CN104356386A - Soluble polyimide containing fluorine and isopropyl structure and preparation method thereof - Google Patents
Soluble polyimide containing fluorine and isopropyl structure and preparation method thereof Download PDFInfo
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- CN104356386A CN104356386A CN201410630669.9A CN201410630669A CN104356386A CN 104356386 A CN104356386 A CN 104356386A CN 201410630669 A CN201410630669 A CN 201410630669A CN 104356386 A CN104356386 A CN 104356386A
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- fluorine
- dianhydride
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Abstract
The invention discloses soluble polyimide containing a fluorine and isopropyl structure and a preparation method thereof. The structural formula of the soluble polyimide containing the fluorine and isopropyl structure is as shown in the specification. A novel soluble polyimide material containing the fluorine and isopropyl structure is prepared by taking a fluorine-containing structure and isopropyl substituted aromatic diamine and aromatic dianhydride in the presence of nitrogen by virtue of a three-step method. The polyimide disclosed by the invention has an excellent dissolving property and further can be better dissolved in low-boiling-point solvents such as THF (tetrahydrofuran), CHCl3 and acetone forepart from being good in dissolving property in high-boiling-point solvents such as DMF (dimethyl formamide), DMAc (dimethylacetamide), NMP (N-methyl pyrrolidinone), DMSO (dimethylsulfoxide) and (m)-Cresol. The material further has comprehensive performances such as good heat stability, high optical transparency, low dielectric constant, low moisture absorption and the like.
Description
Technical field
The invention belongs to polymer material science field, particularly a kind of soluble polyimide and preparation method thereof of fluorine-containing and sec.-propyl structure.
Background technology
Polyimide, as a kind of high temperature polymeric materials, has been widely used in aircraft industry, automotive industry, electric industry etc., especially in high-end technology field as microelectronics, rocket and space travel etc., be one of indispensable high temperature material.Polyimide (PI) is the class high-performance polymer containing imide ring structure in molecular structure, due to the tightly packed and intermolecular stronger interaction force of its stiff backbone structure had, molecular chain, make polyimide material have the shortcomings such as very high melt processing temperature, solubility property is poor, forming process is difficult, thus further limit their application in association area.In order to overcome above-mentioned difficulties, prepare the polyimide material that solubility property is good, be easy to the excellent combination properties such as processing, the R&D work that related scientific research department has dropped into a large amount of human and material resources, financial resources are engaged in this respect.
Soluble polyimide is the focus of Recent study, synthesis is wherein adopted to have the polyimide material of large space steric hindrance and non-co-planar structure, by destroying the upright and outspoken chain structure of main chain and intermolecular interaction force, thus obtain the polyimide material of high soluble.The advantages such as this method monomer synthesize is simple, price is cheap, material excellent combination property are current generally one of methods adopting synthesizing soluble polyimide.The people such as such as Zhang Qinghua report a kind of preparation method (CN101367937) of synthesizing soluble polyimide in polyphosphoric acid; The people such as Jiang Zhenhua have studied soluble fluorine-containing aromatic polyimide and synthetic method (CN 101085833) thereof; Wang claims the people such as meaning to synthesize the method (CN101456954) preparing polyimide containing two assorted naphthalenone structure and trifluoromethyl substituted aroma diamine monomer.
By molecular designing, non-co-planar structure and substituted radical are induced one to prepare soluble polyimide in polyimide structures.Such polyimide material at room temperature not only can be dissolved completely in high boiling point conventional organic solvent, as DMF, DMAc, NMP, DMSO and
m-Cresol etc., can also be dissolved in low boiling point solvent, as CDCl
3, THF and acetone etc., make polyimide also can realize low-temperature curing film forming in some field.This kind of material also has excellent thermal characteristics, optical property and dielectric properties etc. simultaneously.In thermal characteristics, compared with commercial polyimide, although thermal characteristics reduction to a certain extent, its second-order transition temperature (
t g) still remain on more than 300 DEG C, heat decomposition temperature (
t d) more than 500 DEG C, this type of material is enough to meet its service requirements in Application Areass such as aerospace, microelectronics and photoelectrons.
Summary of the invention
The object of this invention is to provide soluble polyimide of a kind of fluorine-containing and sec.-propyl structure and preparation method thereof.
Thinking of the present invention: under nitrogen protection, with the aromatic diamines replaced containing fluorine structure and sec.-propyl and aromatic dianhydride for raw material, by " three-step approach ", prepares fluorine-containing and solubility new type polyimide material that is sec.-propyl structure.
The structural formula of the soluble polyimide of fluorine-containing and sec.-propyl structure of the present invention is:
。
Wherein Ar is the one in following 11 kinds of structures:
。
The preparation method of the soluble polyimide of fluorine-containing and sec.-propyl structure of the present invention is:
(1) under nitrogen protection; mole aromatic diamine monomers such as grade and aromatic dianhydride monomer are fully dissolved in aprotic polar solvent; after stirring, under room temperature, reaction obtains presoma PAA in 24 hours, and total consumption of described monomer makes the solid content mass percent of system be 10%.
(2) use diacetyl oxide as dewatering agent, triethylamine carries out dehydration reaction 6 ~ 10 hours as the presoma PAA that dehydration catalyst is obtained to step (1) at 80 ~ 120 DEG C, obtained performed polymer polyisoimide.
(3) in the obtained performed polymer polyisoimide of step (2), acid catalyst or alkaline catalysts is added, under nitrogen protection 150 ~ 200 DEG C of polyreactions 4 ~ 6 hours, obtained polyimide.
(4) precipitation agent is done with low boiling point organic solvent, by polyimide precipitation obtained for the step (3) being cooled to room temperature, filtration, drying, finally obtain fibrous polyimide material, be fluorine-containing and soluble polyimide that is sec.-propyl structure.
Described aromatic diamines contains fluorine and sec.-propyl structure, chemistry by name 3,3 '-di-isopropyl-4,4 '-diamino-phenyl-3 ' ', 4 ' '-difluoro toluene, its structural formula is:
。
Described aromatic dianhydride is 3, 3 ', 4, 4 '-pyromellitic acid anhydride, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-diphenyl thio-ether tetrformate dianhydride, 3, 3 ', 4, 4 '-diphenyl sulfone tetraformic acid dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) propane dianhydride, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 2 ', 3-Three methyl Benzene dianhydride and 1, 4-two (3, 4-di carboxyl phenyloxy)-2, one in 3 '-di-t-butyl benzene dianhydride.
Described aprotic polar solvent is the one in DMF (DMF), N,N-dimethylacetamide (DMAc) and N-Methyl pyrrolidone (NMP).
Described acid catalyst is dense HCl, and alkaline catalysts is dense KOH, and acid catalyst or alkaline catalysts consumption are 2 ~ 5% of the quality that always feeds intake.
Described low boiling point organic solvent is methyl alcohol or ethanol.
Fluorine-containing and soluble polyimide that is sec.-propyl structure of the present invention can be applied to the new high-tech industry fields such as aerospace, electronics and microelectronics.
The present invention has the following advantages:
(1) polyimide material of the present invention has good solubility energy, dissolves in conventional high boiling organic solvent
n, N'-dimethyl formamide (DMF),
n, N'-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) and meta-cresol (
m-Cresol) etc., low boiling point solvent THF, CHCl can also be dissolved in
3and in acetone, wherein the dissolution characteristics of polymkeric substance in low boiling point solvent, can realize low-temperature curing film-forming process, thus makes material be widely used at microelectronic.
(2) polyimide material of the present invention has superior heat-resistant stability, second-order transition temperature (
t g) more than 300 DEG C, thermolysis starting temperature (
t d) more than 500 DEG C, carbon yield is all more than 68%.
(3) polyimide material of the present invention has excellent optical property, and cutoff wavelength scope is 331 ~ 361nm, and transmitance is the wavelength 417 ~ 463nm of 80%.
(4) polyimide material of the present invention has low-k, and specific inductivity is between 1.80 ~ 3.00.
Accompanying drawing explanation
Fig. 1 is the general structure of the soluble polyimide of fluorine-containing and sec.-propyl structure of the present invention.
Fig. 2 is the structural formula of the soluble polyimide of fluorine-containing and sec.-propyl structure prepared by the embodiment of the present invention 1.
Fig. 3 is the structural formula of the soluble polyimide of fluorine-containing and sec.-propyl structure prepared by the embodiment of the present invention 2.
Fig. 4 is the structural formula of the soluble polyimide of fluorine-containing and sec.-propyl structure prepared by the embodiment of the present invention 3.
Fig. 5 is the structural formula of the soluble polyimide of fluorine-containing and sec.-propyl structure prepared by the embodiment of the present invention 4.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
embodiment 1:
Be equipped with in 50 milliliters of three mouthfuls of round-bottomed flasks of mechanical stirrer, reflux condensing tube, nitrogen airway at one and add 3 respectively, 3 '-di-isopropyl-4,4 '-diamino-phenyl-3 ' ', 4 ' '-difluoro toluene 1.0000 grams (2.5349 mmole), 3,3 ', 4,4 '-pyromellitic acid anhydride 0.5529 gram (2.5349 mmole), under 13.50 grams of DMF room temperatures, reaction obtains presoma PAA in 24 hours.Then add 25 ml acetic anhydride and triethylamine 1.5 milliliters in the PAA obtained, at 100 DEG C, reaction obtains performed polymer polyisoimide in 8 hours.Finally in performed polymer polyisoimide, add 1 milliliter of dense HCl, the lower 160 DEG C of back flow reaction of nitrogen protection 5 hours, the polyimide of obtained thickness.After being cooled to room temperature, pouring in 500 milliliters of ethanol and precipitate, filter and drying, finally obtain fibrous polyimide material, be fluorine-containing and soluble polyimide that is sec.-propyl structure.Its structural formula is shown in Figure of description.
embodiment 2:
Be equipped with in 50 milliliters of three mouthfuls of round-bottomed flasks of mechanical stirrer, reflux condensing tube, nitrogen airway at one and add 3 respectively, 3 '-di-isopropyl-4,4 '-diamino-phenyl-3 ' ', 4 ' '-difluoro toluene 1.0000 grams (2.5349 mmole), 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride 0.7458 gram (2.5349 mmole), under 14.60 grams of DMF room temperatures, reaction obtains presoma PAA in 24 hours.Then add 25 ml acetic anhydride and triethylamine 1.5 milliliters in the presoma PAA obtained, at 100 DEG C, reaction obtains performed polymer polyisoimide in 8 hours.Finally in performed polymer polyisoimide, add 1 milliliter of dense HCl, the lower 180 DEG C of back flow reaction of nitrogen protection 5 hours, the polyimide of obtained thickness.After being cooled to room temperature, pouring in 500 milliliters of ethanol and precipitate, filter and drying, finally obtain fibrous polyimide material, be fluorine-containing and soluble polyimide that is sec.-propyl structure.Its structural formula is shown in Figure of description.
embodiment 3:
Be equipped with in 50 milliliters of three mouthfuls of round-bottomed flasks of mechanical stirrer, reflux condensing tube, nitrogen airway at one and add 3 respectively, 3 '-di-isopropyl-4,4 '-diamino-phenyl-3 ' ', 4 ' '-difluoro toluene 1.0000 grams (2.5349 mmole), 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride 0.7863 gram (2.5349 mmole), under 15.10 grams of DMF room temperatures, reaction obtains presoma PAA in 24 hours.Then add 25 ml acetic anhydride and triethylamine 1.5 milliliters in the PAA obtained, at 100 DEG C, reaction obtains performed polymer polyisoimide in 8 hours.Finally in performed polymer polyisoimide, add 1 milliliter of dense HCl, the lower 170 DEG C of back flow reaction of nitrogen protection 5 hours, the polyimide of obtained thickness.After being cooled to room temperature, pouring in 500 milliliters of ethanol and precipitate, filter and drying, finally obtain fibrous polyimide material, be fluorine-containing and soluble polyimide that is sec.-propyl structure.Its structural formula is shown in Figure of description.
embodiment 4:
Be equipped with in 50 milliliters of three mouthfuls of round-bottomed flasks of mechanical stirrer, reflux condensing tube, nitrogen airway at one and add 3 respectively, 3 '-di-isopropyl-4,4 '-diamino-phenyl-3 ' ', 4 ' '-difluoro toluene 1.0000 grams (2.5349 mmole), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 0.8168 gram (2.5349 mmole), under 17.40 grams of DMF room temperatures, reaction obtains presoma PAA in 24 hours.Then add 25 ml acetic anhydride and triethylamine 1.5 milliliters in the PAA obtained, at 100 DEG C, reaction obtains performed polymer polyisoimide in 8 hours.Finally in performed polymer polyisoimide, add 1 milliliter of dense HCl, the lower 190 DEG C of back flow reaction of nitrogen protection 5 hours, the polyimide of obtained thickness.After being cooled to room temperature, pouring in 500 milliliters of ethanol and precipitate, filter and drying, finally obtain fibrous polyimide material, be fluorine-containing and soluble polyimide that is sec.-propyl structure.Its structural formula is shown in Figure of description.
Claims (3)
1. a soluble polyimide for fluorine-containing and sec.-propyl structure, is characterized in that the structural formula of the soluble polyimide of described fluorine-containing and sec.-propyl structure is:
；
Wherein Ar is the one in following 11 kinds of structures:
。
2. the preparation method of the soluble polyimide of fluorine-containing and sec.-propyl structure according to claim 1, is characterized in that concrete steps are:
(1) under nitrogen protection, mole aromatic diamine monomers such as grade and aromatic dianhydride monomer are fully dissolved in aprotic polar solvent, after stirring, under room temperature, reaction obtains presoma PAA in 24 hours, and total consumption of described monomer makes the solid content mass percent of system be 10%;
(2) use diacetyl oxide as dewatering agent, triethylamine carries out dehydration reaction 6 ~ 10 hours as the presoma PAA that dehydration catalyst is obtained to step (1) at 80 ~ 120 DEG C, obtained performed polymer polyisoimide;
(3) in the obtained performed polymer polyisoimide of step (2), acid catalyst or alkaline catalysts is added, under nitrogen protection 150 ~ 200 DEG C of polyreactions 4 ~ 6 hours, obtained polyimide;
(4) precipitation agent is done with low boiling point organic solvent, by polyimide precipitation obtained for the step (3) being cooled to room temperature, filtration, drying, finally obtain fibrous polyimide material, be fluorine-containing and soluble polyimide that is sec.-propyl structure;
Described aromatic diamines contains fluorine and sec.-propyl structure, chemistry by name 3,3 '-di-isopropyl-4,4 '-diamino-phenyl-3 ' ', 4 ' '-difluoro toluene, its structural formula is:
；
Described aromatic dianhydride is 3, 3 ', 4, 4 '-pyromellitic acid anhydride, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-diphenyl thio-ether tetrformate dianhydride, 3, 3 ', 4, 4 '-diphenyl sulfone tetraformic acid dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) propane dianhydride, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 2 ', 3-Three methyl Benzene dianhydride and 1, 4-two (3, 4-di carboxyl phenyloxy)-2, one in 3 '-di-t-butyl benzene dianhydride,
Described aprotic polar solvent is the one in DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone;
Described acid catalyst is dense HCl, and alkaline catalysts is dense KOH, and acid catalyst or alkaline catalysts consumption are 2 ~ 5% of the quality that always feeds intake;
Described low boiling point organic solvent is methyl alcohol or ethanol.
3. the application of the soluble polyimide of fluorine-containing and sec.-propyl structure according to claim 1 and 2, is characterized in that this fluorine-containing and soluble polyimide that is sec.-propyl structure is applied to aerospace, electronics and microelectronics technology.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514164A (en) * | 2009-04-03 | 2009-08-26 | 东华大学 | Polyalkyl-substituted aromatic diamine monomer and preparation and application thereof |
| 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 CN201410630669.9A patent/CN104356386A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514164A (en) * | 2009-04-03 | 2009-08-26 | 东华大学 | Polyalkyl-substituted aromatic diamine monomer and preparation and application thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| WANG CHENYI, ET AL: "New soluble polyimides with high optical transparency and light color containing pendant trifluoromethyl and methyl groups", 《CHINESE JOURNAL OF CHEMISTRY》 * |
| XIAOHUA HUANG ET AL: ""Synthesis of highly soluble and transparent polyimides"", 《POLYMER INTERNATIONAL》 * |
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Application publication date: 20150218 |