CN105315466A - Preparation method of polyimide with fluorine-silicon modified main chain - Google Patents
Preparation method of polyimide with fluorine-silicon modified main chain Download PDFInfo
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- CN105315466A CN105315466A CN201510911678.XA CN201510911678A CN105315466A CN 105315466 A CN105315466 A CN 105315466A CN 201510911678 A CN201510911678 A CN 201510911678A CN 105315466 A CN105315466 A CN 105315466A
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Abstract
The invention discloses a preparation method of polyimide with a fluorine-silicon modified main chain. The preparation method sequentially comprises the following steps: (A) reacting perfluoroalkyl glycol with toluene diisocynate at room temperature for 8-16 hours, so as to obtain perfluoroalkyl glycol isocyanate; (B) sequentially dissolving perfluoroalkyl glycol isocyanate and aromatic dianhydride into an organic solvent, heating to 50-80 DEG C in the presence of nitrogen, and stirring for 4-6 hours, so as to obtain polyimide with a fluorine-containing main chain; and (C) sequentially adding silicon-containing diamine and aromatic dianhydride into a polyimide solution with the fluorine-containing main chain, reacting at the room temperature for 4-8 hours in the presence of nitrogen so as to obtain a prepolymer of polyimide with a main chain containing fluorine-silicon polyimide, coating, and baking, so as to obtain a polyimide material with the fluorine-silicon modified main chain. A fluorine-silicon modified polyimide membrane prepared by virtue of the preparation method has good hydrophobicity, translucency, film-forming property and adhesion property; furthermore, an operation method is simple and is applicable to industrial expansion.
Description
Technical field
The present invention relates to the preparation method of the fluorinated silicone modified polyimide of a kind of main chain.
Background technology
Polyimide, being described as is most promising engineering plastics in this century, has excellent thermostability, mechanical property and electrical property, has been widely used in Aeronautics and Astronautics and microelectronics industry.Especially the high transparent polyimide that light color is even colourless, may be used for optics or light-electrical domain, as flexible solar radiation protective membrane, and liquid-crystal display alignment films and optics half waveguide material etc.But its wet swelling of traditional polyimide and then cause the deficiency be hydrolyzed to also limit its application in the leading-edge field such as aerospace, precise electronic.One of solution is high heat-resisting low moisture absorption fluorinated polyimide, and fluorinated polyimide because its structure having the fluoro-containing group that height draws electronic action, therefore has lower electronic polarization degree, and low internal cohesive energy and surface free energy, show hydrophobicity.
In addition, while maintenance over-all properties, for overcoming the unworkability of polyimide, researcher has carried out large quantifier elimination: 1) in dianhydride or diamine monomer, introduce perfluoroalkyl unit or asymmetric substituting group can make the solvability of polyimide greatly increase; 2) flexible siloxane blocks is guided to polyimide backbone structure, its processibility of Silicone Containing Polyimides prepared with siliceous dianhydride monomer or siliceous diamine monomer is improved greatly, and has good solubility, hydrophobic nature, ventilation property, shock resistance, ultraviolet resistance and the anti-degradation property in oxygen-enriched environment.In addition Silicone Containing Polyimides also shows the binding property good to the base material such as inorganic materials, metallic substance.
Though fluorinated polyimide has good agent of low hygroscopicity, because its surface energy is very low, make the ductility between itself and other material poor, poor cohesiveness is shown to various base material.The polyimide of Si modification not only has better processibility but also has good binding property, reports the fluorinated silicone modified polyimide material preparation method of a kind of main chain, expanded the research field of polyimide material based on this present invention.
Summary of the invention
The invention provides the preparation method of the fluorinated silicone modified polyimide of a kind of main chain.Method of the present invention is simple to operate, easy suitability for industrialized production.
A preparation method for the fluorinated silicone modified polyimide of main chain, is characterized in that the step of the method is followed successively by:
A, by perfluoroalkyl glycol and tolylene diisocyanate room temperature reaction 8 ~ 16h, can obtain perfluor glycol isocyanic ester;
Perfluor glycol isocyanic ester, aromatic tetrahydric dianhydride are dissolved in organic solvent by B successively, under nitrogen atmosphere, are heated to 50-80 DEG C and stir 4 ~ 6h, namely obtain the polyimide that main chain is fluorine-containing;
Siliceous diamines and aromatic tetrahydric dianhydride join in the fluorine-containing polyimide solution of main chain by C successively, and room temperature reaction 4 ~ 8h under nitrogen atmosphere, namely obtains the performed polymer of main chain fluorine silicon polyimide, and namely coat bake obtains the fluorinated silicone modified polyimide material of main chain.
The mol ratio of described perfluoroalkyl glycol and tolylene diisocyanate is 1: 2 ~ 1: 2.1.
Described perfluoroalkyl glycol is 1H, 1H, 8H, 8H-perfluor-1,8-ethohexadiol, 1H, 1H, 10H, 10H-perfluor-decamethylene-glycol or 1H, 1H, 12H, 12H-perfluor-1,12-dodecanediol.
The mol ratio of described perfluor glycol isocyanic ester and aromatic tetrahydric dianhydride is 1: 1 ~ 1: 1.1.
Organic solvent described in step B is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
The mol ratio of polyimide, siliceous diamines and aromatic tetrahydric dianhydride that main chain described in step C is fluorine-containing is 1: 2: 2 ~ 4: 1: 1.
Described siliceous diamines is 1,3-two (3-aminopropyl)-1,1,3,3-tetramethyl disiloxane.
Described aromatic tetrahydric dianhydride is 4,4 '-bis-Tetra hydro Phthalic anhydride, 4, the two Tetra hydro Phthalic anhydride or 4 of 4 '-oxygen, 4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids.
The temperature of coat bake described in step C is 80 ~ 220 DEG C.
The present invention is simple to operate, and be suitable for industry and amplify, and can prepare the fluorinated polyimide film of hydrophobic nature, light transmission excellence without the need to the professional equipment of any costliness, the fluorinated silicone modified colourless high transparent Kapton obtained can be used as optical material.
Embodiment
Embodiment 1
(1) preparation of perfluor glycol isocyanic ester
2.31g (5mmol) 1H is added successively in the round-bottomed flask of 10mL, 1H, 10H, 10H-perfluor-1,10-decanediol, 5mLN, dinethylformamide, then slowly drips 1.74g (10mmol) tolylene diisocyanate, stirring reaction 12h under normal temperature, obtains water white perfluor glycol isocyanate solution.
(2) preparation of fluorinated polyimide (F-ODPA)
Dry and be connected with in two mouthfuls of round-bottomed flasks of the 25mL of nitrogen and add 1.55g (5mmol) 4 successively, the two Tetra hydro Phthalic anhydride (ODPA) of 4 '-oxygen and 15mLN, dinethylformamide, be warmed up to 60 DEG C, then 5mmol freshly prepd perfluor glycol isocyanic ester is slowly dripped, react 4h in nitrogen atmosphere, obtain water white fluorinated polyimide solution.
(3) preparation of polyimide (F-Si-ODPA) film that main chain is fluorinated silicone modified
Get the fluorinated polyimide solution of 1mmol; 0.124g (0.5mmol) 1 is slowly added under nitrogen atmosphere; two (the 3-aminopropyl)-1,1,3 of 3-; 3-tetramethyl disiloxane; add 0.155g (0.5mmol) 4 subsequently, two Tetra hydro Phthalic anhydride (ODPA) the stirring at normal temperature 4h of 4 '-oxygen, is coated in cleaned glass surface by prepared fluorinated polyimide viscous fluid; in baking oven by following temperature toast successively (80 DEG C, 2h; 100 DEG C, 1h; 120 DEG C, 1h; 150 DEG C, 1h; 180 DEG C, 1h; 220 DEG C, 1h), obtain colourless fluorinated silicone modified Kapton.The Static water contact angles of this Kapton is 90 °, and sticking power can reach more than II level.
Embodiment 2
(1) preparation of perfluor glycol isocyanic ester is with embodiment 1.
(2) preparation of fluorinated polyimide (F-6FDA)
Dry and be connected with in two mouthfuls of round-bottomed flasks of the 50mL of nitrogen and add 2.22g (5mmol) 4 successively, 4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids (6FDA) and 15mLN, dinethylformamide, be warmed up to 70 DEG C, then 5mmol freshly prepd perfluor glycol isocyanic ester is slowly dripped, react 4h in nitrogen atmosphere, obtain water white fluorinated polyimide solution.
(3) preparation of polyimide (F-Si-6FDA) film that main chain is fluorinated silicone modified
Get the fluorinated polyimide solution of 1mmol; 0.248g (1mmol) 1 is slowly added under nitrogen atmosphere; two (the 3-aminopropyl)-1,1,3 of 3-; 3-tetramethyl disiloxane; add 0.444g (1mmol) 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids (6FDA) stirring at normal temperature 4h subsequently, prepared fluorinated polyimide viscous fluid is coated in glass surface; in baking oven by following temperature toast successively (80 DEG C, 2h; 100 DEG C, 1h; 120 DEG C, 1h; 150 DEG C, 1h; 180 DEG C, 1h; 220 DEG C, 1h), obtain colourless fluorinated silicone modified Kapton.The Static water contact angles of this Kapton is 105 °, and sticking power can reach more than II level.
Claims (9)
1. a preparation method for the fluorinated silicone modified polyimide of main chain, is characterized in that the step of the method is followed successively by:
A, by perfluoroalkyl glycol and tolylene diisocyanate room temperature reaction 8 ~ 16h, can obtain perfluor glycol isocyanic ester;
Perfluor glycol isocyanic ester, aromatic tetrahydric dianhydride are dissolved in organic solvent by B successively, under nitrogen atmosphere, are heated to 50-80 DEG C and stir 4 ~ 6h, namely obtain the polyimide that main chain is fluorine-containing;
Siliceous diamines and aromatic tetrahydric dianhydride join in the fluorine-containing polyimide solution of main chain by C successively, and room temperature reaction 4 ~ 8h under nitrogen atmosphere, namely obtains the performed polymer of main chain fluorine silicon polyimide, and namely coat bake obtains the fluorinated silicone modified polyimide material of main chain.
2. the method for claim 1, is characterized in that the mol ratio of described perfluoroalkyl glycol and tolylene diisocyanate is 1: 2 ~ 1: 2.1.
3. method as claimed in claim 1 or 2, is characterized in that described perfluoroalkyl glycol is 1H, 1H, 8H, 8H-perfluor-1,8-ethohexadiol, 1H, 1H, 10H, 10H-perfluor-decamethylene-glycol or 1H, 1H, 12H, 12H-perfluor-1,12-dodecanediol.
4. the method for claim 1, is characterized in that the mol ratio of described perfluor glycol isocyanic ester and aromatic tetrahydric dianhydride is 1: 1 ~ 1: 1.1.
5. the method for claim 1, is characterized in that organic solvent described in step B is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
6. the method for claim 1, is characterized in that the mol ratio of polyimide, siliceous diamines and aromatic tetrahydric dianhydride that main chain described in step C is fluorine-containing is 1: 2: 2 ~ 4: 1: 1.
7. the method as described in claim 1 or 6, is characterized in that described siliceous diamines is 1,3-two (3-aminopropyl)-1,1,3,3-tetramethyl disiloxane.
8. the method as described in claim 1,4 or 6, is characterized in that described aromatic tetrahydric dianhydride is 4,4 '-bis-Tetra hydro Phthalic anhydride, 4, the two Tetra hydro Phthalic anhydride or 4 of 4 '-oxygen, 4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids.
9. the method for claim 1, is characterized in that the temperature of coat bake described in step C is 80 ~ 220 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762166A (en) * | 2018-12-26 | 2019-05-17 | 哈尔滨工程大学 | A kind of preparation method of polyimide precursor and Kapton |
| WO2022107541A1 (en) * | 2020-11-19 | 2022-05-27 | 日産化学株式会社 | Liquid crystal aligning agent, method for producing polymer, liquid crystal alignment film and liquid crystal display element |
| CN115312241A (en) * | 2022-08-19 | 2022-11-08 | 安徽新特华宇新材料科技有限公司 | Polyimide composite insulated cable for space navigation |
| CN115975190A (en) * | 2022-12-29 | 2023-04-18 | 深圳市研一新材料有限责任公司 | Preparation method and application of modified polyimide binder |
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| CN115216009B (en) | 2022-08-17 | 2023-05-30 | 哈尔滨工程大学 | Preparation method of thermoplastic multi-component hybrid polyimide film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04325523A (en) * | 1991-01-24 | 1992-11-13 | Cheil Synthetics Inc | Manufacture of siloxane-modified polyimide resin |
| US5484879A (en) * | 1990-12-17 | 1996-01-16 | Occidental Chemical Corporation | Polyimides containing fluorine |
| CN101012333A (en) * | 2006-12-29 | 2007-08-08 | 江苏大学 | Fluorine-containing polyimide/SiO2 organic-inorganic hybridization material and its preparing method and application |
| CN101293964A (en) * | 2007-04-28 | 2008-10-29 | 汉高股份两合公司 | Organosilicon polyimide based polyalcohol, prepared elastomer, preparing process and and uses thereof |
-
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- 2015-12-11 CN CN201510911678.XA patent/CN105315466B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484879A (en) * | 1990-12-17 | 1996-01-16 | Occidental Chemical Corporation | Polyimides containing fluorine |
| JPH04325523A (en) * | 1991-01-24 | 1992-11-13 | Cheil Synthetics Inc | Manufacture of siloxane-modified polyimide resin |
| CN101012333A (en) * | 2006-12-29 | 2007-08-08 | 江苏大学 | Fluorine-containing polyimide/SiO2 organic-inorganic hybridization material and its preparing method and application |
| CN101293964A (en) * | 2007-04-28 | 2008-10-29 | 汉高股份两合公司 | Organosilicon polyimide based polyalcohol, prepared elastomer, preparing process and and uses thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762166A (en) * | 2018-12-26 | 2019-05-17 | 哈尔滨工程大学 | A kind of preparation method of polyimide precursor and Kapton |
| CN109762166B (en) * | 2018-12-26 | 2021-02-12 | 哈尔滨工程大学 | Polyimide precursor and preparation method of polyimide film |
| WO2022107541A1 (en) * | 2020-11-19 | 2022-05-27 | 日産化学株式会社 | Liquid crystal aligning agent, method for producing polymer, liquid crystal alignment film and liquid crystal display element |
| CN115312241A (en) * | 2022-08-19 | 2022-11-08 | 安徽新特华宇新材料科技有限公司 | Polyimide composite insulated cable for space navigation |
| CN115975190A (en) * | 2022-12-29 | 2023-04-18 | 深圳市研一新材料有限责任公司 | Preparation method and application of modified polyimide binder |
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Effective date of registration: 20200619 Address after: 730000 room 316, 3 / F, comprehensive service building, zone B, comprehensive bonded zone, No. 2888 Qilianshan Avenue, Lanzhou New Area, Lanzhou City, Gansu Province Patentee after: Gansu Zhongan Ruike Technology Co., Ltd Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences |