CN102604090B - Preparation method of liquid crystalline polyimide solution - Google Patents
Preparation method of liquid crystalline polyimide solution Download PDFInfo
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- CN102604090B CN102604090B CN 201210005400 CN201210005400A CN102604090B CN 102604090 B CN102604090 B CN 102604090B CN 201210005400 CN201210005400 CN 201210005400 CN 201210005400 A CN201210005400 A CN 201210005400A CN 102604090 B CN102604090 B CN 102604090B
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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, higher thermostability and chemical stability, and the performance that good stability of the dimension etc. are excellent, in aerospace, the 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 so that polyimide indissoluble infusibility again when having very high second-order transition temperature, thermostability is high and unreactiveness is good characteristics, affected its processing characteristics.Therefore, seeking can be so that the solvent of polyimide dissolving be one of gordian technique of preparation high performance polyimide fibers.
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: DMF (DMF), N,N-dimethylacetamide (DMAc) and N-Methyl pyrrolidone (NMP).This kind solvent has higher boiling point, and is easy to presoma polyamic acid formation complex compound, is difficult to remove in the course of processing, affects the performance of goods.And single stage method is take phenols such as meta-cresol, para-chlorophenols as solvent, although can prepare High performance polyimide fibres, as among the US5378420 take meta-cresol as solvent, made High performance polyimide fibres, but phenol solvent toxicity is large, 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 the fiber preparation.
Polyphosphoric acid is at preparation PBZT, and PBI in the process of the difficult dissolving polymers such as PBO and M5, has shown that it is for rigid polymer good solubility energy.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, PBI and PBZT and modified copolymer success thereof synthetic in PPA, and spin 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 the method technique is simple, and cost is low, has overcome the phenol solvent problem large 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 to get 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 described step (1)
2O
5The quality percentage composition be 82%-86%.
The heterocyclic diamine monomer that contains in the described step (2) is the diamine monomer that contains benzoglyoxaline, benzoxazole and benzothiazole heterocycle.
The described heterocyclic diamine monomer that contains is
Dianhydride monomer in the described step (2) is
Beneficial effect
(1) the present invention has made polyimide liquid crystal solution on the basis that solves the solvable problem of polyimide, for further high performance polyimide fibers or thin film technology, has established technical foundation.
(2) technique of the present invention is simple, and cost is low, has overcome the phenol solvent problem large 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 for explanation the present invention 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 limited range 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 the P that can obtain clarifying 2 hours under nitrogen protection
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is for 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, stirring makes it at 120 ℃ of polyase 13 h, 150 ℃ of polymerization 4h, at 220 ℃ of reaction 1h, obtain the liquid crystal state polyimide solution again.Productive rate is 93%, and limiting viscosity is 1.86 (vitriol oil is solvent, 25 ℃ of lower mensuration).
Embodiment 2
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 15 gram P
2O
5150 ℃ were stirred the P that can obtain clarifying 2 hours under nitrogen protection
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is for 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 liquid crystal state polyimide solution again.Productive rate is 92%, and limiting viscosity is 1.50 (vitriol oil is solvent, 25 ℃ of lower mensuration).
Embodiment 3
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 6 gram P
2O
5120 ℃ were stirred the P that can obtain clarifying 2 hours under nitrogen protection
2O
5Content is 82% poly phosphoric acid solution, is cooled to 100 ℃, and is for 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 liquid crystal state polyimide solution again.Productive rate is 95%, and limiting viscosity is 2.91 (vitriol oil is solvent, 25 ℃ of lower mensuration).
Embodiment 4
In the 100ml flask, add 60 gram P
2O
5Content is 80% polyphosphoric acid, adds 26 gram P
2O
5150 ℃ were stirred the P that can obtain clarifying 2 hours under nitrogen protection
2O
5Content is 86% poly phosphoric acid solution, is cooled to 120 ℃, and is for 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, stirring makes it at 150 ℃ of polyase 13 h, 180 ℃ of polyase 13 h, at 220 ℃ of reaction 2h, obtain the liquid crystal state polyimide solution again.Productive rate is 93%, and limiting viscosity is 1.93 (vitriol oil is solvent, 25 ℃ of lower mensuration).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 the P that can obtain clarifying 2 hours under nitrogen protection
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is for 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 liquid crystal state polyimide solution again.Productive rate is 92%, and limiting viscosity is 2.40 (vitriol oil is solvent, 25 ℃ of lower mensuration).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 the P that can obtain clarifying 2 hours under nitrogen protection
2O
5Content is 84% poly phosphoric acid solution, is cooled to 120 ℃, and is for 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 liquid crystal state polyimide solution again.Productive rate is 95%, and limiting viscosity is 1.97 (vitriol oil is solvent, 25 ℃ of lower mensuration).
Claims (2)
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 to get P
2O
5Poly phosphoric acid solution, be cooled to 100-120 ℃;
(2) with mol ratio be 1:0.98-1:1.02 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; Wherein, containing the heterocyclic diamine monomer is
X is-S-; Dianhydride monomer is
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 described step (1)
2O
5The quality percentage composition be 82%-86%.
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| TWI513737B (en) * | 2013-11-29 | 2015-12-21 | Daxin Materials Corp | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display |
| 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 |
Citations (5)
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|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63256625A (en) * | 1987-04-14 | 1988-10-24 | Agency Of Ind Science & Technol | Aromatic-heterocyclic ring-containing polyamide-imide |
| US8536299B2 (en) * | 2008-12-08 | 2013-09-17 | 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (4)
| Title |
|---|
| M. Berrada等.Preparation and characterization of new soluble.《Journal Of Materials Chemistry》.2002,第12卷(第12期), |
| Preparation and characterization of new soluble;M. Berrada等;《Journal Of Materials Chemistry》;20021016;第12卷(第12期);第3551-3559页 * |
| 丁孟贤,何天白.聚酰亚胺新型材料.《聚酰亚胺新型材料》.1998, * |
| 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.《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》.2009, |
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