CN104927054A - Soluble polyimide comprising tertiary butyl and morpholinyl structure and preparation method of soluble polyimide - Google Patents
Soluble polyimide comprising tertiary butyl and morpholinyl structure and preparation method of soluble polyimide Download PDFInfo
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- CN104927054A CN104927054A CN201510368072.6A CN201510368072A CN104927054A CN 104927054 A CN104927054 A CN 104927054A CN 201510368072 A CN201510368072 A CN 201510368072A CN 104927054 A CN104927054 A CN 104927054A
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- dianhydride
- tertiary butyl
- soluble polyimide
- morpholinyl
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Abstract
The invention discloses soluble polyimide comprising a tertiary butyl and morpholinyl structure and a preparation method of the soluble polyimide. The structural formula of the soluble polyimide comprising the tertiary butyl and morpholinyl structure is shown as follows. The soluble polyimide comprising the tertiary butyl and morpholinyl structure is obtained through reaction between aromatic diamine of a non-coplanar structure and various different tetracid dihydrides according to a 'two-step method'. The polyimide has excellent solubility property, can dissolve in high-boiling-point organic solvents including N, N'- dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) and m-cresol and can also dissolve in low-boiling-point organic solvents including tetrahydrofuran (THF), chloroform (CHC13), dichloromethane (CH2C12), ethyl acetate and acetone.
Description
Technical field
The invention belongs to polymer material science field, particularly a kind of soluble polyimide containing the tertiary butyl and morpholinyl 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.Such as Shen Yu congruence people reports a kind of preparation method (CN1057782C) of polyimide of side chain with azo-functional group; Poplar scholar bravely waits people to report a kind of thermoset polyimide resin and its preparation method and application (CN1085692C); The people such as Huang Wei report soluble polyimide material containing tert-butyl and preparation method thereof (CN1148399C).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 morpholinyl 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 morpholinyl structure and preparation method thereof.
The structural formula containing the soluble polyimide of the tertiary butyl and morpholinyl 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 morpholinyl structure of the present invention is:
(1) under nitrogen protection; equimolar aromatic diamine monomers and aromatic dianhydride monomer are fully dissolved in aprotic polar solvent N; in N-N,N-DIMETHYLACETAMIDE; in reaction system, the total consumption of monomer makes its solid content be 10%; at room temperature stirring reaction 24 hours, obtained presoma polyamic acid solution.
(2) polyamic acid solution that step (1) is obtained is dissolved in diacetyl oxide-pyridine mixing solutions that volume ratio is 6:4, at room temperature stirring reaction 1 hour, stirring reaction 8 hours obtained polyimide solutions at 120 DEG C again, be cooled to room temperature, slowly pour in methyl alcohol or ethanol and obtain faint yellow threadiness and precipitate and filter, much filtrate is put at vacuum drying oven 80 DEG C after drying, i.e. the obtained soluble polyimide containing the tertiary butyl and morpholinyl structure.
Described aromatic diamine monomers contains the tertiary butyl and morpholinyl structure, chemistry by name 3,3 '-di-t-butyl-4,4 '-diamino-phenyl-4 '-morpholino phenyl 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, two [the 4-(3 of 1-, 4-di carboxyl phenyloxy) phenyl] hexanaphthene dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) propane dianhydride or 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride.
Advantage of the present invention:
(1) soluble polyimide containing the tertiary butyl and morpholinyl structure 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.
(2) soluble polyimide containing the tertiary butyl and morpholinyl structure 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%.
(3) soluble polyimide containing the tertiary butyl and morpholinyl structure of the present invention has excellent optical property, and cutoff wavelength scope is 300 ~ 350nm, and transmitance is the wavelength 400 ~ 550nm of 80%.
(4) soluble polyimide containing the tertiary butyl and morpholinyl structure 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 morpholinyl structure of the present invention.
Fig. 2 is the structural formula containing the soluble polyimide of the tertiary butyl and morpholinyl 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 morpholinyl 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 morpholinyl structure prepared by the embodiment of the present invention 3.
Fig. 5 is the structural formula containing the soluble polyimide of the tertiary butyl and morpholinyl 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 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-4 ' 1.0000 grams ,-morpholino phenyl methane (2.1201 mmole), 3,3 ', 4,4 '-pyromellitic acid anhydride 0.4624 gram (2.1201 mmole), N,N-dimethylacetamide 13.20 grams, stirred at ambient temperature reacts and obtains presoma polyamic acid solution in 24 hours.Then add in diacetyl oxide-pyridine mixing solutions that 8ml volume ratio is 6:4 by obtaining presoma polyamic acid solution, stirred at ambient temperature reacts 1 hour, at 120 DEG C, stirring reaction obtains the polyimide solution of thickness for 8 hours, after being cooled to room temperature, pour in 500 ml ethanol and precipitate, filter, much filtrate is put at vacuum drying oven 80 DEG C after drying, and namely obtained faint yellow threadiness is containing the soluble polyimide of the tertiary butyl and morpholinyl structure.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-4 ' 1.0000 grams ,-morpholino phenyl methane (2.1201 mmole), 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride 0.6238 gram (2.1201 mmole), N,N-dimethylacetamide 14.61 grams, stirred at ambient temperature reacts and obtains presoma polyamic acid solution in 24 hours.Then added by the presoma polyamic acid solution obtained in diacetyl oxide-pyridine mixing solutions that 8ml volume ratio is 6:4, stirred at ambient temperature reacts 1 h, and at 120 DEG C, stirring reaction 8 h obtains the polyimide solution of thickness.After being cooled to room temperature, slowly pouring in 500ml ethanol and precipitate, filter, much filtrate is put at vacuum drying oven 80 DEG C after drying, and namely obtained faint yellow threadiness is containing the soluble polyimide of the tertiary butyl and morpholinyl structure.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-4 ' 1.0000 grams ,-morpholino phenyl methane (2.1201 mmole), 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride 0.6577 gram (2.1201 mmole), N,N-dimethylacetamide 15.00 grams, at room temperature stirring reaction obtains presoma polyamic acid solution in 24 hours.Then obtained presoma polyamic acid solution is added in diacetyl oxide-pyridine mixing solutions that 8 ml volume ratios are 6:4, at room temperature stirring reaction 1 hour, then stirring reaction 8 h obtains the polyimide solution of thickness at 120 DEG C.After being cooled to room temperature, slowly pouring in 500ml ethanol and precipitate, filter, much filtrate is put at vacuum drying oven 80 DEG C after drying, finally namely obtained faint yellow threadiness containing the soluble polyimide of the tertiary butyl and morpholinyl structure.Its structural formula is as follows:
。
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-t-butyl-4,4 '-diamino-phenyl-4 ' 1.0000 grams ,-morpholino phenyl methane (2.1201 mmole), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 0.6831 gram (2.1201 mmole), N,N-dimethylacetamide 15.15 grams, at room temperature stirring reaction obtains presoma polyamic acid solution in 24 hours.Then obtained presoma polyamic acid solution is added diacetyl oxide-pyridine mixing solutions that 8 ml volume ratios are 6:4, stirred at ambient temperature reaction 1h, at 120 DEG C, stirring reaction 8h obtains the polyimide solution of thickness.After being cooled to room temperature, slowly pouring in 500ml ethanol and precipitate, filter, much filtrate is put at vacuum drying oven 80 DEG C after drying, finally namely obtained faint yellow threadiness containing the soluble polyimide of the tertiary butyl and morpholinyl structure.Its structural formula is as follows:
。
Claims (2)
1. contain a soluble polyimide for the tertiary butyl and morpholinyl structure, it is characterized in that this structural formula containing the soluble polyimide of the tertiary butyl and morpholinyl 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 morpholinyl structure according to claim 1, is characterized in that concrete steps are:
(1) under nitrogen protection, equimolar aromatic diamine monomers and aromatic dianhydride monomer are fully dissolved in aprotic polar solvent N, in N-N,N-DIMETHYLACETAMIDE, in reaction system, the total consumption of monomer makes its solid content be 10%, at room temperature stirring reaction 24 hours, obtained presoma polyamic acid solution;
(2) polyamic acid solution that step (1) is obtained is dissolved in diacetyl oxide-pyridine mixing solutions that volume ratio is 6:4, at room temperature stirring reaction 1 hour, stirring reaction 8 hours obtained polyimide solutions at 120 DEG C again, be cooled to room temperature, slowly pour in methyl alcohol or ethanol and obtain faint yellow threadiness and precipitate and filter, much filtrate is put at vacuum drying oven 80 DEG C after drying, i.e. the obtained soluble polyimide containing the tertiary butyl and morpholinyl structure;
Described aromatic diamine monomers contains the tertiary butyl and morpholinyl structure, chemistry by name 3,3 '-di-t-butyl-4,4 '-diamino-phenyl-4 '-morpholino phenyl 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, two [the 4-(3 of 1-, 4-di carboxyl phenyloxy) phenyl] hexanaphthene dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) propane dianhydride or 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2260017C1 (en) * | 2004-01-06 | 2005-09-10 | Институт синтетических полимерных материалов (ИСПМ) им. Н.С. Ениколопова РАН | Branched co-polyimides based on 4,5-bis-(3-aminophenoxy)phthalic acid and aminophenoxyphthalic acids |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2260017C1 (en) * | 2004-01-06 | 2005-09-10 | Институт синтетических полимерных материалов (ИСПМ) им. Н.С. Ениколопова РАН | Branched co-polyimides based on 4,5-bis-(3-aminophenoxy)phthalic acid and aminophenoxyphthalic acids |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 徐永芬 等: "２,５－双（４－氨基－２－三氟甲基苯氧基）叔丁基苯及其聚酰亚胺的制备和性能研究", 《化工新型材料》 * |
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