CN106398210A - BTDA type 13BDAPB branched polyimide resin film and preparation method thereof - Google Patents
BTDA type 13BDAPB branched polyimide resin film and preparation method thereof Download PDFInfo
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- CN106398210A CN106398210A CN201610964348.1A CN201610964348A CN106398210A CN 106398210 A CN106398210 A CN 106398210A CN 201610964348 A CN201610964348 A CN 201610964348A CN 106398210 A CN106398210 A CN 106398210A
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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
Abstract
The invention relates to a BTDA type 13BDAPB branched polyimide resin film and a preparation method thereof. The mass ration of 13BDAPB and BTDA type linear polyimide resin in raw materials of the film is 1: (100 to 800). The preparation method comprises the followings steps: mixing aromatic binary primary amine with a strongly-polar nonprotic organic solvent, stirring under room temperature, cooling to below 5 DEG C, adding BTDA, stirring, and reacting for 1 to 6 h at the temperature of 5 to 10 DEG C so as to obtain a BTDA type polyamide acid resin solution; mixing the resin solution and 13BDAPB at room temperature, stirring, carrying out film formation, heating and warming, carrying out a dehydration thermal imidization reaction, cooling, and demolding. The method disclosed by the invention is mild in reaction conditions, simple in operation, low in cost and environmentally-friendly, is beneficial to realizing industrialization scale production, and can be applied to the high-tech fields such as flexible solar cells, space telescopes, large generator main insulation, electromagnetic wire lapping electrical insulating materials and flexible copper-clad plates.
Description
Technical field
The invention belongs to Kapton and its preparation field, particularly to a kind of branched polyamides of BTDA type 13BDAPB
Imide resin film and preparation method thereof.
Background technology
Kapton is the very excellent macromolecular material of a class combination property, have 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, traditional Kapton, such as the KAPTON film that DUPONT company of the U.S. produces and domestic H are thin
Film, their molecular structure is pyromellitic acid anhydride type, and that is, its principal monomer raw material is pyromellitic acid anhydride and 4,4'-
Diaminodiphenyl ether.
NASA (NASA) plans to be used for exploring further in transmitting in 2009 space telescope (NGST) of future generation
The origin in universe, wherein multilayer insulation sunshading board material (MLI) is to realize one of key material of this plan.For this reason, opening
Sent out under space environment can steady operation novel polyimide film material：LaRCTM- CP1 and LaRCTM- CP2, it is specific
Molecular structure is as follows：
Its shortcoming is：(1) double (3,4- dicarboxyphenyi) the hexafluoropropane dianhydride monomer of raw materials 2,2- is extremely high
Expensive, lead to film product cost very high, seriously hinder the application of its further genralrlization；(2) due to double (the 3,4- dicarboxyl of 2,2-
Phenyl) hexafluoropropane dianhydride monomer and aromatic dicarboxylic primary amine reactivity low, the polyamides being difficult to be obtained HMW is sub-
Polyimide resin, therefore, leads to the combination property of its film product to be greatly reduced, particularly its mechanical property.
Japanese NTT company is also with double (3,4- dicarboxyphenyi) hexafluoro of the low 2,2- of expensive, reactivity
Propane dianhydride monomer, has been obtained with pyromellitic acid anhydride or the exploitation of 3,3'- bis- (trifluoromethyl) -4,4'- benzidine
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 communicates, 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- aminobenzene of 2,2-
Epoxide) phenyl] preparation of propane and its research of soluble polyimide, insulating materials, 2001,34 (6):3-6] disclose 2,
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] disclose the system of double [4- (4- amino-benzene oxygen) phenyl] HFC-236fa of 2,2-
Preparation Method；(6) [synthesis of 4,4'- double (4- amino-benzene oxygen) diphenyl sulfides and its polyimides and performance study, 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, its preparation bag
Include following steps：(1) at room temperature, binary primary amine is dissolved in highly polar aprotic organic solvent system, ice-water bath cools down
To within the temperature range of 5 DEG C -10 DEG C, add aromatic dicarboxylic anhydride, stirring, react 4-10 within the temperature range of 5 DEG C -10 DEG C
After hour, obtain homogeneous, transparent, thick polyamic acid resin solution；(2) adjust the viscous of this polyamic acid resin solution
Degree, film forming in casting machine, hot imidization, obtain the Kapton of homogeneous phase transparent, 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, in highly polar aprotic organic solvent system, at room temperature after stirring reaction 5-8 hour, obtains homogeneous phase transparent thick
Polybenzimidazoles acid amides acid solution, then, casting film-forming in casting machine, hot imidization, demoulding, winding, obtain tough and tensile transparent
Polybenzimidazole imide membrane.
Chinese invention patent CN101580637A discloses the present invention relates to a kind of alicyclic-containing polyimide film, and it is prepared
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, add aromatic dicarboxylic anhydride, stirring, 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 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 casting machine, 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, its preparation bag
Include：Fluorinated aromatic binary primary amine and highly polar aprotic organic solvent are added in polymerization bottle, stirs under room temperature, be completely dissolved
Afterwards, ice-water bath is cooled to less than 5 DEG C, adds aromatic dicarboxylic anhydride, stirring, reaction 3 is 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；Adjust above-mentioned fluorine-containing aromatic adoption with highly polar aprotic organic solvent
The viscosity of amic acid resin solution, 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 film, its master
Step is wanted to include：Using aromatic series quaternary amine and the aromatic binary carboxylic acid of specific molecular structure, aoxidize two in polyphosphoric acids/five
In the presence of phosphorus system, in nitrogen atmosphere, carry out solution polycondensation reaction, prepared kermesinus in -200 DEG C of temperature ranges of room temperature
Rubber elastomer shaped polymer.During cooling is fallen back, in resin pulper, blend into powder, alkali cleaning is extremely neutral, 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, carry out polymerisation, water white homogeneously thick polyamic acid is obtained molten
Liquid.Adjust viscosity, casting film-forming, heat temperature raising, desolvation, part imidization occurs simultaneously, demoulding stretches, further
Depth hot imidization, winding, obtain colorless transparent aromatic polyimide film product.
The heat resistance of the film that above-mentioned prior art obtains, 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 BTDA type
13BDAPB 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 BTDA type 13BDAPB branched polyimide resin film and
Its preparation method, this preparation method reaction condition is 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 uses species few and easy recovery, can iterative cycles again
With environmentally friendly；And this Kapton has excellent dimensional stability, mechanical property and heat resistance, also has simultaneously
Standby very excellent electric property and optical property.
A kind of BTDA type 13BDAPB branched polyimide resin film of the present invention, in the raw material of described film, 1,3- is double
The mass ratio of (2,4- diamino phenoxy) benzene 13BDAPB and BTDA Linear polyamic acid resin is 1:100-800.
Described BTDA Linear 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.
Described 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- aminobenzene 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) benzonitrile, 2,6-, 2,6- double (3- amino-benzene oxygen) toluene, 2,6-
Double (3- amino-benzene oxygen) benzotrifluoride of double (4- amino-benzene oxygen) benzotrifluoride, 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-butylbenzene 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) 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-236fa 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 sulfide of 4,4'-, 4,
Double (4- amino-benzene oxygen) diphenyl sulfide 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.
Described 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.
Described 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 BTDA type 13BDAPB branched polyimide resin film of the present invention, including：
(1) aromatic dicarboxylic primary amine and highly polar aprotic organic solvent are mixed in polymerization bottle, stir under room temperature, 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 double to BTDA type polyamic acid resin solution and 1,3- (2,4- diamino phenoxy) benzene in proportion at room temperature
Mixing, stirring, obtain homogeneous phase solution, film forming in casting machine, heat temperature raising, carry out dehydration fever imidization, cooling, take off
Film, obtains BTDA type 13BDAPB branched polyimide resin film.
In described step (2), the time of stirring is 1～6h.
In described step (2), the condition of dehydration hot imidization is：Rise to 150 DEG C from room temperature, be incubated 10 minutes, continue to heat up
To 250 DEG C, it is incubated 10 minutes, is continuously heating to 350 DEG C, 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；It is advantageously implemented industrial-scale production, and can be applicable to flexible solar battery, space prestige
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, to implement the present invention, is very beneficial for the industrialization of product；
(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 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 this Kapton has excellent dimensional stability, mechanical property
Energy and heat resistance, also possess very excellent electric property and optical property simultaneously；
(5) the branching type Kapton (the addition reaction of 13BDAPB tetramine) of the present invention is thin with respect to non-branching type
Film has 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 restriction the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, people in the art
Member can make 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- aminophenyl) -5- aminobenzimidazoles (APABI) and 1600 grams of N- methyl -2-
Pyrrolidones (NMP) adds in polymerization bottle, stirs, after being completely dissolved, ice-water bath is cooled to less than 5 DEG C under room temperature, adds 325.2
Gram (1.01 moles) 3,3', 4,4'- tetracarboxylic acid benzophenone dianhydride (BTDA), stirring, after 5 DEG C of reactions 1 hour, obtain 2127.4
Gram homogeneous, transparent, thick BTDA type polyamic acid resin solution, is denoted as BTDA-PAA-1.CAP2000+ is flown using rich Le
Vertebral plate viscosimeter, surveys its viscosity, and performance data is as shown in table 1.
Embodiment 2
By double for 146.0 grams of (0.5 mole) 1,3- (4- amino-benzene oxygen) benzene (134BAPB), 19.8 grams of (0.1 moles) 4,
4'- MDA, 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, obtain 2727.1 grams of homogeneous, transparent, thick BTDA type polyamic acid resin solution, be denoted as BTDA-PAA-2.Adopt
Fly CAP2000+ vertebral plate viscosimeter 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) add in 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, obtain 3827.8 grams all
Phase, transparent, thick BTDA type polyamic acid resin solution, are denoted as BTDA-PAA-3.CAP2000+ vertebral plate is flown using rich Le
Viscosimeter, 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 1,3- pair of (2,4- diamino phenoxy) benzene
(13BDAPB), mix at room temperature, stirring reaction, after 1 hour, obtains 1010 grams of homogeneous phase solutions, is denoted as PAA-1.Using
Bo Le flies CAP2000+ vertebral plate viscosimeter, surveys its viscosity, performance data is as shown in table 1.
By 3000 grams of BTDA-PAA-2 type polyamic acid resin solution and 10 grams of 1,3- pair of (2,4- diamino phenoxy) benzene
(13BDAPB), mix at room temperature, stirring reaction, after 3 hours, obtains 3010 grams of homogeneous phase solutions, is denoted as PAA-2.Using
Bo Le flies CAP2000+ vertebral plate viscosimeter, surveys its viscosity, performance data is as shown in table 1.
By 2400 grams of BTDA-PAA-3 type polyamic acid resin solution and 3 grams of 1,3- pair of (2,4- diamino phenoxy) benzene
(13BDAPB), mix at room temperature, stirring reaction, after 6 hours, obtains 2403 grams of homogeneous phase solutions, is denoted as PAA-3.Using
Bo Le flies CAP2000+ vertebral plate viscosimeter, surveys its viscosity, performance data is as shown in table 1.
The viscosity data (mPa.s) of table 1 polyamic acid resin solution
Embodiment 5
By the homogeneous phase solution of above-described embodiment 1- embodiment 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：Rise to 150 DEG C 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 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 13BDAPB 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 BTDA type 13BDAPB branched polyimide film PI-2；Homogeneous by PAA-3
Solution film forming obtains tough and tensile transparent BTDA type 13BDAPB branched polyimide film PI-3.Performance data is as shown in table 2.From
Can be seen that in table 2：The branching type Kapton prepared in embodiment has significantly comprehensive with respect to non-branching type film
Close performance advantage.
The performance data of table 2 Kapton
Claims (8)
1. a kind of BTDA type 13BDAPB branched polyimide resin film it is characterised in that in the raw material of described film 1,3- double
The mass ratio of (2,4- diamino phenoxy) benzene 13BDAPB and BTDA Linear polyamic acid resin is 1:100-800.
2. a kind of BTDA type 13BDAPB branched polyimide resin film according to claim 1 is it is characterised in that institute
State BTDA Linear polyamic acid resin be by mol ratio be 1:The aromatic dicarboxylic primary amine of 1.01-1.08 and 3,3 ', 4,4 '-four
Formic acid benzophenone dianhydride reacts in highly polar aprotic organic solvent and obtains.
3. a kind of BTDA type 13BDAPB branched polyimide resin film according to claim 2 is it is characterised in that institute
Stating aromatic dicarboxylic primary amine is 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) benzonitrile 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-butylbenzene of 2,5-, 2,5- double (3- amino-benzene oxygen) 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) 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-236fa 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- trifluoro 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-aminophenoxyl) -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 sulfide 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 BTDA type 13BDAPB branched polyimide resin film according to claim 2 is it is characterised in that institute
The mass ratio stating highly polar aprotic organic solvent with total reactant is 3-6：1；Wherein, the quality of total reactant refers to aromatic series
Binary primary amine and 3,3 ', the quality sum of 4,4 '-tetracarboxylic acid benzophenone dianhydride.
5. a kind of BTDA type 13BDAPB branched polyimide resin film according to claim 4 is it is characterised in that institute
State highly polar aprotic organic solvent be 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 BTDA type 13BDAPB branched polyimide resin film as claimed in claim 1, including：
(1) aromatic dicarboxylic primary amine is mixed with highly polar aprotic organic solvent, stir under room temperature, be cooled to less than 5 DEG C, plus
Enter 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride BTDA, stirring, 5 DEG C -10 DEG C reaction 1～6h, obtain BTDA type polyamic acid
Resin solution；
(2) BTDA type polyamic acid resin solution and double (2,4- diamino phenoxy) benzene of 1,3- are mixed in proportion at room temperature
Close, stirring, film forming in casting machine, heat temperature raising, carry out dehydration fever imidization, cooling, demoulding, obtain BTDA type
13BDAPB branched polyimide resin film.
7. the preparation method of a kind of BTDA type 13BDAPB branched polyimide resin film according to claim 6, it is special
Levy and be, in described step (2), the time of stirring is 1～6h.
8. the preparation method of a kind of BTDA type 13BDAPB branched polyimide resin film according to claim 6, it is special
Levy and be, in described step (2), the condition of dehydration hot imidization is：Rise to 150 DEG C from room temperature, be incubated 10 minutes, continue to heat up
To 250 DEG C, it is incubated 10 minutes, is continuously heating to 350 DEG C, be incubated 10 minutes.
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Citations (3)
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|---|---|---|---|---|
| US6500904B1 (en) * | 2001-11-02 | 2002-12-31 | General Electric Company | High molecular weight poly(imide)s and methods of synthesis thereof |
| CN101245024A (en) * | 2008-03-21 | 2008-08-20 | 东华大学 | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene |
| CN106008185A (en) * | 2016-06-03 | 2016-10-12 | 吉林大学 | Tetramine monomer and preparation method and application thereof |
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2016
- 2016-11-04 CN CN201610964348.1A patent/CN106398210A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500904B1 (en) * | 2001-11-02 | 2002-12-31 | General Electric Company | High molecular weight poly(imide)s and methods of synthesis thereof |
| CN101245024A (en) * | 2008-03-21 | 2008-08-20 | 东华大学 | Process for producing 1,3-bis(2,4-diaminophenyloxy)benzene |
| CN106008185A (en) * | 2016-06-03 | 2016-10-12 | 吉林大学 | Tetramine monomer and preparation method and application thereof |
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| Title |
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| 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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