CN106519675A - BTDA-type bisphenol-A tetramine branched polyimide resin film and preparation method thereof - Google Patents
BTDA-type bisphenol-A tetramine branched polyimide resin film and preparation method thereof Download PDFInfo
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- CN106519675A CN106519675A CN201610962676.8A CN201610962676A CN106519675A CN 106519675 A CN106519675 A CN 106519675A CN 201610962676 A CN201610962676 A CN 201610962676A CN 106519675 A CN106519675 A CN 106519675A
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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
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- 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
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention relates to a BTDA-type bisphenol-A tetramine branched polyimide resin film and a preparation method thereof. The mass ratio of BDAPP-type linear polyamide acid resin to BTDA-type linear polyamide acid resin in the raw materials of the film is 1: (100 to 800). The preparation method comprises the following steps: mixing aromatic primary diamine with a strongly-polar aprotic organic solvent, stirring at room temperature, cooling to a temperature of below 5 DEG C, adding BTDA, stirring, and reacting for 1-6h at 5-10 DEG C to obtain a BTDA-type polyamide acid resin solution; and mixing the resin solution with BDAPP at room temperature, stirring, carrying out film formation, heating, carrying out a dehydration thermal-imidization reaction, cooling, and carrying out film release to obtain the product. The method disclosed by the invention is moderate in reaction condition, simple to operate, low in cost, environment-friendly, beneficial to realizing large-scale industrial production, and capable of being applied to the high-technology fields of flexible solar cells, space telescopes, large motor main insulation, electromagnetic wire-lapping electrical insulation materials, flexible copper-clad plates and the like.
Description
Technical field
The invention belongs to Kapton and its preparation field, more particularly to a kind of BTDA 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 in the space telescope (NGST) of future generation of transmitting in 2009 for further exploring
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 of bisphenol A-type polyimide monomer and application,
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 3 to be reacted 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, alkali cleaning to neutrality, after drying are blended into
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 are 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 BTDA 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 BTDA 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 BTDA 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 BTDA Linear polyamic acid resins is 1:100-
800。
The BTDA Linears polyamic acid resin be by mol ratio be 1:1.01-1.08 aromatic dicarboxylic primary amine and 3,
3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride reacts in highly polar aprotic organic solvent and obtains.
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 aromatic dicarboxylic primary amine and 3,3 ', the quality sum of 4,4 '-tetracarboxylic acid benzophenone dianhydride.
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 BTDA 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 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride BTDA, stirs, 5 DEG C -10
DEG C reaction 1～6h, obtain homogeneous, transparent, thick BTDA type polyamic acid resin solution；
(2) by BTDA 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 BTDA type bisphenol-A tetramine branched polyimide resin films.
In the step (2), the time of stirring is 1～6h.
In the 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 possessing 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 160.0 grams of (0.8 mole) 4,4'- diaminodiphenyl ethers (44ODA), 19.8 grams of (0.1 mole) 4,4'- diaminourea
Diphenyl-methane, 22.4 grams of (0.1 mole) 2- (4- aminophenyls) -5- aminobenzimidazoles (APABI) and 1600 grams of N- methyl -2-
During ketopyrrolidine (NMP) adds polymerization bottle, stir under room temperature, after being completely dissolved, ice-water bath is cooled to less than 5 DEG C, add 325.2
After gram (1.01 moles) 3,3', 4,4'- tetracarboxylic acid benzophenone dianhydride (BTDA), stirring, 5 DEG C of reactions 1 hour, 2127.4 are obtained
Gram homogeneous, transparent, thick BTDA type polyamic acid resin solution, is denoted as BTDA-PAA-1.CAP2000+ is flown using rich Le
Vertebral plate viscometer, surveys its viscosity, and performance data is as shown in table 1.
Embodiment 2
By 146.0 grams of (0.5 mole) 1,3- double (4- amino-benzene oxygens) benzene (134BAPB), 19.8 grams of (0.1 moles) 4,
4'- MDAs, 43.2 grams of (0.4 mole) p-phenylenediamine (PPDA), 1000 grams of DMAC N,N' dimethyl acetamides (DMAc)
Add in polymerization bottle with 1180 grams of METHYLPYRROLIDONEs (NMP), stir under room temperature, after being completely dissolved, ice-water bath is cooled to
Less than 5 DEG C, add 338.1 grams of (1.05 moles) 3,3', 4,4'- tetracarboxylic acids benzophenone dianhydride (BTDA), stirring, 8 DEG C of reactions 3
After hour, 2727.1 grams of homogeneous, transparent, thick BTDA type polyamic acid resin solution are obtained, BTDA-PAA-2 is denoted as.Adopt
Fly CAP2000+ vertebral plate viscometers with rich Le, survey its viscosity, performance data is as shown in table 1.
Embodiment 3
By 200.0 grams of (1.0 moles) 4,4'- diaminodiphenyl ethers (DADPE) and 3280 grams of METHYLPYRROLIDONEs
(NMP) in adding polymerization bottle, stir under room temperature, after being completely dissolved, ice-water bath is cooled to less than 5 DEG C, add 347.8 gram (1.08
Mole) 3,3', 4,4'- tetracarboxylic acids benzophenone dianhydride (BTDA), stirring, after 10 DEG C are reacted 6 hours, 3827.8 grams of acquisition is
Phase, transparent, thick BTDA type polyamic acid resin solution, are denoted as BTDA-PAA-3.CAP2000+ vertebral plates are flown using rich Le
Viscometer, surveys its viscosity, and performance data is as shown in table 1.
Embodiment 4
By 1000 grams of BTDA-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 viscosity is surveyed, performance data is as shown in table 1.
By 3000 grams of BTDA-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 viscosity is surveyed, performance data is as shown in table 1.
By 2400 grams of BTDA-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 viscosity is surveyed, performance data is as shown in table 1.
The viscosity data (mPa.s) of 1 polyamic acid resin solution of table
Embodiment 5
By the homogeneous phase solution of above-described embodiment 1- embodiments 4 in casting machine film forming, heat temperature raising, carry out dehydration fever imines
Change 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 BTDA-PI-1 is obtained by BTDA-PAA-1 homogeneous phase solution film forming；By BTDA-
PAA-2 homogeneous phase solution film forming obtains tough and tensile transparent Kapton BTDA-PI-2；By BTDA-PAA-3 homogeneous phase solution film forming
Obtain tough and tensile transparent Kapton BTDA-PI-3.Performance data is as shown in table 2.
Tough and tensile transparent BTDA type bisphenol-A tetramine branched polyimide thin film PI-1 are obtained by PAA-1 homogeneous phase solution film forming；
Tough and tensile transparent BTDA 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 BTDA type bisphenol-A tetramine branched polyimide thin film PI-3.Performance data such as 2 institute of table
Show.As can be seen from Table 2：The branching type Kapton prepared in embodiment has notable relative to non-branching type thin film
Combination property superiority.
The performance data of 2 Kapton of table
Claims (8)
1. a kind of BTDA 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 BTDA Linear polyamic acid resins is 1:100-
800。
2. a kind of BTDA types bisphenol-A tetramine branched polyimide resin film according to claim 1, it is characterised in that
The BTDA Linears polyamic acid resin be by mol ratio be 1:The aromatic dicarboxylic primary amine of 1.01-1.08 and 3,3 ', 4,4 '-
Tetracarboxylic acid benzophenone dianhydride reacts in highly polar aprotic organic solvent and obtains.
3. a kind of BTDA 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 BTDA 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
Race's binary primary amine and 3,3 ', the quality sum of 4,4 '-tetracarboxylic acid benzophenone dianhydride.
5. a kind of BTDA 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 BTDA 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 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride BTDA, stir, 5 DEG C of -10 DEG C of 1～6h of reaction obtain BTDA type polyamic acids
Resin solution；
(2) by BTDA 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
BTDA type bisphenol-A tetramine branched polyimide resin films.
7. the preparation method of a kind of BTDA types bisphenol-A tetramine branched polyimide resin film according to claim 6, its
It is characterised by, in the step (2), the time of stirring is 1～6h.
8. the preparation method of a kind of BTDA types bisphenol-A tetramine branched polyimide resin film according to claim 6, its
It is characterised by, in the 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.
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