CN104804189A - Semi-alicyclic polyimide containing phenolic hydroxyl groups, and preparation method and application thereof - Google Patents
Semi-alicyclic polyimide containing phenolic hydroxyl groups, and preparation method and application thereof Download PDFInfo
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- CN104804189A CN104804189A CN201510207932.8A CN201510207932A CN104804189A CN 104804189 A CN104804189 A CN 104804189A CN 201510207932 A CN201510207932 A CN 201510207932A CN 104804189 A CN104804189 A CN 104804189A
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Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to semi-alicyclic polyimide containing phenolic hydroxyl groups and a preparation method and an application thereof. The semi-alicyclic polyimide containing phenolic hydroxyl groups has a structure as shown in formula I shown in the description. The preparation method comprises the following steps: dissolving 2,2'-bis(3-amino-4-hydroxyphenyl) propane in a strong polar aprotic organic solvent under N2 protection, then adding 1,2,4,5-cyclohexane tetracarboxylic dianhydride, stirring for 0.5-3 h, adding an azeotropic dehydrating agent and a catalyst, heating to 180-200 DEG C, and performing reflux for 3-5 h; cooling mixed liquid after reflux, using a preciptant to precipitate a solid product in the mixed liquid, and then filtering, washing and drying the solid product to obtain the semi-alicyclic polyimide containing the phenolic hydroxyl groups. The invention further provides a polyimide film, and the film is prepared from the semi-alicyclic polyimide containing the phenolic hydroxyl groups.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of phenolic hydroxy group half alicyclic ring polyimide and preparation method thereof and application.
The field of the invention object is the preparation method providing above-mentioned phenolic hydroxy group half alicyclic ring polyimide.
Another object of the present invention is to the application that above-mentioned phenolic hydroxy group half alicyclic ring polyimide is provided.
Object of the present invention is realized by following proposal:
A kind of phenolic hydroxy group half alicyclic ring polyimide, has structure shown in formula I:
Wherein, be repeating unit in square brackets, bracket represent repeat connect; Described n repeateding unit number, and n be greater than 0 positive integer; N is preferably the positive integer of 0 ~ 5000; The more preferably positive integer of 22 ~ 5000;
The preparation method of described phenolic hydroxy group half alicyclic ring polyimide, comprises following steps:
(1) N
2under protection, by 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane (BAHPP) are dissolved in strong polar non-proton organic solvent, then add 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (H-PMDA), after stirring 0.5 ~ 3h, adds azeotropy dehydrant and catalyzer, be warmed up to 180 ~ 200 DEG C, backflow 3 ~ 5h;
(2) by the mixed solution cooling after backflow in step (1), with the solid product in precipitating agent precipitating mixed solution, then solid product is filtered, washing, dry, obtain phenolic hydroxy group half alicyclic ring polyimide;
The mol ratio of 2,2 ＇ described in step (1)-bis-(3-amino-4-hydroxylphenyl) propane and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is 1:(1 ~ 1.03);
Described in step (1) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride accounts for 10% ~ 20% of total reaction system quality (BAHPP, H-PMDA, strong polar non-proton organic solvent, azeotropy dehydrant and catalyst quality sum);
The mass ratio of the azeotropy dehydrant described in step (1) and strong polar non-proton organic solvent is (0.9 ~ 1.1): 6;
Strong polar non-proton organic solvent described in step (1) is preferably METHYLPYRROLIDONE;
Azeotropy dehydrant described in step (1) is dimethylbenzene;
Catalyzer described in step (1) is γ-valerolactone and pyridine catalyst system;
Cooling described in step (2) is preferably cooled to 20 ~ 30 DEG C;
Mixed solution described in step (2) is preferably poured in the precipitating agent under high-speed stirring state, precipitating solid product;
Precipitating agent described in step (2) is at least one in first alcohol and water;
Precipitating agent described in step (2) is preferably methanol aqueous solution, and wherein in methanol aqueous solution, the volume ratio of methyl alcohol and water is preferably (0.1 ~ 1): 1;
Phenolic hydroxy group half alicyclic ring polyimide synthetic route of the present invention is as follows:
A kind of Kapton, is prepared by above-mentioned phenolic hydroxy group half alicyclic ring polyimide;
The preparation method of described Kapton, comprises following steps:
(1) above-mentioned phenolic hydroxy group half alicyclic ring polyimide is dissolved in strong polar non-proton organic solvent, obtains polyimide solution;
(2) after then polyimide solution being left standstill 0.5 ~ 3h, vacuum defoamation, coats on sheet glass by the polyimide solution after deaeration, and dry, demoulding, obtains Kapton;
Strong polar non-proton organic solvent described in step (1) is at least one in DMF, N,N-dimethylacetamide, N-ethyl-2-pyrrolidone, METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO);
The massfraction of the polyimide solution described in step (1) is 10% ~ 25%;
The condition optimization of the drying described in step (2) is dry 3 ~ 30min at 80 ~ 95 DEG C;
Drying described in step (2), demoulding to be preferably after dry, cooling demoulding again;
Phenolic hydroxyl group and alicyclic structure are introduced in PI molecular chain by the present invention simultaneously, while introducing function base phenolic hydroxyl group, substantially improve the optical property of PI, expand its range of application, especially in photosensitive PI Material Field.
The present invention has following advantage and effect relative to prior art:
(1) in the phenolic hydroxy group half alicyclic ring polyimide for preparing of the present invention containing phenolic hydroxyl group, consistency or the adhesiveproperties of itself and other materials can be improved.While the excellent properties keeping PI intrinsic, adhesiveproperties or the consistency of PI and other materials can be improved, also can be used to prepare photo-sensistive polyimide material.
(2) contain alicyclic structure in the phenolic hydroxy group half alicyclic ring polyimide that the present invention prepares, effectively can reduce in PI molecule and intermolecular load transfer effect, improve the transmittance in ultraviolet-visible light region.
(3) the phenolic hydroxy group half alicyclic ring polyimide resistance toheat for preparing of the present invention is good, and excellent in optical properties, its visible light transmissivity, up to 94.2%, has a good application prospect.
(4) product yield is very high, reaches more than 95%.
(5) technique that membrane-film preparation process is used is comparatively ripe, the equipment of existing production Kapton can be utilized completely to implement the present invention, be conducive to the industrialization of product.
Background technology
Polyimide (PI) starts from the 1950's as a kind of macromolecular material development, the mid-1960s, first du pont company by Kapton (Kapton) and varnish (Pyre ML) commercialization, starts the epoch that a PI is flourish thus.PI material high and low temperature resistance is given prominence to, excellent in stability, specific inductivity and thermal expansivity is low, flame retardant resistance is outstanding, has been widely used in the fields such as Aeronautics and Astronautics, microelectronics, liquid crystal.
PI can be divided into following several main Types by finished product form: film, resin, fiber, coating, foam, sizing agent etc.Wherein being most widely used with most important form is thin-film material, and its total quantity consumed ranks forefront three at polyimide material meta.PI as thin-film material not only can high-low temperature resistant, dimensional stabilizing, good toughness, and can the use of long-time safety and stability.Wherein excellent with the Apical film performance of the Upilex film of the Kapton film of du pont company, Ube Industries Ltd. and Japanese Zhong Yuan, occupy the market of the overwhelming majority.But the adhesiveproperties of business-like PI film and other materials exists certain defect, therefore, while the excellent properties keeping PI intrinsic, in order to improve adhesiveproperties or the consistency of itself and other materials, phenolic hydroxyl group can be introduced in the molecular structure of PI.The PI of phenolic hydroxy group also can be applicable to photo-sensistive polyimide (PSPI) material.And alicyclic structure is introduced in PI molecule, effectively can suppress in PI molecule and the formation of Intermolecular charge transfer complex, therefore significantly can weaken the absorption of aromatic series PI in ultraviolet-visible light region, and introduce alicyclic structure, the solvability of PI can also be improved.
About the research work of phenolic hydroxy group or alicyclic-containing polyimide Material Field has many reports:
Chinese invention patent CN101003716A discloses a kind of preparation method of binder of polyimide of containing phenolic hydroxyl group.
Chinese invention patent CN1927908A discloses a kind of preparation method of phenolic hydroxyl group containing polyimide powder.
Chinese invention patent CN102516541A discloses a kind of polyimide of phenolic hydroxy group.
Chinese invention patent CN102650080A discloses polyimide fiber spinning solution based on 3,3 '-diamino-4,4 '-dihydroxybiphenyl and preparation thereof.
Chinese invention patent CN102660796A discloses polyimide fiber spinning solution based on two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-and preparation thereof.
Chinese invention patent CN101580637A discloses a kind of containing ester ring Kapton and preparation method thereof.
Chinese invention patent CN101922061A discloses a kind of polyimide fiber and preparation method thereof.
Chinese invention patent CN102898644A discloses a kind of soluble fluorine-containing aromatic half alicyclic ring polyimide film material and preparation method thereof.
The people such as Liu Jingang (synthesis and characteries of Semi-alicyclic Polyimides With High Refractive Indices And High Transparency, polymer journal, 2008, (5): 460-465) molecular structure disclosing alicyclic-containing polyimide film and preparation method thereof.
Summary of the invention
In order to overcome the deficiencies in the prior art and shortcoming, primary and foremost purpose of the present invention is to provide a kind of phenolic hydroxy group half alicyclic ring polyimide.
Accompanying drawing explanation
Fig. 1 is fourier transform infrared spectrometry (FTIR) spectrogram of phenolic hydroxy group half alicyclic ring polyimide (PI) that embodiment 1 prepares.
Fig. 2 is that the differential scanning calorimeter (DSC) of phenolic hydroxy group half alicyclic ring polyimide (PI) that embodiment 1 prepares scans spectrogram.
Fig. 3 is thermogravimetic analysis (TGA) (TGA) spectrogram of phenolic hydroxy group half alicyclic ring polyimide (PI) that embodiment 1 prepares.
Fig. 4 is the Kapton absorbance spectrum at different wavelengths that embodiment 1 prepares.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 41.09g METHYLPYRROLIDONE are added in reaction flask, after stirring and dissolving, add 1 in batches, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2.24g (10mmol) altogether, after stirring reaction 0.5h, add 6.85g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine), be warmed up to 180 DEG C of backflow azeotropic dehydration 4h;
(2) mixed solution after backflow in step (1) is cooled to 30 DEG C, then the volume ratio poured under high-speed stirring state is precipitated product in the methanol aqueous solution of 1:1 (methyl alcohol: water), filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried phenolic hydroxy group half alicyclic ring polyimide powder 1.00g to be dissolved in 4.00g METHYLPYRROLIDONE, obtain polyimide solution;
(4) after then polyimide solution being left standstill 3h, vacuum defoamation, polyimide solution after deaeration is poured on clean sheet glass, use scraper blade coating, careful is put into sheet glass in the air dry oven of modulated good level, dries 10min, naturally cool to room temperature at 90 DEG C, put into water and soak demoulding, obtain Kapton.
Embodiment 2
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 41.69g METHYLPYRROLIDONE are added in reaction flask, after stirring and dissolving, add 1 in batches, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2.31g (10.3mmol) altogether, after stirring reaction 0.5h, add 6.95g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine), be warmed up to 180 DEG C of backflow azeotropic dehydration 5h;
(2) mixed solution after backflow in step (1) is cooled to 25 DEG C, then the volume ratio poured under high-speed stirring state is precipitated product in the methanol aqueous solution of 0.1:1 (methyl alcohol: water), filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried phenolic hydroxy group half alicyclic ring polyimide powder 1.00g to be dissolved in 9.00g METHYLPYRROLIDONE, obtain polyimide solution;
(4) after then polyimide solution being left standstill 30min, vacuum defoamation, polyimide solution after deaeration is poured on clean sheet glass, use scraper blade coating, careful is put into sheet glass in the air dry oven of modulated good level, dries 30min, naturally cool to room temperature at 80 DEG C, put into water and soak demoulding, obtain Kapton.
Embodiment 3
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 40.99g METHYLPYRROLIDONE are added in reaction flask, after stirring and dissolving, add 1 in batches, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2.24g (10mmol) altogether, after stirring reaction 0.5h, add 6.94g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine), be warmed up to 200 DEG C of backflow azeotropic dehydration 3h;
(2) mixed solution after backflow in step (1) is cooled to 20 DEG C, then pours precipitated product in the methyl alcohol under high-speed stirring state into, filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried phenolic hydroxy group half alicyclic ring polyimide powder 1.00g to be dissolved in 5.67g DMF, obtain polyimide solution;
(4) after then polyimide solution being left standstill 2h, vacuum defoamation, polyimide solution after deaeration is poured on clean sheet glass, use scraper blade coating, careful is put into sheet glass in the air dry oven of modulated good level, dries 6min, naturally cool to room temperature at 90 DEG C, put into water and soak demoulding, obtain Kapton.
Embodiment 4
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 20.43g METHYLPYRROLIDONE are added in reaction flask, after stirring and dissolving, add 1 in batches, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2.24g (10mmol) altogether, after stirring reaction 3h, add 3.40g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine), be warmed up to 200 DEG C of backflow azeotropic dehydration 3.5h;
(2) mixed solution after backflow in step (1) is cooled to 30 DEG C, then pours precipitated product in the water under high-speed stirring state into, filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried phenolic hydroxy group half alicyclic ring polyimide powder 1.00g to be dissolved in 3.00g N,N-dimethylacetamide, obtain polyimide solution;
(4) after then polyimide solution being left standstill 3h, polyimide solution after deaeration is poured on clean sheet glass by vacuum defoamation, use scraper blade coating, careful is put in the air dry oven of modulated good level by sheet glass, 3min is dried at 95 DEG C, naturally cool to room temperature, put into water and soak demoulding, obtain Kapton.
Embodiment 5
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 20.57gN-N-methyl-2-2-pyrrolidone N-are added in reaction flask, after stirring and dissolving, add 1 in batches, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2.26g (10.1mmol) altogether, after stirring reaction 2h, add 3.37g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine), be warmed up to 180 DEG C of backflow azeotropic dehydration 3.5h;
(2) mixed solution after backflow in step (1) is cooled to 30 DEG C, then the volume ratio poured under high-speed stirring state is precipitated product in the methanol aqueous solution of 0.5:1 (methyl alcohol: water), filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried polyimide powder 1.00g to be dissolved in 9.00g N,N-dimethylacetamide, obtain polyimide solution;
(4) after then polyimide solution being left standstill 30min, polyimide solution after deaeration is poured on clean sheet glass by vacuum defoamation, use scraper blade coating, careful is put in the air dry oven of modulated good level by sheet glass, 15min is dried at 85 DEG C, naturally cool to room temperature, put into water and soak demoulding, obtain Kapton.
Embodiment 6
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 27.54g METHYLPYRROLIDONE are added in reaction flask, after stirring and dissolving, add 1 in batches, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2.24g (10mmol) altogether, after stirring reaction 0.5h, add 4.59g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine), be warmed up to 180 DEG C of backflow azeotropic dehydration 5h;
(2) mixed solution after backflow in step (1) is cooled to 25 DEG C, then the volume ratio poured under high-speed stirring state is precipitated product in the methanol aqueous solution of 0.25:1 (methyl alcohol: water), filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried phenolic hydroxy group half alicyclic ring polyimide powder 1.00g to be dissolved in 9.00g dimethyl sulfoxide (DMSO), obtain polyimide solution;
(4) after then polyimide solution being left standstill 30min, polyimide solution after deaeration is poured on clean sheet glass by vacuum defoamation, use scraper blade coating, careful is put in the air dry oven of modulated good level by sheet glass, 20min is dried at 90 DEG C, naturally cool to room temperature, put into water and soak demoulding, obtain Kapton.
Embodiment 7
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 27.54g METHYLPYRROLIDONE are added in reaction flask, after stirring and dissolving, add 1 in batches, 2,4,5-cyclohexanetetracarboxylic acid dianhydride, 2.24g (10mmol) altogether, after stirring reaction 3h, add 4.59g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine), be warmed up to 180 DEG C of backflow azeotropic dehydration 3.5h;
(2) mixed solution after backflow in step (1) is cooled to 20 DEG C, then pours precipitated product in the water under high-speed stirring state into, filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried phenolic hydroxy group half alicyclic ring polyimide powder 1.00g to be dissolved in 5.67g N-ethyl-2-pyrrolidone, obtain polyimide solution;
(4) after then polyimide solution being left standstill 1.5h, vacuum defoamation, polyimide solution after deaeration is poured on clean sheet glass, use scraper blade coating, careful is put into sheet glass in the air dry oven of modulated good level, dries 3min, naturally cool to room temperature at 95 DEG C, put into water and soak demoulding, obtain Kapton.
Embodiment 8
(1) N
2under protection, 2.58g (10mmol) 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane and 27.54g METHYLPYRROLIDONE are added in reaction flask; after stirring and dissolving; add 1,2,4 in batches; 5-cyclohexanetetracarboxylic acid dianhydride; 2.24g (10mmol), after stirring reaction 2h, adds 4.59g dimethylbenzene and catalyzer (0.10g γ-valerolactone and 0.16g pyridine) altogether; be warmed up to 190 DEG C of backflow azeotropic dehydration 3.5h
(2) mixed solution after backflow in step (1) is cooled to 30 DEG C, then pour precipitated product in the methanol aqueous solution of the 1:1.5 (methyl alcohol: water) under high-speed stirring state into, filter, washing, vacuum-drying, obtains phenolic hydroxy group half alicyclic ring polyimide yellow powder;
(3) get dried phenolic hydroxy group half alicyclic ring polyimide powder 1.00g to be dissolved in 4.00g dimethyl sulfoxide (DMSO), obtain polyimide solution;
(4) after then polyimide solution being left standstill 2h, vacuum defoamation, polyimide solution after deaeration being got appropriate above-mentioned solution is poured on clean sheet glass, use scraper blade coating, careful is put into sheet glass in the air dry oven of modulated good level, dries 15min, naturally cool to room temperature at 90 DEG C, put into water and soak demoulding, obtain Kapton.
Effect example
Utilize the phenolic hydroxy group half alicyclic ring polyimide powder of fourier transform infrared spectroscopy to gained in embodiment 1 ~ 8 to detect, find that this pressed powder has obvious imide ring vibration performance absorption peak (1772cm
-1, 1708cm
-1and 1392cm
-1) and obvious OH absorption peak (3465cm
-1), and the charateristic avsorption band 1660cm of polyamic acid
-1, 1559cm
-1undiscovered.Wherein, Fig. 1 is fourier transform infrared spectrometry (FTIR) spectrogram of phenolic hydroxy group half alicyclic ring polyimide (PI) that embodiment 1 prepares.
DSC scanning is carried out to the polyimide of gained in embodiment 1 ~ 8, its second-order transition temperature is in table 1, wherein, Fig. 2 is that the differential scanning calorimeter (DSC) of phenolic hydroxy group half alicyclic ring polyimide (PI) that embodiment 1 prepares scans spectrogram.
Thermogravimetic analysis (TGA) is carried out to the phenolic hydroxy group half alicyclic ring polyimide of gained in embodiment 1 ~ 8, its incipient degradation temperature is in table 1, wherein, Fig. 3 is thermogravimetic analysis (TGA) (TGA) spectrogram of phenolic hydroxy group half alicyclic ring polyimide (PI) that embodiment 1 prepares.
UV-2550 ultraviolet-visible spectrophotometer is utilized to record the ultraviolet cut-on wavelength of the Kapton of gained in embodiment 1 ~ 8, the transmittance at 450nm place and visible ray maximum transmission, it the results are shown in Table 1, wherein, Fig. 4 is the Kapton absorbance spectrum at different wavelengths that embodiment 1 prepares.
The phenolic hydroxy group half alicyclic ring polyimide that table 1 embodiment 1 ~ 8 prepares and film properties analysis thereof
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a phenolic hydroxy group half alicyclic ring polyimide, is characterized in that having structure shown in formula I:
Wherein, described n repeateding unit number, and n be greater than 0 positive integer.
2. the preparation method of phenolic hydroxy group half alicyclic ring polyimide according to claim 1, is characterized in that comprising following steps:
(1) N
2under protection, by 2,2 ＇-bis-(3-amino-4-hydroxylphenyl) propane is dissolved in strong polar non-proton organic solvent, then adds 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, after stirring 0.5 ~ 3h, add azeotropy dehydrant and catalyzer, be warmed up to 180 ~ 200 DEG C, backflow 3 ~ 5h;
(2) by the mixed solution cooling after backflow in step (1), with the solid product in precipitating agent precipitating mixed solution, then solid product is filtered, washing, dry, obtain phenolic hydroxy group half alicyclic ring polyimide.
3. the preparation method of phenolic hydroxy group half alicyclic ring polyimide according to claim 2, is characterized in that:
The mol ratio of 2,2 ＇ described in step (1)-bis-(3-amino-4-hydroxylphenyl) propane and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is 1:(1 ~ 1.03).
4. the preparation method of phenolic hydroxy group half alicyclic ring polyimide according to claim 2, is characterized in that:
2,2 ＇ described in step (1)-bis-(3-amino-4-hydroxylphenyl) propane and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride account for 10% ~ 20% of total reaction system quality.
5. the preparation method of phenolic hydroxy group half alicyclic ring polyimide according to claim 2, is characterized in that:
The mass ratio of the azeotropy dehydrant described in step (1) and strong polar non-proton organic solvent is (0.9 ~ 1.1): 6.
6. the preparation method of phenolic hydroxy group half alicyclic ring polyimide according to claim 2, is characterized in that:
Azeotropy dehydrant described in step (1) is dimethylbenzene.
7. the preparation method of phenolic hydroxy group half alicyclic ring polyimide according to claim 2, is characterized in that:
Catalyzer described in step (1) is γ-valerolactone and pyridine catalyst system.
8. the preparation method of phenolic hydroxy group half alicyclic ring polyimide according to claim 2, is characterized in that:
Strong polar non-proton organic solvent described in step (1) is METHYLPYRROLIDONE;
Precipitating agent described in step (2) is at least one in first alcohol and water.
9. a Kapton, is characterized in that being prepared by phenolic hydroxy group half alicyclic ring polyimide according to claim 1.
10. the preparation method of Kapton according to claim 9, comprises following steps:
(1) phenolic hydroxy group half alicyclic ring polyimide according to claim 1 is dissolved in strong polar non-proton organic solvent, obtains polyimide solution;
(2) after then polyimide solution being left standstill 0.5 ~ 3h, vacuum defoamation, coats on sheet glass by the polyimide solution after deaeration, and dry, demoulding, obtains Kapton.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150225523A1 (en) * | 2012-09-27 | 2015-08-13 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin composition |
| CN105304469A (en) * | 2015-09-25 | 2016-02-03 | 京东方科技集团股份有限公司 | Polyimide substrate, preparation method of polyimide substrate and flexible displayer |
| CN106700070A (en) * | 2015-07-31 | 2017-05-24 | 中科院广州化学有限公司南雄材料生产基地 | Soluble polyimides containing phenolic hydroxyl group and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150225523A1 (en) * | 2012-09-27 | 2015-08-13 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin composition |
| US10557003B2 (en) * | 2012-09-27 | 2020-02-11 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin composition |
| CN106700070A (en) * | 2015-07-31 | 2017-05-24 | 中科院广州化学有限公司南雄材料生产基地 | Soluble polyimides containing phenolic hydroxyl group and preparation method and application thereof |
| CN105304469A (en) * | 2015-09-25 | 2016-02-03 | 京东方科技集团股份有限公司 | Polyimide substrate, preparation method of polyimide substrate and flexible displayer |
| CN105304469B (en) * | 2015-09-25 | 2018-03-27 | 京东方科技集团股份有限公司 | A kind of polyimide substrate, its preparation method and flexible display |
| US10344182B2 (en) | 2015-09-25 | 2019-07-09 | Boe Technology Group Co., Ltd. | Polyimide substrate and method for preparing the same, and flexible display |
| CN109694574A (en) * | 2018-12-17 | 2019-04-30 | 无锡创彩光学材料有限公司 | A kind of high adhesiveness Kapton, preparation method and flexible copper-clad plate |
| CN111498827A (en) * | 2020-04-12 | 2020-08-07 | 辽宁科技大学 | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof |
| CN111498827B (en) * | 2020-04-12 | 2022-12-30 | 辽宁科技大学 | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof |
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Application publication date: 20150729 |