CN104927054B - Soluble polyimide containing the tert-butyl group and morpholine based structures and preparation method thereof - Google Patents
Soluble polyimide containing the tert-butyl group and morpholine based structures and preparation method thereof Download PDFInfo
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- CN104927054B CN104927054B CN201510368072.6A CN201510368072A CN104927054B CN 104927054 B CN104927054 B CN 104927054B CN 201510368072 A CN201510368072 A CN 201510368072A CN 104927054 B CN104927054 B CN 104927054B
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Abstract
The invention discloses a kind of soluble polyimide containing the tert-butyl group and morpholine based structures and preparation method thereof.Structural formula of the soluble polyimide containing the tert-butyl group and morpholine based structures is:;The soluble polyimide material containing the tert-butyl group and morpholine based structures is prepared using being reacted by " two-step method " from various different tetracarboxylic dianhydrides with non-co-planar structure aromatic diamines.Polyimide material of the invention has outstanding solubility property, can not only be dissolved completely in high boiling organic solvent N, N ' dimethylformamide(DMF), N, N ' dimethylacetylamides(DMAc), N methyl pyrrolidones(NMP), dimethyl sulfoxide (DMSO)(DMSO)And in metacresol, and can also preferably be dissolved in lower boiling solvents tetrahydrofurane(THF), chloroform(CHCl3), dichloromethane(CH2Cl2), in ethyl acetate and acetone.
Description
Technical field
The invention belongs to polymer material science field, more particularly to a kind of solubility containing the tert-butyl group and morpholine based structures
Polyimides and preparation method thereof.
Background technology
Polyimides is the important feature heat-resistant polymer of a class, can be used as matrices of composite material, electronic seal
Package material, gas separate be applied in film modern high-tech field, and have been widely used for space flight and aviation, auto industry,
Electronic and electrical industry etc..Polyimides(PI)It is the class high-performance polymer containing imide ring structure in molecular structure.Although
This kind of exotic material has excellent thermal property and a mechanical property, but have by them stiff backbone structure, with
And intermolecular presence strong interaction and strand it is tightly packed, cause the polyimides of most of commercialization all to have very
Melt temperature high, and insoluble in organic solvent(It is dissolved only in the concentrated sulfuric acid mostly), difficulty is brought to its processing and forming.Additionally, passing
The polyimides of system is due to electric charge complexing transferance in the aromatic conjugated property and strand of molecular backbone height, and its film is most
With very deep color and poor optical transparence.In order to overcome above-mentioned difficulties, solubility property is prepared good, easy to process etc.
The polyimide material of excellent combination property, related scientific research department has put into substantial amounts of human and material resources, financial resources and has been engaged in this respect
R&D work.
Soluble polyimide is the focus of Recent study, wherein having large space steric hindrance and non-co-planar using synthesis
The polyimide material of structure, by destroying the upright and outspoken chain structure and intermolecular interaction force of main chain, so as to obtain height
Solvable polyimide material.The advantages of the method monomer synthesizes cheap simple, price, material excellent combination property, is current
Generally use one of method of synthesizing soluble polyimide.Such as Shen Yu congruence people report a kind of side chain with azo-functional group
Polyimides preparation method(CN1057782C);Poplar scholar is brave et al. to report a kind of thermoset polyimide resin and its system
Preparation Method and application(CN1085692C);Huang Wei et al. reports soluble polyimide material containing tert-butyl and preparation method thereof
(CN1148399C).Such material has good hot property, excellent solubility property, optical transparence high, low dielectric normal
The combination properties such as several and low hydroscopicity, are widely used in fields such as Aero-Space, microelectronics and photoelectrons.
Non-co-planar structure and substituted radical are incorporated into polyimide structures by MOLECULE DESIGN prepare soluble poly
Acid imide.The large-substituent tert-butyl group and morpholinyl are introduced in polyimides, the solubility property of polyimides is improve, not only may be used
To be dissolved in high boiling organic solvent N, N '-dimethylformamide(DMF), N, N '-dimethylacetylamide(DMAc), N- methyl pyrroles
Pyrrolidone(NMP), dimethyl sulfoxide (DMSO)(DMSO)And in metacresol, and can also preferably be dissolved in lower boiling solvent tetrahydrochysene furan
Mutter(THF), chloroform(CHCl3), dichloromethane(CH2Cl2), in ethyl acetate and acetone so that the polyimides low-temperature solid of indissoluble
Chemical conversion film is possibly realized.This kind of polyimide material also has excellent hot property, optical property and dielectric properties etc..Hot
Energy aspect, compared with the polyimides of commercialization, although hot property reduction to a certain extent, but its glass transition temperature(T g)
Still remain in more than 300 DEG C, heat decomposition temperature(T d)More than 500 DEG C, such material is in Aero-Space, microelectronics and light
The application fields such as electronics are sufficient for its use requirement.
The content of the invention
It is an object of the invention to provide a kind of soluble polyimide containing the tert-butyl group and morpholine based structures and its preparation side
Method.
The structural formula of the soluble polyimide containing the tert-butyl group and morpholine based structures of the invention is:
。
Wherein Ar is the one kind in following 11 kinds of aromatic structure formulas:
。
The preparation process of the soluble polyimide containing the tert-butyl group and morpholine based structures of the invention is:
(1) under nitrogen protection, equimolar aromatic diamine monomers and aromatic dianhydride monomer are substantially dissolved in non-proton
In polar solvent DMA, the total consumption of monomer makes its solid content be 10% in reaction system, is stirred at room temperature anti-
Answer 24 hours, presoma polyamic acid solution is obtained.
(2) it is 6 polyamic acid solution obtained in step (1) to be dissolved in into volume ratio:4 acetic anhydride-pyridine mixed solution,
Stirring reaction 1 hour, then 8 hours prepared polyimide solutions of stirring reaction at 120 DEG C at room temperature, is cooled to room temperature, slowly
Pour into and faint yellow threadiness precipitation obtained in methyl alcohol or ethanol and is filtered, much filtrate is put into after drying at 80 DEG C of vacuum drying chamber,
The soluble polyimide containing the tert-butyl group and morpholine based structures is obtained.
The aromatic diamine monomers contain the tert-butyl group and morpholine based structures, chemistry entitled 3,3 '-di-t-butyl -4,4 '-two
Aminophenyl -4 '-morpholino phenyl methane, its structural formula is:
。
The aromatic dianhydride monomer be 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- double (3,4- di carboxyl phenyloxies) -2,2 ', 3- trimethylbenzenes two
Double (3,4- dicarboxyphenyis) hexafluoropropane dianhydrides of acid anhydride, 2,2-, double [4- (3,4- di carboxyl phenyloxies) phenyl] hexamethylenes of 1,1-
Double (3,4- dicarboxyphenyis) propane dianhydrides of dianhydride, 2,2- or double [4- (3,4- di carboxyl phenyloxies) phenyl] HFC-236fas of 2,2-
Dianhydride.
Advantages of the present invention:
(1) soluble polyimide containing the tert-butyl group and morpholine based structures of the invention has good dissolubility energy, can
It is dissolved in conventional high boiling organic solventN,N'- dimethylformamide(DMF)、N,N'- dimethylacetylamide(DMAc), N- methyl
Pyrrolidones(NMP), dimethyl sulfoxide (DMSO)(DMSO)And metacresol(m-Cresol)Deng, moreover it is possible to be dissolved in low boiling point solvent THF,
CHCl3、CH2Cl2, in ethyl acetate and acetone.Wherein dissolution characteristics of the polymer in low boiling point solvent, are capable of achieving low-temperature solid
Chemical conversion membrane process, so that material is widely used in microelectronic.
(2) soluble polyimide containing the tert-butyl group and morpholine based structures of the invention has superior heat-resistant stability,
Glass transition temperature(T g)More than 300 DEG C, initial temperature is thermally decomposed(T d)Scope is more than 500 DEG C, and carbon yield is all 60%
More than.
(3) soluble polyimide containing the tert-butyl group and morpholine based structures of the invention has excellent optical property, cuts
Only wave-length coverage is 300 ~ 350nm, and transmitance is 80% 400 ~ 550nm of wavelength.
(4) soluble polyimide containing the tert-butyl group and morpholine based structures of the invention has low-k, and dielectric is normal
Number is all between 1.50 ~ 3.00.
Brief description of the drawings
Fig. 1 is the general structure of the soluble polyimide containing the tert-butyl group and morpholine based structures of the invention.
Fig. 2 is the structural formula of the soluble polyimide containing the tert-butyl group and morpholine based structures prepared by the embodiment of the present invention 1.
Fig. 3 is the structural formula of the soluble polyimide containing the tert-butyl group and morpholine based structures prepared by the embodiment of the present invention 2.
Fig. 4 is the structural formula of the soluble polyimide containing the tert-butyl group and morpholine based structures prepared by the embodiment of the present invention 3.
Fig. 5 is the structural formula of the soluble polyimide containing the tert-butyl group and morpholine based structures prepared by the embodiment of the present invention 4.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within claims appended by the application and limited
Scope.
Embodiment 1:
During mechanical agitator, reflux condensing tube, 50 milliliters of three neck round bottom flask of nitrogen wireway are housed at one respectively
Add 3,3 '-di-t-butyl -4,4 '-diamino-phenyl -4 ' 1.0000 grams of-morpholino phenyl methane(2.1201 mMs), 3,
0.4624 gram of 3 ', 4,4 '-pyromellitic acid anhydride(2.1201 mMs), 13.20 grams of DMA, at room temperature
Stirring reaction obtains presoma polyamic acid solution in 24 hours.Then presoma polyamic acid solution will be obtained and will add 8ml volumes
Than being 6:In 4 acetic anhydride-pyridine mixed solution, stirring reaction 1 hour, stirring reaction 8 hours at 120 DEG C at room temperature
Sticky polyimide solution is obtained, after being cooled to room temperature, is poured into 500 ml ethanol and is precipitated, filtering, much filtrate is put into vacuum
After being dried at 80 DEG C of drying box, that is, soluble polyimide of the faint yellow threadiness containing the tert-butyl group and morpholine based structures is obtained.Its
Structural formula is as follows:
。
Embodiment 2:
During mechanical agitator, reflux condensing tube, 50 milliliters of three neck round bottom flask of nitrogen wireway are housed at one respectively
Add 3,3 '-di-t-butyl -4,4 '-diamino-phenyl -4 ' 1.0000 grams of-morpholino phenyl methane(2.1201 mMs), 3,
0.6238 gram of 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride(2.1201 mMs), 14.61 grams of DMA, at room temperature
Stirring reaction obtains presoma polyamic acid solution in 24 hours.Then the presoma polyamic acid solution that will be obtained adds 8ml bodies
Product is than being 6:In 4 acetic anhydride-pyridine mixed solution, the h of stirring reaction 1 at room temperature, the h of stirring reaction 8 is obtained at 120 DEG C
Sticky polyimide solution.After being cooled to room temperature, precipitation in 500ml ethanol is poured slowly into, filtering, much filtrate is put into vacuum and does
After being dried at 80 DEG C of dry case, that is, soluble polyimide of the faint yellow threadiness containing the tert-butyl group and morpholine based structures is obtained.Its knot
Structure formula is as follows:
。
Embodiment 3:
During mechanical agitator, reflux condensing tube, 50 milliliters of three neck round bottom flask of nitrogen wireway are housed at one respectively
Add 3,3 '-di-t-butyl -4,4 '-diamino-phenyl -4 ' 1.0000 grams of-morpholino phenyl methane(2.1201 mMs), 3,
0.6577 gram of 3 ', 4,4 '-diphenyl ether tetraformic dianhydride(2.1201 mMs), 15.00 grams of DMA, in room
The lower stirring reaction of temperature obtains presoma polyamic acid solution in 24 hours.Then obtained presoma polyamic acid solution is added 8
Ml volume ratios are 6:In 4 acetic anhydride-pyridine mixed solution, reaction 1 hour is stirred at room temperature, then is stirred at 120 DEG C anti-
8 h are answered to obtain sticky polyimide solution.After being cooled to room temperature, precipitation in 500ml ethanol, filtering, much filtrate are poured slowly into
It is put into after drying at 80 DEG C of vacuum drying chamber, solubility of the faint yellow threadiness containing the tert-butyl group and morpholine based structures is finally obtained
Polyimides.Its structural formula is as follows:
。
Embodiment 4:
During mechanical agitator, reflux condensing tube, 50 milliliters of three neck round bottom flask of nitrogen wireway are housed at one respectively
Add 3,3 '-di-t-butyl -4,4 '-diamino-phenyl -4 ' 1.0000 grams of-morpholino phenyl methane(2.1201 mMs), 3,
0.6831 gram of 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA)(2.1201 mMs), 15.15 grams of DMA, in room
The lower stirring reaction of temperature obtains presoma polyamic acid solution in 24 hours.Then obtained presoma polyamic acid solution is added 8
Ml volume ratios are 6:4 acetic anhydride-pyridine mixed solution, stirring reaction 1h at room temperature, stirring reaction 8h is obtained at 120 DEG C
Sticky polyimide solution.After being cooled to room temperature, precipitation in 500ml ethanol is poured slowly into, filtering, much filtrate is put into vacuum and does
After being dried at 80 DEG C of dry case, soluble polyimide of the faint yellow threadiness containing the tert-butyl group and morpholine based structures is finally obtained.
Its structural formula is as follows:
。
Claims (2)
1. a kind of soluble polyimide containing the tert-butyl group and morpholine based structures, it is characterised in that this contains the tert-butyl group and morpholine base junction
The structural formula of the soluble polyimide of structure is:
;
Wherein Ar is the one kind in following 11 kinds of aromatic structure formulas:
。
2. the preparation method of the soluble polyimide containing the tert-butyl group and morpholine based structures according to claim 1, it is special
Levy is to concretely comprise the following steps:
(1) under nitrogen protection, equimolar aromatic diamine monomers and aromatic dianhydride monomer are substantially dissolved in aprotonic polar
In solvent DMA, the total consumption of monomer makes its solid content be 10% in reaction system, and reaction 24 is stirred at room temperature
Hour, presoma polyamic acid solution is obtained;
(2) it is 6 polyamic acid solution obtained in step (1) to be dissolved in into volume ratio:4 acetic anhydride-pyridine mixed solution, in room temperature
Lower stirring reaction 1 hour, then 8 hours prepared polyimide solutions of stirring reaction at 120 DEG C, are cooled to room temperature, are poured slowly into
Faint yellow threadiness precipitation is obtained in methyl alcohol or ethanol and is filtered, much filtrate is put into after drying at 80 DEG C of vacuum drying chamber, that is, make
The soluble polyimide of the tert-butyl group and morpholine based structures must be contained;
The aromatic diamine monomers contain the tert-butyl group and morpholine based structures, chemistry entitled 3,3 '-di-t-butyl -4,4 '-diaminourea
Phenyl -4 '-morpholino phenyl methane, its structural formula is:
;
The aromatic dianhydride monomer be 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 (BTDA),
3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride, 1,4- double (3,4- di carboxyl phenyloxies) -2,2 ', 3- trimethylbenzenes dianhydride, 2,
Double [4- (3,4- di carboxyl phenyloxies) phenyl] the hexamethylene dianhydrides of double (3,4- dicarboxyphenyis) hexafluoropropane dianhydrides of 2-, 1,1-,
Double (3,4- dicarboxyphenyis) propane dianhydrides of 2,2- or double [4- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydrides of 2,2-.
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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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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 |
---|
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;徐永芬 等;《化工新型材料》;20130228;第41卷(第2期);第65-68页 * |
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