CN106496559A - The preparation method of high printing opacity soluble polyimide - Google Patents
The preparation method of high printing opacity soluble polyimide Download PDFInfo
- Publication number
- CN106496559A CN106496559A CN201611019364.XA CN201611019364A CN106496559A CN 106496559 A CN106496559 A CN 106496559A CN 201611019364 A CN201611019364 A CN 201611019364A CN 106496559 A CN106496559 A CN 106496559A
- Authority
- CN
- China
- Prior art keywords
- solution
- 6fda
- polyimide
- hexafluorodianhydride
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses the preparation method of high printing opacity soluble polyimide, comprises the following steps：(1) synthesis of polyimide acid；(2) imidization of polyimide acid：Polyimides acid monomers spin-coating film prepared by step (1), then dries 2 5h under the conditions of 45 70 DEG C, obtained thin film is carried out thermal annealing imidization process and obtains polyimides.The preparation method of the present invention is simple, and obtained multiple Kaptons are respectively provided with high transparent, high-fire resistance, high solubility.Preparation process is simple, easily realizes industrialization production.
Description
Technical field
The present invention relates to the preparation method of polyimides, more particularly to the preparation method of high printing opacity soluble polyimide.
Background technology
Aromatic polyimide is the high performance macromolecular material of well-known excellent heat stability, good dielectric
Performance, chemical resistance and dimensional stability (Der Jang Liaw et al., " Advanced Polyimide Materials:
Syntheses,Physical Properties and Applications,”Progress in Polymer Science
37,7(2012):907–74,doi:10.1016/j.progpolymsci.2012.02.005. " Der Jang Liaw etc. first
Enter polyimide material：Synthesis, physical property and application. Polymers Containing Phosphorus .37,7 (2012):907–74”).However, big
Most conventional fragrant adoption imide membranes are usually light yellow to dark brown thin film, and after complete imidizate, material
There is high softening temperature and be difficult to re-dissolved property, polyimide-type materials are limited in photoelectric material such as flexible solar spoke
Penetrate the fields such as protection, the liquid crystal indicator of alignment films application (Stephen Z.D.Cheng et al.,
“Organosoluble,Segmented Rigid-Rod Polyimide Film.1.Structure Formation,”
Macromolecules 24,no.21(October 1991):5856–62,doi:10.1021/ma00021a021.
" Stephen Z.D.Cheng etc. solvable Kapton .1 structures. macromole .24, no.21 (1991):5856–62.”).
High colorless transparency polyimides (PI) is the hot research topic in functional polyalkylene acid imide investigation of materials field
One of.Colorless transparency PI materials are respectively provided with many high-tech sectors and are widely applied, such as in optical-fibre communications field
For making optical waveguide, it is used as the baseplate material of solar battery array and antenna-reflected/collection in aerospace field
(Chin-Ping Yang, Sheng-Huei Hsiao, and the Kuen-Lin Wu, " Organosoluble and such as equipment material
Light-Colored Fluorinated Polyimides Derived from 2,3-bis(4-Amino-2-
Trifluoromethylphenoxy)naphthalene and Aromatic Dianhydrides,”Polymer 44,
no.23(2003):7067–78,doi:http://dx.doi.org/10.1016/j.polymer.2003.08.032.
" Chin-Ping Yang, Sheng-Huei Hsiao and Kuen-Lin Wu etc. by aromatic carboxylic acid dianhydride and double (the 4- ammonia of 2,3-
Base -2- trifluoromethylbenzene oxygen side bases) the high printing opacity fluorinated polyimide of naphthalene synthesizing soluble. polymer .44,23 (2003):7067–
78”).The introducing of fluoro-containing group can effectively improve the dissolubility of polyimides and optical transparence (Fengchun Yang et
al.,“Synthesis and Characterization of Fluorinated Polyimides Derived from
Novel Unsymmetrical Diamines,”Journal of Fluorine Chemistry 131,no.7(2010):
767–75,doi:10.1016/j.jfluchem.2010.03.014. " Yang Fengchun etc. synthesized by Novel asymmetric diamine
The synthesis of fluorinated polyimide and sign. fluorine chemistry magazine .131,7 (2010):767–75”).Recent study finds, fluorine-containing
Polyimides typically exhibit preferable solubility property, especially replace the Polyetherimide of structure containing trifluoromethyl.This kind of
Polyimides typically obtained by fluorine-containing bis ether diamine monomer and common dianhydride monomer polycondensation (Yu Liu et al.,
“Synthesis and Properties of Soluble Fluorinated Poly(ether Imide)s with
Different Pendant Groups,”Polymer 49,no.25(2008):5439–45,doi:http://
Dx.doi.org/10.1016/j.polymer.2008.09.050. " Liu Yu etc. the solubility polyethers containing different side-chain radicals
Imido synthesis and performance. polymer .49,25 (2008):5439–45”).However, due to such fluorochemical polyether acid imide point
The flexible ether linkage of larger proportion is introduced in sub- main chain so that the resistance to elevated temperatures of this quasi-polyimide has declined, its glass
Change temperature mostly in 200～300 DEG C of (C Y Wang et al., " Synthesis and Characterization of
Fluorinated Polyimide with High Solubility and Optical Transparency,”Acta
Chimica Sinica 68,no.5(2010):449–52,<Go to ISI>://WOS:000275970300013. " Wang Chenyi
Deng, the synthesis and preparation of the fluorinated polyimide of high-dissolvability and light transmission, chemical journal .68,5 (2010):449–52”).
Therefore, the polyimides with good light permeability, excellent dissolubility, high temperature tolerance need further to explore.
Content of the invention
It is an object of the invention to overcoming the shortcomings of prior art, there is provided a kind of dissolving with good light permeability, excellent
Property, the preparation method of the high printing opacity soluble polyimide of high temperature tolerance.
In order to achieve the above object, the technical solution used in the present invention is：
The preparation method of high printing opacity soluble polyimide, comprises the following steps：
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 0-40 DEG C, diamine monomer is added solvent N', N- diformazans
In yl acetamide, stirring makes diamine monomer fully dissolve to obtain the first solution, be passed through nitrogen in course of dissolution into the first solution
Air in gas exclusion system, in the first described solution, the weight/mass percentage composition of diamine monomer is 5-30%；
The preparation process of the second described solution is：Under the conditions of 0-40 DEG C, hexafluorodianhydride (6FDA) is added solvent N', N- diformazans
In yl acetamide, stirring makes hexafluorodianhydride (6FDA) fully dissolve and obtains the second solution, the matter of hexafluorodianhydride (6FDA) in the second described solution
Amount percentage composition is 5-30%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 0-40 DEG C, reaction
10-25h terminates, and obtains polyimide acid, then preserves under dry environment under the conditions of 0 DEG C, diamidogen in described mixed solution
Monomer is 0.9-1.2 with the molal weight ratio of hexafluorodianhydride (6FDA)；
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 2-5h under the conditions of 45-70 DEG C, will
Obtained thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 60-80 DEG C with the speed of 1-10 DEG C/min, are incubated 2-6h；
2 ＞ of ＜ are warming up to 150-180 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-4h；
3 ＞ of ＜ are warming up to 250-300 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-4h；
4 ＞ of ＜ are warming up to 350-400 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-2h.
The invention has the beneficial effects as follows：
The preparation method of the present invention is simple, and obtained multiple Kaptons are respectively provided with high transparent, high-fire resistance, height
Degree dissolubility.Preparation process is simple, easily realizes industrialization production.The material of gained has excellent mechanical property, good chi
Very little and chemical stability, excellent pliability and Lightness.It is flexible aobvious that thin film can be applicable to flexible thin-film solar cell, OLED
Show the fields such as substrate, optical waveguide material, be with a wide range of applications.
Description of the drawings
Fig. 1 is the UV-Vis transmission curves of the fluorinated polyimide of the preparation of embodiment 5 using the inventive method；
Fig. 2 is that the means of differential scanning calorimetry (DSC) of the fluorinated polyimide prepared by the embodiment 5 using the inventive method is bent
Line.
Specific embodiment
Describe the present invention with reference to specific embodiment.
It is that the present invention is further illustrated below the present invention, rather than limits the preferred scope of the present invention.Which reacts
Process and explanation step are as follows：
The preparation method of the high printing opacity soluble polyimide of the present invention, comprises the following steps：
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 0-40 DEG C, diamine monomer is added solvent N', N- diformazans
In yl acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, in course of dissolution into the first solution
Air in nitrogen exclusion system is passed through, the weight/mass percentage composition of diamine monomer is 5-30% in the first described solution；Described
Diamine monomer be 2,2'- bis- (trifluoromethyl) benzidine (TFDB), 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl]
Propane] phenoxy group] one kind in double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of aniline (BAPP) or 2,2-；
The preparation process of the second described solution is：Under the conditions of 0-40 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N',
In N- dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, described second
In solution, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 5-30%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 0-40 DEG C, reaction
10-25h terminates, and obtains polyimide acid (PAA), then preserves under dry environment under the conditions of 0 DEG C, in described mixed solution
Diamine monomer is 0.9-1.2 with the molal weight ratio of hexafluorodianhydride (6FDA).Diamine monomer and hexafluoro in preferred described mixed solution
The mass ratio of dianhydride is 1:1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 2-5h under the conditions of 45-70 DEG C, will
Obtained thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 60-80 DEG C with the speed of 1-10 DEG C/min, are incubated 2-6h；
2 ＞ of ＜ are warming up to 150-180 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-4h；
3 ＞ of ＜ are warming up to 250-300 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-4h；
4 ＞ of ＜ are warming up to 350-400 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-2h.
Polyimides acid monomers spin-coating film in this step may refer to imaging science and photochemistry publishing house 2012
The method disclosed in page 91 to 101 " spin-coating method prepares the progress of function film " that publishes.
In the inventive method, each reaction monomers structural formula is：
The molecular structural formula of the polyimide polymer that the inventive method is prepared is：
The molecular weight distribution of polyimides is 100,000～300,000.
Embodiment 1
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 0 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 5% in the first described solution；Described diamidogen
Monomer is 2,2'- bis- (trifluoromethyl) benzidine (TFDB)；
The preparation process of the second described solution is：Under the conditions of 0 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 5%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 0 DEG C, reaction 10h knots
Beam, obtains polyimide acid (PAA), then preserves under dry environment under the conditions of 0 DEG C, diamine monomer in described mixed solution
Compare 0.9 with the molal weight that hexafluorodianhydride (6FDA) is pressed：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 2h under the conditions of 45 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 60 DEG C with the speed of 1 DEG C/min, are incubated 2h；
2 ＞ of ＜ are warming up to 150 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h；
3 ＞ of ＜ are warming up to 250 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h；
4 ＞ of ＜ are warming up to 350 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h.
The fluorinated polyimide prepared by 2,2'- bis- (trifluoromethyl) benzidine (TFDB) in embodiment 1 is in N', N-
In dimethyl pyrrolidone, dissolubility is 180mg/mL, illustrates that fluorinated polyimide dissolubility prepared by the condition is good.
The fluorinated polyimide prepared from 2,2'- bis- (trifluoromethyl) benzidine (TFDB) in embodiment 1 exists
The transmittance in light area is more than 75%, has good transmittance.
Embodiment 2
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 25 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 20% in the first described solution；Described two
Amine monomers are 2,2'- bis- (trifluoromethyl) benzidine (TFDB)；
The preparation process of the second described solution is：Under the conditions of 25 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 20%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 25 DEG C, reacts 20h
Terminate, obtain polyimide acid (PAA), then preserve under dry environment under the conditions of 0 DEG C, diamidogen list in described mixed solution
Body compares 1 with the molal weight that hexafluorodianhydride (6FDA) is pressed：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 3h under the conditions of 50 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 70 DEG C with the speed of 2 DEG C/min, are incubated 4h；
2 ＞ of ＜ are warming up to 160 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 2h；
3 ＞ of ＜ are warming up to 280 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 2h；
4 ＞ of ＜ are warming up to 360 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 1.5h.
The fluorinated polyimide prepared by 2,2'- bis- (trifluoromethyl) benzidine (TFDB) in embodiment 2 is in N', N-
In dimethyl pyrrolidone, dissolubility is 180mg/mL, illustrates that fluorinated polyimide dissolubility prepared by the condition is good.
The fluorinated polyimide prepared by diamine monomer 2,2'- bis- (trifluoromethyl) benzidine (TFDB) in example 2
Transmittance in visible region is more than 77%, has good transmittance.
Embodiment 3
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 40 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 30% in the first described solution；Described two
Amine monomers are 2,2'- bis- (trifluoromethyl) benzidine (TFDB)；
The preparation process of the second described solution is：Under the conditions of 40 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 30%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 40 DEG C, reacts 25h
Terminate, obtain polyimide acid (PAA), then preserve under dry environment under the conditions of 0 DEG C, diamidogen list in described mixed solution
Body is 1.2 with the molal weight ratio of hexafluorodianhydride (6FDA)：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 5h under the conditions of 70 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 80 DEG C with the speed of 10 DEG C/min, are incubated 6h；
2 ＞ of ＜ are warming up to 180 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 4h；
3 ＞ of ＜ are warming up to 300 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 4h；
4 ＞ of ＜ are warming up to 400 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 2h.
The fluorinated polyimide prepared by 2,2'- bis- (trifluoromethyl) benzidine (TFDB) in embodiment 3 is in N', N-
In dimethyl pyrrolidone, dissolubility is 185mg/mL, illustrates that fluorinated polyimide dissolubility prepared by the condition is good.
The fluorinated polyimide prepared by diamine monomer 2,2'- bis- (trifluoromethyl) benzidine (TFDB) in example 3
Transmittance in visible region is more than 76%, has good transmittance.
Embodiment 4
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 0 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 5% in the first described solution；Described diamidogen
Monomer is 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP)；
The preparation process of the second described solution is：Under the conditions of 0 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 5%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 0 DEG C, reaction 10h knots
Beam, obtains polyimide acid (PAA), then preserves under dry environment under the conditions of 0 DEG C, diamine monomer in described mixed solution
Compare 0.9 with the molal weight that hexafluorodianhydride (6FDA) is pressed：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 2h under the conditions of 45 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 60 DEG C with the speed of 1 DEG C/min, are incubated 2h；
2 ＞ of ＜ are warming up to 150 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h；
3 ＞ of ＜ are warming up to 250 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h；
4 ＞ of ＜ are warming up to 350 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h.
Prepared by 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP) in embodiment 4
Fluorinated polyimide dissolubility in N', N- dimethyl pyrrolidones is 175mg/mL, and fluorine-containing polyamides prepared by the condition is described
Imines dissolubility is good.
Prepared by 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP) in embodiment 4
Transmittance of the fluorinated polyimide in visible region is more than 75%, and thin film has good light transmission.
Embodiment 5
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 25 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 20% in the first described solution；Described two
Amine monomers are 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP)；
The preparation process of the second described solution is：Under the conditions of 25 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 20%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 25 DEG C, reacts 20h
Terminate, obtain polyimide acid (PAA), then preserve under dry environment under the conditions of 0 DEG C, diamidogen list in described mixed solution
Body compares 1 with the molal weight that hexafluorodianhydride (6FDA) is pressed：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 3h under the conditions of 50 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 70 DEG C with the speed of 2 DEG C/min, are incubated 4h；
2 ＞ of ＜ are warming up to 160 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 2h；
3 ＞ of ＜ are warming up to 280 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 2h；
4 ＞ of ＜ are warming up to 360 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 1.5h.
Prepared by 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP) in embodiment 5
Fluorinated polyimide dissolubility in N', N- dimethyl pyrrolidones is 200mg/mL, and solution clear illustrates that such is fluorine-containing
Polyimides dissolubility is fine.
Fig. 1 is made by 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP) in example 5
The UV-Vis transmission curves of standby fluorinated polyimide, it can be seen that Kapton removes printing opacity in visible ray
Degree up to more than 80%, illustrates that such fluorinated polyimide has good light transmission.
Fig. 2 is means of differential scanning calorimetry (DSC) curve of the fluorinated polyimide prepared by embodiment 5.
It can be seen that by 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] benzene in example 5
The glass transition temperature of fluorinated polyimide prepared by amine (BAPP) is respectively 252.0 DEG C, 254.8 DEG C and 233.7 DEG C, says
Its fluorinated polyimide bright has good thermostability.
Embodiment 6
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 40 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 30% in the first described solution；Described two
Amine monomers are 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP)；
The preparation process of the second described solution is：Under the conditions of 40 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 30%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 40 DEG C, reacts 25h
Terminate, obtain polyimide acid (PAA), then preserve under dry environment under the conditions of 0 DEG C, diamidogen list in described mixed solution
Body is 1.2 with the molal weight ratio of hexafluorodianhydride (6FDA)：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 5h under the conditions of 70 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 80 DEG C with the speed of 10 DEG C/min, are incubated 6h；
2 ＞ of ＜ are warming up to 180 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 4h；
3 ＞ of ＜ are warming up to 300 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 4h；
4 ＞ of ＜ are warming up to 400 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 2h.
Prepared by 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP) in embodiment 6
Fluorinated polyimide dissolubility in N', N- dimethyl pyrrolidones is 180mg/mL, and fluorine-containing polyamides prepared by the condition is described
Imines dissolubility is good.
What in example 6 prepared by 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] phenoxy group] aniline (BAPP) is fluorine-containing
Transmittance of the polyimides in visible region is more than 73%, has good transmittance.
Embodiment 7
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 0 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 5% in the first described solution；Described diamidogen
Monomer is double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2-；
The preparation process of the second described solution is：Under the conditions of 0 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 5%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 0 DEG C, reaction 10h knots
Beam, obtains polyimide acid (PAA), then preserves under dry environment under the conditions of 0 DEG C, diamine monomer in described mixed solution
Compare 0.9 with the molal weight that hexafluorodianhydride (6FDA) is pressed：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 2h under the conditions of 45 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 60 DEG C with the speed of 1 DEG C/min, are incubated 2h；
2 ＞ of ＜ are warming up to 150 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h；
3 ＞ of ＜ are warming up to 250 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h；
4 ＞ of ＜ are warming up to 350 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 1 DEG C/min, are incubated 1h.
The fluorine-containing polyamides prepared by double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2- in embodiment 7
Imines dissolubility in N', N- dimethyl pyrrolidones is 170mg/mL, and fluorinated polyimide dissolving prepared by the condition is described
Property is good.
The fluorine-containing polyamides prepared by double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2- in embodiment 7
Transmittance of the imines in visible region is more than 70%, and thin film has good light transmission.
Embodiment 8
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 25 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 18% in the first described solution；Described two
Amine monomers are double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2-；
The preparation process of the second described solution is：Under the conditions of 25 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 18%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 25 DEG C, reacts 18h
Terminate, obtain polyimide acid (PAA), then preserve under dry environment under the conditions of 0 DEG C, diamidogen list in described mixed solution
Body compares 1 with the molal weight that hexafluorodianhydride (6FDA) is pressed：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 3h under the conditions of 48 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 70 DEG C with the speed of 2 DEG C/min, are incubated 4h；
2 ＞ of ＜ are warming up to 160 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 2h；
3 ＞ of ＜ are warming up to 280 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 2h；
4 ＞ of ＜ are warming up to 360 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 2 DEG C/min, are incubated 1.5h.
The fluorine-containing polyamides prepared by double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2- in embodiment 8
Imines dissolubility in N', N- dimethyl pyrrolidones is 195mg/mL, and fluorinated polyimide dissolving prepared by the condition is described
Property is good.
The fluorine-containing polyamides prepared by double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2- in example 8 is sub-
Transmittance of the amine in visible region is more than 78%, has good transmittance.
Embodiment 9
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 40 DEG C, diamine monomer is added solvent N', N- dimethyl
In acetamide (DMAc), stirring makes diamine monomer fully dissolve and obtains the first solution, leads in course of dissolution into the first solution
Enter air in nitrogen exclusion system, the weight/mass percentage composition of diamine monomer is 30% in the first described solution；Described two
Amine monomers are double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2-；
The preparation process of the second described solution is：Under the conditions of 40 DEG C, hexafluorodianhydride (6FDA) (6FDA) is added solvent N', N-
In dimethyl acetylamide (DMAc), stirring makes hexafluorodianhydride (6FDA) (6FDA) fully dissolving obtain the second solution, molten described second
In liquid, the weight/mass percentage composition of hexafluorodianhydride (6FDA) is 30%；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 40 DEG C, reacts 25h
Terminate, obtain polyimide acid (PAA), then preserve under dry environment under the conditions of 0 DEG C, diamidogen list in described mixed solution
Body is 1.2 with the molal weight ratio of hexafluorodianhydride (6FDA)：1.
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 5h under the conditions of 70 DEG C, will be obtained
Thin film carries out thermal annealing imidization process and obtains polyimides, and annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 80 DEG C with the speed of 10 DEG C/min, are incubated 6h；
2 ＞ of ＜ are warming up to 180 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 4h；
3 ＞ of ＜ are warming up to 300 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 4h；
4 ＞ of ＜ are warming up to 400 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 10 DEG C/min, are incubated 2h.
The fluorine-containing polyamides prepared by double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2- in embodiment 9
Imines dissolubility in N', N- dimethyl pyrrolidones is 182mg/mL, and fluorinated polyimide dissolving prepared by the condition is described
Property is good.
The fluorine-containing polyamides prepared by double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (6FBAPP) of 2,2- in example 9 is sub-
Transmittance of the amine in visible region is more than 73%, has good transmittance.
Claims (3)
1. the preparation method of high printing opacity soluble polyimide, it is characterised in that comprise the following steps：
(1) synthesis of polyimide acid, concretely comprises the following steps：
A () carries out the preparation of the first solution and the second solution respectively；
The preparation process of the first described solution is：Under the conditions of 0-40 DEG C, diamine monomer is added solvent N', N- dimethyl second
In amide, stirring makes diamine monomer fully dissolve and obtains the first solution, is passed through nitrogen row in course of dissolution into the first solution
Except air in system, in the first described solution, the weight/mass percentage composition of diamine monomer is 5-30%；
The preparation process of the second described solution is：Under the conditions of 0-40 DEG C, hexafluorodianhydride (6FDA) is added solvent N', N- dimethyl second
In amide, stirring makes hexafluorodianhydride (6FDA) fully dissolve and obtains the second solution, the quality hundred of hexafluorodianhydride (6FDA) in the second described solution
It is 5-30% to divide content；
B () adds the second solution to obtain mixed solution in the first described solution, reacted at 0-40 DEG C, reacts 10-25h
Terminate, obtain polyimide acid, then under dry environment under the conditions of 0 DEG C preserve, in described mixed solution diamine monomer with
The molal weight ratio of hexafluorodianhydride (6FDA) is 0.9-1.2；
(2) imidization of polyimide acid：
Polyimides acid monomers spin-coating film prepared by step (1), then dries 2-5h under the conditions of 45-70 DEG C, will be obtained
Thin film carry out thermal annealing imidization process obtain polyimides, annealing is comprised the following steps that：
1 ＞ of ＜ are warming up to 60-80 DEG C with the speed of 1-10 DEG C/min, are incubated 2-6h；
2 ＞ of ＜ are warming up to 150-180 DEG C by the temperature of 1 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-4h；
3 ＞ of ＜ are warming up to 250-300 DEG C by the temperature of 2 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-4h；
4 ＞ of ＜ are warming up to 350-400 DEG C by the temperature of 3 ＞ of step ＜ with the speed of 1-10 DEG C/min, are incubated 1-2h.
2. the preparation method of described high printing opacity soluble polyimide according to claim 1, it is characterised in that：Described
Diamine monomer be 2,2'- bis- (trifluoromethyl) benzidine, 4- [4- [2- [4- (4- amino-benzene oxygens) phenyl] propane] benzene
Epoxide] one kind in double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa of aniline or 2,2-.
3. according to claims 1 or 2 described in high printing opacity soluble polyimide preparation method, its feature exists
In：In described mixed solution, diamine monomer is 1 with the mass ratio of hexafluorodianhydride (6FDA):1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611019364.XA CN106496559A (en) | 2016-11-17 | 2016-11-17 | The preparation method of high printing opacity soluble polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611019364.XA CN106496559A (en) | 2016-11-17 | 2016-11-17 | The preparation method of high printing opacity soluble polyimide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106496559A true CN106496559A (en) | 2017-03-15 |
Family
ID=58323371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611019364.XA Pending CN106496559A (en) | 2016-11-17 | 2016-11-17 | The preparation method of high printing opacity soluble polyimide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106496559A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602856A (en) * | 2017-09-05 | 2018-01-19 | 中国科学院宁波材料技术与工程研究所 | A kind of Thermocurable polyimide prepolymer with highly dissoluble, preparation method and applications |
| CN111378278A (en) * | 2018-12-28 | 2020-07-07 | 南京理工大学 | High-temperature-resistant thermal control film and preparation method thereof |
| CN112876678A (en) * | 2021-01-13 | 2021-06-01 | 常州大学 | Soluble polyimide containing hexamethyl substitution structure and preparation method and application thereof |
| CN113801322A (en) * | 2021-10-01 | 2021-12-17 | 武汉纺织大学 | Soluble high-transparency polyimide, polyimide coated fabric and preparation method |
| CN114300062A (en) * | 2021-12-07 | 2022-04-08 | 北京理工大学 | Model prediction method for NTO-based formula drug column polymer coating acidic protection |
| CN114292399A (en) * | 2021-12-07 | 2022-04-08 | 北京理工大学 | Preparation method of soluble fluorinated polyimide and application of soluble fluorinated polyimide in NTO (nitrilotriacetic acid) acid protection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110311796A1 (en) * | 2007-08-20 | 2011-12-22 | Kolon Industries, Inc. | Polyimide film |
| CN103282414A (en) * | 2010-12-31 | 2013-09-04 | 可隆工业株式会社 | Transparent polyimide film and preparation method thereof |
| CN105440284A (en) * | 2015-12-11 | 2016-03-30 | 中国航空工业集团公司北京航空材料研究院 | Preparation method for colorless transparent high-temperature-resistant polyimide nanometer composite film |
-
2016
- 2016-11-17 CN CN201611019364.XA patent/CN106496559A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110311796A1 (en) * | 2007-08-20 | 2011-12-22 | Kolon Industries, Inc. | Polyimide film |
| CN103282414A (en) * | 2010-12-31 | 2013-09-04 | 可隆工业株式会社 | Transparent polyimide film and preparation method thereof |
| CN105440284A (en) * | 2015-12-11 | 2016-03-30 | 中国航空工业集团公司北京航空材料研究院 | Preparation method for colorless transparent high-temperature-resistant polyimide nanometer composite film |
Non-Patent Citations (5)
| Title |
|---|
| AKIRA SHIMAZU ET AL.: ""Relationships Between Chemical Structures and Solubility,Diffusivity, and Permselectivity of 1,3-Butadiene and n-Butane in 6FDA-Based Polyimides"", 《JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS》 * |
| AKIRA SHIMAZU ET AL.: ""Relationships between the Chemical Structures and the Solubility, Diffusivity, and Permselectivity of Propylene and Propane in 6FDA-Based Polyimides"", 《JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS》 * |
| 周学良等: "《精细化工产品手册.功能高分子材料》", 30 April 2002, 化学工业出版社 * |
| 彭治汉等: "《塑料工业手册 聚酰胺》", 30 November 2001, 化学工业出版社 * |
| 西鹏等: "《高技术纤维概论》", 31 March 2012, 中国纺织出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602856A (en) * | 2017-09-05 | 2018-01-19 | 中国科学院宁波材料技术与工程研究所 | A kind of Thermocurable polyimide prepolymer with highly dissoluble, preparation method and applications |
| CN107602856B (en) * | 2017-09-05 | 2020-08-04 | 中国科学院宁波材料技术与工程研究所 | Thermosetting polyimide prepolymer with high solubility, preparation method and application thereof |
| CN111378278A (en) * | 2018-12-28 | 2020-07-07 | 南京理工大学 | High-temperature-resistant thermal control film and preparation method thereof |
| CN111378278B (en) * | 2018-12-28 | 2022-05-27 | 南京理工大学 | High-temperature-resistant thermal control film and preparation method thereof |
| CN112876678A (en) * | 2021-01-13 | 2021-06-01 | 常州大学 | Soluble polyimide containing hexamethyl substitution structure and preparation method and application thereof |
| CN113801322A (en) * | 2021-10-01 | 2021-12-17 | 武汉纺织大学 | Soluble high-transparency polyimide, polyimide coated fabric and preparation method |
| CN114300062A (en) * | 2021-12-07 | 2022-04-08 | 北京理工大学 | Model prediction method for NTO-based formula drug column polymer coating acidic protection |
| CN114292399A (en) * | 2021-12-07 | 2022-04-08 | 北京理工大学 | Preparation method of soluble fluorinated polyimide and application of soluble fluorinated polyimide in NTO (nitrilotriacetic acid) acid protection |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106496559A (en) | The preparation method of high printing opacity soluble polyimide | |
| US10745519B2 (en) | Polyimide resin, polyimide solution, film, and method for producing same | |
| CN104640907B (en) | Polyimides and its formed body | |
| CN102634022B (en) | Colorless highly-transparent polyimide film as well as preparation method and application thereof | |
| KR101385279B1 (en) | Asymmetric diamine compounds containing two functional groups, and polymers therefrom | |
| CN107531902A (en) | Polyimide resin and the film using the polyimide resin | |
| JP2013144752A (en) | Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition | |
| CN102666659A (en) | Optical film, optical film manufacturing method, transparent substrate, image display device, and solar cell | |
| JP7527610B2 (en) | Polyimide powder, polyimide varnish, polyimide film and polyimide porous film | |
| CN107286344A (en) | A kind of preparation method of transparent polyimide film | |
| TWI659064B (en) | Resin composition for display substrate, resin film for display substrate, and method for manufacturing resin film for display substrate | |
| JP2012077144A (en) | Polyamideimide resin, manufacturing method therefor, polyamideimide resin solution, polyamideimide film, and use thereof | |
| CN104927072B (en) | A kind of Kapton and preparation method thereof of solvent resistant low thermal coefficient of expansion | |
| CN106046373B (en) | A kind of solvable polyimide film and preparation method with anti-flammability | |
| CN106496612A (en) | A kind of preparation method of the Kapton of structure-controllable | |
| CN107459649A (en) | A kind of polyimide polymer, a kind of transparent polyimide film and preparation method thereof | |
| CN108341950A (en) | A kind of preparation method of black polyamide thin film | |
| Wang et al. | Synthesis and characterization of an aromatic diamine and its polyimides containing asymmetric large side groups | |
| CN101585923A (en) | Polyimide film with high visible light permeability and preparation thereof | |
| CN105906808B (en) | One kind contains tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof | |
| CN112961349B (en) | High-performance transparent polyimide, polyimide film and preparation method thereof | |
| TWI638857B (en) | Resin composition for display substrate, resin film for display substrate, and method for producing resin film for display substrate | |
| CN106832278A (en) | One class high transparency copoly type fluorine-containing polyimide film material and preparation method thereof | |
| CN111808423A (en) | Polyimide film with high heat resistance and low thermal expansion coefficient and preparation method thereof | |
| CN104861162B (en) | Containing the soluble polyimide and preparation method thereof of the tertiary butyl and fluorine-triphenylamine structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170315 |