CN106519673A - BPDA type fluorine-containing branched polyimide resin film and preparation method thereof - Google Patents
BPDA type fluorine-containing branched polyimide resin film and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to a BPDA type fluorine-containing branched polyimide resin film and a preparation method thereof. In the raw materials of the film, BDAPFP and BPDA linear polyamic acid resin are in a mass ratio of 1:100-800. The preparation method comprises the steps of: mixing aromatic binary primary amine with a strong polar non-protonic organic solvent, conducting stirring at room temperature, performing cooling to a temperature below 5DEG C, adding BPDA, conducting stirring, and carrying out reaction at 5DEG C-10DEG C for 1-6h to obtain a BPDA type polyamic acid resin solution; mixing the resin solution with BDAPFP at room temperature, conducting stirring, film-forming and heating, carrying out dehydration thermal imidization reaction, and performing cooling and demoulding, thus obtaining the BPDA type fluorine-containing branched polyimide resin film. The method provided by the invention has the advantages of mild reaction conditions, simple operation, low cost, and environmental friendliness, is conducive to realizing large-scale industrial production. And the film can be applied to flexible solar cells, space telescopes, large generator main insulation, electromagnetic wire wrapped electrical insulating materials, flexible copper-clad plates and other high-tech fields.
Description
Technical field
The invention belongs to Kapton and its preparation field, the fluorine-containing branched polyimide of more particularly to a kind of BPDA types
Resin 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.Contain with regard to BPDA types at present
Fluorine branched polyimide resin film and preparation method thereof, there is not yet disclosed document or patent report.
The content of the invention
The technical problem to be solved be to provide a kind of fluorine-containing branched polyimide resin film of BPDA types and its
Preparation method, the preparation method reaction condition are gentle, and course of reaction is carried out at ambient pressure, simple to operate；Reaction raw materials source side
Just, low cost, is not related to also not produce corrosive substance, organic solvent using species is 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 also possessing non-
The electric property of Chang Youyi and optical property.
A kind of fluorine-containing branched polyimide resin film of BPDA types of the present invention, the double [4- of 2,2- in the raw material of the thin film
(2,4- diamino phenoxies) phenyl] mass ratio of HFC-236fa BDAPFP and BPDA Linear polyamic acid resins is 1:100-
800。
The BPDA Linears polyamic acid resin be by mol ratio be 1:1.01-1.08 aromatic dicarboxylic primary amine and 3,
3', 4,4'- biphenyl tetracarboxylic 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 the quality sum of aromatic dicarboxylic primary amine and 3,3', 4,4'- biphenyl tetracarboxylic 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 fluorine-containing branched polyimide resin film of BPDA types 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'- biphenyl tetracarboxylic dianhydride BPDA, stirs, and 5 DEG C -10 DEG C anti-
1～6h is answered, homogeneous, transparent, thick BPDA type polyamic acid resin solution is obtained；
(2) by BPDA type polyamic acid resin solution and double [4- (2,4- diamino phenoxies) phenyl] HFC-236fa of 2,2-
Mix at room temperature in proportion, stir, obtain homogeneous phase solution, the film forming in casting machine, heat temperature raising carry out dehydration hot imidization
Reaction, cooling, demoulding obtain the fluorine-containing branched polyimide resin film of BPDA types.
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 BDAPFP 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 180.0 grams of (0.9 mole) 4,4 '-diaminodiphenyl ethers (DADPE), 10.8 (0.1 mole) p-phenylenediamine
(PPDA), during and 1470 grams of N,N-dimethylacetamide (DMAc) add polymerization bottle, stir under room temperature, after being completely dissolved, ice-water bath
Less than 5 DEG C are cooled to, add 297.1 grams of (1.01 moles) 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) to stir, 5 DEG C anti-
After answering 1 hour, 1957.9 grams of homogeneous, transparent, thick BPDA type polyamic acid resin solution are obtained, BPDA-PAA- is denoted as
1.CAP2000+ vertebral plate viscometers are flown using rich Le, its viscosity is surveyed, performance data is as shown in table 1.
Embodiment 2
By 262.8 grams of (0.9 mole) 1,4- double (4- amino-benzene oxygens) benzene (144BAPB), 10.8 (0.1 mole) isophthalic two
Amine (MPDA), 2000 grams of DMAC N,N' dimethyl acetamides (DMAc) and 920 grams of METHYLPYRROLIDONEs (NMP) add polymerization bottle
In, stir under room temperature, after being completely dissolved, ice-water bath is cooled to less than 5 DEG C, addition 308.9 grams (1.05 moles) 3,3 ', 4,4 '-
Biphenyl tetracarboxylic dianhydride (BPDA), stirring, after 8 DEG C are reacted 4 hours, obtain 3502.5 grams of homogeneous, transparent, thick BPDA types
Polyamic acid resin solution, is denoted as BPDA-PAA-2.CAP2000+ vertebral plate viscometers are flown using rich Le, its viscosity, performance number is surveyed
According to as shown in table 1.
Embodiment 3
By 51.8 grams of (0.1 mole) 2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa (BAPFP), 180.0
During (0.9 mole) 4,4 '-diaminodiphenyl ether (DADPE) and 3290 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, add 317.7 grams of (1.08 moles) 3,3 ', 4,4 '-biphenyl
Tetracarboxylic dianhydride (BPDA), stirring, after 10 DEG C are reacted 6 hours, obtain 3839.5 grams of homogeneous, transparent, thick BPDA types and gather
Amic acid resin solution, is denoted as BPDA-PAA-3.CAP2000+ vertebral plate viscometers are flown using rich Le, its viscosity, performance data is surveyed
As shown in table 1.
Embodiment 4
By 1000 grams of BPDA-PAA-1 type polyamic acid resin solution and 10 grams of 2,2- couple of [4- (2,4- diamino phenoxies)
Phenyl] HFC-236fa (BDAPFP), mix homogeneously at room temperature, stirring reaction obtain 1010 grams of homogeneous phase solutions after 1 hour, remember
Make BFPAA-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 BPDA-PAA-2 type polyamic acid resin solution and 10 grams of 2,2- couple of [4- (2,4- diamino phenoxies)
Phenyl] HFC-236fa (BDAPFP), mix homogeneously at room temperature, stirring reaction obtain 3010 grams of homogeneous phase solutions after 3 hours, remember
Make BFPAA-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 BPDA-PAA-3 type polyamic acid resin solution and 3 grams of 2,2- couple of [4- (2,4- diamino phenoxies)
Phenyl] HFC-236fa (BDAPFP), mix homogeneously at room temperature, stirring reaction obtain 2403 grams of homogeneous phase solutions after 6 hours, remember
Make BFPAA-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, retains 10 points
Clock, is continuously heating to 250 DEG C, retains 10 minutes, is continuously heating to 350 DEG C, retains 10 minutes.
Tough and tensile transparent Kapton BPDA-PI-1 is obtained by BPDA-PAA-1 homogeneous phase solution film forming；By BPDA-
PAA-2 homogeneous phase solution film forming obtains tough and tensile transparent Kapton BPDA-PI-2；By BPDA-PAA-3 homogeneous phase solution film forming
Obtain tough and tensile transparent Kapton BPDA-PI-3.Performance data is as shown in table 2.
The fluorine-containing branched polyimide thin film BFPI-1 of tough and tensile transparent BPDA types is obtained by BFPAA-1 homogeneous phase solution film forming；
The fluorine-containing branched polyimide thin film BFPI-2 of tough and tensile transparent BPDA types is obtained by BFPAA-2 homogeneous phase solution film forming；By BFPAA-3
Homogeneous phase solution film forming obtains the fluorine-containing branched polyimide thin film BFPI-3 of tough and tensile transparent BPDA types.Performance data is as shown in table 2.
As can be seen from Table 2：The branching type Kapton prepared in embodiment has significant relative to non-branching type thin film
Combination property superiority.
The performance data of 2 Kapton of table
Claims (8)
1. a kind of fluorine-containing branched polyimide resin film of BPDA types, it is characterised in that the double [4- of 2,2- in the raw material of the thin film
(2,4- diamino phenoxies) phenyl] mass ratio of HFC-236fa BDAPFP and BPDA Linear polyamic acid resins is 1:100-
800。
2. the fluorine-containing branched polyimide resin film of a kind of BPDA types according to claim 1, it is characterised in that described
BPDA Linear polyamic acid resins be by mol ratio be 1:The aromatic dicarboxylic primary amine and 3,3', 4,4'- biphenyl of 1.01-1.08
Tetracarboxylic dianhydride reacts in highly polar aprotic organic solvent and obtains.
3. a kind of fluorine-containing branched polyimide resin film of BPDA types according to claim 2, it is characterised in that the virtue
Fragrant race's binary primary amine is p-phenylenediamine, o-phenylenediamine, m-diaminobenzene., trimethyl m-diaminobenzene., benzidine, 2,2'- dimethyl
Benzidine, 2,2'- bis- (trifluoromethyl) benzidine, 2- (4- aminophenyls) -5- aminobenzimidazoles, 4,4'- diaminourea
Diphenyl ether, 3,4'- diaminodiphenyl ethers, 3,3'- diaminodiphenyl ethers, 4,4'- MDAs, 4,4'- diaminourea two
Benzene 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- double (3- amino-benzene oxygens) benzene, 1,3-
Double (4- amino-benzene oxygens) benzene of double (3- amino-benzene oxygens) benzene, 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, double (the 3- ammonia of 1,2-
Phenoxyl) benzene, double (4- amino-benzene oxygens) benzene of 1,2-, double (4- amino-benzene oxygens) benzonitriles of 2,6-, double (the 3- aminobenzenes of 2,6-
Epoxide) benzonitrile, double (4- amino-benzene oxygens) toluene of 2,6-, double (3- amino-benzene oxygens) toluene of 2,6-, double (the 4- aminobenzenes of 2,6-
Epoxide) benzotrifluoride, double (3- amino-benzene oxygens) benzotrifluorides of 2,6-, double (4- amino-benzene oxygens) toluene of 2,5-, the double (3- of 2,5-
Amino-benzene oxygen) toluene, double (4- amino-benzene oxygens) tert-butylbenzenes of 2,5-, double (3- amino-benzene oxygens) tert-butylbenzenes of 2,5-, 2,
Double (4- amino-benzene oxygens) benzene of 5- di-t-butyls -1,4-, double (3- amino-benzene oxygens) benzene of 2,5- di-t-butyls -1,4-, 4,4'- are double
Double (4- amino-benzene oxygens) diphenyl sulphone (DPS)s of (4- amino-benzene oxygens) benzophenone, 4,4'-, double (3- amino-benzene oxygens) hexichol of 4,4'-
Double (3- amino-benzene oxygens) diphenyl sulphone (DPS)s of ketone, 4,4'-, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,4-, the double (2- of 1,3-
Trifluoromethyl-4-aminophenoxyl) benzene, double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane of 2,2-, 2,2- be double
(3- amino-4-hydroxylphenyls) HFC-236fa, 2,2- double (3- amino-4-hydroxylphenyls) propane, 3,3'- diaminourea -4,4'- two
Double [4- (2- trifluoromethyl-4-aminophenoxyls) benzene of xenol, 3,3'- diaminourea -4,4' dihydroxydiphenyl sulfone, 2,2-
Base] HFC-236fa, double (2- trifluoromethyl-4-aminophenoxyls) toluene of 2,5-, the double (2- trifluoromethyl -4- aminobenzene oxygen of 2,5-
Base) tert-butyl benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 2,5- di-t-butyls -1,4-, double (the 2- fluoroforms of 4,4'-
Base -4- amino-benzene oxygens) diphenyl sulphone (DPS), double (2- the trifluoromethyl-4-aminophenoxyls) -3,3' of 4,4'-, 5,5'- tetramethyl hexichol
Double (2- trifluoromethyl-4-aminophenoxyls) biphenyl of sulfone, 4,4'-, double (the 2- trifluoromethyl-4-aminophenoxyls) -3 of 4,4'-,
Double (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether of 3', 5,5'- tetramethyl biphenyl, 4,4'-, double (the 4- aminobenzene oxygen of 4,4'-
Base) diphenyl ether, double (3- amino-benzene oxygens) diphenyl ether of 4,4'-, double (3- amino-benzene oxygens) diphenyl sulfides of 4,4'-, 4,4'- be double
Double (4- the amino-benzene oxygens) -3,3' of (4- amino-benzene oxygens) diphenyl sulfide, 4,4'-, the double (3- of 5,5'- tetramethyl biphenyls, 4,4'-
Amino-benzene oxygen) -3,3', double [4- (4- amino-benzene oxygens) phenyl] propane of 5,5'- tetramethyl biphenyls, 2,2-, the double [4- of 2,2-
(4- amino-benzene oxygens) phenyl] HFC-236fa, double (4- amino-benzene oxygens) benzoic acid of 3,5-, in 3,5- diaminobenzoic acids extremely
Few one kind.
4. the fluorine-containing branched polyimide resin film of a kind of BPDA types according to claim 2, it is characterised in that described strong
Polar non-proton organic solvent is 3-6 with the mass ratio of total reactant：1；Wherein, the quality of total reactant refers to aromatic dicarboxylic
The quality sum of primary amine and 3,3', 4,4'- biphenyl tetracarboxylic dianhydride.
5. the fluorine-containing branched polyimide resin film of a kind of BPDA types according to claim 4, it is characterised in that described strong
Polar non-proton organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- second
At least one in base -2-Pyrrolidone, dimethyl sulfoxide.
6. the preparation method of the fluorine-containing branched polyimide resin film of a kind of BPDA types as claimed in claim 1, including：
(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'- biphenyl tetracarboxylic dianhydride BPDA, stir, 5 DEG C of -10 DEG C of 1～6h of reaction obtain BPDA type polyamic acid resins
Solution；
(2) by BPDA type polyamic acid resin solution and 2,2- double [4- (2,4- diamino phenoxies) phenyl] HFC-236fa by than
Example mixes at room temperature, stirs, and the film forming in casting machine, heat temperature raising carry out dehydration fever imidization, cools down, and demoulding is obtained
To the fluorine-containing branched polyimide resin film of BPDA types.
7. the preparation method of the fluorine-containing branched polyimide resin film of a kind of BPDA types according to claim 6, its feature
It is that the time of stirring is 1～6h in step (2).
8. the preparation method of the fluorine-containing branched polyimide resin film of a kind of BPDA types according to claim 6, its feature
It is that the condition of dehydration hot imidization is in step (2)：150 DEG C are risen to from room temperature, 10 minutes is incubated, is continuously heating to
250 DEG C, 10 minutes are incubated, 350 DEG C are continuously heating to, be incubated 10 minutes.
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