CN104387586A - Soluble transparent fluorine-containing polyimide material and preparation method thereof - Google Patents
Soluble transparent fluorine-containing polyimide material and preparation method thereof Download PDFInfo
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- CN104387586A CN104387586A CN201410630668.4A CN201410630668A CN104387586A CN 104387586 A CN104387586 A CN 104387586A CN 201410630668 A CN201410630668 A CN 201410630668A CN 104387586 A CN104387586 A CN 104387586A
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- 0 C*c(cc(C(c(cc1)ccc1F)c(cc1)cc(C(C)C)c1N)cc1)c1N Chemical compound C*c(cc(C(c(cc1)ccc1F)c(cc1)cc(C(C)C)c1N)cc1)c1N 0.000 description 1
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Abstract
The invention discloses a soluble transparent fluorine-containing polyimide material and a preparation method thereof. The structural general formula of the soluble transparent fluorine-containing polyimide material is disclosed in the specification. The preparation method comprises the following steps: in a nitrogen protective atmosphere, sufficiently dissolving fluorine-containing structure and equal mole of isopropyl aromatic diamine and aromatic dianhydride monomers in N,N'-dimethyl acetamide until the total solid content is 5-15 wt%, and reacting at room temperature for 24 hours to generate a precursor PAA (polyacrylic acid); adding acetic anhydride into the prepared precursor PAA as a dehydrating agent, heating to 80-110 DEG C to perform dehydration and cyclization reaction for 8-10 hours by using pyridine as a catalyst, and cooling to room temperature to obtain a brown yellow thick liquid; pouring the prepared brown yellow thick liquid into methanol to precipitate, filtering for separation, sufficiently dissolving the product in N-methylpyrrolidone, reprecipitating with methanol twice, filtering the obtained product, and drying to obtain the light yellow fibrous polymer which is the soluble transparent fluorine-containing polyimide material.
Description
Technical field
The invention belongs to polymer material science field, particularly relate to a kind of soluble transparent fluorinated polyimide material and preparation method thereof.
Background technology
Polyimide refers in structure a base polymer with imide ring, traditional polyimide is substantially insoluble in conventional organic solvent, as N, N'-dimethyl formamide (DMF), N, N'-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), meta-cresol, tetrahydrofuran (THF) (THF), chloroform (CDCl
3), acetone etc.And second-order transition temperature is general all more than 280 DEG C.This base polymer indissoluble difficulty is melted, and processing difficulties, is difficult to application in practice.In the recent period, the polyimide material that fluorinated polyimide and synthesis have large space steric hindrance and a non-co-planar structure becomes the focus of research recently.Such as He Fei peak etc. are about the preparation method (CN 1597735) of soluble polyimide; The bright grade of week Yu is about the report (CN 102504255) of a kind of soluble fluorinated polyimide material and preparation method thereof; The people such as grade recklessly known have studied soluble fluorine-containing aromatic half alicyclic ring polyimide film material and preparation method thereof (CN 102898644).
The present invention is from Molecular Structure Design and practical application angle, the new type polyimide of synthesis fluorine and sec.-propyl structure.Dissolve in N, N'-dimethyl formamide (DMF), N, N'-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), meta-cresol, tetrahydrofuran (THF) (THF), chloroform (CDCl
3), the high temperature resistant novel poly-phthalimide material of the Conventional solvents such as acetone, its second-order transition temperature, between 200 ~ 350 DEG C, can meet the demand of high temperature resistant life-time service.There is high optical transparence simultaneously, low specific inductivity, the over-all propertieies such as excellent mechanical property.
Summary of the invention
The object of this invention is to provide a kind of soluble transparent fluorinated polyimide material and preparation method thereof.
The general structure of soluble transparent fluorinated polyimide material of the present invention is:
。
Wherein Ar is the one in following aromatic structure formula:
。
The preparation method of soluble transparent fluorinated polyimide material of the present invention is:
(1) under nitrogen protection; by waiting mole aromatic diamines containing fluorine structure and sec.-propyl and aromatic dianhydride monomer to be fully dissolved in N, in N'-N,N-DIMETHYLACETAMIDE (DMAc), its total solid content mass percent is made to be 5 ~ 15%; at room temperature react 24 hours, generate presoma PAA.
(2) in the obtained presoma PAA of step (1), add diacetyl oxide as dewatering agent, pyridine, as catalyzer, is warmed up to 80 ~ 110 DEG C of cyclodehydrations reactions 8 ~ 10 hours, is then cooled to room temperature, obtained brown color thick liquid.
(3) brown color thick liquid obtained for step (2) is poured in methyl alcohol precipitate, filtering separation, products therefrom N-Methyl pyrrolidone (NMP) fully dissolves, with methyl alcohol reprecipitation twice, products therefrom filtration drying, obtain faint yellow fibrous polymer, be soluble transparent fluorinated polyimide material.
The described structural formula containing the aromatic diamine monomers of fluorine structure and sec.-propyl is:
。
Advantage of the present invention:
Soluble transparent fluorinated polyimide material of the present invention can be dissolved in N, N'-dimethyl formamide (DMF), N, N'-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), meta-cresol, tetrahydrofuran (THF) (THF), chloroform (CDCl
3), the Conventional solvents such as acetone, synthesis technique is simple, be easy to purify, and the second-order transition temperature of such polyimide material is all more than 280 DEG C, excellent combination property, there is high temperature resistant, the feature such as radiation hardness, high strength, good electrical properties, can be used as the body material etc. of high temperature material, radiation hardness material or high performance composite.
Accompanying drawing explanation
Fig. 1 is the general structure of soluble transparent fluorinated polyimide material of the present invention.
Fig. 2 is the structural formula of soluble transparent fluorinated polyimide material prepared by the embodiment of the present invention 1.
Fig. 3 is the structural formula of soluble transparent fluorinated polyimide material prepared by the embodiment of the present invention 2.
Fig. 4 is the structural formula of soluble transparent fluorinated polyimide material prepared by the embodiment of the present invention 3.
Fig. 5 is the structural formula of soluble transparent fluorinated polyimide material prepared by the embodiment of the present invention 4.
Embodiment
embodiment 1:
Under nitrogen protection, one is equipped with mechanical stirrer, 3 are added respectively in the 50ml there-necked flask of reflux condensing tube and nitrogen airway, 3 ˊ-di-isopropyl-4, 4 ˊ-diamino-phenyl-4 ˊ ˊ-toluene fluoride 1.0000 grams (2.6560mmol), 3, 3 ˊ, 4, 4 ˊ-pyromellitic acid anhydride 0.5793 gram (2.6560mmol), 13.26 gram DMAc, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent, then toward the pyridine wherein adding 25 ml acetic anhydride and 1.5 milliliters, be warmed up to 95 DEG C of reactions 9 hours, be cooled to room temperature, obtained brown color viscous liquid, products therefrom is poured in the methyl alcohol of 500 milliliters and precipitate, filter, products therefrom 400 milliliters of NMP dissolve, with 500 ml methanol reprecipitation twice, products therefrom filtration drying, obtain faint yellow fibrous polymer, be soluble transparent fluorinated polyimide material.Its structural formula is shown in Figure of description.
embodiment 2:
Under nitrogen atmosphere, one is equipped with in the 50ml there-necked flask of mechanical stirrer, reflux condensing tube and nitrogen airway and adds 3 respectively, 3 ˊ-di-isopropyl-4,4 ˊ-diamino-phenyl-4 ˊ ˊ-toluene fluoride 1.0000 grams (2.6560mmol), 3,3 ˊ, 4,4 ˊ-benzophenone tetracarboxylic dianhydride 0.8558 gram (2.6560mmol), DMAc 15.12 grams, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent, then toward wherein adding 25 ml acetic anhydride and 1.5 milliliters of pyridines, 95 DEG C of reactions 9 hours are warmed up to; Be cooled to room temperature, obtained brown color viscous liquid, products therefrom is poured in the methyl alcohol of 500 milliliters and precipitate, filter, products therefrom 400 milliliters of NMP dissolve, with 500 ml methanol reprecipitations twice, and products therefrom filtration drying, obtain faint yellow fibrous polymer, be soluble transparent fluorinated polyimide material.Its structural formula is shown in Figure of description.
embodiment 3:
Under nitrogen atmosphere, one is equipped with mechanical stirrer, 3 are added respectively in the 50ml there-necked flask of reflux condensing tube and nitrogen airway, 3 ˊ-di-isopropyl-4, 4 ˊ-diamino-phenyl-4 ˊ ˊ-toluene fluoride 1.0000 grams (2.6560mmol), 3, 3 ˊ, 4, 4 ˊ-bibenzene tetracarboxylic dianhydride 0.7814 gram (2.6560 mmol), 14.58 gram DMAc, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent, then toward the pyridine wherein adding 25 ml acetic anhydride and 1.5 milliliters, be warmed up to 95 DEG C of reactions 9 hours, be cooled to room temperature, obtained brown color viscous liquid, products therefrom is poured in the methyl alcohol of 500 milliliters and precipitate, filter, products therefrom 400 milliliters of NMP dissolve, with 500 ml methanol reprecipitation twice, products therefrom filtration drying, obtain faint yellow fibrous polymer, be soluble transparent fluorinated polyimide material.Its structural formula is shown in Figure of description.
embodiment 4:
Under nitrogen atmosphere, one is equipped with mechanical stirrer, 3 are added respectively in the 50ml there-necked flask of reflux condensing tube and nitrogen airway, 3 ˊ-di-isopropyl-4, 4 ˊ-diamino-phenyl-4 ˊ ˊ-toluene fluoride 1.0000 grams (2.6560mmol), 3, 3 ˊ, 4, 4 ˊ-diphenyl ether tetraformic dianhydride 0.8239 gram (2.6560mmol), 15.81 gram DMAc, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent, then toward wherein adding 25 ml acetic anhydride and 1.5 milliliters of pyridines, be warmed up to 95 DEG C of reactions 9 hours, be cooled to room temperature, obtained brown color viscous liquid, products therefrom is poured in the methyl alcohol of 500 milliliters and precipitate, filter, products therefrom 400 milliliters of NMP dissolve, with 500 ml methanol reprecipitation twice, products therefrom filtration drying, obtain faint yellow fibrous polymer, be soluble transparent fluorinated polyimide material.Its structural formula is shown in Figure of description.
Claims (2)
1. a soluble transparent fluorinated polyimide material, is characterized in that the general structure of described soluble transparent fluorinated polyimide material is:
；
Wherein Ar is the one in following aromatic structure formula:
。
2. the preparation method of soluble transparent fluorinated polyimide material according to claim 1, is characterized in that concrete steps are:
(1) under nitrogen protection, by waiting mole aromatic diamines containing fluorine structure and sec.-propyl and aromatic dianhydride monomer to be fully dissolved in N, in N'-N,N-DIMETHYLACETAMIDE, its total solid content mass percent is made to be 5 ~ 15%, at room temperature react 24 hours, generate presoma PAA;
(2) in the obtained presoma PAA of step (1), add diacetyl oxide as dewatering agent, pyridine, as catalyzer, is warmed up to 80 ~ 110 DEG C of cyclodehydrations reactions 8 ~ 10 hours, is then cooled to room temperature, obtained brown color thick liquid;
(3) brown color thick liquid obtained for step (2) is poured in methyl alcohol precipitate, filtering separation, products therefrom N-Methyl pyrrolidone fully dissolves, with methyl alcohol reprecipitation twice, products therefrom filtration drying, obtain faint yellow fibrous polymer, be soluble transparent fluorinated polyimide material;
The described structural formula containing the aromatic diamine monomers of fluorine structure and sec.-propyl is:
。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234218A (en) * | 2020-03-07 | 2020-06-05 | 桂林理工大学 | Preparation method of soluble polyimide containing amino phenylsulfonyl hexafluoropropane structure |
| CN113249816A (en) * | 2021-05-21 | 2021-08-13 | 上海邃铸科技有限公司 | Transparent fiber and preparation method thereof |
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| CN101514164A (en) * | 2009-04-03 | 2009-08-26 | 东华大学 | Polyalkyl-substituted aromatic diamine monomer and preparation and application thereof |
| CN103483206A (en) * | 2013-09-27 | 2014-01-01 | 桂林理工大学 | Diamine monomer containing asymmetric and non-coplanar structure, and preparation method of diamine monomer |
| CN103497336A (en) * | 2013-10-14 | 2014-01-08 | 桂林理工大学 | Soluble polyimide with tertiary butyl and non-coplanar structure and preparation method thereof |
| CN103524738A (en) * | 2013-10-14 | 2014-01-22 | 桂林理工大学 | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure |
-
2014
- 2014-11-11 CN CN201410630668.4A patent/CN104387586A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| CN101514164A (en) * | 2009-04-03 | 2009-08-26 | 东华大学 | Polyalkyl-substituted aromatic diamine monomer and preparation and application thereof |
| CN103483206A (en) * | 2013-09-27 | 2014-01-01 | 桂林理工大学 | Diamine monomer containing asymmetric and non-coplanar structure, and preparation method of diamine monomer |
| CN103497336A (en) * | 2013-10-14 | 2014-01-08 | 桂林理工大学 | Soluble polyimide with tertiary butyl and non-coplanar structure and preparation method thereof |
| CN103524738A (en) * | 2013-10-14 | 2014-01-22 | 桂林理工大学 | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure |
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| Title |
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| WANG CHENYI, ET AL: "New soluble polyimides with high optical transparency and light color containing pendant trifluoromethyl and methyl groups", 《CHINESE JOURNAL OF CHEMISTRY》, vol. 30, no. 7, 7 May 2012 (2012-05-07), pages 1555 - 1560 * |
| 张丽娟, 等: "含氟聚酰亚胺的研究进展", 《绝缘材料》, vol. 42, no. 3, 31 December 2009 (2009-12-31), pages 14 - 19 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234218A (en) * | 2020-03-07 | 2020-06-05 | 桂林理工大学 | Preparation method of soluble polyimide containing amino phenylsulfonyl hexafluoropropane structure |
| CN111234218B (en) * | 2020-03-07 | 2022-12-27 | 桂林理工大学 | Preparation method of soluble polyimide containing amino phenylsulfonyl hexafluoropropane structure |
| CN113249816A (en) * | 2021-05-21 | 2021-08-13 | 上海邃铸科技有限公司 | Transparent fiber and preparation method thereof |
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