CN104987506A - Soluble polyimide containing tert-butyl and benzofuran structure and preparation method of soluble polyimide - Google Patents
Soluble polyimide containing tert-butyl and benzofuran structure and preparation method of soluble polyimide Download PDFInfo
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- CN104987506A CN104987506A CN201510368092.3A CN201510368092A CN104987506A CN 104987506 A CN104987506 A CN 104987506A CN 201510368092 A CN201510368092 A CN 201510368092A CN 104987506 A CN104987506 A CN 104987506A
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- dianhydride
- soluble polyimide
- cumarone
- tertiary butyl
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Abstract
The invention discloses soluble polyimide containing a tert-butyl and benzofuran structure and a preparation method of the soluble polyimide. The structural formula of the soluble polyimide containing the tert-butyl and benzofuran structure is shown in the description; the soluble polyimide is prepared from aromatic amine with a noncoplanar structure and various different tetracid dianhydrides through a three-step method. The polyimide material provided by the invention has an excellent dissolving property, and not only can be completely dissolved in high-boiling-point organic solvents comprising N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) and m-cresol, but also can be better dissolved in low-boiling-point solvents comprising tetrahydrofuran (THF), chloroform (CHCl3), dichloromethane (CH2Cl2), ethyl acetate and acetone.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of soluble polyimide containing the tertiary butyl and cumarone structure and preparation method thereof.
Background technology
Polyimide is the important functional high-temperature polymer of a class, not only can be used as matrices of composite material, electronic package material, gas delivery be applied in film modern high-tech field, and be widely used in space flight and aviation, automotive industry, electric industry etc.Polyimide (PI) is the class high-performance polymer containing imide ring structure in molecular structure.Although this kind of high temperature material has excellent thermal property and mechanical property, but the stiff backbone structure had due to them and the strong interaction of intermolecular existence and the tightly packed of molecular chain, most of commercial polyimide is caused all to have very high melt temperature, be insoluble to again organic solvent (being mostly only dissolved in the vitriol oil), bring difficulty to its forming process.In addition, traditional polyimide is due to electric charge complexing transferance in the aromatic conjugated property of molecular backbone chain height and molecular chain, and its film has very dark color and poor optical transparence mostly.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 Huang Wei report the soluble polyimide luminous material and preparation method thereof (CN1171931C) containing naphthalene structure; The people such as Yu Xinhai report based on 3, the polyimide fiber spinning solution of 3 '-diamino-4,4 '-dihydroxybiphenyl and preparation (CN102650080B) thereof; The people such as wangkai guest report nonlinear optical organic polymkeric substance based on fluorinated polyimide and synthetic method (CN101942091B) thereof.This type of material has the over-all propertieies such as good thermal characteristics, excellent solubility property, high optical transparence, low-k and low rate of moisture absorption, is widely used in fields such as aerospace, microelectronics and photoelectrons.
By molecular designing non-co-planar structure and substituted radical be incorporated in polyimide structures and prepare soluble polyimide.The large-substituent tertiary butyl and benzofuryl is introduced in polyimide, improve the solubility property of polyimide, not only can be dissolved in high boiling organic solvent N, N '-dimethyl formamide (DMF), N, in N '-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) and meta-cresol, and lower boiling solvents tetrahydrofurane (THF), chloroform (CHCl can also be dissolved in preferably
3), methylene dichloride (CH
2cl
2), in ethyl acetate and acetone, make the polyimide low-temperature curing film forming of indissoluble become possibility.This kind of polyimide material also has excellent thermal characteristics, optical property and dielectric properties etc.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 a kind of soluble polyimide containing the tertiary butyl and cumarone structure and preparation method thereof.
The structural formula containing the soluble polyimide of the tertiary butyl and cumarone structure of the present invention is:
。
Wherein Ar is the one in following 11 kinds of aromatic structure formulas:
。
The preparation process containing the soluble polyimide of the tertiary butyl and cumarone 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 hexamethylphosphoramide; the total consumption of monomer of reaction system makes its solid content be 10%, reacts 24 hours obtained presoma PAA after stirring under room temperature.
(2) use diacetyl oxide as dewatering agent, pyridine carries out dehydration reaction 6 ~ 10 hours as the PAA that dehydration catalyst is obtained to step (1) at 80 ~ 120 DEG C, obtained performed polymer polyisoimide.
(3) by polyisoimide obtained for step (2) under catalyst action in the nitrogen atmosphere of 150 ~ 200 DEG C polyreaction within 4 ~ 6 hours, obtain the polymers soln of thickness, be cooled to room temperature, add methyl alcohol wherein or ethanol does precipitation agent, filter, drying, namely obtained threadiness contains the soluble polyimide of the tertiary butyl and cumarone structure.
Described aromatic diamine monomers contains the tertiary butyl and cumarone based structures, chemistry by name 3,3 '-di-t-butyl-4,4 '-diamino-phenyl-3 '-cumarone methane, and its structural formula is:
。
Described aromatic dianhydride monomer 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 '-diphenyl sulfone tetraformic acid dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-diphenyl thio-ether tetrformate dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 2 ', 3-Three methyl Benzene dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 1, 1-two (3, 4-di carboxyl phenyloxy) benzophenone dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) propane dianhydride or 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride.
Described catalyzer is HCl and/or KOH, and the mass percent that its consumption accounts for total charging capacity is 2 ~ 5%.
Advantage of the present invention:
(1) preparation method of the present invention is simple to operate, is easy to large-scale promotion.
(2) 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
3, CH
2cl
2, in ethyl acetate and acetone.Wherein the dissolution characteristics of polymkeric substance in low boiling point solvent, can realize low-temperature curing film-forming process, thus material is widely used at microelectronic.
(3) 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) scope is more than 500 DEG C, carbon yield is all more than 60%.
(4) polyimide material of the present invention has excellent optical property, and cutoff wavelength scope is 300 ~ 350 nm, and transmitance is wavelength 400 ~ 550 nm of 80%.
(5) polyimide material of the present invention has low-k, and specific inductivity is all between 1.50 ~ 3.00.
Accompanying drawing explanation
Fig. 1 is the general structure containing the soluble polyimide of the tertiary butyl and cumarone structure of the present invention.
Fig. 2 is the structural formula containing the soluble polyimide of the tertiary butyl and cumarone structure prepared by the embodiment of the present invention 1.
Fig. 3 is the structural formula containing the soluble polyimide of the tertiary butyl and cumarone structure prepared by the embodiment of the present invention 2.
Fig. 4 is the structural formula containing the soluble polyimide of the tertiary butyl and cumarone structure prepared by the embodiment of the present invention 3.
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 claims limited range appended by the application 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-t-butyl-4,4 '-diamino-phenyl-3 ' 1.0000 grams ,-cumarone methane (2.3442 mmole), 3,3 ', 4,4 '-pyromellitic acid anhydride 0.5113 gram (2.3442 mmole), hexamethylphosphoramide 13.60 grams, stirs, and under room temperature, reaction obtains presoma PAA in 24 hours.Then add 25 ml acetic anhydride and pyridine 2 milliliters in the PAA obtained, at 100 DEG C, reaction obtains performed polymer polyisoimide in 8 hours.Finally in polyisoimide, add 1 milliliter of dense HCl, nitrogen protection back flow reaction 5 hours at 150 ~ 200 DEG C, finally obtains the polymers soln of thickness.After being cooled to room temperature, add 500 milliliters of ethanol, precipitation, filter and drying, finally obtain fibrous polyimide material.Its structural formula is as follows:
。
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-t-butyl-4,4 '-diamino-phenyl-3 ' 1.0000 grams ,-cumarone methane (2.3442 mmole), 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride 0.6897 gram (2.3442 mmole), hexamethylphosphoramide 15.20 grams, after stirring, under room temperature, reaction obtains presoma PAA in 24 hours.Then add 25 ml acetic anhydride and pyridine 1 milliliter in the PAA obtained, at 100 DEG C, reaction obtains performed polymer polyisoimide in 8 hours.Finally in polyisoimide, add 1 milliliter of dense HCl, in 150 ~ 200 DEG C of back flow reaction 5 hours under nitrogen protection.Finally obtain the polymers soln of thickness.After being cooled to room temperature, add 500 milliliters of ethanol, precipitation, filter and drying, finally obtain fibrous polyimide material.Its structural formula is as follows:
。
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-t-butyl-4,4 '-diamino-phenyl-3 ' 1.0000 grams ,-cumarone methane (2.3442 mmole), 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride 0.7272 gram (2.3442 mmole), hexamethylphosphoramide 15.54 grams, after stirring, under room temperature, reaction obtains presoma PAA in 24 hours.Then add 25 ml acetic anhydride and pyridine 1.5 milliliters in the PAA obtained, at 100 DEG C, reaction obtains performed polymer polyisoimide in 8 hours.Finally in polyisoimide, add 1 milliliter of dense HCl, in 150 ~ 200 DEG C of back flow reaction 5 hours under nitrogen protection.Finally obtain the polymers soln of thickness.After being cooled to room temperature, add 500 milliliters of ethanol, precipitation, filter and drying, finally obtain fibrous polyimide material.Its structural formula is as follows:
。
Claims (2)
1. contain a soluble polyimide for the tertiary butyl and cumarone structure, it is characterized in that this structural formula containing the soluble polyimide of the tertiary butyl and cumarone structure is:
；
Wherein Ar is the one in following 11 kinds of aromatic structure formulas:
。
2. the preparation method containing the soluble polyimide of the tertiary butyl and cumarone 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 hexamethylphosphoramide, the total consumption of monomer of reaction system makes its solid content be 10%, reacts 24 hours obtained presoma PAA after stirring under room temperature;
(2) use diacetyl oxide as dewatering agent, pyridine carries out dehydration reaction 6 ~ 10 hours as the PAA that dehydration catalyst is obtained to step (1) at 80 ~ 120 DEG C, obtained performed polymer polyisoimide;
(3) by polyisoimide obtained for step (2) under catalyst action in the nitrogen atmosphere of 150 ~ 200 DEG C polyreaction within 4 ~ 6 hours, obtain the polymers soln of thickness, be cooled to room temperature, add methyl alcohol wherein or ethanol does precipitation agent, filter, drying, namely obtained threadiness contains the soluble polyimide of the tertiary butyl and cumarone structure;
Described aromatic diamine monomers contains the tertiary butyl and cumarone based structures, chemistry by name 3,3 '-di-t-butyl-4,4 '-diamino-phenyl-3 '-cumarone methane, and its structural formula is:
；
Described aromatic dianhydride monomer 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 '-diphenyl sulfone tetraformic acid dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-diphenyl thio-ether tetrformate dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 2 ', 3-Three methyl Benzene dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 1, 1-two (3, 4-di carboxyl phenyloxy) benzophenone dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) propane dianhydride or 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride,
Described catalyzer is HCl and/or KOH, and the mass percent that its consumption accounts for total charging capacity is 2 ~ 5%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784462A (en) * | 2016-12-09 | 2017-05-31 | 德阳九鼎智远知识产权运营有限公司 | A kind of lithium battery for new-energy automobile |
| CN114920934A (en) * | 2022-06-29 | 2022-08-19 | 深圳职业技术学院 | Preparation method and application of photosensitive polyimide resin |
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| WO2007086550A1 (en) * | 2006-01-27 | 2007-08-02 | Nippon Steel Chemical Co., Ltd. | Laminate for wiring board |
| 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 |
| CN104356387A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide material having non-coplanar structure and preparation method thereof |
| CN104370751A (en) * | 2014-11-11 | 2015-02-25 | 桂林理工大学 | Diamine monomers containing asymmetric non-coplanar structure and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007086550A1 (en) * | 2006-01-27 | 2007-08-02 | Nippon Steel Chemical Co., Ltd. | Laminate for wiring board |
| 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 |
| CN104356387A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide material having non-coplanar structure and preparation method thereof |
| CN104370751A (en) * | 2014-11-11 | 2015-02-25 | 桂林理工大学 | Diamine monomers containing asymmetric non-coplanar structure and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784462A (en) * | 2016-12-09 | 2017-05-31 | 德阳九鼎智远知识产权运营有限公司 | A kind of lithium battery for new-energy automobile |
| CN114920934A (en) * | 2022-06-29 | 2022-08-19 | 深圳职业技术学院 | Preparation method and application of photosensitive polyimide resin |
| CN114920934B (en) * | 2022-06-29 | 2024-03-22 | 深圳职业技术学院 | Preparation method and application of photosensitive polyimide resin |
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