CN106519682A - HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof - Google Patents

HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof Download PDF

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CN106519682A
CN106519682A CN201610964374.4A CN201610964374A CN106519682A CN 106519682 A CN106519682 A CN 106519682A CN 201610964374 A CN201610964374 A CN 201610964374A CN 106519682 A CN106519682 A CN 106519682A
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double
amino
benzene
hqda
benzene oxygens
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虞鑫海
周志伟
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Donghua University
Shanghai Ruitu Electronic Material Co Ltd
National Dong Hwa University
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Donghua University
Shanghai Ruitu Electronic Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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

Abstract

The invention relates to an HQDA type bisphenol A tetramine branched polyimide resin film and a preparation method thereof. A mass ratio of BDAPP type linear polyimide resin to HQDA type linear polyimide resin in raw materials of the film is 1 to (100-800). The preparation method comprises the following steps: mixing aromatic binary primary amine with a strong-polarity aprotic organic solvent to obtain a mixture, stirring the mixture at the room temperature, cooling the mixture to a temperature lower than 5 DEG C, adding HQDA into the mixture, stirring, and reacting for 1-6 hours at a temperature ranging from 5 DEG C to 10 DEG C to obtain an HQDA type polyimide resin solution; and mixing the resin solution with BDAPP at the room temperature to obtain a mixed solution, stirring the mixed solution, enabling the mixed solution to form a film, heating the film, carrying out dehydration thermal imidization reaction on the film, cooling the film, and de-molding the film to obtain the HQDA type bisphenol A tetramine branched polyimide resin film. The preparation method is gentle in reaction condition, is simple to operate, is low in cost, is environmentally friendly, is beneficial for realizing industrial large-scale production, and can be applied to the high-tech fields such as flexible solar cells, space telescopes, large generator main insulation, electromagnetic wire wrapping electrical insulating materials, flexible copper-coated foil plates and the like.

Description

A kind of HQDA types bisphenol-A tetramine branched polyimide resin film and preparation method thereof
Technical field
The invention belongs to Kapton and its preparation field, more particularly to a kind of HQDA types bisphenol-A tetramine is branched to be gathered Imide resin thin film and preparation method thereof.
Background technology
Kapton is the very excellent macromolecular material of a class combination property, with especially excellent thermostability, Lower temperature resistance, anti-flammability, electric property and mechanical property, are widely used in electronics microelectronics, printed wiring board, electric wire electricity The high-tech areas such as cable, generator stator winding insulation, ship shipping, Aero-Space, laser, photoelectricity.
But, the KAPTON thin film and domestic H of traditional Kapton, such as U.S. DUPONT companies production is thin Film, their molecular structure are pyromellitic acid anhydride type, i.e., its principal monomer raw material is pyromellitic acid anhydride and 4,4'- Diaminodiphenyl ether.
NASA (NASA) plans to be used for further exploring in the space telescope (NGST) of future generation of transmitting in 2009 The origin in universe, wherein multilayer insulation sunshading board material (MLI) is to realize one of key material of this plan.For this purpose, opening Sent out under space environment can steady operation novel polyimide film material：LaRCTM- CP1 and LaRCTM- CP2, which is specific Molecular structure is as follows：
Its shortcoming is：(1) double (3,4- dicarboxyphenyis) the hexafluoropropane dianhydride monomers of raw materials 2,2- are extremely held high It is expensive, cause film product cost very high, seriously hinder its further genralrlization application；(2) due to double (the 3,4- dicarboxyls of 2,2- Phenyl) hexafluoropropane dianhydride monomer is low with the reactivity of aromatic dicarboxylic primary amine, it is difficult to the polyamides that high molecular is obtained is sub- Polyimide resin, therefore, cause the combination property of its film product to be greatly reduced, be particularly its mechanical property.
Japanese NTT companies are also with double (3,4- dicarboxyphenyis) hexafluoros of the low 2,2- of expensive, reactivity Propane dianhydride monomer, has been obtained with pyromellitic acid anhydride or the exploitation of bis- (trifluoromethyl) -4,4'- benzidines of 3,3'- The preferable polyimide film material of light transmission rate in visible-range.
Yu Xinhai et al. has done substantial amounts of research and development to the polyimide monomers for preparing Kapton： (1) [synthesis of new type polyimide special type monomer and its sign, insulant communication, 1999,32 (5)：1-4] disclose 1,3- The preparation method of double (3- amino-benzene oxygens) benzene；(2) [synthesis of 3,3'- diaminodiphenyl ethers and its polyimides, insulation material Material, 2001,34 (4)：13-16] disclose the preparation method of 3,3'- diaminodiphenyl ethers；(3) [double [4- (the 3- aminobenzenes of 2,2- Epoxide) phenyl] propane preparation and its research of soluble polyimide, insulant, 2001,34 (6):3-6] 2 are disclosed, The preparation method of double [4- (3- amino-benzene oxygens) phenyl] propane of 2-；(4) [synthesis and application of bisphenol A-type polyimide monomer, Insulant, 2002,35 (4)：3-7] and Chinese invention patent CN1472193A (2004-02-04) disclose the double [4- of 2,2- (4- amino-benzene oxygens) phenyl] propane preparation method；(5) [synthesis of fluorinated polyimide special type body and its sign, chemical industry New material, 2003,31 (10)：24-27,31] disclose the system of double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa of 2,2- Preparation Method；(6) [synthesis and performance study of 4,4'- double (4- amino-benzene oxygens) diphenyl sulfides and its polyimides, insulation material Material, 2008,41 (5)：10-14] disclose the preparation method of double (4- amino-benzene oxygens) diphenyl sulfides of 4,4'-.
Chinese invention patent CN101585923A discloses a kind of polyimide film with high visible light permeability, and which prepares bag Include following steps：(1) at room temperature, binary primary amine is dissolved in highly polar aprotic organic solvent system, ice-water bath cooling To within the temperature range of 5 DEG C -10 DEG C, aromatic dicarboxylic anhydride, stirring is added to react 4-10 within the temperature range of 5 DEG C -10 DEG C After hour, homogeneous, transparent, thick polyamic acid resin solution is obtained；(2) adjust the viscous of the polyamic acid resin solution Degree, the film forming in casting machine, hot imidization obtain the Kapton of homogeneous phase transparent, and its visible light transmissivity is up to 94% (50 microns of thickness).
Chinese invention patent CN101921483A discloses a kind of polybenzimidazole imide membrane and preparation method thereof, its Preparation includes：By aromatic dicarboxylic primary amine, 2- (4- aminophenyls) -5- aminobenzimidazoles (APABI) and aromatic acid Acid anhydride at room temperature after stirring reaction 5-8 hour, obtains homogeneous phase transparent thick in highly polar aprotic organic solvent system Polybenzimidazoles amide acid solution, then, the casting film-forming in casting machine, hot imidization, demoulding, winding obtain tough and tensile transparent Polybenzimidazole imide membrane.
Chinese invention patent CN101580637A is disclosed the present invention relates to a kind of alicyclic-containing polyimide film, its preparation Including：Under room temperature, alicyclic ring binary primary amine, aromatic dicarboxylic primary amine are dissolved in highly polar aprotic organic solvent, stirring is in After homogeneous phase solution, aromatic dicarboxylic anhydride, stirring is added after reacting 1-3 hours at room temperature, to obtain homogeneous, transparent, thick The solution of polyamic acid resin containing alicyclic ring；Wherein, the mol ratio of alicyclic ring binary primary amine and aromatic dicarboxylic primary amine is 1：1-5；Virtue The molal quantity of fragrant race's dibasic acid anhydride is equal to the molal quantity sum of alicyclic ring binary primary amine and aromatic dicarboxylic primary amine；With highly polar non-matter Sub- organic solvent adjusts the viscosity of the above-mentioned solution of polyamic acid resin containing alicyclic ring, and the film forming in casting machine, heat temperature raising are taken off Hydro-thermal imidization, cooling, demoulding obtain the alicyclic-containing polyimide film of homogeneous phase transparent.
Chinese invention patent CN101597428A discloses full aromatic fluorine containing transparent polyimide film, and which prepares bag Include：Fluorinated aromatic binary primary amine and highly polar aprotic organic solvent are added in polymerization bottle, is stirred under room temperature, is completely dissolved Afterwards, ice-water bath is cooled to less than 5 DEG C, adds aromatic dicarboxylic anhydride, stirring to react 3 within the temperature range of 5 DEG C -10 DEG C little Shi Hou, obtains homogeneous, transparent, thick fluorinated aromatic polyamic acid resin solution；Wherein, aromatic dicarboxylic anhydride rubs Your number is equal to the molal quantity of fluorinated aromatic binary primary amine；Above-mentioned fluorine-containing aromatic adoption is adjusted with highly polar aprotic organic solvent The viscosity of amic acid resin solution, the film forming in casting machine, heat temperature raising carry out dehydration fever imidization, cooling, demoulding, Obtain full aromatic fluorine containing transparent polyimide film.
Chinese invention patent CN101456964A discloses a kind of preparation method of aromatic polybenzimidazole thin film, its master Step is wanted to include：Using the aromatic series quaternary amine and aromatic binary carboxylic acid of specific molecular structure, two are aoxidized in polyphosphoric acids/five In the presence of phosphorus system, in nitrogen atmosphere, solution polycondensation reaction is carried out in -200 DEG C of temperature ranges of room temperature, kermesinus is obtained Rubber elastomer shaped polymer.During cooling is fallen back, in resin pulper, powder is blended into, alkali cleaning to neutrality, after drying Suitable solvent is selected to be dissolved, casting film-forming, heat temperature raising, desolvation obtain aromatic polybenzimidazole thin film.
Chinese invention patent CN101392059A discloses a kind of colorless transparent aromatic polyimide film and its preparation Method, it is characterised in that：Using the primary aromatic amine and aromatic anhydride of specific molecular structure, highly polar non-proton organic molten In agent system, polyreaction is carried out in 0 DEG C of -35 DEG C of temperature range, water white homogeneous thick polyamic acid is obtained molten Liquid.Viscosity, casting film-forming, heat temperature raising, desolvation is adjusted, while there is part imidization, demoulding stretching, further Depth hot imidization, winding obtain colorless transparent aromatic polyimide film product.
The heat resistance of the thin film that above-mentioned prior art is obtained, electric property, mechanical property, hydrophobic performance, dimensionally stable The combination property of performance etc. need comprehensive raising, could meet the use requirement of more high-end field.It is double with regard to HQDA types at present Phenol A tetramine branched polyimide resin films and preparation method thereof, there is not yet disclosed document or patent report.
The content of the invention
The technical problem to be solved is to provide a kind of HQDA types bisphenol-A tetramine branched polyimide resin film And preparation method thereof, the preparation method reaction condition is gentle, and course of reaction is carried out at ambient pressure, simple to operate；Reaction raw materials come Source is convenient, and low cost is not related to also not produce corrosive substance, and organic solvent uses species few and easy recovery, can iterative cycles Use again, it is environmentally friendly；And the Kapton has excellent dimensional stability, mechanical property and thermostability, while Possess very excellent electric property and optical property.
A kind of HQDA types bisphenol-A tetramine branched polyimide resin film of the present invention, 2,2- in the raw material of the thin film The mass ratio of double [4- (2,4- diamino phenoxies) phenyl] propane BDAPP and HQDA Linear polyamic acid resins is 1:100- 800。
The HQDA Linears polyamic acid resin be by mol ratio be 1:1.01-1.08 aromatic dicarboxylic primary amine and 1, Double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 4- react in highly polar aprotic organic solvent and obtain.
The aromatic dicarboxylic primary amine is p-phenylenediamine, o-phenylenediamine, m-diaminobenzene., trimethyl m-diaminobenzene., biphenyl two Amine, 2,2'- dimethyl diphenyl diamidogen, 2,2'- bis- (trifluoromethyl) benzidine, 2- (4- aminophenyls) -5- amino benzo miaows Azoles, 4,4'- diaminodiphenyl ethers, 3,4'- diaminodiphenyl ethers, 3,3'- diaminodiphenyl ethers, 4,4'- MDAs, 4,4' diaminodiphenyl sulfone, 3,3'- dimethyl -4,4'- MDAs, 3,3'- diethyl base -4,4'- diaminourea two Phenylmethane, 3,3', double (the 3- aminobenzenes of 5,5'- tetramethyl -4,4'- MDAs, 3,3'- DADPSs, 1,4- Epoxide) benzene, double (3- amino-benzene oxygens) benzene of 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, Double (3- amino-benzene oxygens) benzene of 1,2-, double (4- amino-benzene oxygens) benzene of 1,2-, 2,6- double (4- amino-benzene oxygens) benzonitrile, 2,6- Double (4- amino-benzene oxygens) toluene of double (3- amino-benzene oxygens) benzonitriles, 2,6-, 2,6- double (3- amino-benzene oxygens) toluene, 2,6- Double (3- amino-benzene oxygens) benzotrifluorides of double (4- amino-benzene oxygens) benzotrifluorides, 2,6-, double (4- amino-benzene oxygens) first of 2,5- Double (3- amino-benzene oxygens) toluene of benzene, 2,5-, double (4- amino-benzene oxygens) tert-butylbenzenes of 2,5-, 2,5- are double (3- amino-benzene oxygens) Double (4- amino-benzene oxygens) benzene of tert-butylbenzene, 2,5- di-t-butyls -1,4-, double (the 3- aminobenzene oxygen of 2,5- di-t-butyls -1,4- Base) benzene, double (4- amino-benzene oxygens) benzophenone of 4,4'-, double (4- amino-benzene oxygens) diphenyl sulphone (DPS)s of 4,4'-, double (the 3- ammonia of 4,4'- Phenoxyl) benzophenone, double (3- amino-benzene oxygens) diphenyl sulphone (DPS)s of 4,4'-, 1,4- be double (2- trifluoromethyl-4-aminophenoxyls) Double (2- trifluoromethyl-4-aminophenoxyls) benzene of benzene, 1,3-, 2,2- are double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] Double (3- amino-4-hydroxylphenyls) HFC-236fa of propane, 2,2-, 2,2- double (3- amino-4-hydroxylphenyls) propane, 3,3'- bis- Double [4- (2- trifluoromethyl -4- the ammonia of amino -4,4' dihydroxy diphenyl, 3,3'- diaminourea -4,4' dihydroxydiphenyl sulfone, 2,2- Phenoxyl) phenyl] HFC-236fa, double (2- trifluoromethyl-4-aminophenoxyls) toluene of 2,5-, 2,5- it is double (2- trifluoromethyls- 4- amino-benzene oxygens) tert-butyl benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 2,5- di-t-butyls -1,4-, 4,4'- be double Double (2- the trifluoromethyl-4-aminophenoxyls) -3,3', 5,5'- tetra- of (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS), 4,4'- Double (2- trifluoromethyl-4-aminophenoxyls) biphenyl of methyldiphenyl sulfone, 4,4'-, the double (2- trifluoromethyl -4- aminobenzene oxygen of 4,4'- Base) -3,3', double (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether of 5,5'- tetramethyl biphenyls, 4,4'-, double (the 4- ammonia of 4,4'- Phenoxyl) diphenyl ether, double (3- amino-benzene oxygens) diphenyl ether of 4,4'-, double (3- amino-benzene oxygens) diphenyl sulfides of 4,4'-, 4, Double (4- amino-benzene oxygens) diphenyl sulfides of 4'-, double (4- the amino-benzene oxygens) -3,3' of 4,4'-, 5,5'- tetramethyl biphenyls, 4,4'- Double (3- amino-benzene oxygens) -3,3', double [4- (4- amino-benzene oxygens) phenyl] propane of 5,5'- tetramethyl biphenyls, 2,2-, 2,2- are double In double (4- amino-benzene oxygens) benzoic acid of [4- (4- amino-benzene oxygens) phenyl] HFC-236fa, 3,5-, 3,5- diaminobenzoic acids At least one.
The highly polar aprotic organic solvent is 3-6 with the mass ratio of total reactant：1；Wherein, the quality of total reactant Refer to the quality sum of aromatic dicarboxylic primary amine and double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 1,4-.
The highly polar aprotic organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2- At least one in ketopyrrolidine, N- ethyl-2-pyrrolidones, dimethyl sulfoxide.
A kind of preparation method of the HQDA types bisphenol-A tetramine branched polyimide resin film of the present invention, including：
(1) aromatic dicarboxylic primary amine is mixed in polymerization bottle with highly polar aprotic organic solvent, is stirred under room temperature, it is complete After CL, ice-water bath is cooled to less than 5 DEG C, adds Isosorbide-5-Nitrae-bis- (3,4- di carboxyl phenyloxy) benzene dianhydride HQDA, stirs, 5 DEG C- 10 DEG C of 1～6h of reaction, obtain homogeneous, transparent, thick HQDA type polyamic acid resin solution；
(2) by HQDA type polyamic acid resin solution and 2,2- double [4- (2,4- diamino phenoxies) phenyl] propane by than Example mixes at room temperature, stirs, obtains homogeneous phase solution, the film forming in casting machine, heat temperature raising, carries out dehydration hot imidization anti- Should, cooling, demoulding obtain HQDA type bisphenol-A tetramine branched polyimide resin films.
In step (2), the time of stirring is 1～6h.
In step (2), the condition of dehydration hot imidization is：150 DEG C are risen to from room temperature, 10 minutes are incubated, continues to heat up To 250 DEG C, 10 minutes are incubated, 350 DEG C are continuously heating to, be incubated 10 minutes.
Beneficial effect
(1) preparation method reaction condition of the invention is gentle, and course of reaction is carried out at ambient pressure, simple to operate；Reaction is former Material convenient sources, low cost are not related to also not produce corrosive substance, and organic solvent uses species few and easy recovery, can be repeatedly Recycling, it is environmentally friendly；Industrial-scale production is advantageously implemented, and can be applicable to flexible solar battery, space and hoped The high-tech areas such as remote mirror, large generator main insulation, the wrapped insulating material of electromagnetic wire, flexible copper clad foil plate (FCCL)；
(2) the synthesis technique equipment used by preparation process of the invention is universal, can utilize existing production completely The complete set of equipments of polyimide resin is very beneficial for the industrialization of product implementing the present invention；
(3) production equipment of the invention is general Kapton production equipment, i.e., general casting machine, equipment are thrown Money is few, is very beneficial for the enforcement of the present invention；
(4) the material resin molecular weight adopted in the present invention is easily controlled, and molecular structure is also easily adjusted, and is conducive to preparing The water white Kapton of ideal performance, and the Kapton has excellent dimensional stability, mechanical property Energy and thermostability, while also possess very excellent electric property and optical property；
(5) branching type Kapton of the invention (the addition reaction of BDAPP tetramines) is relative to non-branching type thin film With significant combination property superiority.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limit the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art Member can be made various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiment 1
By 43.2 (0.4 mole) p-phenylenediamine (PPDA), 100.0 grams of (0.5 mole) 4,4'- diaminodiphenyl ethers (44ODA), 22.4 (0.1 mole) 2- (4- aminophenyls) -5- aminobenzimidazoles (APABI) and 1720 grams of N- methyl -2- pyrroles During pyrrolidone (NMP) adds polymerization bottle, stir under room temperature, after being completely dissolved, ice-water bath is cooled to less than 5 DEG C, add 406.0 grams (1.01 moles) Isosorbide-5-Nitrae-bis- (3,4- di carboxyl phenyloxy) benzene dianhydride (HQDA), stirring, after 5 DEG C are reacted 1 hour, obtain 2291.6 Gram homogeneous, transparent, thick HQDA type polyamic acid resin solution, is denoted as HQDA-PAA-1.CAP2000+ is flown using rich Le Vertebral plate viscometer, surveys its 50 DEG C viscosity for 1241mPa.s.
Embodiment 2
By 175.2 grams of (0.6 mole) 1,4- double (4- amino-benzene oxygens) benzene (144BAPB), 10.8 (0.1 moles) to benzene two Amine (PPDA), 67.8 grams of (0.3 mole) 3,3'- dimethyl -4,4'- MDAs (MDT), 2000 grams of N, N- dimethyl During acetamide (DMAc) and 700 grams of METHYLPYRROLIDONEs (NMP) add polymerization bottle, stir under room temperature, after being completely dissolved, Ice-water bath is cooled to less than 5 DEG C, adds 422.1 grams of (1.05 moles) Isosorbide-5-Nitrae-bis- (3,4- di carboxyl phenyloxy) benzene dianhydrides (HQDA), stir, after 8 DEG C are reacted 3 hours, obtain 3375.9 grams of homogeneous, transparent, thick HQDA type polyamic acid resins molten Liquid, is denoted as HQDA-PAA-2.CAP2000+ vertebral plate viscometers are flown using rich Le, its 50 DEG C viscosity are surveyed for 1054mPa.s.
Embodiment 3
By 140.0 grams of (0.7 mole) 4,4'- diaminodiphenyl ethers (44ODA), 59.4 grams of (0.3 mole) 4,4'- diaminourea During diphenyl-methane and 3800 grams of METHYLPYRROLIDONEs (NMP) add polymerization bottle, stir under room temperature, after being completely dissolved, frozen water Bath is cooled to less than 5 DEG C, adds 434.1 grams of (1.08 moles) Isosorbide-5-Nitrae-bis- (3,4- di carboxyl phenyloxy) benzene dianhydrides (HQDA), stirs Mix, after 10 DEG C are reacted 6 hours, obtain 4433.5 grams of homogeneous, transparent, thick HQDA type polyamic acid resin solution, be denoted as HQDA-PAA-3.CAP2000+ vertebral plate viscometers are flown using rich Le, its 50 DEG C viscosity are surveyed for 956mPa.s.
Embodiment 4
By 1000 grams of HQDA-PAA-1 type polyamic acid resin solution and 10 grams of 2,2- couple of [4- (2,4- diamino phenoxies) Phenyl] propane (BDAPP), mix homogeneously at room temperature, stirring reaction obtained 1010 grams of homogeneous phase solutions, are denoted as PAA- after 1 hour 1.CAP2000+ vertebral plate viscometers are flown using rich Le, its 50 DEG C viscosity are surveyed for 1572mPa.s.
By 3000 grams of HQDA-PAA-2 type polyamic acid resin solution and 10 grams of 2,2- couple of [4- (2,4- diamino phenoxies) Phenyl] propane (BDAPP), mix homogeneously at room temperature, stirring reaction obtained 3010 grams of homogeneous phase solutions, are denoted as PAA- after 3 hours 2.CAP2000+ vertebral plate viscometers are flown using rich Le, its 50 DEG C viscosity are surveyed for 1351mPa.s.
By 2400 grams of HQDA-PAA-3 type polyamic acid resin solution and 3 grams of 2,2- couple of [4- (2,4- diamino phenoxies) Phenyl] propane (BDAPP), mix homogeneously at room temperature, stirring reaction obtained 2403 grams of homogeneous phase solutions, are denoted as PAA- after 6 hours 3.CAP2000+ vertebral plate viscometers are flown using rich Le, its 50 DEG C viscosity are surveyed for 1219mPa.s.
Embodiment 5
By the homogeneous phase solution of 1～embodiment of above-described embodiment 4 in casting machine film forming, heat temperature raising, carry out dehydration fever sub- Aminating reaction, cooling, demoulding.Wherein, the concrete technology of dehydration fever imidization is：150 DEG C are risen to from room temperature, 10 points are incubated Clock, is continuously heating to 250 DEG C, is incubated 10 minutes, is continuously heating to 350 DEG C, is incubated 10 minutes.
Tough and tensile transparent Kapton HQDA-PI-1 is obtained by HQDA-PAA-1 homogeneous phase solution film forming；By HQDA- PAA-2 homogeneous phase solution film forming obtains tough and tensile transparent Kapton HQDA-PI-2；By HQDA-PAA-3 homogeneous phase solution film forming Obtain tough and tensile transparent Kapton HQDA-PI-3.Performance data is as shown in table 1.
Tough and tensile transparent HQDA type bisphenol-A tetramine branched polyimide thin film PI-1 are obtained by PAA-1 homogeneous phase solution film forming； Tough and tensile transparent HQDA type bisphenol-A tetramine branched polyimide thin film PI-2 are obtained by PAA-2 homogeneous phase solution film forming；By PAA-3 Homogeneous phase solution film forming obtains tough and tensile transparent HQDA type bisphenol-A tetramine branched polyimide thin film PI-3.Performance data such as 1 institute of table Show.As can be seen from Table 1：The branching type Kapton prepared in embodiment has notable relative to non-branching type thin film Combination property superiority.
The performance data of 1 Kapton of table

Claims (8)

1. a kind of HQDA types bisphenol-A tetramine branched polyimide resin film, it is characterised in that 2,2- in the raw material of the thin film The mass ratio of double [4- (2,4- diamino phenoxies) phenyl] propane BDAPP and HQDA Linear polyamic acid resins is 1:100- 800。
2. a kind of HQDA types bisphenol-A tetramine branched polyimide resin film according to claim 1, it is characterised in that The HQDA Linears polyamic acid resin be by mol ratio be 1:The aromatic dicarboxylic primary amine of 1.01-1.08 it is double with 1,4- (3, 4- di carboxyl phenyloxies) benzene dianhydride reacts in highly polar aprotic organic solvent and obtains.
3. a kind of HQDA types bisphenol-A tetramine branched polyimide resin film according to claim 2, it is characterised in that The aromatic dicarboxylic primary amine is p-phenylenediamine, o-phenylenediamine, m-diaminobenzene., trimethyl m-diaminobenzene., benzidine, 2,2'- Dimethyl diphenyl diamidogen, 2,2'- bis- (trifluoromethyl) benzidine, 2- (4- aminophenyls) -5- aminobenzimidazoles, 4,4'- Diaminodiphenyl ether, 3,4'- diaminodiphenyl ethers, 3,3'- diaminodiphenyl ethers, 4,4'- MDAs, 4,4'- bis- ADP sulfone, 3,3'- dimethyl -4,4'- MDAs, 3,3'- diethyl base -4,4'- MDAs, 3,3', 5,5'- tetramethyl -4,4'- MDAs, 3,3'- DADPSs, 1,4- are double (3- amino-benzene oxygens) Double (3- amino-benzene oxygens) benzene of benzene, 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, 1,3- double (4- amino-benzene oxygens) benzene, 1,2- Double (4- amino-benzene oxygens) benzene of double (3- amino-benzene oxygens) benzene, 1,2-, double (4- amino-benzene oxygens) benzonitriles of 2,6-, 2,6- are double Double (4- amino-benzene oxygens) toluene of (3- amino-benzene oxygens) benzonitrile, 2,6-, double (3- amino-benzene oxygens) toluene of 2,6-, 2,6- are double Double (4- amino-benzene oxygens) toluene of double (3- amino-benzene oxygens) benzotrifluoride of (4- amino-benzene oxygens) benzotrifluoride, 2,6-, 2,5-, Double (3- amino-benzene oxygens) toluene of 2,5-, double (4- amino-benzene oxygens) tert-butylbenzenes of 2,5-, 2,5- double (3- amino-benzene oxygens) are special Double (4- amino-benzene oxygens) benzene of butyl benzene, 2,5- di-t-butyls -1,4-, 2,5- di-t-butyls -1,4- are double (3- amino-benzene oxygens) Double (4- amino-benzene oxygens) benzophenone of benzene, 4,4'-, double (4- amino-benzene oxygens) diphenyl sulphone (DPS)s of 4,4'-, double (the 3- aminobenzenes of 4,4'- Epoxide) benzophenone, double (3- amino-benzene oxygens) diphenyl sulphone (DPS)s of 4,4'-, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,4-, Double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,3-, double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] third of 2,2- Double (3- amino-4-hydroxylphenyls) HFC-236fa of alkane, 2,2-, 2,2- double (3- amino-4-hydroxylphenyls) propane, 3,3'- diaminos Double [4- (2- trifluoromethyl -4- the amino of base -4,4' dihydroxy diphenyl, 3,3'- diaminourea -4,4' dihydroxydiphenyl sulfone, 2,2- Phenoxy group) phenyl] HFC-236fa, double (2- trifluoromethyl-4-aminophenoxyls) toluene of 2,5-, the double (2- trifluoromethyl -4- of 2,5- Amino-benzene oxygen) tert-butyl benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 2,5- di-t-butyls -1,4-, the double (2- of 4,4'- Trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS), double (2- the trifluoromethyl-4-aminophenoxyls) -3,3' of 4,4'-, 5,5'- tetramethyls Double (2- trifluoromethyl-4-aminophenoxyls) biphenyl of base diphenyl sulphone (DPS), 4,4'-, the double (2- trifluoromethyl -4- aminobenzene oxygen of 4,4'- Base) -3,3', double (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether of 5,5'- tetramethyl biphenyls, 4,4'-, double (the 4- ammonia of 4,4'- Phenoxyl) diphenyl ether, double (3- amino-benzene oxygens) diphenyl ether of 4,4'-, double (3- amino-benzene oxygens) diphenyl sulfides of 4,4'-, 4, Double (4- amino-benzene oxygens) diphenyl sulfides of 4'-, double (4- the amino-benzene oxygens) -3,3' of 4,4'-, 5,5'- tetramethyl biphenyls, 4,4'- Double (3- amino-benzene oxygens) -3,3', double [4- (4- amino-benzene oxygens) phenyl] propane of 5,5'- tetramethyl biphenyls, 2,2-, 2,2- are double In double (4- amino-benzene oxygens) benzoic acid of [4- (4- amino-benzene oxygens) phenyl] HFC-236fa, 3,5-, 3,5- diaminobenzoic acids At least one.
4. a kind of HQDA types bisphenol-A tetramine branched polyimide resin film according to claim 2, it is characterised in that The highly polar aprotic organic solvent is 3-6 with the mass ratio of total reactant：1；Wherein, the quality of total reactant refers to fragrance The quality sum of race's binary primary amine and double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 1,4-.
5. a kind of HQDA types bisphenol-A tetramine branched polyimide resin film according to claim 4, it is characterised in that The highly polar aprotic organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2- pyrrolidines At least one in ketone, N- ethyl-2-pyrrolidones, dimethyl sulfoxide.
6. a kind of preparation method of HQDA types bisphenol-A tetramine branched polyimide resin film as claimed in claim 1, wraps Include：
(1) aromatic dicarboxylic primary amine is mixed with highly polar aprotic organic solvent, stirs under room temperature, be cooled to less than 5 DEG C, plus Enter Isosorbide-5-Nitrae-bis- (3,4- di carboxyl phenyloxy) benzene dianhydride HQDA, stir, 5 DEG C of -10 DEG C of 1～6h of reaction obtain HQDA type polyamide Acid resin solution；
(2) by HQDA type polyamic acid resin solution and 2,2- double [4- (2,4- diamino phenoxies) phenyl] propane in proportion in Mix under room temperature, stirring, the film forming in casting machine, heat temperature raising carry out dehydration fever imidization, cool down, demoulding is obtained HQDA type bisphenol-A tetramine branched polyimide resin films.
7. the preparation method of a kind of HQDA types bisphenol-A tetramine branched polyimide resin film according to claim 6, its It is characterised by, in step (2), the time of stirring is 1～6h.
8. the preparation method of a kind of HQDA types bisphenol-A tetramine branched polyimide resin film according to claim 6, its It is characterised by, in step (2), the condition of dehydration hot imidization is：150 DEG C are risen to from room temperature, 10 minutes are incubated, continues to rise Temperature is incubated 10 minutes, is continuously heating to 350 DEG C to 250 DEG C, is incubated 10 minutes.
CN201610964374.4A 2016-11-04 2016-11-04 HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof Pending CN106519682A (en)

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