CN104356387A - Soluble polyimide material having non-coplanar structure and preparation method thereof - Google Patents
Soluble polyimide material having non-coplanar structure and preparation method thereof Download PDFInfo
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- CN104356387A CN104356387A CN201410630670.1A CN201410630670A CN104356387A CN 104356387 A CN104356387 A CN 104356387A CN 201410630670 A CN201410630670 A CN 201410630670A CN 104356387 A CN104356387 A CN 104356387A
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Abstract
The invention discloses a soluble polyimide material having a non-coplanar structure and a preparation method thereof. The soluble polyimide material having the non-coplanar structure has a general formula as shown in the specification. The preparation method comprises the following steps of under the protection of nitrogen, sufficiently dissolving equimolar aromatic diamine containing trifluoromethyl, isopropyl and non-coplanar structure and an aromatic dianhydride monomer in N-methylpyrrolidone (NMP) so that the content of the total solid in percentage by mass is 5-15%, reacting at room temperature for 24 hours to generate a precursor PAA, adding a dehydrating agent and a dehydrating catalyst, carrying out chemical dehydration-cyclization reaction for 6-10 hours at 80-100 DEG C and cooling to room temperature to obtain a brown viscous liquid; dropwise adding chloroform into the brown viscous liquid for sufficiently diluting, pouring the diluted product into methanol or ethanol, precipitating, filtering and finally drying to obtain a fibrous polymer, namely, the soluble polyimide material having the non-coplanar structure.
Description
Technical field
The invention belongs to polymer ambit, particularly relate to a kind of containing trifluoromethyl, sec.-propyl and non-co-planar structure solubility high transparency polyimide material and preparation method thereof.
Background technology
Polyimide is the aromatic heterocyclic polymer of a class containing imide ring on molecular structure main chain, there is the overall characteristic of high-low temperature resistant, radiation hardness, chemical stability excellence, dielectric properties and good mechanical performance, be widely applied in many high-tech areas over nearly 40 years, as aerospace, microelectronics, photoelectron and automotive industry etc.But due to molecule chain rigidity and intermolecular strong interaction, common polyimide material is presented shortcomings such as neither melting is not also dissolved, poor processability, thus further limit their widespread use.In addition, due to height conjugacy and the charge transfer complex effect (CTC) of polyimide molecule structure, material presents color in various degree usually, and in visible-range, the transparency is poor, and they are very restricted equally in the application of optical field.In order to solve above-mentioned shortcoming, prepare that solubility property is good, optical transparence is high and the polyimide material of the excellent combination property such as good thermal stability, researcher has carried out large quantifier elimination in this respect.
Fluorine-containing soluble polyimide correlative study achievement has many reports in recent years, fluorine-containing, especially the polyimide of structure is replaced containing trifluoromethyl, the physicochemical property of the free volume large due to trifluoromethyl and fluorine atom uniqueness, as larger electronegativity, less atomic radius, lower mole polarizability etc., this quasi-polyimide is made to show the better solubility property of more traditional polyimide, optical property, dielectric properties and lower rate of moisture absorption.Synthesis is adopted to have large space steric hindrance and non-co-planar structure soluble polyimide material in addition, also be the focus of Recent study, by destroying the upright and outspoken chain structure of main chain and intermolecular interaction force, destroy the formation of polyimide molecule structure charge transfer Complexes (CTC), improve solubility property and the optical clear performance of polyimide greatly.The advantages such as this method synthesis 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 Wang Xueliang report a kind of soluble high-performance polyimide and preparation method thereof (CN 101851331); The human hairs such as wangkai guest understand nonlinear optical organic polymkeric substance based on fluorinated polyimide and synthetic method (CN 101942091) thereof; The people such as Qiu Fengxian have studied fluorinated polyimide and preparation method and its usage (CN 1978488).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.
Summary of the invention
The object of this invention is to provide a kind of non-co-planar structure soluble polyimide material and preparation method thereof.This non-co-planar structure soluble polyimide material is containing trifluoromethyl, sec.-propyl and non-co-planar structure, and solubility is good, and optical transparence is high.
The general structure of non-co-planar structure soluble polyimide material of the present invention is:
。
Wherein Ar is the one in following 11 kinds of structures:
。
The preparation method of non-co-planar structure soluble polyimide material of the present invention is:
(1) under nitrogen protection; grade mole is fully dissolved in N-Methyl pyrrolidone (NMP) containing trifluoromethyl, sec.-propyl and non-co-planar structure aromatic diamines and aromatic dianhydride monomer; its total solid content mass percent is made to be 5 ~ 15%; react 24 hours under room temperature; generate presoma PAA, then add dewatering agent and dehydration catalyst, through chemical dehydration cyclization 6 ~ 10 hours at 80 ~ 100 DEG C; be cooled to room temperature, obtained brown color viscous liquid.
(2) in the obtained brown color viscous liquid of step (1), drip chloroform fully to dilute, then cut back is poured in methyl alcohol or ethanol and precipitate, filter, dry, finally obtain fibrous polymer, be non-co-planar structure soluble polyimide material.
The described diamine monomer containing trifluoromethyl, sec.-propyl and non-co-planar structure is 3,3 ˊ-di-isopropyl-4,4 ˊ-diamino-phenyl-4 ˊ ˊ-trifluoromethyl toluene, and corresponding structural formula is:
。
Described aromatic dianhydride is 3, 3 ˊ, 4, 4 ˊ-pyromellitic acid anhydride, 3, 3 ˊ, 4, 4 ˊ-bibenzene tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl ether tetraformic dianhydride, 3, 3 ˊ, 4, 4 ˊ-benzophenone tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl thio-ether tetrformate dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl sulfone tetraformic acid dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 3 ˊ-di-t-butyl benzene dianhydride, 3, 3 ˊ-bis-(3, 4-di carboxyl phenyloxy) diphenyl ether dianhydride and 1, 6-two (3, 4-di carboxyl phenyloxy) any one in-naphthalene dianhydride.
Described dewatering agent is diacetyl oxide, and dehydration catalyst is pyridine, picoline or triethylamine.
Non-co-planar structure soluble polyimide material of the present invention can be applied to microelectronics, photoelectron and high temperature material field.
Advantage of the present invention:
(1) polyimide material of the present invention has good solubility energy, not only dissolves in conventional high boiling organic solvent, can also be dissolved in low boiling point solvent, as tetrahydrofuran (THF) (THF), trichloromethane (CHCl
3) and acetone etc.The solubilized characteristic of polymkeric substance in low boiling point solvent, can realize material at low temperature film-forming technique, thus material is used widely at microelectronic.
(2) polyimide material of the present invention has excellent optical property, and cutoff wavelength scope is 307 ~ 362nm, and transmitance is the wavelength 379 ~ 459nm of 80%.This type of material is expected to be applied at microlens optical field.
(3) polyimide material of the present invention has superior heat-resistant stability, second-order transition temperature (
t g) more than 261 DEG C, thermolysis starting temperature (
t d) more than 416 DEG C, carbon yield is all more than 59%; The high-temperature stability of material, is expected to realize material and is applied as high temperature material.
Accompanying drawing explanation
Fig. 1 is the general structure of non-co-planar structure soluble polyimide material of the present invention.
Fig. 2 is the structural formula of non-co-planar structure soluble polyimide material prepared by the embodiment of the present invention 1.
Fig. 3 is the structural formula of non-co-planar structure soluble polyimide material prepared by the embodiment of the present invention 2.
Fig. 4 is the structural formula of non-co-planar structure soluble polyimide material prepared by the embodiment of the present invention 3.
Fig. 5 is the structural formula of non-co-planar structure soluble polyimide material 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:
Under nitrogen protection, one is equipped with mechanical stirrer, 3 are added respectively in 50 milliliters of there-necked flasks of reflux condensing tube and nitrogen airway, 3 ˊ-di-isopropyl-4, 4 ˊ-diamino-phenyl-4 ˊ ˊ-trifluoromethyl toluene 1.000 grams (2.3446 mmol), 3, 3 ˊ, 4, 4 ˊ-pyromellitic acid anhydride 0.5114 gram (2.3446 mmol), 13.43 gram NMP, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent, then toward wherein adding 30 ml acetic anhydride and 2 milliliters of pyridines, be warmed up to 90 DEG C of reactions 8 hours, be cooled to room temperature, finally obtain brown color viscous liquid, drip 8 milliliters of chloroform dilutions, cut back is poured in the ethanol of 400 milliliters and precipitate, filter, dry, finally obtain faint yellow fibrous polymer, be non-co-planar structure soluble 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-trifluoromethyl toluene 1.000 grams (2.3446mmol), 3,3 ˊ, 4,4 ˊ-bibenzene tetracarboxylic dianhydride 0.6898 gram (2.3446mmol), 14.91 grams of NMP, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent.Then toward the picoline wherein adding 30 ml acetic anhydride and 2 milliliters, be warmed up to 90 DEG C of reactions 8 hours, be cooled to room temperature, finally obtain brown color viscous liquid, drip 7 milliliters of chloroform dilutions, cut back is poured in 400 ml methanol and precipitate, filter, drying, finally obtains faint yellow fibrous polymer, is non-co-planar structure soluble 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-trifluoromethyl toluene 1.0000 grams (2.3446mmol), 3, 3 ˊ, 4, 4 ˊ-benzophenone tetracarboxylic dianhydride 0.7555 gram (2.3446mmol), 15.43 gram NMP, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent, then toward wherein adding 30 ml acetic anhydride and 2 milliliters of triethylamines, be warmed up to 90 DEG C of reactions 8 hours, be cooled to room temperature, finally obtain brown color viscous liquid, drip 8 milliliters of chloroform dilutions, cut back is poured in 400 milliliters of ethanol and precipitate, filter and finally obtain faint yellow fibrous polymer, be non-co-planar structure soluble 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-trifluoromethyl toluene 1.0000 grams (2.3446mmol), 3, 3 ˊ, 4, 4 ˊ-diphenyl ether tetraformic dianhydride 0.7273 gram (2.3446mmol), 15.32 gram NMP, react 24 hours under room temperature, the system of obtaining is the presoma PAA of homogeneous phase transparent, then toward wherein adding 30 ml acetic anhydride and 2 milliliters of picolines, be warmed up to 90 DEG C of reactions 8 hours, be cooled to room temperature, finally obtain brown color viscous liquid, drip 7 milliliters of chloroform dilutions, cut back is poured in 400 ml methanol and precipitate, filter, dry, finally obtain faint yellow fibrous polymer, be non-co-planar structure soluble polyimide material.Its structural formula is shown in Figure of description.
Claims (3)
1. a non-co-planar structure soluble polyimide material, is characterized in that the general structure of described non-co-planar structure soluble polyimide material is:
；
Wherein Ar is the one in following 11 kinds of structures:
。
2. the preparation method of non-co-planar structure soluble polyimide material according to claim 1, is characterized in that concrete steps are:
(1) under nitrogen protection, grade mole is fully dissolved in N-Methyl pyrrolidone containing trifluoromethyl, sec.-propyl and non-co-planar structure aromatic diamines and aromatic dianhydride monomer, its total solid content mass percent is made to be 5 ~ 15%, react 24 hours under room temperature, generate presoma PAA, then add dewatering agent and dehydration catalyst, through chemical dehydration cyclization 6 ~ 10 hours at 80 ~ 100 DEG C, be cooled to room temperature, obtained brown color viscous liquid;
(2) in the obtained brown color viscous liquid of step (1), drip chloroform fully to dilute, then cut back is poured in methyl alcohol or ethanol and precipitate, filter, dry, finally obtain fibrous polymer, be non-co-planar structure soluble polyimide material;
The described diamine monomer containing trifluoromethyl, sec.-propyl and non-co-planar structure is 3,3 ˊ-di-isopropyl-4,4 ˊ-diamino-phenyl-4 ˊ ˊ-trifluoromethyl toluene, and corresponding structural formula is:
；
Described aromatic dianhydride is 3, 3 ˊ, 4, 4 ˊ-pyromellitic acid anhydride, 3, 3 ˊ, 4, 4 ˊ-bibenzene tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl ether tetraformic dianhydride, 3, 3 ˊ, 4, 4 ˊ-benzophenone tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl thio-ether tetrformate dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl sulfone tetraformic acid dianhydride, 2, 2-two (3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 3 ˊ-di-t-butyl benzene dianhydride, 3, 3 ˊ-bis-(3, 4-di carboxyl phenyloxy) diphenyl ether dianhydride and 1, 6-two (3, 4-di carboxyl phenyloxy) any one in-naphthalene dianhydride,
Described dewatering agent is diacetyl oxide, and dehydration catalyst is pyridine, picoline or triethylamine.
3. the application of non-co-planar structure soluble polyimide material according to claim 1 and 2, is characterized in that this non-co-planar structure soluble polyimide material is applied to microelectronics, photoelectron and high temperature material field.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987506A (en) * | 2015-06-29 | 2015-10-21 | 桂林理工大学 | Soluble polyimide containing tert-butyl and benzofuran structure and preparation method of soluble polyimide |
| WO2020206968A1 (en) * | 2019-04-10 | 2020-10-15 | 华南理工大学 | High heat resistance, transparent and soluble biphenyl-type polyimide thin film, preparation method therefor and use thereof |
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| 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 |
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2014
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| CN1448384A (en) * | 2002-03-29 | 2003-10-15 | 中国科学院化学研究所 | Polyalkyl substituted aromatic diamidogen containing aromatic lateral group and prep. and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987506A (en) * | 2015-06-29 | 2015-10-21 | 桂林理工大学 | Soluble polyimide containing tert-butyl and benzofuran structure and preparation method of soluble polyimide |
| CN104987506B (en) * | 2015-06-29 | 2017-12-12 | 桂林理工大学 | Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof |
| WO2020206968A1 (en) * | 2019-04-10 | 2020-10-15 | 华南理工大学 | High heat resistance, transparent and soluble biphenyl-type polyimide thin film, preparation method therefor and use thereof |
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