CN106633870A - BPDA type 13BDAPB branched polyimide resin film and preparation method thereof - Google Patents
BPDA type 13BDAPB branched polyimide resin film and preparation method thereof Download PDFInfo
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- CN106633870A CN106633870A CN201610962678.7A CN201610962678A CN106633870A CN 106633870 A CN106633870 A CN 106633870A CN 201610962678 A CN201610962678 A CN 201610962678A CN 106633870 A CN106633870 A CN 106633870A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention relates to a BPDA type 13BDAPB branched polyimide resin film and a preparation method thereof. The mass ratio of 13BDAPB to BPDA type linear polyamic acid resin in the raw material of the film is 1:(100-800). The preparation method comprises the steps as follows: aromatic diprimary amine and a strongly polar aprotic organic solvent are mixed, stirred at the room temperature and cooled to 5 DEG C or lower, BPDA is added and stirred, the mixture reacts for 1-6 h at 5-10 DEG C, and a BPDA type polyamic acid resin solution is obtained; the resin solution and 13BDAPB are mixed at the room temperature, stirred, subjected to film forming, heated, dehydrated, subjected to thermal imidization, cooled and demolded, and the BPDA type 13BDAPB branched polyimide resin film is prepared. The method has the advantages of being mild in reaction condition, simple to operate, low in cost, environment-friendly and good for industrial scale production, and can be applied to high-tech fields such as flexible solar cells, space telescopes, main insulation of large motors, electrical insulation materials for electromagnetic wire wrapping, flexible copper foil and the like.
Description
Technical field
The invention belongs to Kapton and its preparation field, the branched polyamides of more particularly to a kind of BPDA types 13BDAPB
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 films and domestic H of traditional Kapton, such as U.S. DUPONT companies production is thin
Film, their molecular structure is 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 exploration in the space telescope (NGST) of future generation of transmitting in 2009
The origin in universe, wherein multilayer insulation sunshading board material (MLI) are to realize one of the 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 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 HMW is obtained is sub-
Polyimide resin, therefore, the combination property for causing its film product is greatly reduced, 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 obtained with pyromellitic acid anhydride or 3,3'- bis- (trifluoromethyl) -4,4'- benzidines exploitation
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 being used to prepare Kapton：
(1) [synthesis of new type polyimide special type monomer and its sign, insulating materials 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, insulating materials, 2001,34 (6):3-6] 2 are disclosed,
The preparation method of double [4- (3- amino-benzene oxygens) phenyl] propane of 2-；(4) [synthesis of bisphenol A-type polyimide monomer and application,
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 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] system of double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2- is disclosed
Preparation Method；(6) [synthesis and the 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 it 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) the viscous of the polyamic acid resin solution is adjusted
Degree, the film forming in casting machine, hot imidization obtains 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 acid amides acid solution, then, the casting film-forming in casting machine, hot imidization, demoulding, winding obtains 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 to react at room temperature after 1-3 hours, 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 is taken off
Hydro-thermal imidization, cooling, demoulding obtains the alicyclic-containing polyimide film of homogeneous phase transparent.
Chinese invention patent CN101597428A discloses full aromatic fluorine containing transparent polyimide film, and it prepares bag
Include：Fluorinated aromatic binary primary amine and highly polar aprotic organic solvent are added in polymerization bottle, is stirred under room temperature, be completely dissolved
Afterwards, ice-water bath is cooled to less than 5 DEG C, adds aromatic dicarboxylic anhydride, stirring 3 to be reacted within the temperature range of 5 DEG C -10 DEG C little
Shi Hou, obtains homogeneous, transparent, thick fluorinated aromatic polyamic acid resin solution；Wherein, aromatic dicarboxylic anhydride rubs
Your number is equal to the molal quantity of fluorinated aromatic binary primary amine；Above-mentioned fluorine-containing aromatic adoption is adjusted with highly polar aprotic organic solvent
The viscosity of amic acid resin solution, the film forming in casting machine, heat temperature raising carries 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 the aromatic series quaternary amine and aromatic binary carboxylic acid of specific molecular structure, in polyphosphoric acids/five two are aoxidized
In the presence of phosphorus system, in nitrogen atmosphere, solution polycondensation reaction is carried out in -200 DEG C of temperature ranges of room temperature, kermesinus is obtained
Rubber elastomer shaped polymer.During cooling is fallen back, in resin pulper, powder, alkali cleaning to neutrality, after drying are blended into
Suitable solvent is selected to be dissolved, casting film-forming, heat temperature raising, desolvation obtains 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 the primary aromatic amine and aromatic anhydride of specific molecular structure, highly polar non-proton organic molten
In agent system, polymerisation is carried out in 0 DEG C of -35 DEG C of temperature range, water white homogeneous thick polyamic acid is obtained molten
Liquid.Viscosity, casting film-forming, heat temperature raising, desolvation are adjusted, while there is part imidization, demoulding stretching, further
Depth hot imidization, winding obtains 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 BPDA types
13BDAPB branched polyimide resin films and preparation method thereof, there is not yet disclosed document or patent report.
The content of the invention
The technical problem to be solved be to provide a kind of BPDA types 13BDAPB branched polyimide resin film and
Its preparation method, the 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 is not related to also not produce corrosive substance, organic solvent using species is few and easy recovery, can iterative cycles again
With environmentally friendly；And the Kapton has excellent dimensional stability, mechanical property and heat resistance, while also having
Standby very excellent electric property and optical property.
A kind of BPDA types 13BDAPB branched polyimide resin film of the present invention, 1,3- is double in the raw material of the film
The mass ratio of (2,4- diamino phenoxies) benzene 13BDAPB and BPDA Linear polyamic acid resin 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-phenylene diamine (MPD), trimethyl m-phenylene diamine (MPD), biphenyl two
Amine, 2,2'- dimethyl diphenyl diamines, 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-236fas 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', 5,5'- tetramethyl biphenyls, 4,4'- of 4,4'-
Double [4- (4- amino-benzene oxygens) phenyl] propane of double (3- amino-benzene oxygens) -3,3', 5,5'- tetramethyl biphenyls, 2,2-, 2,2- are double
In [4- (4- amino-benzene oxygens) phenyl] HFC-236fa, 3,5- double (4- amino-benzene oxygens) benzoic acid, 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 pyrrolidones, N- ethyl-2-pyrrolidones, dimethyl sulfoxide (DMSO).
A kind of preparation method of the BPDA types 13BDAPB branched polyimide resin film of the present invention, including：
(1) aromatic dicarboxylic primary amine is mixed in polymerization bottle with highly polar aprotic organic solvent, is stirred under room temperature, it is complete
After CL, ice-water bath is cooled to less than 5 DEG C, adds 3,3', 4,4'- 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 (2,4- diamino phenoxies) benzene of 1,3- in proportion at room temperature
Mixing, stirring, obtains homogeneous phase solution, and the film forming in casting machine, heat temperature raising carries out dehydration fever imidization, cooling, takes off
Film, obtains BPDA type 13BDAPB branched polyimide resin films.
The time of stirring is 1～6h in the step (2).
The condition of dehydration hot imidization is in the step (2)：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, are continuously heating to 350 DEG C, 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 is 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, and existing production can be utilized 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 is 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
Can and heat resistance, while also possessing very excellent electric property and optical property；
(5) branching type Kapton of the invention (the addition reaction of 13BDAPB tetramines) is thin relative 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 the content for having read instruction of the present invention, 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 180.0 grams of (0.9 mole) 4,4 '-diaminodiphenyl ethers (DADPE), 10.8 (0.1 mole) p-phenylenediamine
(PPDA) add in polymerization bottle with 1470 grams of DMAs (DMAc), 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, be denoted as BPDA-PAA-
1.CAP2000+ vertebral plate viscosimeters are flown using rich Le, its 50 DEG C viscosity is surveyed for 630mPa.s..
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, 308.9 grams of addition (1.05 moles) 3,3 ', 4,4 '-
Biphenyl tetracarboxylic dianhydride (BPDA), stirring after 8 DEG C are reacted 4 hours, obtains 3502.5 grams of homogeneous, transparent, thick BPDA types
Polyamic acid resin solution, is denoted as BPDA-PAA-2.CAP2000+ vertebral plate viscosimeters are flown using rich Le, surveying its 50 DEG C viscosity is
572mPa.s。
Embodiment 3
By double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas (BAPFP) of 51.8 grams of (0.1 mole) 2,2-, 180.0
(0.9 mole) 4,4 '-diaminodiphenyl ether (DADPE) and 3290 grams of METHYLPYRROLIDONEs (NMP) are added in polymerization bottle,
Stir under room temperature, after being completely dissolved, ice-water bath is cooled to less than 5 DEG C, adds 317.7 grams of (1.08 moles) 3,3 ', 4,4 '-biphenyl
Tetracarboxylic dianhydride (BPDA), stirring after 10 DEG C are reacted 6 hours, obtains 3839.5 grams of homogeneous, transparent, thick BPDA types and gathers
Amic acid resin solution, is denoted as BPDA-PAA-3.CAP2000+ vertebral plate viscosimeters are flown using rich Le, surveying its 50 DEG C viscosity is
425mPa.s。
Embodiment 4
By 1000 grams of BPDA-PAA-1 type polyamic acid resin solution and 10 grams of 1,3- pair of (2,4- diamino phenoxies) benzene
(13BDAPB), it is well mixed at room temperature, stirring reaction obtains 1010 grams of homogeneous phase solutions after 1 hour, is denoted as PAA-1.Using
Bo Le flies CAP2000+ vertebral plate viscosimeters, surveys its 50 DEG C viscosity for 1300mPa.s.
By 3000 grams of BPDA-PAA-2 type polyamic acid resin solution and 10 grams of 1,3- pair of (2,4- diamino phenoxies) benzene
(13BDAPB), it is well mixed at room temperature, stirring reaction obtains 3010 grams of homogeneous phase solutions after 3 hours, is denoted as PAA-2.Using
Bo Le flies CAP2000+ vertebral plate viscosimeters, surveys its 50 DEG C viscosity for 1124mPa.s.
By 2400 grams of BPDA-PAA-3 type polyamic acid resin solution and 3 grams of 1,3- pair of (2,4- diamino phenoxies) benzene
(13BDAPB), it is well mixed at room temperature, stirring reaction obtains 2403 grams of homogeneous phase solutions after 6 hours, is denoted as PAA-3.Using
Bo Le flies CAP2000+ vertebral plate viscosimeters, surveys its 50 DEG C viscosity for 1002mPa.s.
Embodiment 5
By the homogeneous phase solution of above-described embodiment 1- embodiments 4 in casting machine film forming, heat temperature raising, carry out dehydration fever imines
Change reaction, cooling, demoulding.Wherein, the concrete technology of dehydration fever imidization is：150 DEG C are risen to from room temperature, 10 points are incubated
Clock, is continuously heating to 250 DEG C, is incubated 10 minutes, is continuously heating to 350 DEG C, is incubated 10 minutes.
Tough and tensile transparent Kapton 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 1.
Tough and tensile transparent BPDA type 13BDAPB branched polyimide film PI-1 are obtained by PAA-1 homogeneous phase solution film forming；By
PAA-2 homogeneous phase solution film forming obtains tough and tensile transparent BPDA type 13BDAPB branched polyimide film PI-2；It is homogeneous by PAA-3
Solution film forming obtains tough and tensile transparent BPDA type 13BDAPB 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 significant comprehensive relative to non-branching type film
Close performance advantage.
The performance data of the Kapton of table 1
Claims (8)
1. a kind of BPDA types 13BDAPB branched polyimide resin film, it is characterised in that 1,3- is double in the raw material of the film
The mass ratio of (2,4- diamino phenoxies) benzene 13BDAPB and BPDA Linear polyamic acid resin is 1:100-800.
2. a kind of BPDA types 13BDAPB branched polyimide resin film according to claim 1, it is characterised in that institute
State BPDA Linear polyamic acid resins be by mol ratio be 1:The aromatic dicarboxylic primary amine of 1.01-1.08 and 3,3', 4,4'- join
Benzene tertacarbonic acid's dianhydride reacts in highly polar aprotic organic solvent and obtains.
3. a kind of BPDA types 13BDAPB 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- aminophenyls) -5- aminobenzimidazoles, 4,4'- bis-
Amino-diphenylethers, 3,4'- diaminodiphenyl ethers, 3,3'- diaminodiphenyl ethers, 4,4'- MDAs, 4,4'- diaminos
Base diphenyl sulphone (DPS), 3,3'- dimethyl -4,4'- MDAs, 3,3'- diethyl base -4,4'- MDAs, 3,
Double (3- amino-benzene oxygens) benzene of 3', 5,5'- tetramethyl -4,4'- MDAs, 3,3'- DADPSs, 1,4-,
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-, 1,2- are double
Double (4- amino-benzene oxygens) benzene of (3- amino-benzene oxygens) benzene, 1,2-, double (4- amino-benzene oxygens) benzonitriles of 2,6-, the double (3- of 2,6-
Amino-benzene oxygen) benzonitrile, double (4- amino-benzene oxygens) toluene of 2,6-, double (3- amino-benzene oxygens) toluene of 2,6-, the double (4- of 2,6-
Amino-benzene oxygen) benzotrifluoride, double (3- amino-benzene oxygens) benzotrifluorides of 2,6-, double (4- amino-benzene oxygens) toluene of 2,5-, 2,
Double (3- amino-benzene oxygens) toluene of 5-, double (4- amino-benzene oxygens) tert-butylbenzenes of 2,5-, 2,5- double (3- amino-benzene oxygens) spy fourth
Double (3- amino-benzene oxygens) benzene of double (4- amino-benzene oxygens) benzene of base benzene, 2,5- di-t-butyls -1,4-, 2,5- di-t-butyls -1,4-,
Double (4- amino-benzene oxygens) benzophenone of 4,4'-, double (4- amino-benzene oxygens) diphenyl sulphone (DPS)s of 4,4'-, double (the 3- aminobenzene oxygen of 4,4'-
Base) benzophenone, double (3- amino-benzene oxygens) diphenyl sulphone (DPS)s of 4,4'-, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,4-, 1,
Double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane of double (2- trifluoromethyl-4-aminophenoxyls) benzene of 3-, 2,2-,
Double (3- amino-4-hydroxylphenyls) HFC-236fas of 2,2-, double (3- amino-4-hydroxylphenyls) 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-aminophenoxyls) toluene of 2,5-, the double (2- trifluoromethyl -4- amino of 2,5-
Phenoxy group) tert-butyl benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 2,5- di-t-butyls -1,4-, double (the 2- trifluoros of 4,4'-
Methyl -4- amino-benzene oxygens) diphenyl sulphone (DPS), double (2- the trifluoromethyl-4-aminophenoxyls) -3,3' of 4,4'-, 5,5'- tetramethyls two
Double (2- trifluoromethyl-4-aminophenoxyls) biphenyl of benzene 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, in 3,5- double (4- amino-benzene oxygens) benzoic acid, 3,5- diaminobenzoic acids extremely
Few one kind.
4. a kind of BPDA types 13BDAPB branched polyimide resin film according to claim 2, it is characterised in that institute
It is 3-6 that highly polar aprotic organic solvent is stated with the mass ratio of total reactant：1；Wherein, the quality of total reactant refers to aromatic series
The quality sum of binary primary amine and 3,3', 4,4'- biphenyl tetracarboxylic dianhydride.
5. a kind of BPDA types 13BDAPB 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-pyrrolidones, dimethyl sulfoxide (DMSO).
6. a kind of preparation method of BPDA types 13BDAPB branched polyimide resin film as claimed in claim 1, including：
(1) aromatic dicarboxylic primary amine is mixed with highly polar aprotic organic solvent, is stirred 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) BPDA type polyamic acid resin solution and double (2,4- diamino phenoxies) benzene of 1,3- are mixed at room temperature in proportion
Close, stirring, the film forming in casting machine, heat temperature raising carries out dehydration fever imidization, cool down, demoulding obtains BPDA types
13BDAPB branched polyimide resin films.
7. the preparation method of a kind of BPDA types 13BDAPB branched polyimide resin film according to claim 6, it is special
Levy and be, the time of stirring is 1～6h in the step (2).
8. the preparation method of a kind of BPDA types 13BDAPB branched polyimide resin film according to claim 6, it is special
Levy and be, the condition of dehydration hot imidization is in the step (2)：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, are 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 CN201610962678.7A patent/CN106633870A/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 |
Non-Patent Citations (1)
| 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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