CN112625017B - Amide dianhydride, preparation method and application thereof - Google Patents

Amide dianhydride, preparation method and application thereof Download PDF

Info

Publication number
CN112625017B
CN112625017B CN202011386779.7A CN202011386779A CN112625017B CN 112625017 B CN112625017 B CN 112625017B CN 202011386779 A CN202011386779 A CN 202011386779A CN 112625017 B CN112625017 B CN 112625017B
Authority
CN
China
Prior art keywords
dianhydride
formula
mol
transparent polyimide
added
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.)
Active
Application number
CN202011386779.7A
Other languages
Chinese (zh)
Other versions
CN112625017A (en
Inventor
郭海泉
杨正慧
时舜
杨正华
高连勋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN202011386779.7A priority Critical patent/CN112625017B/en
Publication of CN112625017A publication Critical patent/CN112625017A/en
Application granted granted Critical
Publication of CN112625017B publication Critical patent/CN112625017B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to the technical field of flexible electronics and flexible display, in particular to an amide dianhydride, a preparation method and application thereof. The amide dianhydride has a structure shown in a formula (I) or a formula (II): wherein Q is 1 And Q 2 Independently selected from phenyl, cyclohexyl, substituted phenyl or substituted cyclohexyl; y is selected from one or more of a substituted aromatic group, a substituted alicyclic group and a substituted aliphatic group. The transparent polyimide film prepared from the amide dianhydride has better comprehensive performance. Experimental results show that the average light transmittance (measured by a UV spectrometer based on the film thickness of 30 μm) of the transparent polyimide film prepared by the invention at the wavelength of 380-780 nm is not less than 88%, the Coefficient of Thermal Expansion (CTE) at 100-300 ℃ is not more than 25 ppm/DEG C, and the tensile strength>150MPa, modulus>2.0GPa, and the surface energy is 25-40 mN/m.

Description

Amide dianhydride, preparation method and application thereof
Technical Field
The invention relates to the technical field of flexible electronics and flexible display, in particular to an amide dianhydride, a preparation method and application thereof.
Background
In the field of flexible electronics and flexible display, it is generally required to realize thinning, weight saving and flexibility of a device by replacing hard transparent materials such as glass with transparent polymer film materials. Such as flexible OLED displays, flexible LCD displays, flexible solar cells, flexible sensors, flexible transparent heaters, flexible touch, flexible transparent printed circuits, wearable devices, etc. Currently, a wholly aromatic polyimide obtained by polycondensation of aromatic tetracarboxylic dianhydride and aromatic diamine is generally used as a polyimide film material, and the wholly aromatic polyimide film material has a deep amber color and is difficult to be applied to the field of high transparency. Colorless transparent polyimides are generally produced using alicyclic monomers or fluorine-containing monomers in order to achieve high transparency, but these transparent polyimides are generally low in modulus and strength and high in coefficient of thermal expansion. When alicyclic monomers are used, color-generating charge transfer complexes are eliminated, and the color-generating charge transfer complexes have good transparency, but the alicyclic structures have a zigzag conformation, usually a cis-form configuration, and the molecular chains are loosely piled, so that the alicyclic transparent polyimide has a high thermal expansion coefficient, and meanwhile, the heat resistance of the alicyclic polyimide is poor, so that the heat resistance advantage of the polyimide is lost. However, low coefficient of thermal expansion, high heat resistance are necessary properties for flexible electronics, flexible displays, such as flexible display panels, or flexible printed circuits, where a transparent polyimide film material having a low coefficient of linear thermal expansion (CTE not exceeding 25 ppm/K) is required. In flexible electronic and flexible display applications, the required colorless transparent polyimide film needs to have the characteristics of high transparency, high strength, bending resistance, low thermal expansion coefficient, high temperature resistance and the like.
The transparent polyimide film applied to flexible display and flexible electronic needs to form a laminated composite structure with other organic or inorganic layers, so that the interlayer needs to have enough bonding strength, the transparent polyimide generally adopts a fluorine-containing or alicyclic structure with lower polarity, the lower surface energy is caused, the interlayer bonding force is greatly reduced, and the problem in development of the transparent polyimide is also solved. Thus, the current use of transparent polyimides is not satisfactory in many flexible applications.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an amide dianhydride, a preparation method and an application thereof, and the transparent polyimide prepared from the amide dianhydride provided by the present invention has excellent comprehensive properties.
The invention provides an amide dianhydride which has a structure shown in a formula (I) or a formula (II):
wherein Q is 1 And Q 2 Independently selected from phenyl, cyclohexyl, substituted phenyl or substituted cyclohexyl;
y is selected from one or more of a substituted aromatic group, a substituted alicyclic group and a substituted aliphatic group.
In certain embodiments of the invention, Q 1 And Q 2 Independently selected from the structures shown in the formula (Q-1) or the formula (Q-2);
in certain embodiments of the invention, Y is selected from the group consisting of structures having the formula (Y-1), the formula (Y-2), the formula (Y-3), or the formula (Y-4);
Wherein R is 1 、R 2 、R 3 And R is 4 Independently selected from hydrogen, alkyl, cycloalkyl, fluoroalkyl, ester, or halogen;
R 8 one selected from the structures shown in formulas (4-1) to (4-10);
in certain embodiments of the invention, the R 1 、R 2 、R 3 And R is 4 Independently selected from-H, -F, CH 3 or-CF 3 。
In certain embodiments of the invention, Y is selected from those having the structures of formulas (Y-5) through (Y-16);
in certain embodiments of the invention, Y is a di-substituted fatty chain having no more than 20 carbon atoms, the fatty chain comprising from 1 to 2 unsaturated groups.
In certain embodiments of the present invention, the amide dianhydride having a structure represented by formula (i) is selected from the group consisting of the structures represented by formulas (1) to (4);
in certain embodiments of the present invention, the amide dianhydride having a structure represented by formula (ii) is selected from the group consisting of the structures represented by formulae (5) to (15);
substituent R on the aromatic ring 5 、R 6 、R 7 Independently selected from-H, -F, CH 3 or-CF 3 And may contain multiple substituents on the same aromatic ring, which may be the same or different.
The invention also provides a preparation method of the amide dianhydride, which comprises the following steps:
the diacid compound with the structure shown in the formula (T1-1) is subjected to a dehydration cyclization reaction to obtain the amide dianhydride with the structure shown in the formula (I);
Or the tetrahydric acid compound with the structure shown in the formula (T2-1) is subjected to dehydration cyclization reaction to obtain the amide dianhydride with the structure shown in the formula (II);
wherein Q is 1 And Q 2 Independently selected from phenyl, cyclohexyl, and substituted benzeneA group or substituted cyclohexyl;
y is selected from one or more of a disubstituted aromatic group, a disubstituted alicyclic group and a disubstituted aliphatic group.
In the preparation method of the amide dianhydride, Q 1 、Q 2 The selection groups of Y are the same as those of Y, and are not described in detail herein.
In certain embodiments of the present invention, diacid compounds having the structure of formula (T1-1) are prepared by:
amidation reaction of an amine containing an ortho-dicarboxylic group having the structure represented by the formula (T1-2) with an acyl chloride having the structure represented by the formula (T1-3) to obtain a diacid compound having the structure represented by the formula (T1-1);
in certain embodiments of the invention, the amidation reaction is carried out at a temperature of 0 to 40℃and for a time period of 5 to 24 hours.
In certain embodiments of the invention, the amidation reaction is performed in a first solvent.
In certain embodiments of the present invention, the first solvent comprises one or more of dichloromethane, chloroform, ethyl acetate, acetonitrile, acetone, butanone, tetrahydrofuran, 1, 4-dioxane, toluene, N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide.
In certain embodiments of the present invention, the molar ratio of the ortho-dicarboxylic group-containing amine having the structure of formula (T1-2) to the acid chloride having the structure of formula (T1-3) is from 1 to 2:0.95 to 1.05. In certain embodiments, the molar ratio of the ortho-dicarboxy containing amine having the structure of formula (T1-2) to the acid chloride having the structure of formula (T1-3) is 1:1 or 2:1.
in certain embodiments of the invention, the amidation reaction is followed by filtration and drying of the filtered solid material. The method of the present invention is not particularly limited, and filtration and drying methods well known to those skilled in the art may be employed.
After obtaining the diacid compound with the structure shown in the formula (T1-1), the diacid compound with the structure shown in the formula (T1-1) is subjected to a dehydration cyclization reaction to obtain the amide dianhydride with the structure shown in the formula (I).
Specifically, it may be: a diacid compound having a structure represented by the formula (T1-1) is mixed with a third solvent, and azeotropically dehydrated and cyclized by heating.
The third solvent may promote the exit of water from the reaction system for dehydrocyclization elimination, accelerating the equilibrium reaction toward product formation, such as: benzene, toluene, xylene, o-dichlorobenzene, cyclohexanone, tert-butanol, methylcyclohexanone, acetic acid and cyclopentanone. The third solvent may also be a high boiling point solvent added additionally to enhance the solubility of the reactants to promote the reaction, for example: one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone, dimethyl sulfoxide and gamma-butyrolactone.
It may also be: a chemical dehydrating agent is added to a diacid compound having a structure represented by the formula (T1-1) to promote dehydrative ring closure. The chemical dehydrating agent can be selected from one or more of acetic anhydride, sulfoxide chloride and phosphorus trichloride. In certain embodiments of the present invention, the molar ratio of the diacid compound of the structure of formula (T1-1) to the chemical dehydrating agent is 1:2 to 15. In certain embodiments, the diacid compound(s) of the structure of formula (T1-1) and the chemical dehydrating agent are present in a molar ratio of 1: 5. 1: 3. 1: 4. 1: 6. 1: 10. 1:12. 1:15 or 1:12.5.
it may also be: a tertiary amine catalyst is added to the diacid compound of the structure shown in the formula (T1-1), and the tertiary amine catalyst can be selected from one or more of pyridine, picoline, triethylamine and isoquinoline.
In certain embodiments of the invention, the temperature of the dehydrate cyclization reaction is 40-200 ℃ and the time of the dehydrate cyclization reaction is 3-28 hours. In certain embodiments, the temperature of the dehydrate ring closure reaction is 100 ℃, 110 ℃, 130 ℃, 80 ℃, or 120 ℃. In certain embodiments, the dehydrate cyclization reaction is for 3h, 12h, 8h, 4h, 5h, 7h, 10h, 6h, 15h, 9h, or 11h.
In certain embodiments of the present invention, after the dehydrative ring closure reaction, further comprising: cooling, filtering and drying. The method of cooling, filtering and drying is not particularly limited in the present invention, and cooling, filtering and drying methods well known to those skilled in the art may be employed.
In certain embodiments of the present invention, a tetra-acid compound having the structure of formula (T2-1) is prepared according to the following method:
amidation reaction of an amine containing an ortho-dicarboxylic group having the structure represented by the formula (T2-2) with an acyl chloride having the structure represented by the formula (T2-3) to obtain a diacid compound having the structure represented by the formula (T2-1);
in certain embodiments of the invention, the amidation reaction is carried out at a temperature of 0 to 40℃and for a time period of 5 to 24 hours.
In certain embodiments of the invention, the amidation reaction is performed in a second solvent.
In certain embodiments of the present invention, the second solvent comprises one or more of dichloromethane, chloroform, ethyl acetate, acetonitrile, acetone, butanone, tetrahydrofuran, 1, 4-dioxane, toluene, N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide.
In certain embodiments of the present invention, the molar ratio of the ortho-dicarboxyl containing amine having the structure of formula (T2-2) to the acid chloride having the structure of formula (T2-3) is 2:0.95 to 1.05.
In certain embodiments of the invention, the amidation reaction is followed by filtration and drying of the filtered solid material. The method of the present invention is not particularly limited, and filtration and drying methods well known to those skilled in the art may be employed.
After the tetrahydric acid compound with the structure shown in the formula (T2-1) is obtained, the tetrahydric acid compound with the structure shown in the formula (T2-1) is subjected to a dehydration cyclization reaction to obtain the amide dianhydride with the structure shown in the formula (II).
Specifically, it may be: a tetrahydric acid compound having a structure represented by formula (T2-1) is mixed with a fourth solvent and subjected to azeotropic dehydration cyclization by heating.
The fourth solvent may promote the exit of water from the reaction system for the elimination of the dehydrative ring closure, accelerating the equilibrium reaction toward product formation, such as: benzene, toluene, xylene, o-dichlorobenzene, cyclohexanone, tert-butanol, methylcyclohexanone, acetic acid and cyclopentanone. The fourth solvent may be a high boiling point solvent added additionally to improve the solubility of the reactants and promote the reaction, for example: one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone, dimethyl sulfoxide and gamma-butyrolactone.
It may also be: a chemical dehydrating agent is added to a tetrahydric acid compound having a structure represented by formula (T2-1) to promote dehydrative ring closure. The chemical dehydrating agent can be selected from one or more of acetic anhydride, sulfoxide chloride and phosphorus trichloride. In certain embodiments of the present invention, the molar ratio of the tetrahydric compound having the structure of formula (T2-1) to the chemical dehydrating agent is 1:2 to 6.
It may also be: a tertiary amine catalyst is added to the tetra-acid compound having the structure represented by the formula (T2-1), and the tertiary amine catalyst may be selected from one or more of pyridine, picoline, triethylamine and isoquinoline.
In certain embodiments of the invention, the temperature of the dehydrate cyclization reaction is 40-200 ℃ and the time of the dehydrate cyclization reaction is 4-28 hours.
In certain embodiments of the present invention, after the dehydrative ring closure reaction, further comprising: cooling, filtering and drying. The method of cooling, filtering and drying is not particularly limited in the present invention, and cooling, filtering and drying methods well known to those skilled in the art may be employed.
The preparation method of the amide dianhydride provided by the invention can obtain the amide dianhydride with higher yield.
The invention also provides a transparent polyimide prepared from the amide dianhydride; or the amide dianhydride prepared by the preparation method.
Specifically, the transparent polyimide is prepared by performing polycondensation reaction on dianhydride monomer and diamine monomer to obtain polyamic acid precursor, and then imidizing to obtain the transparent polyimide. The dianhydride monomer includes the amide dianhydride described above.
In certain embodiments of the invention, the dianhydride monomer further comprises hexafluorodianhydride and/or biphenyl dianhydride. In certain embodiments of the invention, the molar ratio of amide dianhydride to hexafluorodianhydride described above is from 1 to 4:1. 1:1 or 4:1. in certain embodiments of the present invention, the molar ratio of amide dianhydride to biphenyl dianhydride described above is 3:2.
in some embodiments of the present invention, the diamine monomer is selected from the group consisting of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 3 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, p-phenylenediamine, m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, N- (4-aminophenyl) -4-aminobenzamide, 4-aminobenzoic acid (4-aminophenol) ester, 1, 3-bis (4, 4 '-aminophenoxy) benzene, 4' -diamino-1, 5-phenoxypentane, 3 '-dimethyl-4, 4' -benzidine, 3 '-dimethoxy-4, 4' -benzidine 4,4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 2' -diaminodiphenyl propane, bis (3, 5-diethyl-4-aminophenyl) methane, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene 1, 3-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) diphenylsulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -diaminodiphenylpropane, trans-1, 4-cyclohexanediamine, cis-1, 4-cyclohexanediamine, one or two of 1, 3-diaminocyclohexane, 1, 4-cyclohexanediamine, 4 '-diaminodicyclohexylmethane and 4,4' -methylenebis (2-methylcyclohexylamine).
In certain embodiments of the invention, the molar ratio of dianhydride monomer to diamine monomer is 100: 95-105. In certain embodiments, the molar ratio of dianhydride monomer to diamine monomer is 100:100.
in certain embodiments of the invention, the transparent polyimide is prepared according to the following method:
a) Carrying out polycondensation reaction on dianhydride monomer and diamine monomer to obtain polyimide precursor solution;
b) Imidizing the polyimide precursor solution to obtain transparent polyimide.
The components and proportions of the dianhydride monomer and the diamine monomer mentioned in the preparation method of the transparent polyimide are the same, and are not repeated here.
In certain embodiments of the present invention, the dianhydride monomer and diamine monomer are subjected to a polycondensation reaction in a fifth solvent.
In certain embodiments of the present invention, the fifth solvent comprises one or two of N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, m-cresol, N-methylcaprolactam, sulfolane, dimethylsulfoxide (DMSO), cyclohexanone, hexamethylphosphoramide, and gamma-butyrolactone.
In certain embodiments of the invention, the temperature of the polycondensation reaction is no higher than 60 ℃ and the polycondensation reaction time is 10min to 30h. In certain embodiments, the temperature of the polycondensation reaction is from 0 ℃ to 50 ℃. In certain embodiments, the temperature of the polycondensation reaction is 25 ℃, 10 ℃, 0 ℃, 30 ℃, 15 ℃, 20 ℃, or 5 ℃. In certain embodiments, the polycondensation reaction is for a period of 12h, 24h, 15h, 13h, 10h, 17h, or 18h.
In certain embodiments of the invention, the polycondensation reaction is conducted under shielding gas conditions. In certain embodiments, the shielding gas is nitrogen.
In certain embodiments of the invention, filtration is also included after the polycondensation reaction. The method of the filtration is not particularly limited in the present invention, and filtration methods well known to those skilled in the art may be employed.
In certain embodiments of the present invention, the polyimide precursor solutionHas a rotational viscosity of 4.7X10 4 mPa/s, and the logarithmic viscosity was 1.5dL/g.
After the polyimide precursor solution is obtained, imidizing the polyimide precursor solution to obtain transparent polyimide.
In certain embodiments of the invention, the imidization may be thermal imidization or chemical imidization.
In certain embodiments of the invention, the thermal imidization may be performed by heating to gradually increase the temperature from 80 ℃ to 400 ℃ to effect the dehydrative ring closure of the amic acid to effect imidization.
In certain embodiments of the invention, the chemical imidization is achieved by the addition of a chemical dehydrating agent to effect the dehydrative cyclization of the amic acid.
In certain embodiments of the invention, the chemical dehydrating agent is selected from acetic anhydride or benzoic anhydride. The catalysis can be carried out using organic bases such as pyridine, triethylamine or isoquinoline as catalysts. In certain embodiments of the invention, the molar ratio of the chemical dehydrating agent to dianhydride monomer is from 2 to 10:1. in certain embodiments, the molar ratio of the chemical dehydrating agent to dianhydride monomer is 5: 1. 4: 1. 3:1 or 7:1. in certain embodiments of the invention, the molar ratio of the catalyst to dianhydride monomer is from 2 to 10:1. in certain embodiments, the molar ratio of catalyst to dianhydride monomer is 5: 1. 4: 1. 3:1 or 7:1.
In certain embodiments of the present invention, the temperature of the dehydrative ring closure of amic acid by addition of chemical dehydrating agents is-20 to 200 ℃ for a period of 2 to 10 hours. In certain embodiments, the temperature of the dehydrate ring closure is 25 ℃, 27 ℃, 20 ℃, 10 ℃, or 15 ℃. In certain embodiments, the dehydrate cyclization time is 4 hours, 2 hours, or 3 hours.
And imidizing the polyimide precursor solution to obtain a transparent polyimide solution.
In certain embodiments of the present invention, after the imidizing, further comprising: and mixing the transparent polyimide solution with a sixth solvent to separate out white precipitate, filtering and drying to obtain the transparent polyimide.
In certain embodiments of the invention, the sixth solvent is selected from methanol or ethanol.
The method of the present invention is not particularly limited, and filtration and drying methods well known to those skilled in the art may be employed.
In certain embodiments of the present invention, the raw materials for preparing the transparent polyimide further include a filler. The filler comprises one or more of silicon dioxide, tetraalkoxysilane, polysiloxane, siloxane surfactant and siloxane coupling agent, and can be specifically one or three selected from nano silicon dioxide, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, polyether siloxane and polyphenyl silsesquioxane. The filler is added either before or after polymerization to give the polyamic acid precursor. The mass ratio of the filler to the polyamic acid precursor is 0.01-30: 100. in certain embodiments, the mass ratio of the filler to the polyamic acid precursor is 0.1 to 15:100.
The invention also provides a transparent polyimide film, which is prepared from the transparent polyimide.
In some embodiments of the present invention, the transparent polyimide film is obtained by coating a solution of transparent polyimide on the surface of a support and performing imidization.
In some embodiments of the present invention, the solution of the transparent polyimide may be a solution of the transparent polyimide obtained after imidization as described above, or a solution of a precursor of the polyimide as described above, or a solution of the transparent polyimide prepared by dissolving the transparent polyimide in a seventh solvent. In certain embodiments of the present invention, the seventh solvent is selected from one or more of m-cresol, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone, and γ -butyrolactone. In certain embodiments of the invention, the solution of transparent polyimide has a mass concentration of 20%.
In certain embodiments of the invention, the support is a glass sheet.
In certain embodiments of the invention, the imidization may be thermal imidization or chemical imidization.
In certain embodiments of the invention, the thermal imidization may be achieved by increasing the temperature stepwise from 80 ℃ to 400 ℃ using a heating method. In certain embodiments, the temperature is heated from 80 ℃ to 280 ℃, or the temperature is heated from 80 ℃ to 300 ℃, or the temperature is heated from 80 ℃ to 320 ℃. In certain embodiments of the invention, the temperature of the thermal sub-treatment is 250 to 350 ℃.
In certain embodiments of the invention, the chemical imidization is achieved by adding a chemical dehydrating agent.
In certain embodiments of the invention, the chemical dehydrating agent is selected from acetic anhydride or benzoic anhydride. The catalysis can be carried out using organic bases such as pyridine or triethylamine as catalysts. In certain embodiments of the invention, the mass ratio of the chemical dehydrating agent to the dianhydride monomer is 2 to 10:1. in certain embodiments of the invention, the mass ratio of the catalyst to dianhydride monomer is from 2 to 10:1.
in certain embodiments of the present invention, the temperature of the dehydrative ring closure of amic acid by addition of chemical dehydrating agents is-20 to 200 ℃ for a period of 2 to 10 hours.
In the invention, the polyimide film formed through imidization can be subjected to imidization again, so that thermal hysteresis and residual stress can be removed from the film, the thermal stability is improved, and the thermal expansion coefficient is reduced.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In certain embodiments of the invention, the polyimide film has a thickness of 10 to 250 μm. In certain embodiments, the polyimide film has a thickness of 10 to 100 μm.
The polyimide film surface can be directly formed with a functional layer necessary for flexible display; the polyimide film may be peeled off from the surface of the support body to obtain a self-supporting film material, and the necessary functional layer may be displayed on the surface of the support body in a flexible manner.
The transparent polyimide provided by the invention has excellent characteristics of transparency, high heat resistance, low linear thermal expansion coefficient and the like, has higher surface energy, and is suitable for improving interlayer binding force. For example, when the multilayer composite film structure is constructed by using the composite film structure, the thermal expansion coefficient is low, the interlayer bonding force is enough, the thermal expansion performance of inorganic or metal film layer materials can be adapted, and the interlayer bonding can be improved, so that the dimensional stability of the horizontal and vertical methods of the composite film in the high-temperature processing process is improved, and the risks of deformation and delamination are reduced.
The transparent polyimide film prepared from the amide dianhydride has better comprehensive performance. Experimental results show that the average light transmittance (measured by a UV spectrometer based on the film thickness of 30 μm) of the transparent polyimide film prepared by the invention at the wavelength of 380-780 nm is not lower than 88%, the Coefficient of Thermal Expansion (CTE) at 100-300 ℃ is not more than 25 ppm/DEG C, the tensile strength is >150MPa, the modulus is >2.0GPa, the surface energy is 25-40 mN/m, the surface energy is higher, and the adhesion between the transparent polyimide film and a functional layer is facilitated.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 2 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 2 of the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 5 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 5 of the present invention;
FIG. 7 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 6 of the present invention;
FIG. 8 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 6 of the present invention;
FIG. 9 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 16 of the present invention;
FIG. 10 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 16 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials used in the following examples are all generally commercially available.
The instrumentation and parameter conditions used in the examples are as follows:
1. nuclear magnetic resonance: bruker type 300 nuclear magnetic resonance spectrometer, bruker, germany;
2. infrared spectroscopy: vertex 70 Fourier transform Infrared Spectroscopy (FTIR) instrument, bruker, germany, test range 4000-600cm -1 ；
3. Coefficient of Thermal Expansion (CTE): testing was performed using a Thermo plas TMA Thermo-mechanical analyzer (TMA, TA company Q400); test conditions: 10 ℃/min, 100-300 ℃ interval;
4. tensile test: NSTRON-1121 type electronic universal testing machine, stretching rate is 5mm/min;
5. optical transmittance: a Shimadzu Uv-2550 ultraviolet visible spectrum tester, average light transmittance at 380-780 nm wavelength;
6. glass transition temperature (Tg): DSC Perkin-Elmer DSC-7 is used for testing the film material, the nitrogen atmosphere is adopted, and the heating rate is 10 ℃/min;
7. rotational viscosity: a digital viscometer, room temperature;
8. logarithmic viscosity ([ eta ] inh): ubbelohde viscometer, 30 ℃.
Example 1
3.623g (0.02 mol) of 4-aminophthalic acid and 80g of tetrahydrofuran were charged into the reaction vessel, and 4.2114g (0.02 mol) of trimellitic chloride was added in portions at 10℃with stirring, and the reaction was carried out for 15 hours. Filtering, and drying the filtered solid powder to obtain diacid. The obtained diacid was added to 100g of xylene, heated under reflux at 100℃for 3 hours, cooled, filtered and dried to obtain 6.556g of amide dianhydride having the structure represented by the formula (1) in 97.2% yield. 1H NMR (400 MHz, DMSO-d 6) δ11.31 (s, 1H), 8.64 (s, 1H), 8.51 (d, J=6.1 Hz, 2H), 8.27 (d, J=8.0 Hz, 2H), 8.12 (d, J=8.3 Hz, 1H) 13C NMR (101 MHz, DMSO-d 6) δ 164.7,162.3,141.0,139.3,134.5,132.6,132.2,132.1,129.8,127.7,127.5,126.7,119.8.
FIG. 1 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 1 of the present invention.
Example 2
3.623g (0.02 mol) of 4-aminophthalic acid and 100g of acetonitrile were charged into a reaction vessel, stirred, 4.3324g (0.02 mol) of hydrogenated trimellitic chloride was added in portions at 10℃and the reaction was carried out for 12 hours. Filtering, and drying the filtered solid powder to obtain diacid. The obtained diacid was added to 120g of cyclohexanone, heated and refluxed at 110℃for 12 hours, cooled, filtered, and dried to obtain 6.518g of amide dianhydride having the structure represented by the formula (2), and the yield was 95.0%.1H NMR (300 MHz, DMSO-d 6) δ10.73 (s, 1H), 8.32 (s, 1H), 7.98 (dd, J=21.6, 8.3Hz, 2H), 3.67-3.47 (m, 1H), 3.29 (dd, J=18.2, 8.0Hz, 1H), 2.55 (s, 1H), 2.20 (d, J=5.3 Hz, 1H), 2.08 (dd, J=13.5, 4.3Hz, 1H), 1.82 (t, J=24.0 Hz, 2H), 1.62 (dd, J=24.1, 11.0Hz, 1H), 1.41 (dd, J=21.8, 11.9Hz, 1H) 13C NMR (101 MHz, DMSO-d 6) δ 172.9,172.2,162.3,146.3,132.2,129.8,126.7,119.8,42.0,40.4,36.4,28.6,26.6,22.6.
FIG. 3 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 2 of the present invention.
FIG. 4 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 2 of the present invention.
Example 3
3.7438g (0.02 mol) of 1, 2-dicarboxy-4-aminocyclohexane and 85g of methylene chloride were charged into the reaction vessel, stirred, and 4.2114g (0.02 mol) of trimellitic chloride was added in portions at 20℃to conduct the reaction for 10 hours. Filtering, and drying the filtered solid powder to obtain diacid. The obtained diacid was added to a mixed solution of 150g toluene and 10.209g (0.1 mol) acetic anhydride, heated under reflux at 130 ℃ for 8 hours, cooled, filtered, and dried to obtain 6.5869g of an amide dianhydride having a structure represented by formula (3) in 96% yield. 1H NMR (300 MHz, DMSO-d 6) delta 8.60-8.58 (m, 2H), 8.37 (d, 1H), 8.03 (s, 1H), 3.54-3.49 (m, 1H), 2.9 (m, 2H), 2.05 (m, 2H), 1.79 (m, 2H), 1.54 (m, 2H) 13C NMR (101 MHz, DMSO-d 6) delta 172.2,167.2,162.3,139.3,134.5,132.6,132.1,127.7,127.5,48.8,42.4,34.5,29.1,25.3,20.7.
Example 4
3.7438g (0.02 mol) of 1, 2-dicarboxy-4-aminocyclohexane and 68g of tetrahydrofuran were charged into the reaction vessel, and the mixture was stirred, 4.6926g (0.02 mol) of hydrogenated trimellitic chloride was added in portions at 15℃to conduct the reaction for 16 hours. Filtering, and drying the filtered solid powder to obtain diacid. The obtained diacid was added to a mixed solution of 80g of xylene and 10.209g of acetic anhydride (0.1 mol), heated to 80 ℃ for reaction for 4 hours, cooled, filtered and dried to obtain 6.777g of amide dianhydride having a structure represented by formula (4) in 97% yield. 1H NMR (300 MHz, DMSO-d 6) δ8.03 (s, 1H), 3.54 (m, 1H), 2.9 (m, 4H), 2.38 (m, 1H), 2.04 (m, 2H), 1.80-1.74 (m, 6H), 1.55-1.49 (m, 4H) 13C NMR (101 MHz, DMSO-d 6) δ 173.3,172.2,48.6,46.0,42.4,42.0,36.4,34.5,29.1,28.6,26.6,25.3,22.6,20.7.
Example 5
3.623g (0.02 mol) of 4-aminophthalic acid and 69g of tetrahydrofuran were charged into the reaction vessel, and 2.0302g (0.01 mol) of terephthaloyl chloride was added thereto in portions at 20℃with stirring to conduct the reaction for 20 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 6.13g (0.06 mol) of acetic anhydride and 100g of xylene, heated to 120℃for reaction for 5 hours, cooled, filtered and dried to obtain 4.38g of bisamide dianhydride having a structure represented by the formula (5) in 96% yield. 1H NMR (300 MHz, DMSO-d 6) δ13.21 (s, 3H), 10.75 (s, 2H), 8.17-8.07 (m, 6H), 8.03 (dd, J=8.6, 1.9Hz, 2H), 7.79 (d, J=8.5 Hz, 2H) 13C NMR (101 MHz, DMSO-d 6) δ 165.6,163.3,162.7,146.2,136.7,132.6,128.3,126.6,126.4,125.0,115.3.
FIG. 5 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 5 of the present invention.
FIG. 6 is a nuclear magnetic resonance spectrum of an amide dianhydride of example 5 of the present invention.
Example 6
3.623g (0.02 mol) of 4-aminophthalic acid and 69g of tetrahydrofuran were charged into the reaction vessel, and 2.0302g (0.01 mol) of isophthaloyl chloride was added thereto in portions at 20℃with stirring, and the reaction was carried out for 20 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 8.16g (0.08 mol) of acetic anhydride and 100 xylenes, heated to 120℃for reaction for 5 hours, cooled, filtered and dried to obtain 4.335g of bisamide dianhydride having the structure represented by the formula (6) in 95% yield. 1H NMR (300 MHz, DMSO-d 6) δ13.10 (s, 4H), 10.78 (s, 2H), 8.59 (s, 1H), 8.20 (dd, J=7.8, 1.4Hz, 2H), 8.09 (d, J=2.0 Hz, 2H), 8.03 (dd, J=8.5, 2.1Hz, 2H), 7.75 (dd, J=14.6, 8.1Hz, 3H) 13C NMR (101 MHz, DMSO-d 6) δ 165.7,163.3,162.7,146.1,134.3,132.8,131.5,129.0,127.6,126.6,126.5,125.1,115.1.
FIG. 7 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 6 of the present invention.
FIG. 8 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 6 of the present invention.
Example 7
3.623g (0.02 mol) of 4-aminophthalic acid and 69g of 1, 4-dioxane were charged into a reaction vessel, stirred, and 2.0907g (0.01 mol) of 1, 4-cyclohexanedicarboxylic acid chloride was added in portions at 30℃to conduct the reaction for 15 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 12.25g (0.12 mol) of acetic anhydride and 90g of toluene, heated to 110℃for reaction for 7 hours, cooled, filtered and dried to obtain 4.39g of bisamide dianhydride having a structure represented by the formula (7) in 95% yield. 1H NMR (300 MHz, DMSO-d 6) δ8.66 (s, 2H), 8.40 (d, 2H), 8.21 (dd, 2H), 7.23 (s, 2H), 2.38 (m, 2H), 1.91 (m, 4H), 1.66 (m, 4H) 13C NMR (101 MHz, DMSO-d 6) δ 172.9,162.3,146.3,132.2,129.8,126.7,119.8,42.8,26.2.
Example 8
3.623g (0.02 mol) of 4-aminophthalic acid and 50g of ethyl acetate were charged into a reaction vessel, and 2.7912g (0.01 mol) of 4,4' -biphenyldicarboxylic acid dichloride was added in portions at 10℃with stirring, and the reaction was carried out for 20 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 8.16g (0.08 mol) of acetic anhydride and 75g of toluene, heated to 110℃for reaction for 10 hours, cooled, filtered and dried to obtain 5g of bisamide dianhydride having a structure represented by the formula (8) in 94% yield. 1H NMR (300 MHz, DMSO-d 6) δ9.15 (s, 2H), 8.66 (d, 2H), 8.52 (dd, 2H), 8.40 (d, 2H), 8.21 (dd, 2H), 8.09 (dd, 2H), 7.76 (m, 2H), 7.59 (m, 2H) 13C NMR (101 MHz, DMSO-d 6) δ 164.7,162.3,141.0,132.6,132.2,132.1,129.8,128.0,127.7,126.7,126.5,121.2,119.8.
Example 9
3.623g (0.02 mol) of 4-aminophthalic acid and 50g of ethyl acetate were charged into a reaction vessel, and 2.6114g (0.01 mol) of 1, 3-adamantane dicarboxylic acid chloride was added thereto in portions at 10℃with stirring to conduct a reaction for 14 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 20.42g (0.2 mol) of acetic anhydride and 120g of xylene, heated to 120℃for reaction for 6 hours, cooled, filtered and dried to obtain 4.99g of bisamide dianhydride having a structure represented by the formula (9) in 97% yield. 1H NMR (300 MHz, DMSO-d 6) δ8.66 (s, 2H), 8.40 (d, 2H), 8.21 (dd, 2H), 7.23 (s, 2H), 2.36 (t, 1H), 1.83 (m, 3H), 1.65 (m, 2H), 1.58 (m, 3H), 1.49 (m, 2H), 1.43 (m, 1H), 1.24 (m, 2H), 13C NMR (101 MHz, DMSO-d 6) δ 174.6,172.9,162.3,146.3,132.2,129.8,126.7,119.8,45.2,39.3,37.0,36.7,36.1,34.2,26.3.
Example 10
3.623g (0.02 mol) of 4-aminophthalic acid and 60g of butanone were charged into the reaction vessel, and 4.2914g (0.01 mol) of 2,2' -bis (4-chlorocarbonylphenyl) hexafluoropropane was added in portions at 30℃with stirring, and the reaction was carried out for 24 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 25.52g (0.25 mol) of acetic anhydride and 120g of xylene, heated to 120℃for reaction for 10 hours, cooled, filtered and dried to obtain 6.48g of bisamide dianhydride having a structure represented by the formula (10) in 95% yield. 1H NMR (300 MHz, DMSO-d 6) δ9.15 (s, 2H), 8.66 (dd, 2H), 8.40 (d, 2H), 8.21 (dd, 2H), 7.95 (d, 4H), 7.58 (d, 4H) 13C NMR (101 MHz, DMSO-d 6) δ 164.7,162.3,149.5,141.0,132.2,131.7,129.8,128.3,128.0,126.7,119.8,106.2,66.3.
Example 11
3.623g (0.02 mol) of 4-aminophthalic acid and 80g of tetrahydrofuran were charged into the reaction vessel, and 4.4332g (0.01 mol) of 9, 9-bis (4-chloroformylphenyl) fluorene were added thereto in portions at 25℃with stirring, and the reaction was carried out for 12 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 10.21g (0.1 mol) of acetic anhydride and 80g of toluene, heated to 110℃for reaction for 6 hours, cooled, filtered and dried to obtain 6.55g of bisamide dianhydride having a structure represented by the formula (11) in 94% yield. 1H NMR (300 MHz, DMSO-d 6) δ9.15 (s, 2H), 8.66 (d, 2H), 8.40 (d, 2H), 8.21 (dd, 2H), 7.91 (d, 4H), 7.87 (dd, 2H), 7.55 (dd, 2H), 7.41 (d, 4H), 7.38 (m, 2H), 7.28 (m, 2H) 13C NMR (101 MHz, DMSO-d 6) δ 164.7,162.3,151.1,141.9,141.0,132.2,131.7,129.8,128.7,128.3,128.1,128.0,126.7,126.2,119.8,62.9.
Example 12
3.7438g (0.02 mol) of 4-aminocyclohexane-1, 2-dicarboxylic acid, 65g of dimethylacetamide were charged into the reaction vessel, stirred, and 2.5308g (0.01 mol) of 2, 7-naphthalenedicarboxylic acid chloride was added in portions at 25℃to conduct the reaction for 10 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 24.5g (0.24 mol) of acetic anhydride and 70g of xylene, heated to 120℃and reacted for 15 hours, cooled, filtered and dried to obtain 5.1g of bisamide dianhydride having a structure represented by the formula (12) in 98% yield. 1H NMR (300 MHz, DMSO-d 6) δ8.48 (s, 2H), 8.13 (d, 2H), 8.03 (m, 2H), 7.98 (m, 2H), 3.54 (m, 2H), 2.9 (m, 4H), 2.05 (m, 4H), 1.79 (m, 4H), 1.54 (m, 4H) 13C NMR (101 MHz, DMSO-d 6) δ 172.2,167.2,137.4,134.9,131.2,130.0,127.9,126.5,48.8,42.4,34.5,29.1,25.3,20.7.
Example 13
3.623g (0.02 mol) of 4-aminophthalic acid and 50g of N-methylpyrrolidone were charged into a reaction vessel, stirred, and 2.2108g (0.01 mol) of 2, 5-bischloroformyl-bicyclo [ 2.2.1 ] heptane were added in portions at 20℃to conduct the reaction for 16 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 30.63g (0.3 mol) of acetic anhydride and 100g of toluene, heated to 110℃for reaction for 10 hours, cooled, filtered and dried to obtain 4.55g of bisamide dianhydride having a structure represented by the formula (13) in 96% yield. 1H NMR (300 MHz, DMSO-d 6) δ8.66 (d, 2H), 8.40 (d, 2H), 8.21 (dd, 2H), 7.23 (s, 2H), 2.37 (m, 2H), 2.13 (m, 1H), 1.88 (m, 3H), 1.66-1.62 (m, 4H) 13C NMR (101 MHz, DMSO-d 6) δ 172.9,162.3,146.3,132.2,129.8,126.7,119.8,42.8,41.0,35.8,30.8.
Example 14
3.623g (0.02 mol) of 4-aminophthalic acid, 55g of acetonitrile and stirred, 3.4318g (0.01 mol) of 3,3' -sulfonylxylenyl chloride were added in portions at 25℃and the reaction was carried out for 10 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 25.52g (0.25 mol) of acetic anhydride and 60g of toluene, heated to 110℃for reaction for 9 hours, cooled, filtered and dried to obtain 5.78g of bisamide dianhydride having a structure represented by the formula (14) in 97% yield. 1H NMR (300 MHz, DMSO-d 6) δ9.15 (s, 2H), 8.66 (dd, 2H), 8.45 (m, 2H), 8.40 (d, 2H), 8.28 (m, 2H), 8.21 (dd, 2H), 8.03 (m, 2H), 7.80 (t, 2H). 13C NMR (101 MHz, DMSO-d 6) δ 164.7,162.3,142.5,141.0,135.2,132.5,132.2,131.7,129.8,126.7,121.3,119.8.
Example 15
3.623g (0.02 mol) of 4-aminophthalic acid and 60g of methylene chloride were charged into a reaction vessel, and 2.6316g (0.01 mol) of 3, 8-bischloroformylbicyclo [ 4.4.0 ] decane were added in portions at 25℃with stirring, and the reaction was carried out for 15 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 30.63g (0.3 mol) of acetic anhydride and 110g of xylene, heated to 120℃for reaction for 11 hours, cooled, filtered and dried to obtain 4.9g of bisamide dianhydride having a structure represented by the formula (15) in a yield of 95%.1H NMR (300 MHz, DMSO-d 6) δ8.66 (d, 2H), 8.40 (d, 2H), 8.21 (dd, 2H), 7.23 (s, 2H), 2.37 (m, 2H), 1.91 (m, 4H), 1.64 (m, 2H), 1.53 (m, 4H), 1.27 (m, 4H) 13C NMR (101 MHz, DMSO-d 6) δ 172.9,162.3,146.3,132.2,129.8,126.7,119.8,43.7,40.5,27.5,24.1,22.5.
Example 16
3.623g (0.02 mol) of 4-aminophthalic acid and 50g of tetrahydrofuran were charged into a reaction vessel, and 2.7498g (0.01 mol) of 2,3,5, 6-tetrafluoroterephthaloyl chloride was added in portions at 30℃with stirring, and the reaction was carried out for 11 hours. Filtering, and drying the filtered solid powder to obtain the tetra-acid. The obtained tetracarboxylic acid was added to a solution containing 30.63g (0.3 mol) of acetic anhydride and 90g of toluene, heated to 120℃for reaction for 6 hours, cooled, filtered and dried to obtain 5.07g of bisamide dianhydride having a structure represented by the formula (16) in 96% yield. 1 H NMR(400MHz,DMSO)δ＝11.87(s,2H),8.41(s,2H),8.14(d,J＝8.2,2H),8.06(d,J＝8.3,2H).13C NMR(101MHz,DMSO-d6)δ162.9,162.5,156.1,144.3,133.2,126.9,126.5,126.2,114.7。
FIG. 9 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 16 of the present invention.
FIG. 10 is a nuclear magnetic resonance spectrum of an amide dianhydride according to example 16 of the present invention.
Example 17
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 37.26g of dimethylacetamide were added to the reaction vessel, and the mixture was dissolved by stirring at 6 ℃. 3.3724g (0.01 mol) of a dianhydride compound having a structure represented by the formula (1) was added in portions, and polymerized under nitrogen at 25℃for 12 hours, and filtered to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.7X10 4 mPa/s, logarithmViscosity 1.5dL/g. 5.1g (0.05 mol) of acetic anhydride and 5.06g (0.05 mol) of triethylamine were added to the precursor solution and reacted at 25℃for 4 hours. The reaction mixture was slowly poured into ethanol to precipitate a white filiform precipitate, which was filtered off and dried to obtain a transparent polyimide resin. The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20 percent, the solution is coated on the surface of a glass plate, and the glass plate is placed in an oven to be heated to 200 ℃ to form the transparent polyimide film.
Example 18
To the reaction vessel were added 1.1419g (0.01 mol) of trans-1, 4-cyclohexanediamine and 25.6g of N-methyl-2-pyrrolidone, and the mixture was heated to 70℃to dissolve all the solids, cooled to room temperature, and 1.2g of acetic acid was added thereto and stirred for 10 minutes. 3.3724g (0.01 mol) of a dianhydride compound having a structure represented by the formula (1) was added in portions, and polymerized under nitrogen at 10℃for 12 hours, and filtered to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 3.0X10 4 mPa/s, logarithmic viscosity 1.2dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 280 ℃ in a gradient way to form the transparent polyimide film.
Example 19
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 37.6g of dimethylacetamide were added to the reaction vessel, and the mixture was dissolved by stirring at a temperature of not more than 10 ℃. 3.4329g (0.01 mol) of a dianhydride compound having a structure represented by the formula (2) was added in portions, and polymerized under nitrogen at 0℃for 24 hours, and filtered to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.6X10 4 mPa/s, logarithmic viscosity 1.6dL/g. 5.1g (0.05 mol) of acetic anhydride and 5.06g (0.05 mol) of triethylamine were added to the precursor solution, and after stirring uniformly, the reaction mixture was coated on the surface of a glass plate and placed in an oven to heat to 200℃to form a transparent polyimide film.
Example 20
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 37.6g of N-methyl-2-pyrrolidone were added to the reaction vessel, and the mixture was dissolved by stirring at 6 ℃. 3.4329g (0.01 mol) of a dianhydride compound having a structure represented by the formula (3) was sequentially added under a nitrogen atmosphereThe reaction was carried out at 30℃for 15 hours, and the reaction mixture was filtered to obtain a precursor solution of transparent polyimide. The rotational viscosity was measured to be 4.7X10 4 mPa/s, logarithmic viscosity 1.6dL/g. 5.1g (0.05 mol) of acetic anhydride and 5.06g (0.05 mol) of pyridine were added to the precursor solution and reacted at 27℃for 2 hours. The reaction mixture was slowly poured into methanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a transparent polyimide resin. The resin is dissolved in gamma-butyrolactone to form a solution with the mass fraction of 20 percent, the solution is coated on the surface of a glass plate, and the glass plate is placed in an oven to be heated to 200 ℃ to form the transparent polyimide film.
Example 21
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 38g of dimethylacetamide were added to the reaction vessel, and the mixture was dissolved by stirring at a temperature of not more than 10 ℃. 3.4934g (0.01 mol) of a dianhydride compound having a structure represented by formula (4) was successively added, and polymerized under nitrogen at 15℃for 24 hours, followed by filtration to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.8X10 4 mPa/s, logarithmic viscosity 1.7dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 300 ℃ in a gradient way to form the transparent polyimide film.
Example 22
1.1419g (0.01 mol) of trans-1, 4-cyclohexanediamine and 32.33g of dimethylacetamide are added into a reaction vessel, and the temperature is controlled to be not more than 15 ℃, and the mixture is stirred and dissolved. The solid was completely dissolved by heating to 70 ℃, cooled to room temperature, 1.2g of acetic acid was added and stirred for 15min. 4.5636g (0.01 mol) of a dianhydride compound having a structure represented by the formula (5) was successively added, and polymerized under nitrogen at 20℃for 13 hours, followed by filtration to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.9X10 4 mPa/s, logarithmic viscosity 1.6dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 300 ℃ in a gradient way to form the transparent polyimide film.
Example 23
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 44g of dimethylacetamide and an ice-water bath were added to the reaction vessel, and the mixture was dissolved by stirring. Ei-yi4.5636g (0.01 mol) of a dianhydride compound having a structure represented by the formula (6) was added thereto in a lump, and polymerized at 5℃under nitrogen for 10 hours, followed by filtration to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.6X10 4 mPa/s, logarithmic viscosity 1.5dL/g. To the precursor solution, 4.08g (0.04 mol) of acetic anhydride and 5.17g (0.04 mol) of isoquinoline were added, and reacted at 20℃for 2 hours, and the reaction mixture was slowly poured into ethanol to precipitate a white filiform precipitate, which was filtered off and dried to obtain a transparent polyimide resin. The resin is dissolved in N-methyl pyrrolidone to form a solution with the mass fraction of 20 percent, the solution is coated on the surface of a glass plate, and the glass plate is placed in an oven to be heated to 200 ℃ to form the transparent polyimide film.
Example 24
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 0.12g of nano-silica and 44.4g of dimethylacetamide are added into a reaction vessel, and the mixture is stirred and dissolved at a temperature of 6 ℃. 4.6241g (0.01 mol) of a dianhydride compound having a structure represented by the formula (7) was added in portions, and polymerized under nitrogen at 25℃for 17 hours, and filtered to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.8X10 4 mPa/s, logarithmic viscosity 1.7dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 300 ℃ in a gradient way to form the transparent polyimide film.
Example 25
1.1419g (0.01 mol) of trans-1, 4-cyclohexanediamine and 32.33g of dimethylacetamide are added into a reaction vessel, and the temperature is controlled to be not more than 15 ℃, and the mixture is stirred and dissolved. Heating to 70deg.C to dissolve the solid completely, cooling to room temperature, adding 1.2g acetic acid, stirring for 15min, sequentially adding 0.10g 3-aminopropyl trimethoxysilane, 0.25g tetramethoxysilane, 36.6g N-methyl-2-pyrrolidone, stirring, and controlling temperature to 6deg.C. 5.3246g (0.01 mol) of a dianhydride compound having a structure represented by the formula (8) was added in portions, and polymerized under nitrogen at 20℃for 18 hours, and filtered to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.8X10 4 mPa/s, logarithmic viscosity 1.9dL/g. Coating the precursor solution on the surface of a glass plate, placing the glass plate in an oven, and heating the glass plate from 80 ℃ to 320 ℃ in a gradient way to form transparent glass platePolyimide film.
Example 26
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 47.3g of N-methyl-2-pyrrolidone were added to the reaction vessel, and the mixture was dissolved by stirring in an ice water bath. 5.1448g (0.01 mol) of a dianhydride compound having a structure represented by the formula (9) was added in portions, and polymerized at 0℃under nitrogen for 12 hours, followed by filtration to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.7X10 4 mPa/s, logarithmic viscosity 1.7dL/g. 3.06g (0.03 mol) of acetic anhydride and 3.87g (0.03 mol) of isoquinoline were added to the precursor solution and reacted at 10℃for 2 hours. The reaction mixture was coated on the surface of a glass plate and placed in an oven and heated to 250 c to form a transparent polyimide film.
Example 27
1.1419g (0.01 mol) of trans-1, 4-cyclohexanediamine and 45g of N-methyl-2-pyrrolidone are added into a reaction vessel, and the temperature is controlled to be not more than 15 ℃ and the mixture is stirred and dissolved. Heating to 80 ℃ to dissolve the solid completely, cooling to room temperature, adding 1.2g of acetic acid, stirring for 10min, adding 6.8248g (0.01 mol) of dianhydride compound with a structure shown in formula (10) in portions, carrying out polymerization reaction for 18h at 15 ℃ under nitrogen, and filtering to form a precursor solution of transparent polyimide. The rotational viscosity was measured to be 3.8X10 4 mPa/s, logarithmic viscosity 1.4dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 320 ℃ in a gradient way to form the transparent polyimide film.
Example 28
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 50.47g of dimethylacetamide were added to the reaction vessel, and dissolved in an ice-water bath under stirring. 3.4833g (0.005 mol) of a dianhydride compound having a structure represented by formula (11) and 2.2212g (0.005 mol) of hexafluorodianhydride were sequentially added, and polymerized at 25℃under nitrogen for 18 hours, and filtered to form a precursor solution of transparent polyimide. The rotational viscosity was measured to be 4.6X10 4 mPa/s, logarithmic viscosity 1.6dL/g. 4.08g of acetic anhydride and 3.16g of pyridine were added to the polymerization system and reacted at 10℃for 4 hours. Coating the reaction mixture on the surface of a glass plate, and heating the glass plate to 280 ℃ in an oven to form transparent polyamideAn imine film.
Example 29
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 45.85g of N-methyl-2-pyrrolidone were added to the reaction vessel, and the mixture was dissolved by stirring at 15 ℃. 3.111g (0.006 mol) of a dianhydride compound having a structure represented by formula (12) and 1.1769g (0.004 mol) of biphenyl dianhydride were sequentially added, and polymerized under nitrogen at 5℃for 24 hours, followed by filtration to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 3.7X10 4 mPa/s, logarithmic viscosity 1.4dL/g. 7.14g (0.07 mol) of acetic anhydride and 5.54g (0.07 mol) of pyridine were added to the precursor solution and reacted at 25℃for 3 hours. The reaction mixture was slowly poured into methanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin is dissolved in gamma-butyrolactone to form a solution with the mass fraction of 20 percent, the solution is coated on the surface of a glass plate, and the glass plate is placed in an oven to be heated to 150 ℃ to form a transparent polyimide film.
Example 30
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 44.14g of dimethylacetamide were added to the reaction vessel, and dissolved in an ice-water bath with stirring. 3.699g (0.008 mol) of a dianhydride compound having a structure represented by formula (13) and 0.888g (0.002 mol) of hexafluorodianhydride were successively added, and polymerized under nitrogen at 25℃for 24 hours, and filtered to form a precursor solution of transparent polyimide. The rotational viscosity was measured to be 3.8X10 4 mPa/s, logarithmic viscosity 1.4dL/g. 5.1g (0.05 mol) of acetic anhydride and 5.06g (0.05 mol) of triethylamine were added to the precursor solution and reacted at 15℃for 2 hours. The reaction mixture was coated on the surface of a glass plate and heated to 300 ℃ in an oven to form a transparent polyimide film.
Example 31
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 51.93g of N-methyl-2-pyrrolidone were charged into the reaction vessel. 5.9652g (0.01 mol) of a dianhydride compound having a structure represented by the formula (14) was added in portions, and polymerized under nitrogen at 0℃for 24 hours, and filtered to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.0X10 4 mPa/s, logarithmic viscosity 1.4dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 320 ℃ in a gradient way to form the transparent polyimide film.
Example 32
1.1419g (0.01 mol) of trans-1, 4-cyclohexanediamine and 36g of N-methyl-2-pyrrolidone were added to the reaction vessel, and the mixture was dissolved by stirring at 20 ℃. Heating to 70 ℃ to dissolve the solid completely, cooling to room temperature, adding 1.2g of acetic acid, stirring for 15min, adding 5.1650g (0.01 mol) of dianhydride compound with a structure shown in formula (15) in portions, polymerizing at 15 ℃ for 15h under nitrogen, and filtering to form a precursor solution of transparent polyimide. The rotational viscosity was measured to be 4.5X10 4 mPa/s, logarithmic viscosity 1.6dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 300 ℃ in a gradient way to form the transparent polyimide film.
Example 33
3.2023g (0.01 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 50g of dimethylacetamide were added to the reaction vessel, and the mixture was dissolved by stirring at a temperature of not more than 30 ℃. 5.2832g (0.01 mol) of a dianhydride compound having a structure represented by the formula (16) was successively added, and polymerized under nitrogen at 30℃for 18 hours, followed by filtration to form a precursor solution of a transparent polyimide. The rotational viscosity was measured to be 4.5X10 4 mPa/s, logarithmic viscosity 1.3dL/g. The precursor solution is coated on the surface of a glass plate, and the glass plate is placed in an oven, and the glass plate is heated from 80 ℃ to 200 ℃ in a gradient way to form the transparent polyimide film.
The properties of the transparent polyimide films of examples 17 to 33 were measured, and the measurement results are shown in Table 1.
TABLE 1 results of Performance test of transparent polyimide films of examples 17 to 33
TABLE 2 contact angle and surface energy of transparent polyimide films of examples 17 to 33
As is clear from tables 1 and 2, the transparent polyimide film prepared according to the present invention has an average light transmittance (measured by UV spectrometer based on film thickness of 30 μm) of not less than 88% at a wavelength of 380 to 780nm, a Coefficient of Thermal Expansion (CTE) of not more than 25 ppm/DEG C at 100 to 300 ℃, a tensile strength of >150MPa, a modulus of >2.0GPa, and a surface energy of 25 to 40mN/m.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (1)

1. The transparent polyimide film is prepared by coating a solution of transparent polyimide on the surface of a support and carrying out imidization reaction;
The transparent polyimide is prepared according to the following method:
a) Carrying out polycondensation reaction on dianhydride monomer and diamine monomer to obtain polyimide precursor solution;
b) Imidizing the polyimide precursor solution to obtain transparent polyimide;
the diamine monomer is trans-1, 4-cyclohexanediamine or 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl;
when the diamine monomer is trans-1, 4-cyclohexanediamine, the dianhydride monomer is a dianhydride compound with a structure shown in a formula (1) or a dianhydride compound with a structure shown in a formula (5);
when the diamine monomer is 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, the dianhydride monomer is a dianhydride compound with a structure shown in a formula (4), a dianhydride compound with a structure shown in a formula (6), a dianhydride compound with a structure shown in a formula (7) or a dianhydride compound with a structure shown in a formula (9);
（1）；/>（4）；
（5）；/>（6）；
（7）；/>（9）；
the thickness of the transparent polyimide film is 10-250 mu m;
the thermal expansion coefficient of the transparent polyimide film at 100-300 ℃ is not more than 23 ppm/DEG C, the tensile strength is not less than 201 MPa, the modulus is not less than 2.17 GPa, and the surface energy is 33.51-38.56 mN/m.
CN202011386779.7A 2020-12-01 2020-12-01 Amide dianhydride, preparation method and application thereof Active CN112625017B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011386779.7A CN112625017B (en) 2020-12-01 2020-12-01 Amide dianhydride, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011386779.7A CN112625017B (en) 2020-12-01 2020-12-01 Amide dianhydride, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112625017A CN112625017A (en) 2021-04-09
CN112625017B true CN112625017B (en) 2023-12-19

Family

ID=75307337

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011386779.7A Active CN112625017B (en) 2020-12-01 2020-12-01 Amide dianhydride, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112625017B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7120867B2 (en) * 2018-09-28 2022-08-17 保土谷化学工業株式会社 Charge control agent and toner using the same
CN116144023B (en) * 2023-03-30 2023-08-04 广东粤港澳大湾区黄埔材料研究院 Polyimide, and preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012072118A (en) * 2010-09-01 2012-04-12 Nippon Fine Chem Co Ltd Amide group-bearing alicyclic tetracarboxylic dianhydride, and resin obtained by using the same
JP2015218179A (en) * 2014-05-14 2015-12-07 日本精化株式会社 Tetracarboxylic acid dianhydride, and polyimide obtained by using the same
CN106459411A (en) * 2014-06-10 2017-02-22 延世大学校原州产学协力团 Method for preparing polyimide using water as dispersion medium and method for recovering water
JP2017198975A (en) * 2016-04-25 2017-11-02 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film and production method of the same, liquid crystal element, polymer and compound
CN111040164A (en) * 2019-12-24 2020-04-21 威海新元科盛新材料有限公司 Colorless transparent non-fluorine polyimide film with low thermal expansion coefficient and preparation method and application thereof
CN111117241A (en) * 2019-12-31 2020-05-08 山东华夏神舟新材料有限公司 High-transparency low-expansion polyimide film and preparation method thereof
CN111909377A (en) * 2020-08-17 2020-11-10 吉林大学 Dianhydride monomer containing 2, 5-furandimethanol residue and preparation method thereof, polyimide film and preparation method thereof
CN112194790A (en) * 2020-06-16 2021-01-08 中国科学院长春应用化学研究所 Low-thermal-expansion transparent polyimide film and preparation method thereof
CN112194792A (en) * 2020-06-16 2021-01-08 中国科学院长春应用化学研究所 High-strength low-thermal-expansion transparent polyimide and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012072118A (en) * 2010-09-01 2012-04-12 Nippon Fine Chem Co Ltd Amide group-bearing alicyclic tetracarboxylic dianhydride, and resin obtained by using the same
JP2015218179A (en) * 2014-05-14 2015-12-07 日本精化株式会社 Tetracarboxylic acid dianhydride, and polyimide obtained by using the same
CN106459411A (en) * 2014-06-10 2017-02-22 延世大学校原州产学协力团 Method for preparing polyimide using water as dispersion medium and method for recovering water
JP2017198975A (en) * 2016-04-25 2017-11-02 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film and production method of the same, liquid crystal element, polymer and compound
CN111040164A (en) * 2019-12-24 2020-04-21 威海新元科盛新材料有限公司 Colorless transparent non-fluorine polyimide film with low thermal expansion coefficient and preparation method and application thereof
CN111117241A (en) * 2019-12-31 2020-05-08 山东华夏神舟新材料有限公司 High-transparency low-expansion polyimide film and preparation method thereof
CN112194790A (en) * 2020-06-16 2021-01-08 中国科学院长春应用化学研究所 Low-thermal-expansion transparent polyimide film and preparation method thereof
CN112194792A (en) * 2020-06-16 2021-01-08 中国科学院长春应用化学研究所 High-strength low-thermal-expansion transparent polyimide and preparation method thereof
CN111909377A (en) * 2020-08-17 2020-11-10 吉林大学 Dianhydride monomer containing 2, 5-furandimethanol residue and preparation method thereof, polyimide film and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Synthesis and characterization of amide-bridged colorless polyimide films with low CTE and high optical performance for flexible OLED displays;Zhenghui Yang等;《Polym. Chem.》;20210826;第12卷;第5364-5376页 *
无色透明聚酰亚胺薄膜研究进展;任小龙等;《中国塑料》;20150531;第29卷(第05期);第5-13页 *

Also Published As

Publication number Publication date
CN112625017A (en) 2021-04-09

Similar Documents

Publication Publication Date Title
JP6531812B2 (en) Polyimide precursor and polyimide
JP6516048B2 (en) Polyimide precursor and polyimide
KR101545666B1 (en) Diamine, polyimide, and polyimide film and utilization thereof
CN112194792B (en) High-strength low-thermal-expansion transparent polyimide and preparation method thereof
CN112194791A (en) Transparent polyimide film and preparation method thereof
JP6485358B2 (en) Polyimide precursor composition, polyimide production method, polyimide, polyimide film, and substrate
JP5182886B2 (en) NOVEL DIAMINE, POLYIMIDE PRECURSOR, POLYIMIDE, COATING OPTICAL COMPENSATION FILM COMPRISING THE SAME, AND METHOD FOR PRODUCING THE SAME
CN112194790B (en) Low-thermal-expansion transparent polyimide film and preparation method thereof
KR20130091217A (en) Poly(amide-imide) block copolymer, article including same, and display device including the article
JP7047852B2 (en) Polyimide precursors, polyimides, polyimide films, varnishes, and substrates
KR20110010009A (en) Manufacturing method of polyimide, polyimide manufactured by thereof and film manufactured using said polyimide
CN112625017B (en) Amide dianhydride, preparation method and application thereof
CN111533909B (en) Polyamide imide, polyamide imide film and display device
US20170335062A1 (en) Polyamic acid, polyimide resin and polyimide film
KR20110010008A (en) Manufacturing method of a novel polymer, a novel polymer manufactured by thereof and film manufactured using said polymer
JP2012041531A (en) Polyimide precursor and polyimide
JP2022172466A (en) Novel diamine compound, polyimide precursor and polyimide film that employ the same, and applications thereof
CN111471176B (en) Polyimide precursor, polyimide, film and display device
CN112480093B (en) Dianhydride containing amide and imide structures, and preparation method and application thereof
WO2008007629A1 (en) Polyamic acid and polyimide
JP6078995B2 (en) Polyimide precursor, polyimide precursor solution composition, polyimide, polyimide solution composition, polyimide film, substrate, and molded product
KR102078760B1 (en) Poly(amide-imide) copolymers, method for preparing thereof, and colorless and transparent film comprising the poly(amide-imide) copolymers
JP5166312B2 (en) Polyimide copolymer, coating type optical compensation film comprising the same, and method for producing the same
WO2019172460A2 (en) Tetracarboxylic dianhydride, carbonyl compound, polyimide precursor resin, and polyimide
CN113348200A (en) Method for producing polyimide resin powder

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant