CN106479177A - A kind of BPADA type BDATHQ branched polyimide resin film and preparation method thereof - Google Patents
A kind of BPADA type BDATHQ branched polyimide resin film and preparation method thereof Download PDFInfo
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- CN106479177A CN106479177A CN201610961922.8A CN201610961922A CN106479177A CN 106479177 A CN106479177 A CN 106479177A CN 201610961922 A CN201610961922 A CN 201610961922A CN 106479177 A CN106479177 A CN 106479177A
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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
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- 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
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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
- 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
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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
- 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 present invention relates to a kind of BPADA type BDATHQ branched polyimide resin film and preparation method thereof, in the raw material of the film, the mass ratio of BDATHQ and BPADA Linear polyamic acid resin is 1:100‑800.Preparation method includes：Aromatic dicarboxylic primary amine is mixed with highly polar aprotic organic solvent, is stirred at room temperature, less than 5 DEG C are cooled to, BPADA is added, stir, 5 DEG C 10 DEG C 1～6h of reaction, obtain BPADA type polyamic acid resin solution；To mix under resin solution and BDATHQ room temperature, stirring, film forming, heat temperature raising, hot imidization will be dehydrated, and cool down, demoulding, obtain final product.Method of the present invention reaction condition is gentle, simple to operate, low cost, environmentally friendly, beneficial to industrial-scale production is realized, the high-tech areas such as the wrapped insulating material of flexible solar battery, space telescope, large generator main insulation, electromagnetic wire, flexible copper clad foil plate are can be applicable to.
Description
Technical field
The invention belongs to Kapton and its preparation field, the branched polyamides of more particularly to a kind of BPADA type BDATHQ
Imide resin film and preparation method thereof.
Background technology
Kapton is the very excellent macromolecular material of a class combination property, with especially excellent heat resistance,
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 film of traditional Kapton, such as U.S. DUPONT company production and domestic H are 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 exploring further 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, its are specific
Molecular structure is as follows：
Its shortcoming is：(1) double (3,4- dicarboxyphenyi) the hexafluoropropane dianhydride monomers of raw materials 2,2- are extremely held high
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 HMW is obtained is sub-
Polyimide resin, therefore, causes the combination property of its film product to be greatly reduced, is particularly its mechanical property.
Japanese NTT company is also with double (3,4- dicarboxyphenyi) 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'- benzidine 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, insulating materials are communicated, and 1999,32 (5)：1-4] disclose 1,3-
The preparation method of double (3- amino-benzene oxygen) 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 ether；(3) [double [4- (the 3- aminobenzenes of 2,2-
Epoxide) phenyl] preparation of propane and its research of soluble polyimide, insulating materials, 2001,34 (6):3-6] 2 are disclosed,
The preparation method of double [4- (3- amino-benzene oxygen) phenyl] propane of 2-；(4) [synthesis of bisphenol A-type polyimide monomer and application,
Insulating materials, 2002,35 (4)：3-7] and Chinese invention patent CN1472193A (2004-02-04) disclose the double [4- of 2,2-
(4- amino-benzene oxygen) 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] system of 2,2- double [4- (4- amino-benzene oxygen) phenyl] HFC-236fa is disclosed
Preparation Method；(6) [synthesis and the performance study of 4,4'- double (4- amino-benzene oxygen) diphenyl sulfides and its polyimides, insulation material
Material, 2008,41 (5)：10-14] disclose the preparation method of double (4- amino-benzene oxygen) diphenyl sulfide 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 is cooled down
To within the temperature range of 5 DEG C -10 DEG C, aromatic dicarboxylic anhydride is added, stir, within the temperature range of 5 DEG C -10 DEG C, react 4-10
After hour, homogeneous, transparent, thick polyamic acid resin solution is obtained；(2) the viscous of the polyamic acid resin solution is adjusted
Degree, film forming in the casting machine, hot imidization, the Kapton of homogeneous phase transparent is obtained, 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- aminophenyl) -5- aminobenzimidazole (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 acid amides acid solution, then, casting film-forming in the 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 is added, stir, at room temperature after reaction 1-3 hour, 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, film forming in the casting machine, and heat temperature raising is 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, stirs, and reacts 3 little within the temperature range of 5 DEG C -10 DEG C
Shi Hou, obtains homogeneous, transparent, thick fluorinated aromatic polyamic acid resin solution；Wherein, the rubbing of aromatic dicarboxylic anhydride
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, film forming in the casting machine, heat temperature raising, dehydration fever imidization is carried out, cooling, demoulding,
Obtain full aromatic fluorine containing transparent polyimide film.
Chinese invention patent CN101456964A discloses a kind of preparation method of aromatic polybenzimidazole film, its master
Step is wanted to include：Using aromatic series quaternary amine and the aromatic binary carboxylic acid of specific molecular structure, two are aoxidized in polyphosphoric acids/five
In the presence of phosphorus system, in nitrogen atmosphere, in -200 DEG C of temperature ranges of room temperature, solution polycondensation reaction is carried out, 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 film.
Chinese invention patent CN101392059A discloses a kind of colorless transparent aromatic polyimide film and its preparation
Method, it is characterised in that：Using primary aromatic amine and the aromatic anhydride of specific molecular structure, highly polar non-proton organic molten
In agent system, in 0 DEG C of -35 DEG C of temperature range, polymerisation is carried out, water white homogeneously thick polyamic acid is obtained molten
Liquid.Viscosity, casting film-forming, heat temperature raising, desolvation is adjusted, while there is part imidization, demoulding is stretched, further
Depth hot imidization, winding, obtain colorless transparent aromatic polyimide film product.
The heat resistance of the 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.At present with regard to BPADA type
BDATHQ branched polyimide resin film and preparation method thereof, there is not yet disclosed document or patent report.
Content of the invention
The technical problem to be solved be provide a kind of BPADA type BDATHQ branched polyimide resin film 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 are originated
Convenient, low cost, be not related to also not produce corrosive substance, organic solvent using the few and easy recovery of species, can iterative cycles again
With environmentally friendly；And the Kapton has excellent dimensional stability, mechanical property and heat resistance, while also have
Standby very excellent electric property and optical property.
A kind of BPADA type BDATHQ branched polyimide resin film of the present invention, in the raw material of the film, 2,5- are double
The mass ratio of (2,4- diamino phenoxy) toluene BDATHQ and BPADA Linear polyamic acid resin is 1:100-800.
The BPADA Linear polyamic acid resin be by mol ratio be 1:1.01-1.08 aromatic dicarboxylic primary amine with
Double [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2- react in highly polar aprotic organic solvent and obtain.
The aromatic dicarboxylic primary amine is p-phenylenediamine, o-phenylenediamine, m-phenylene diamine (MPD), trimethyl m-phenylene diamine (MPD), biphenyl two
Amine, 2,2'- dimethyl diphenyl diamines, 2,2'- bis- (trifluoromethyl) benzidine, 2- (4- aminophenyl) -5- amino benzo miaow
Azoles, 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ether, 3,3'- diaminodiphenyl ether, 4,4'- MDA,
4,4' diaminodiphenyl sulfone, 3,3'- dimethyl -4,4'- MDA, 3,3'- diethyl base -4,4'- diaminourea two
Phenylmethane, 3,3', double (the 3- aminobenzenes of 5,5'- tetramethyl -4,4'- MDA, 3,3'- DADPS, 1,4-
Epoxide) benzene, double (3- amino-benzene oxygen) benzene of 1,3-, double (4- amino-benzene oxygen) benzene of 1,4-, double (4- amino-benzene oxygen) benzene of 1,3-,
Double (3- amino-benzene oxygen) benzene of 1,2-, double (4- amino-benzene oxygen) benzene of 1,2-, 2,6- double (4- amino-benzene oxygen) benzonitrile, 2,6-
Double (4- amino-benzene oxygen) toluene of double (3- amino-benzene oxygen) benzonitriles, 2,6-, 2,6- double (3- amino-benzene oxygen) toluene, 2,6-
Double (3- amino-benzene oxygen) benzotrifluorides of double (4- amino-benzene oxygen) benzotrifluorides, 2,6-, double (4- amino-benzene oxygen) first of 2,5-
Double (3- amino-benzene oxygen) toluene of benzene, 2,5-, double (4- amino-benzene oxygen) tert-butylbenzenes of 2,5-, 2,5- are double (3- amino-benzene oxygen)
Double (4- amino-benzene oxygen) benzene of tert-butylbenzene, 2,5- di-t-butyl -1,4-, double (the 3- aminobenzene oxygen of 2,5- di-t-butyl -1,4-
Base) benzene, double (4- amino-benzene oxygen) benzophenone of 4,4'-, double (4- amino-benzene oxygen) diphenyl sulphone (DPS)s of 4,4'-, double (the 3- ammonia of 4,4'-
Phenoxyl) benzophenone, double (3- amino-benzene oxygen) diphenyl sulphone (DPS) of 4,4'-, 1,4- be double (2- trifluoromethyl-4-aminophenoxyl)
Double (2- trifluoromethyl-4-aminophenoxyl) benzene of benzene, 1,3-, 2,2- are double [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl]
Double (3- amino-4-hydroxylphenyl) HFC-236fas of propane, 2,2-, 2,2- double (3- amino-4-hydroxylphenyl) 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-aminophenoxyl) toluene of 2,5-, 2,5- double (2- trifluoromethyl-
4- amino-benzene oxygen) tert-butyl benzene, double (2- trifluoromethyl-4-aminophenoxyl) benzene of 2,5- di-t-butyl -1,4-, 4,4'- be double
Double (2- the trifluoromethyl-4-aminophenoxyl) -3,3', 5,5'- tetra- of (2- trifluoromethyl-4-aminophenoxyl) diphenyl sulphone (DPS), 4,4'-
Double (2- trifluoromethyl-4-aminophenoxyl) biphenyl of methyldiphenyl sulfone, 4,4'-, the double (2- trifluoromethyl -4- aminobenzene oxygen of 4,4'-
Base) -3,3', double (2- trifluoromethyl-4-aminophenoxyl) diphenyl ether of 5,5'- tetramethyl biphenyl, 4,4'-, double (the 4- ammonia of 4,4'-
Phenoxyl) diphenyl ether, double (3- amino-benzene oxygen) diphenyl ether of 4,4'-, double (3- amino-benzene oxygen) diphenyl sulfides of 4,4'-, 4,
Double (4- amino-benzene oxygen) diphenyl sulfides of 4'-, double (4- the amino-benzene oxygen) -3,3' of 4,4'-, 5,5'- tetramethyl biphenyl, 4,4'-
Double (3- amino-benzene oxygen) -3,3', double [4- (4- amino-benzene oxygen) phenyl] propane of 5,5'- tetramethyl biphenyl, 2,2-, 2,2- are double
In double (4- amino-benzene oxygen) benzoic acid of [4- (4- amino-benzene oxygen) phenyl] HFC-236fa, 3,5-, 3,5- diaminobenzoic acid
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 [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-.
The highly polar aprotic organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2-
At least one in pyrrolidones, N- ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO).
A kind of preparation method of the BPADA type BDATHQ 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, stirs under room temperature, complete
After CL, ice-water bath is cooled to less than 5 DEG C, adds double [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-
BPADA, stirring, 5 DEG C -10 DEG C 1～6h of reaction, obtain homogeneous, transparent, thick BPADA type polyamic acid resin solution；
(2) by BPADA type polyamic acid resin solution and double (2,4- diamino phenoxy) toluene of 2,5- in proportion in room
Temperature is lower to be mixed, and stirring obtains homogeneous phase solution, film forming in the casting machine, and heat temperature raising carries out dehydration fever imidization, cooling,
Demoulding, obtains BPADA type BDATHQ branched polyimide resin film.
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, continue 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) the preparation method reaction condition of the present invention is gentle, and course of reaction is carried out at ambient pressure, simple to operate；Reaction is former
Material convenient sources, low cost, it is not related to also not produce corrosive substance, organic solvent uses species few and easy recovery, can be repeatedly
Recycling, environmentally friendly；Industrial-scale production is advantageously implemented, and can be applicable to flexible solar battery, space and hope
The remote high-tech area such as 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 the preparation process of the present 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 present invention is general Kapton production equipment, i.e., general casting machine, and equipment is thrown
Money is few, is very beneficial for the enforcement of the present invention；
(4) the material resin molecular weight for adopting 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 heat resistance, while also possess very excellent electric property and optical property；
(5) the branching type Kapton (the addition reaction of BDATHQ tetramine) of the present invention is with respect to non-branching type 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 present invention instruction, 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), 22.6 grams of (0.1 mole) 3,3'- diformazans
Base -4,4'- MDA (MDT), 22.4 (0.1 mole) 2- (4- aminophenyl) -5- aminobenzimidazole (APABI)
Add in polymerization bottle with 2200 grams of METHYLPYRROLIDONEs (NMP), stir under room temperature, after being completely dissolved, ice-water bath is cooled to
Less than 5 DEG C, double [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) of 525.7 grams of (1.01 moles) 2,2- are added,
Stirring, after 5 DEG C are reacted 1 hour, obtains 2930.7 grams of homogeneous, transparent, thick BPADA type polyamic acid resin solution, note
Make BPADA-PAA-1.CAP2000+ vertebral plate viscosimeter is flown using rich Le, its 50 DEG C viscosity is surveyed for 1034mPa.s.
Embodiment 2
By double for 116.8 grams of (0.4 mole) 1,3- (4- amino-benzene oxygen) benzene (134BAPB), 64.8 (0.6 moles) to benzene two
Amine (PPDA), 1400 grams of DMAC N,N' dimethyl acetamides (DMAc) and 1500 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, adds the double [4- of 546.5 grams of (1.05 moles) 2,2-
(3,4- di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA), stirring, after 8 DEG C of reactions 3 hours, obtain 3628.1 grams homogeneous,
Transparent, thick BPADA type polyamic acid resin solution, is denoted as BPADA-PAA-2.Fly CAP2000+ vertebral plate using rich Le to glue
Degree meter, surveys its 50 DEG C viscosity for 956mPa.s.
Embodiment 3
108.0 grams of (1.0 moles) p-phenylenediamine (PPDA) and 4000 grams of METHYLPYRROLIDONEs (NMP) are added and are gathered
Close in bottle, stir under room temperature, after being completely dissolved, ice-water bath is cooled to less than 5 DEG C, add 562.1 grams of (1.08 moles) 2,2- double
[4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA), stirring, after 10 DEG C are reacted 6 hours, obtain 4670.1 grams all
Phase, transparent, thick BPADA type polyamic acid resin solution, are denoted as BPADA-PAA-3.CAP2000+ vertebra is flown using rich Le
Plate viscosimeter, surveys its 50 DEG C viscosity for 869mPa.s.
Embodiment 4
By 1000 grams of BPADA-PAA-1 type polyamic acid resin solution and 10 grams of 2,5- pair of (2,4- diamino phenoxy) first
Benzene (BDATHQ), is mixed at room temperature, and stirring reaction was obtained 1010 grams of homogeneous phase solutions, is denoted as PAA-1 after 1 hour.Using
Bo Le flies CAP2000+ vertebral plate viscosimeter, surveys its 50 DEG C viscosity for 1375mPa.s.
By 3000 grams of BPADA-PAA-2 type polyamic acid resin solution and 10 grams of 2,5- pair of (2,4- diamino phenoxy) first
Benzene (BDATHQ), is mixed at room temperature, and stirring reaction was obtained 3010 grams of homogeneous phase solutions, is denoted as PAA-2 after 3 hours.Using
Bo Le flies CAP2000+ vertebral plate viscosimeter, surveys its 50 DEG C viscosity for 1284mPa.s.
By 2400 grams of BPADA-PAA-3 type polyamic acid resin solution and 3 grams of 2,5- pair of (2,4- diamino phenoxy) first
Benzene (BDATHQ), is mixed at room temperature, and stirring reaction was obtained 2403 grams of homogeneous phase solutions, is denoted as PAA-3 after 6 hours.Using
Bo Le flies CAP2000+ vertebral plate viscosimeter, surveys its 50 DEG C viscosity for 1113mPa.s.
Embodiment 5
By the homogeneous phase solution of 1～embodiment of above-described embodiment 4 in the 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, be incubated 10 points
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 BPADA-PI-1 is obtained by BPADA-PAA-1 homogeneous phase solution film forming；By
BPADA-PAA-2 homogeneous phase solution film forming obtains tough and tensile transparent Kapton BPADA-PI-2；Homogeneous by BPADA-PAA-3
Solution film forming obtains tough and tensile transparent Kapton BPADA-PI-3.Performance data is as shown in table 1.
Tough and tensile transparent BPADA type BDATHQ branched polyimide film PI-1 is obtained by PAA-1 homogeneous phase solution film forming；By
PAA-2 homogeneous phase solution film forming obtains tough and tensile transparent BPADA type BDATHQ branched polyimide film PI-2；Homogeneous by PAA-3
Solution film forming obtains tough and tensile transparent BPADA type BDATHQ branched polyimide film PI-3.Performance data is as shown in table 1.From
Can be seen that in table 1：The branching type Kapton prepared in embodiment has significantly comprehensive with respect to non-branching type film
Close performance advantage.
The performance data of 1 Kapton of table
Claims (8)
1. a kind of BPADA type BDATHQ branched polyimide resin film, it is characterised in that 2,5- are double in the raw material of the film
The mass ratio of (2,4- diamino phenoxy) toluene BDATHQ and BPADA Linear polyamic acid resin is 1:100-800.
2. a kind of BPADA type BDATHQ branched polyimide resin film according to claim 1, it is characterised in that institute
State BPADA Linear polyamic acid resin be by mol ratio be 1:The aromatic dicarboxylic primary amine of 1.01-1.08 [4- double with 2,2-
(3,4- di carboxyl phenyloxy) phenyl] propane dianhydride reacts in highly polar aprotic organic solvent and obtains.
3. a kind of BPADA type BDATHQ branched polyimide resin film according to claim 2, it is characterised in that institute
Aromatic dicarboxylic primary amine is stated for p-phenylenediamine, o-phenylenediamine, m-phenylene diamine (MPD), trimethyl m-phenylene diamine (MPD), benzidine, 2,2'- bis-
Methyl biphenyl diamines, 2,2'- bis- (trifluoromethyl) benzidine, 2- (4- aminophenyl) -5- aminobenzimidazole, 4,4'- bis-
Amino-diphenylethers, 3,4'- diaminodiphenyl ether, 3,3'- diaminodiphenyl ether, 4,4'- MDA, 4,4'- diamino
Base diphenyl sulphone (DPS), 3,3'- dimethyl -4,4'- MDA, 3,3'- diethyl base -4,4'- MDA, 3,
Double (3- amino-benzene oxygen) benzene of 3', 5,5'- tetramethyl -4,4'- MDA, 3,3'- DADPS, 1,4-,
Double (3- amino-benzene oxygen) benzene of 1,3-, double (4- amino-benzene oxygen) benzene of 1,4-, double (4- amino-benzene oxygen) benzene of 1,3-, 1,2- are double
Double (4- amino-benzene oxygen) benzene of (3- amino-benzene oxygen) benzene, 1,2-, double (4- amino-benzene oxygen) benzonitriles of 2,6-, the double (3- of 2,6-
Amino-benzene oxygen) benzonitrile, double (4- amino-benzene oxygen) toluene of 2,6-, double (3- amino-benzene oxygen) toluene of 2,6-, the double (4- of 2,6-
Amino-benzene oxygen) benzotrifluoride, double (3- amino-benzene oxygen) benzotrifluoride of 2,6-, double (4- amino-benzene oxygen) toluene of 2,5-, 2,
Double (3- amino-benzene oxygen) toluene of 5-, double (4- amino-benzene oxygen) tert-butylbenzenes of 2,5-, 2,5- double (3- amino-benzene oxygens) spy fourth
Double (3- amino-benzene oxygen) benzene of double (4- amino-benzene oxygen) benzene of base benzene, 2,5- di-t-butyl -1,4-, 2,5- di-t-butyl -1,4-,
Double (4- amino-benzene oxygen) benzophenone of 4,4'-, double (4- amino-benzene oxygen) diphenyl sulphone (DPS)s of 4,4'-, double (the 3- aminobenzene oxygen of 4,4'-
Base) benzophenone, double (3- amino-benzene oxygen) diphenyl sulphone (DPS) of 4,4'-, double (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, 1,
Double [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of double (2- trifluoromethyl-4-aminophenoxyl) benzene of 3-, 2,2-,
Double (3- amino-4-hydroxylphenyl) HFC-236fas of 2,2-, double (3- amino-4-hydroxylphenyl) propane of 2,2-, 3,3'- diaminourea-
Double [4- (2- trifluoromethyl -4- aminobenzene the oxygen of 4,4' dihydroxy diphenyl, 3,3'- diaminourea -4,4' dihydroxydiphenyl sulfone, 2,2-
Base) phenyl] HFC-236fa, double (2- trifluoromethyl-4-aminophenoxyl) toluene of 2,5-, the double (2- trifluoromethyl -4- amino of 2,5-
Phenoxy group) tert-butyl benzene, double (2- trifluoromethyl-4-aminophenoxyl) benzene of 2,5- di-t-butyl -1,4-, double (the 2- trifluoros of 4,4'-
Methyl -4- amino-benzene oxygen) diphenyl sulphone (DPS), double (2- the trifluoromethyl-4-aminophenoxyl) -3,3' of 4,4'-, 5,5'- tetramethyl two
Double (2- trifluoromethyl-4-aminophenoxyl) biphenyl of benzene sulfone, 4,4'-, double (the 2- trifluoromethyl-4-aminophenoxyls) -3 of 4,4'-,
Double (2- trifluoromethyl-4-aminophenoxyl) 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 oxygen) diphenyl ether of 4,4'-, double (3- amino-benzene oxygen) diphenyl sulfides of 4,4'-, 4,4'- be double
Double (4- the amino-benzene oxygen) -3,3' of (4- amino-benzene oxygen) diphenyl sulfide, 4,4'-, the double (3- of 5,5'- tetramethyl biphenyl, 4,4'-
Amino-benzene oxygen) -3,3', double [4- (4- amino-benzene oxygen) phenyl] propane of 5,5'- tetramethyl biphenyl, 2,2-, the double [4- of 2,2-
(4- amino-benzene oxygen) phenyl] HFC-236fa, double (4- amino-benzene oxygen) benzoic acid of 3,5-, in 3,5- diaminobenzoic acid extremely
Few one kind.
4. a kind of BPADA type BDATHQ branched polyimide resin film according to claim 2, it is characterised in that institute
The mass ratio for highly polar aprotic organic solvent being stated with total reactant is 3-6：1；Wherein, the quality of total reactant refers to aromatic series
Binary primary amine and the quality sum of double [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-.
5. a kind of BPADA type BDATHQ branched polyimide resin film according to claim 4, it is characterised in that institute
State highly polar aprotic organic solvent for N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE,
At least one in N- ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO).
6. a kind of preparation method of BPADA type BDATHQ branched polyimide resin film as claimed in claim 1, including：
(1) aromatic dicarboxylic primary amine is mixed with highly polar aprotic organic solvent, stirs under room temperature, less than 5 DEG C are cooled to, plus
Enter double [4- (3,4- di carboxyl phenyloxy) phenyl] the propane dianhydride BPADA of 2,2-, stir, 5 DEG C -10 DEG C 1～6h of reaction, obtain
BPADA type polyamic acid resin solution；
(2) by double to BPADA type polyamic acid resin solution and 2,5- (2,4- diamino phenoxy) toluene in proportion at room temperature
Mixing, stirring, film forming in the casting machine, heat temperature raising, dehydration fever imidization is carried out, cooling, demoulding, obtain BPADA type
BDATHQ branched polyimide resin film.
7. the preparation method of a kind of BPADA type BDATHQ branched polyimide resin film according to claim 6, its are special
Levy and be, the time of stirring is 1～6h in step (2).
8. the preparation method of a kind of BPADA type BDATHQ branched polyimide resin film according to claim 6, its are special
Levy and be, the condition of dehydration hot imidization is in step (2)：150 DEG C are risen to from room temperature, 10 minutes are incubated, continue to heat up
To 250 DEG C, 10 minutes are incubated, 350 DEG C are continuously heating to, be incubated 10 minutes.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004087793A1 (en) * | 2003-03-28 | 2004-10-14 | Pi R & D Co. Ltd. | Crosslinked polyimide, composition comprising the same and method for producing the same |
| CN101250124A (en) * | 2008-04-02 | 2008-08-27 | 东华大学 | Method for preparing 2,5-di(2,4-diamino phenoxy) toluene |
-
2016
- 2016-11-04 CN CN201610961922.8A patent/CN106479177A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004087793A1 (en) * | 2003-03-28 | 2004-10-14 | Pi R & D Co. Ltd. | Crosslinked polyimide, composition comprising the same and method for producing the same |
| CN101250124A (en) * | 2008-04-02 | 2008-08-27 | 东华大学 | Method for preparing 2,5-di(2,4-diamino phenoxy) toluene |
Non-Patent Citations (1)
| Title |
|---|
| 虞鑫海等: ""1,4-双（2,4-二氨基苯氧基）苯的合成及其支化型聚酰亚胺薄膜"", 《绝缘材料》 * |
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Application publication date: 20170308 |