solvent, is one of gordian technique of preparation polyimide high-performance fiber.
The preparation polyimide fiber is mainly single stage method and two-step process at present.What wherein two-step process used is non-proton type polar solvent, as: N, dinethylformamide (DMF), DMAC N,N (DMAc) and N-Methyl pyrrolidone (NMP).This kind solvent has higher boiling point, and is easy to presoma polyamic acid formation complex compound, in the course of processing, is difficult to remove, and influences the performance of goods.And single stage method is a solvent with phenols such as meta-cresol, para-chlorophenols; Although can prepare the high-performance polyimide fiber; As being solvent with the meta-cresol among the US5378420, made the high-performance polyimide fiber, but phenol solvent toxicity is big; Big for environment pollution, also limited its further application.In other research, although the PI of some structure can be in phenylformic acid and Whitfield's ointment one-step synthesis, be subject to the characteristic of solvent itself, limited its application in fiber production.
Polyphosphoric acid is at preparation PBZT, and PBI in the process of difficult dissolving polymers such as PBO and M5, has shown that it is for rigid polymer good solubility ability.In CN200410099003.1, PBO is synthetic in PPA to have obtained liquid crystal solution, and successfully spinning has obtained high-performance fiber.In US 2010/0145004, PBO, what PBI and PBZT and modified copolymer thereof were successful synthesizes in PPA, and spins out the high strength fibre of good thermal stability.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of polyimide liquid crystal solution, and this method technology is simple, and cost is low, has overcome the phenol solvent problem big to environmental influence.
The preparation method of a kind of polyimide liquid crystal solution of the present invention comprises:
(1) in 100-150 ℃, under the nitrogen protection with P
2O
5Mix with polyphosphoric acid, stir P
2O
5Poly phosphoric acid solution, be cooled to 100-120 ℃;
(2) be 1 with mol ratio: 0.98-1: 1.02 contain the heterocyclic diamine monomer and dianhydride monomer is added in the above-mentioned poly phosphoric acid solution; The solid content of reactant is 5wt%-20wt%; Under nitrogen protection, be warming up to 120-220 ℃, react after 4-6 hour, obtain polyimide liquid crystal solution.
P in the polyphosphoric acid in the said step (1)
2O
5The quality percentage composition be 82%-86%.
Contain the heterocyclic diamine monomer for containing benzoglyoxaline, benzoxazole and benzothiazole heterocyclic diamine monomer in the said step (2).
The said heterocyclic diamine monomer that contains does
In
one or more; Wherein, X be-O-,-S-or
Dianhydride monomer in the said step (2) does
Beneficial effect
(1) the present invention has made polyimide liquid crystal solution on the basis that solves the solvable problem of polyimide, for the further preparation of polyimide high-performance fiber or film, has established technical foundation.
(2) technology of the present invention is simple, and cost is low, has overcome the phenol solvent problem big to environmental influence, has a good application prospect.
Description of drawings
Fig. 1 is the infrared spectrum of BPDA-BOA and BTDA-BOA;
Fig. 2 is the polarizing microscope photo of BPDA-BOA and BTDA-BOA liquid crystal: (a) BTDA-BOA; (b) BPDA-BOA.
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 the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to 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
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 15 gram P
2O
5150 ℃ were stirred 2 hours under nitrogen protection, can obtain clarifying P
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is subsequent use.
Load weighted 3.60 gram 6-amino-2-(p-aminophenyl) benzoglyoxalines (BIA) and 4.73 gram BPDA BPDA are joined in the flask; Adopt stage intensification, stir and make it at 120 ℃ of polyase 13 h 150 ℃ of polymerization 4h; At 220 ℃ of reaction 1h, obtain the mesomorphism polyimide solution again.Productive rate is 93%, and limiting viscosity is 1.86 (vitriol oil is a solvent, measures down for 25 ℃).
Embodiment 2
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 15 gram P
2O
5150 ℃ were stirred 2 hours under nitrogen protection, can obtain clarifying P
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is subsequent use.
Load weighted 3.42 gram 6-amino-2-(p-aminophenyl) benzoglyoxalines (BIA) and 4.92 gram BTDA are joined in the flask; Adopt stage intensification, stir and make it at 150 ℃ of polymerization 5h 160 ℃ of polymerization 5h; At 180 ℃ of reaction 2h, obtain the mesomorphism polyimide solution again.Productive rate is 92%, and limiting viscosity is 1.50 (vitriol oil is a solvent, measures down for 25 ℃).
Embodiment 3
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 6 gram P
2O
5120 ℃ were stirred 2 hours under nitrogen protection, can obtain clarifying P
2O
5Content is 82% poly phosphoric acid solution, is cooled to 100 ℃, and is subsequent use.
Load weighted 3.50 gram 6-amino-2-(p-aminophenyl) benzoglyoxalines (BIA) and 4.84 gram ODPA are joined in the flask; Adopt stage intensification, stir and make it at 140 ℃ of polymerization 4h 170 ℃ of polymerization 4h; At 210 ℃ of reaction 2h, obtain the mesomorphism polyimide solution again.Productive rate is 95%, and limiting viscosity is 2.91 (vitriol oil is a solvent, measures down for 25 ℃).
Embodiment 4
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 26 gram P
2O
5150 ℃ were stirred 2 hours under nitrogen protection, can obtain clarifying P
2O
5Content is 86% poly phosphoric acid solution, is cooled to 120 ℃, and is subsequent use.
With load weighted 3.60 gram 5-amino-2-(4-aminophenyl)-1; 3-benzoxazole (BOA) and 4.73 gram BPDA BPDA join in the flask; Adopt stage intensification, stir and make it at 150 ℃ of polyase 13 h 180 ℃ of polyase 13 h; At 220 ℃ of reaction 2h, obtain the mesomorphism polyimide solution again.Productive rate is 93%, and limiting viscosity is 1.93 (vitriol oil is a solvent, measures down for 25 ℃).Infrared spectrogram and polarizing microscope photo are seen Fig. 1 and Fig. 2.
Embodiment 5
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 15 gram P
2O
5150 ℃ were stirred 2 hours under nitrogen protection, can obtain clarifying P
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is subsequent use.
With load weighted 3.42 gram 5-amino-2-(4-aminophenyl)-1,3-benzoxazole (BOA) and 4.92 gram BTDA join in the flask, adopt stage intensification; Stirring makes it at 130 ℃ of polymerization 5h; 170 ℃ of polymerization 5h at 220 ℃ of reaction 1h, obtain the mesomorphism polyimide solution again.Productive rate is 92%, and limiting viscosity is 2.40 (vitriol oil is a solvent, measures down for 25 ℃).Infrared spectrogram and polarizing microscope photo are seen Fig. 1 and Fig. 2.
Embodiment 6
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 15 gram P
2O
5150 ℃ were stirred 2 hours under nitrogen protection, can obtain clarifying P
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is subsequent use.
With load weighted 3.50 gram 5-amino-2-(4-aminophenyl)-1,3-benzoxazole (BOA) and 4.84 gram ODPA join in the flask, adopt stage intensification; Stirring makes it at 150 ℃ of polyase 13 h; 180 ℃ of polyase 13 h at 220 ℃ of reaction 1h, obtain the mesomorphism polyimide solution again.Productive rate is 95%, and limiting viscosity is 1.97 (vitriol oil is a solvent, measures down for 25 ℃).
Claims (5)
1. the preparation method of a polyimide liquid crystal solution comprises:
(1) in 100-150 ℃, under the nitrogen protection with P
2O
5Mix with polyphosphoric acid, stir P
2O
5Poly phosphoric acid solution, be cooled to 100-120 ℃;
(2) be 1 with mol ratio: 0.98-1: 1.02 contain the heterocyclic diamine monomer and dianhydride monomer is added in the above-mentioned poly phosphoric acid solution; The solid content of reactant is 5wt%-20wt%; Under nitrogen protection, be warming up to 120-220 ℃, react after 4-6 hour, obtain polyimide liquid crystal solution.
2. the preparation method of a kind of polyimide liquid crystal solution according to claim 1 is characterized in that: P in the polyphosphoric acid in the said step (1)
2O
5The quality percentage composition be 82%-86%.
3. the preparation method of a kind of polyimide liquid crystal solution according to claim 1 is characterized in that: contain the heterocyclic diamine monomer for containing benzoglyoxaline, benzoxazole and benzothiazole heterocyclic diamine monomer in the said step (2).
4. the preparation method of a kind of polyimide liquid crystal solution according to claim 3 is characterized in that: the said heterocyclic diamine monomer that contains does
Among
one or more; Wherein, X be-O-,-S-or
5. the preparation method of a kind of polyimide liquid crystal solution according to claim 1 is characterized in that: the dianhydride monomer in the said step (2) does
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|---|---|---|---|
| CN 201210005400 CN102604090B (en) | 2012-01-09 | 2012-01-09 | Preparation method of liquid crystalline polyimide solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739842A (en) * | 2013-12-20 | 2014-04-23 | 深圳瑞华泰薄膜科技有限公司 | Thermoplastic polyimide and method for preparing flexible copper-clad plate from thermoplastic polyimide |
| CN104673328A (en) * | 2013-11-29 | 2015-06-03 | 达兴材料股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN109761816A (en) * | 2018-12-29 | 2019-05-17 | 金宁人 | One birdss of the same feather flock together (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer and monomer, preparation and application |
Citations (7)
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|---|---|---|---|---|
| JPS63256625A (en) * | 1987-04-14 | 1988-10-24 | Agency Of Ind Science & Technol | Aromatic-heterocyclic ring-containing polyamide-imide |
| US5098985A (en) * | 1988-10-11 | 1992-03-24 | The Dow Chemical Company | Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties |
| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation of poly-p-phenylene benzodioxazole fibers |
| CN101016381A (en) * | 2007-02-07 | 2007-08-15 | 哈尔滨工业大学 | Method of preparing polybenzoxazole-imide and its fiber |
| CN101367937A (en) * | 2008-10-15 | 2009-02-18 | 东华大学 | Preparation method for synthesizing soluble polyimide in polyphosphoric acids |
| JP2010006940A (en) * | 2008-06-26 | 2010-01-14 | Teijin Ltd | Solid polymer electrolyte composition |
| US20100145004A1 (en) * | 2008-12-08 | 2010-06-10 | University Of Dayton | Rigid-rod copolymer compositions and the polymeric fibers fabricated from those compositions for enhanced flame resistance |
-
2012
- 2012-01-09 CN CN 201210005400 patent/CN102604090B/en not_active Expired - Fee Related
Patent Citations (7)
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|---|---|---|---|---|
| JPS63256625A (en) * | 1987-04-14 | 1988-10-24 | Agency Of Ind Science & Technol | Aromatic-heterocyclic ring-containing polyamide-imide |
| US5098985A (en) * | 1988-10-11 | 1992-03-24 | The Dow Chemical Company | Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties |
| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation of poly-p-phenylene benzodioxazole fibers |
| CN101016381A (en) * | 2007-02-07 | 2007-08-15 | 哈尔滨工业大学 | Method of preparing polybenzoxazole-imide and its fiber |
| JP2010006940A (en) * | 2008-06-26 | 2010-01-14 | Teijin Ltd | Solid polymer electrolyte composition |
| CN101367937A (en) * | 2008-10-15 | 2009-02-18 | 东华大学 | Preparation method for synthesizing soluble polyimide in polyphosphoric acids |
| US20100145004A1 (en) * | 2008-12-08 | 2010-06-10 | University Of Dayton | Rigid-rod copolymer compositions and the polymeric fibers fabricated from those compositions for enhanced flame resistance |
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|---|
| M. BERRADA等: "Preparation and characterization of new soluble", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 12, no. 12, 16 October 2002 (2002-10-16) * |
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| 王娟: "《聚苯并噁唑-酰亚胺的合成及其纤维的结构与性能研究" 哈尔滨工业大学硕士论文》", 15 February 2009, article "聚苯并噁唑-酰亚胺的合成及其纤维的结构与性能研究" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673328A (en) * | 2013-11-29 | 2015-06-03 | 达兴材料股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN103739842A (en) * | 2013-12-20 | 2014-04-23 | 深圳瑞华泰薄膜科技有限公司 | Thermoplastic polyimide and method for preparing flexible copper-clad plate from thermoplastic polyimide |
| CN103739842B (en) * | 2013-12-20 | 2016-08-31 | 深圳瑞华泰薄膜科技有限公司 | A kind of TPI and the method preparing flexibility coat copper plate with it |
| CN109761816A (en) * | 2018-12-29 | 2019-05-17 | 金宁人 | One birdss of the same feather flock together (hydroxyl) to penylene benzo diimidazole-benzoxazoles PBIO liquid crystal copolymer and monomer, preparation and application |
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| Publication number | Publication date |
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| CN102604090B (en) | 2013-10-23 |
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