CN105112002B - High-temperature-resistant BAHPFP (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) adhesive and preparation method thereof - Google Patents

Abstract

The invention relates to a high-temperature-resistant BAHPFP (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) adhesive and a preparation method thereof. The adhesive is composed of a BAHPFP phenolic hydroxyl polyamide resin, a polyphenyl ether resin, a polyfunctional epoxy resin, isocyanate, a nitrogenous organic compound, an organic metal compound and an organic solvent. The preparation method comprises the following steps: (1) preparing the BAHPFP phenolic hydroxyl polyamide resin; (2) preparing a mixed resin component A; (3) preparing a mixed resin component B; and (4) uniformly mixing the component A and component B at room temperature, adding the organic metal compound and nitrogenous organic compound, and uniformly mixing. The preparation method is convenient to operate and low in production cost. The obtained product has favorable adhesive property in the hot state, has the characteristics of low dielectric loss and excellent high temperature resistance, can be used for bonding metals, glass, ceramics, resin-base composite materials and other substrates, and has favorable market application prospects.

Description

A kind of high temperature resistant BAHPFP type adhesive and preparation method thereof

Technical field

The invention belongs to polymeric material field, more particularly to a kind of high temperature resistant BAHPFP type adhesive and its preparation side Method.

Background technology

Epoxy resin has excellent caking property, moulding processability, electrical insulation properties and excellent mechanical property Deng in being widely used in the fields such as Aero-Space, electronic apparatus, automobile, naval vessel.But epoxy resin there is also some and lack Point, such as thermostability is low, much not as good as aromatic heterocyclic polymer systems such as polyimides, polybenzimidazoles, polybenzoxazoles, Epoxy-resin systems mechanical property, electric property in high temperature environments etc. declines notable, it is difficult to meet practical application request.Cause This, the resistant, toughened focus for being modified, being current scientific and technical personnel both at home and abroad research is carried out to epoxy resin.

It is well known that epoxy resin has many excellent performances：(1) good adhesive property：Adhesive strength is high, bonding Wide, it is with many metals (such as ferrum, steel, copper, aluminum, metal alloy) or nonmetallic materials (such as glass, ceramics, timber, plastics Deng) adhesive strength it is very high, have even more than by the viscous material intensity of itself, therefore can be used for many stress members In, it is one of main component of structural adhesive；(2) good processing characteristics：The motility of Formulaion of epoxy resin, processing work The multiformity of skill and product propertiess is the most prominent in macromolecular material；(3) good stability：The solidification of epoxy resin Mainly by the ring opening polyaddition of epoxy radicals, therefore low-molecular material is not produced in solidification process, its cure shrinkage is heat One of minimum kind, generally 1%-2% in thermosetting resin, if selecting appropriate filler that shrinkage factor can be made to be down to 0.2% Left and right；Epoxy main chains after solidification are ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore with excellent resistance to acids and bases.

Therefore, epoxy resin is widely used in the every field of national economy：Either high-technology field is still Field of general technology, either can see its trace in defence and military or civilian industry, or even daily life.

Chinese invention patent CN103146330A discloses a kind of double [4- (2,4- diamino phenoxies) phenyl] six of 2,2- Fluoro-propane type high temperature resistant epoxy adhesive and preparation method thereof, is 1 by mass ratio:The component A of 1-2 and B component are constituted, wherein, A Component is the copolymer reacted with epoxy resin by double [4- (2,4- diamino phenoxies) phenyl] HFC-236fa of 2,2-；B Component is in highly polar non-matter by double [4- (2,4- diamino phenoxies) phenyl] HFC-236fa of 2,2- with aromatic dicarboxylic anhydride The solid content reacted in sub- organic solvent and toluene is the homogeneous phase transparent solution of 15%-30%.Preparation method includes：Room temperature Under, by A, B component in mass ratio 1:1-2 is uniformly mixed.

It is resistance to that Chinese invention patent CN103131369A discloses a kind of double (2,4- diamino phenoxies) the diphenyl sulphone (DPS) types of 4,4'- High-temp epoxy adhesive and preparation method thereof, is 1 by mass ratio:The component A of 1-2 and B component are constituted, wherein component A be by 4, The copolymer that 4 '-bis- (2,4- diamino phenoxies) diphenyl sulphone (DPS)s react with epoxy resin；B component is by 4,4 '-bis- (2,4- Diamino phenoxy) diphenyl sulphone (DPS) and consolidating that aromatic dicarboxylic anhydride reacts in highly polar aprotic organic solvent and toluene Content is the homogeneous phase transparent solution of 15%-30%.Preparation method includes：Under room temperature, by A, B component in mass ratio 1:1-2 is stirred Mix homogeneously.

Chinese invention patent CN103146331A discloses a kind of double (2,4- diamino phenoxies) the resistance to height of biphenyl type of 4,4'- Temperature epoxy adhesive and preparation method thereof, is 1 by mass ratio:The component A of 1-2 and B component are constituted, wherein component A be by 4,4 '- The copolymer that double (2,4- diamino phenoxies) biphenyl react with epoxy resin；B component is by 4,4 '-bis- (2,4- diaminos Phenoxyl) solid content that reacts in highly polar aprotic organic solvent and toluene with aromatic dicarboxylic anhydride of biphenyl is The homogeneous phase transparent solution of 15%-30%.Preparation method includes：Under room temperature, by A, B component in mass ratio 1:1-2 stirring mixing is equal It is even.

Chinese invention patent CN103030787A discloses a kind of benzimidazole-epoxy matrix resin and preparation method thereof, Resin is made up of the component of A, B two.Preparation method, comprises the steps：(1) by N, N, N ', N '-four glycidyl group -2,2- is double [4- (4- amino-benzene oxygens) phenyl] propane is put in reactor with 2- (4- aminophenyls) -5- aminobenzimidazoles, and heating rises Temperature adds reactive diluent and organic solvent to 70-80 DEG C of stirring reaction 15min-30min, stirs, and obtains component A； (2) firming agent and organic solvent are mixed, stirring and dissolving is uniform, that is, obtain B component；(3) when using, A, B component are mixed, is stirred Mix uniform.

Chinese invention patent CN103013414A discloses a kind of alpha-cyano-β-ethoxy ethyl acrylate modified epoxy tree Fat adhesive and preparation method thereof, adhesive is consisted of：Mass ratio is 100:100～50:60～30:5～20:30～80 Epoxy resin, epoxy ester resin, endurable active toughener, alpha-cyano-β-ethoxy ethyl acrylate and firming agent.Preparation method, bag Include following steps：Epoxy resin is mixed with endurable active toughener, after 60 DEG C of -80 DEG C of reaction 15-20min, epoxy-ester tree is added Fat and alpha-cyano-β-ethoxy ethyl acrylate, are uniformly mixed, and obtain component A；Firming agent is B component；When using, will A, B component mix homogeneously, obtain final product.

Polyimide resin is a family macromolecule material with extremely excellent heat resistance.Conventional polyimide structures, Its heat decomposition temperature is generally individually more than 500 DEG C, while also having obdurability.Therefore, thermosetting resin, such as ring are also frequently utilized for The heat-resisting plasticized modifier of oxygen tree fat, bimaleimide resin etc..But, the compatibility of polyimides system and epoxy resin It is poor, it is difficult to be obtained and have polyimide high temperature-resistant concurrently and have the excellent caking property of epoxy resin and technological binding agent body again System.So, carry out modified epoxy resin system using conventional polyimide resin, to obtain the binding agent of excellent combination property, It is relatively difficult.

Chinese patent CN1927908A discloses a kind of preparation method of phenolic hydroxyl group containing polyimide powder, due to phenolic hydroxyl group Presence, its polyimide powder can with epoxy reaction, formed covalent bond, such that it is able to improve thermoplastic polyimide resin With the compatibility of epoxy resin, and epoxy-resin systems can be further made to reach good toughening effect.

Chinese invention patent CN101962436A discloses a kind of heat resist modification multi-functional epoxy used for advanced composite material Matrix resin and preparation method thereof, is primarily characterized in that：Using double (the 2,4- dimaleimide phenoxyls) benzene of 1,4- Four maleimide resins obtain the novel fire resistant of high tenacity with polyfunctional epoxy resin, nbr carboxyl terminal CTBN reactions Resin, adds organic solvent, and stirring and dissolving is uniform, obtains the viscous liquid of homogeneous phase transparent, i.e. component A；Firming agent with it is organic Solvent mixes, and stirring and dissolving is uniform, obtains final product B component；A, B component are mixed, is stirred, obtained final product used for advanced composite material Heat resist modification multi-functional epoxy's substrate resin solution.

Yu Xinhai et al.【The development [J] of high-temperature resistant single-component epoxy adhesive. bonding, 2008,29 (12)：16-19】It is public A kind of preparation method of high-temperature resistant single-component epoxy adhesive is opened, has been primarily characterized in that：With maleic anhydride (MA) as end-blocking Agent, with double (3- amino-4-hydroxylphenyls) HFC-236fa (BAHPFP) of 2,2-, double [4- (4- amino-benzene oxygens) phenyl] third of 2,2- Material synthesis are obtained based on double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides (BPADA) of alkane (BAPOPP), 2,2- Phenolic hydroxy group polyetherimide resin (HPEI)；With the synthesized HPEI for obtaining as resistant, toughened dose, with N, N, N', N'- tetra- Glycidyl -4,4'- MDAs (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent Deng preparation has obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.

The method, although by polyetherimide resin of the synthesis containing active reactive group (hydroxyl, unsaturated double-bond) (HPEI) toughening modifying, has been carried out to epoxy resin, and has achieved preferable technique effect.But, there is also some shortcomings：

(1) reactable group is limited, and the content of particularly unsaturated double-bond is low.Because maleic anhydride is as end-blocking Agent is come what is used, and the consumption of maleic anhydride is little.

The monomers such as (2) 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa (BAHPFP) are expensive, cause polyethers acyl The cost of imide resin (HPEI) and adhesive is very high, is unfavorable for large-scale promotion application, can only be confined to some special dimensions.

Chinese invention patent CN103483552A discloses a kind of carbon fibre composite matrix resin and its preparation side Method, the carbon fibre composite matrix resin is by N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether (TGDADPE) double [4- (2- trifluoromethyl-4-maleimide phenoxyls) benzene of epoxy resin, ES216 epoxy resin, 2,2- Base] propane, 3,3 '-dimethyl -4,4 '-bis- (4- carboxyl phthalimide groups) diphenyl-methanes, firming agent and organic solvent composition；Its Preparation method, comprises the steps：(1) by N, N, N ', N '-four glycidyl group -4,4 ' diaminodiphenyl ether (TGDADPE) rings Oxygen tree fat and 3,3 '-dimethyl -4,4 '-bis- (4- carboxyl phthalimide groups) diphenyl-methanes are put in reactor, in 80 DEG C -100 Stirring reaction is after -1 hour 0.5 hour in DEG C temperature range, add ES216 epoxy resin and 2,2- it is double [4- (2- trifluoromethyls - 4- maleimide phenoxyls) phenyl] propane, continue stirring reaction -1 hour 0.5 hour, organic solvent is added, stirring is equal It is even, obtain component A；(2) firming agent and organic solvent are mixed, stirring and dissolving obtains B component in homogeneous；(3) when using, by A groups Part, B component mix homogeneously.

Chinese invention patent CN103408727A disclose a kind of TGBAPOPP mold bases resin used for advanced composite material and Its preparation method, the matrix resin is by N, N, N ', double [4- (4- amino-benzene oxygens) phenyl] third of N '-four glycidyl group -2,2- Alkane (TGBAPOPP), o-cresol formaldehyde epoxy resin, N- isopropyl-N '-diphenyl-para-phenylene diamine, 2,2,4- trimethyl -1,2- diaminos Double [4- (4- maleimide phenoxyls) phenyl] propane of base quinoline, 2,2-, firming agent and organic solvent composition；Preparation method Comprise the steps：By N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane, orthoresols Double [4- (4- maleimide phenoxyls) phenyl] propane of formaldehyde epoxy resin, 2,2- are put in reactor, in 90 DEG C -100 DEG C Within the temperature range of react certain hour after, under room temperature add N- isopropyl-N '-diphenyl-para-phenylene diamine solution, 2,2,4- front threes Base -1,2- dihyaroquinoline solution, is uniformly mixed, and adds curing agent solution, is uniformly mixed.

Chinese invention patent CN103483553A discloses a kind of TGDADPE types epoxy matrix resin used for advanced composite material And preparation method thereof, the matrix resin is 100 by mass ratio:5-10:10-20:1-5:The N of 80-200, N, N ', N '-four shrinks Glyceryl -4,4 '-diaminodiphenyl ether epoxy resin (TGDADPE), aromatic diamine, aromatic dicarboxylic anhydride, firming agent With organic solvent composition；Its preparation method comprises the steps：By N, N, N ', N '-four glycidyl group -4,4 '-diaminourea two Phenylate epoxy resin (TGDADPE) and aromatic diamine are put in reactor, are reacted within the temperature range of 50 DEG C -90 DEG C After 30min-40min, room temperature is cooled to, adds the homogeneous phase solution of aromatic dicarboxylic anhydride, firming agent and organic solvent, stirring is mixed Close uniform.

The content of the invention

The technical problem to be solved is to provide a kind of high temperature resistant BAHPFP type adhesive and preparation method thereof, should The preparation technology of adhesive is easy to operate, and raw material sources are convenient, low production cost, can complete to prepare on common apparatus, technique Property it is good, products obtained therefrom it is hot it is lower there is good combination property, with low dielectric loss and excellent high-temperature stability, can answer For insulating material, resistant mechanism material etc., with good market application foreground.

The present invention a kind of high temperature resistant BAHPFP type adhesive, the adhesive be by mass ratio be 100:20-100:10- 30:20-50:1-5:1-3:The BAHPFP type phenolic hydroxy group polyimide resins of 480-1000, polyphenylene oxide resin, multi-functional epoxy What resin, isocyanates, organic compounds containing nitrogen, organo-metallic compound and organic solvent were constituted；BAHPFP type hydroxyls containing phenol Base polyimide resin be by mol ratio be 2:1-3:The 2,2- of 4-6 double (3- amino-4-hydroxylphenyls) HFC-236fa, aromatic series Diamidogen and 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride reaction is formed.

Described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group p-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-diaminobenzene. epoxy resin, N, N, O- triglycidyl group para-aminophenol epoxy resin, N, N, O- triglycidyl meta-aminophenol epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-MDA ring Oxygen tree fat, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-diethyl -4,4 '-MDA epoxy resin, 3,3 '-two chloro- N, N, N ', N ' - Four glycidyl group -4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-diaminourea two Phenylate epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-DADPS epoxy resin, N, N, N ', N '-four contracts Water glyceryl -3,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-DADPS ring Oxygen tree fat, N, N, N ', N '-four glycidyl group -4,4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group P-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-diaminobenzene. epoxy resin, N, N, N ', the (+)-2,3-Epoxy-1-propanols of N '-four Base -1,4- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,4- is double (3- amino-benzene oxygens) Benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,3- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four Glycidyl -1,3- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the double (2- tri- of N '-four glycidyl group -1,4- Methyl fluoride -4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the double (2- trifluoromethyl -4- ammonia of N '-four glycidyl group -1,3- Phenoxyl) benzene epoxy resin, N, N, N ', the glycidyl -4,4 of N ', O- five '-diaminourea -4 "-hydroxyl tritan. epoxy Resin, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four shrinks Glyceryl -2,2- double [4- (3- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double [4- (3- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', the double [4- (2- tri- of N '-four glycidyl group -2,2- Methyl fluoride -4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- ammonia Phenoxyl) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen Base) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group - 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 ' - Double (4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl -4- Amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) hexichol Ketone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone Epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ', N ' - Four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resins, N, N, N ', N ', O, O '-six contracting One or more in double (3- amino-4-hydroxylphenyls) the HFC-236fa epoxy resin of water glyceryl -2,2-.

Described organic compounds containing nitrogen is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine, picoline, dimethyl pyrazole Pyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, N, accelerine, N, N- dimethyl open-chain crown ethers, DMP-30, benzyl One kind in base dimethylamine, 2,4,6- tri- (dimethylamino methyl) phenol, DBU, 1,8- diazabicyclo [5.4.0] hendecene -7 Or it is several.

The one kind of described organo-metallic compound in aluminium acetylacetonate, dibutyl tin laurate, lead benzoate Or it is several.

Described isocyanates are selected from hexamethylene diisocyanate, toluene di-isocyanate(TDI), diphenylmethane diisocyanates Ester, triphenylmethane triisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate trimer, toluene diisocyanate One or more in acid esters trimer, '-diphenylmethane diisocyanate trimer, isoflurane chalcone diisocyanate trimer.

Described aromatic diamine selected from p-phenylenediamine, m-diaminobenzene., o-phenylenediamine, 4,4 '-MDA, 3, 3 '-dimethyl -4,4 ' MDA, 4,4 '-diaminodiphenyl ether, 4,4 '-benzidine, 3,3 '-dimethyl -4, 4 ' benzidines, 2,2 '-dimethyl -4,4 ' benzidine, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, Double (3- amino-benzene oxygens) benzene of 4,4 '-DADPS, 3,3 '-DADPS, 1,3-, double (the 3- aminobenzene oxygen of 1,4- Base) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, the double (2- trifluoromethyl -4- amino of 1,3- Phenoxy group) benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,4-, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '- Double (3- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS)s, 4,4 '-bis- (4- amino Phenoxy group) diphenyl ether, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) two Phenylate, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (2- tri- Methyl fluoride -4- amino-benzene oxygens) diphenyl sulfide, 4,4 '-bis- (4- amino-benzene oxygens) benzophenone, 4,4 '-bis- (3- aminobenzene oxygen Base) benzophenone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone, 4,4 '-bis- (4- amino-benzene oxygens) connection Benzene, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl, 4,4 '-bis- (4- Amino-benzene oxygen) diphenyl-methane, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl -4- aminobenzenes Epoxide) diphenyl-methane, double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa of 2,2-, double [4- (3- amino-benzene oxygens) benzene of 2,2- Base] HFC-236fa, double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fa of 2,2-, double [4- (the 4- amino of 2,2- Phenoxy group) phenyl] propane, double [4- (3- amino-benzene oxygens) phenyl] propane of 2,2-, the double [4- (2- trifluoromethyl -4- amino of 2,2- Phenoxy group) phenyl] propane, one or more in double (4- aminophenyls) HFC-236fa of 2,2-.

Described organic solvent selected from benzene,toluene,xylene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, Methyltetrahydrofuran, butyl acetate, ethyl acetate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2- pyrroles One or more in pyrrolidone, N- ethyl-2-pyrrolidones, dimethyl sulfoxide, glycol monoethyl ether, ethylene glycol monoethyl ether.

A kind of preparation method of high temperature resistant BAHPFP type adhesive of the present invention, comprises the steps：

(1) double (3- amino-4-hydroxylphenyls) HFC-236fa of 2,2- and highly polar aprotic organic solvent are put into into reaction In kettle, after stirring and dissolving, less than 5 DEG C are cooled to, add 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction 1 hour -2 Hour, aromatic diamine is added, continue stirring reaction -2 hours 1 hour, dehydrant and catalyst are added, it is heated to 80 DEG C of -100 DEG C dehydration imidizations -5 hours 2 hours, after being cooled to room temperature, add precipitating agent, stirring to separate out hard resin, mistake Filter, acetone drip washing 2-3 time is vacuum dried -4 hours 3 hours at 90 DEG C, and BAHPFP type phenolic hydroxy group polyimide resins are obtained；

(2) BAHPFP type phenolic hydroxy group polyimide resins and organic solvent are added in reactor, is heated to reflux, stirred After dissolving, less than 60 DEG C are cooled to, add isocyanates, be heated to backflow, stirring reaction -3 hours 1 hour is cooled to Less than 60 DEG C, polyfunctional epoxy resin is added, stirring reaction 0.5 hour, obtains component A at being heated to 80 DEG C -90 DEG C；

(3) polyphenylene oxide resin and organic solvent are added in reactor, is heated to reflux, after stirring and dissolving, be cooled to 60 DEG C Hereinafter, isocyanates are added, is heated to backflow, stirring reaction -3 hours 1 hour is cooled to less than 60 DEG C, adds many officials Energy epoxy resin, stirring reaction 0.5 hour, obtains B component at being heated to 80 DEG C -90 DEG C；

(4) under room temperature, by component A, B component mix homogeneously, organo-metallic compound and organic compounds containing nitrogen are added, is stirred Mix mix homogeneously.

Highly polar aprotic organic solvent in the step (1) is selected from N,N-dimethylformamide, N, N- dimethyl second One or more in amide, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, dimethyl sulfoxide；Wherein, it is highly polar Aprotic organic solvent is 4-6 with the mass ratio of reactant:1；The quality of reactant refers to double (the 3- amino-4-hydroxy benzene of 2,2- Base) HFC-236fa, aromatic diamine and 3,3 ', the quality sum of 4,4 '-tetracarboxylic diphenyl ether dianhydride.

One kind in acetic anhydride, propionic andydride, chloracetic acid acid anhydride, the trifluoroacetic anhydride (TFAA) of dehydrant in the step (1) or It is several；Wherein, dehydrant and the mass ratio of reactant are 3-6:1；The quality of reactant refers to double (the 3- amino-4-hydroxies of 2,2- Phenyl) HFC-236fa, aromatic diamine and 3,3 ', the quality sum of 4,4 '-tetracarboxylic diphenyl ether dianhydride.

Catalyst in the step (1) is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine, picoline, dimethyl pyrazole One or more in pyridine；Wherein, catalyst and the mass ratio of reactant are 0.01-0.1：1；The quality of reactant refers to 2,2- Double (3- amino-4-hydroxylphenyls) HFC-236fa, aromatic diamine and 3,3 ', the quality of 4,4 '-tetracarboxylic diphenyl ether dianhydride it With.

Precipitating agent in the step (1) is selected from methanol, ethanol, propanol, ethylene glycol, Propylene Glycol, tetrahydrofuran, methyl four One or more in hydrogen furan, glycol monoethyl ether, ethylene glycol monoethyl ether；Wherein, precipitating agent is non-proton organic with highly polar The mass ratio of solvent is 2-5:1.

Acetone in the step (1) is 1-2 with the mass ratio of highly polar aprotic organic solvent:1.

Beneficial effect

(1) present invention has good combination property, with low dielectric loss and excellent high-temperature stability；

(2) present invention can apply to insulating material, high temperature structural materials etc., apply front with good market Scape；

(3) preparation process is simple, low cost, easy to operate, reaction raw materials convenient sources of the invention, can set general Preparation process is completed in standby, industrialized production is advantageously implemented.

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 double (3- amino-4-hydroxylphenyls) HFC-236fa (BAHPFP) of 73.2 grams of (0.2 mole) 2,2- and 910 grams of N, N- Dimethyl acetylamide is put in reactor, after stirring and dissolving, is cooled to less than 5 DEG C, adds 124.0 grams of (0.4 moles) 3,3 ', 4, 4 '-tetracarboxylic diphenyl ether dianhydride (ODPA), stirring reaction 2 hours adds double (the 3- aminobenzene oxygen of 29.2 grams of (0.1 mole) 1,3- Base) benzene, continue stirring reaction 1 hour, 680 grams of acetic anhydrides and 2.3 grams of pyridines are added, it is heated to 100 DEG C of dehydration imidizations Reaction 2 hours, after being cooled to room temperature, adds 1820 grams of methanol, stirring to separate out hard resin, filters, 910 grams of acetone drip washing 2-3 It is secondary, it is vacuum dried 3 hours at 90 DEG C, 207.4 grams of BAHPFP type phenolic hydroxy group polyimide resin (theoretical yields 215.6 are obtained Gram), it is denoted as HFPI-1, yield 96.2%.

Embodiment 2

By 73.2 grams of (0.2 mole) 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa (BAHPFP), 2000 grams of N- first Base -2-Pyrrolidone and 200 grams of DMFs are put in reactor, after stirring and dissolving, are cooled to less than 5 DEG C, plus Enter 186.0 grams (0.6 mole) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride (ODPA), stirring reaction 1 hour adds 82.0 grams Double [4- (3- amino-benzene oxygens) phenyl] propane of (0.2 mole) 2,2- and 29.2 grams of (0.1 mole) 1,3- pair of (4- aminobenzene oxygen Base) benzene, continue stirring reaction 2 hours, 2000 grams of acetic anhydrides and 37.0 grams of lutidines are added, it is heated to 80 DEG C of dehydrations Imidization 5 hours, after being cooled to room temperature, adds 10000 grams of ethanol and 1000 grams of methanol, stirring to separate out hard resin, mistake Filter, 4400 grams of acetone drip washing 2-3 time is vacuum dried 4 hours at 90 DEG C, and 346.4 grams of BAHPFP type phenolic hydroxy groups polyamides Asias are obtained Polyimide resin (352.4 grams of theoretical yield), is denoted as HFPI-2, yield 98.3%.

Embodiment 3

The BAHPFP type phenolic hydroxy group polyimide resins and 200 grams of DMAC N,N' dimethyl acetamides of 50.0 grams of HFPI-1 are added In entering reactor, it is heated to reflux, after stirring and dissolving, is cooled to less than 60 DEG C, adds 4.0 grams of '-diphenylmethane diisocyanates (MDI) backflow, is heated to, stirring reaction 1 hour is cooled to less than 60 DEG C, adds 1.5 grams of N, N, O- triglycidyl group Para-aminophenol epoxy resin, stirring reaction 0.5 hour at being heated to 80 DEG C obtains 255.5 grams of component As.

10.0 grams of polyphenylene oxide resins and 40 grams of dimethylbenzene are added in reactor, is heated to reflux, after stirring and dissolving, be cooled to Less than 60 DEG C, 6.0 grams of toluene diisocyanate trimers are added, be heated to backflow, stirring reaction 1 hour is cooled to 60 Below DEG C, 3.5 grams of N, N, N are added ', N '-four glycidyl group -4,4 '-MDA epoxy resin is heated to 80 DEG C Lower stirring reaction 0.5 hour, obtains 59.5 grams of B components.

Under room temperature, by component A, B component mix homogeneously, 0.5 gram of aluminium acetylacetonate and 0.5 gram 2,4,6- tri- (diformazans are added Aminomethyl) phenol, it is uniformly mixed, 316.0 grams of high temperature resistant BAHPFP type adhesive are obtained, it is denoted as J-1.

Embodiment 4

By the BAHPFP type phenolic hydroxy group polyimide resins of 50.0 grams of HFPI-2,150 grams of METHYLPYRROLIDONEs and 100 grams of DMFs are added in reactor, are heated to reflux, and after stirring and dissolving, are cooled to less than 60 DEG C, add 12.0 Gram toluene diisocyanate trimer and 8.0 grams of '-diphenylmethane diisocyanates (MDI), are heated to backflow, stirring reaction 3 Hour, less than 60 DEG C are cooled to, add 10.0 grams of N, N, O- triglycidyl group para-aminophenol epoxy resin to be heated to 90 DEG C Lower stirring reaction 0.5 hour, obtains 330.0 grams of component As.

50.0 grams of polyphenylene oxide resins, 50 grams of tetrahydrofurans and 200 grams of dimethylbenzene are added in reactor, is heated to reflux, stirred After mixing dissolving, less than 60 DEG C are cooled to, add 5.0 grams of isoflurane chalcone diisocyanates (IPDI), be heated to backflow, stirred Reaction 3 hours, is cooled to less than 60 DEG C, adds 5.0 grams of N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-two Diaminodiphenylmethane epoxy resin, stirring reaction 0.5 hour at being heated to 80 DEG C obtains 310.0 grams of B components.

Under room temperature, by component A, B component mix homogeneously, 1.5 grams of dibutyl tin laurates and 2.5 grams of 1,8- phenodiazines are added Miscellaneous bicyclic [5.4.0] hendecene -7, are uniformly mixed, and obtain 644.0 grams of high temperature resistant BAHPFP type adhesive, are denoted as J-2.

Embodiment 5

By the BAHPFP type phenolic hydroxy group polyimide resins of 30.0 grams of HFPI-1 and 20.0HFPI-2,220 grams of N- methyl- 2-Pyrrolidone is added in reactor, is heated to reflux, and after stirring and dissolving, is cooled to less than 60 DEG C, adds 7.0 grams of isophorones two Isocyanates (IPDI) and 5.0 grams of '-diphenylmethane diisocyanates (MDI), are heated to backflow, and stirring reaction 2 hours is cold But to less than 60 DEG C, 6.0 grams of N, N, O- triglycidyl group para-aminophenol epoxy resin are added to stir at being heated to 85 DEG C anti- Answer 0.5 hour, obtain 288.0 grams of component As.

40.0 grams of polyphenylene oxide resins, 80 grams of METHYLPYRROLIDONEs and 100 grams of dimethylbenzene are added in reactor, plus Hot reflux, after stirring and dissolving, is cooled to less than 60 DEG C, adds 8.0 grams of toluene di-isocyanate(TDI)s, is heated to backflow, stirs Reaction 3 hours, is cooled to less than 60 DEG C, adds 4.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-MDA Epoxy resin, stirring reaction 0.5 hour at being heated to 90 DEG C obtains 232.0 grams of B components.

Under room temperature, by component A, B component mix homogeneously, 0.5 gram of aluminium acetylacetonate and 0.5 gram of di lauric dibutyl are added Stannum, 1.0 grams of N, N- dimethyl open-chain crown ether and 1.0 gram 2,4,6- tri- (dimethylamino methyl) phenol are uniformly mixed, and obtain To 523.0 grams of high temperature resistant BAHPFP type adhesive, J-3 is denoted as.

Embodiment 6

The high temperature resistant BAHPFP type adhesive of appropriate 3～embodiment of embodiment 5, i.e. J-1～J-3 are taken respectively, and difference is equal It is coated on evenly in standard rustless steel test piece, after room temperature hangs 0.5 hour, overlapping is clamped, and being put in convection oven is carried out admittedly Change：Start to warm up to 100 DEG C from room temperature, insulation reaction 2 hours is continuously heating to 150 DEG C, and insulation reaction 2 hours continues to heat up To 200 DEG C, insulation reaction 2 hours naturally cools to room temperature.Room temperature (25 DEG C) and high temperature are carried out to it using electronic tensile machine Tensile shear strength (σ) test under (240 DEG C) state, as a result as shown in table 1.

The high temperature resistant BAHPFP type adhesive of appropriate 3～embodiment of embodiment 5, i.e. J-1～J-3, in polytetrafluoro are taken respectively Film is pushed away on vinyl film, in being placed in vacuum drying oven, the square coupons that size is 5mm × 5mm × 1mm is made into, solidifies work Skill is：Start to warm up to 100 DEG C from room temperature, insulation reaction 2 hours is continuously heating to 150 DEG C, and insulation reaction 2 hours continues to rise To 200 DEG C, insulation reaction 2 hours naturally cools to room temperature to temperature.

Its specific insulation ρ v (1MHz, 25 DEG C) are tested using the megger of Guilin Electro Scientific institute production, as a result It is shown in Table 1.

Using the TH2828S testers of Changzhou Tong Hui Electron equipment Co., Ltd test its dielectric loss (D) (1MHz, 25 DEG C), the results are shown in Table 1.

Using precision electronic balance, the square coupons of above-mentioned drying are weighed after (W1), be soaked in deionized water (25 DEG C) In, after 72 hours, take out, surface is dried with filter paper, weigh (W2), and the data for being calculated water absorption rate (φ) are as shown in table 1.

Using precision electronic balance, the square coupons of above-mentioned drying are weighed after (G1), be positioned over climatic chamber (85 DEG C, RH85%) in, after 72 hours, take out, surface is dried with filter paper, weigh (G2), is calculated the data of hydroscopicity (ψ) such as Shown in table 1.

The performance data of the high temperature resistant BAHPFP type adhesive of table 1

Claims (13)

1. a kind of high temperature resistant BAHPFP type adhesive, it is characterised in that：The adhesive be by mass ratio be 100:20-100: 10-30:20-50:1-5:1-3:It is the BAHPFP type phenolic hydroxy group polyimide resins of 480-1000, polyphenylene oxide resin, multifunctional What epoxy resin, isocyanates, organic compounds containing nitrogen, organo-metallic compound and organic solvent were constituted；BAHPFP types contain Phenolic hydroxyl group polyimide resin be by mol ratio be 2:1-3:The 2,2- of 4-6 double (3- amino-4-hydroxylphenyls) HFC-236fa, virtues Fragrant race's diamidogen and 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride reaction is formed.

2. a kind of high temperature resistant BAHPFP type adhesive according to claim 1, it is characterised in that：Described multi-functional epoxy Resin is selected from N, N, N ', N '-four glycidyl group p-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-diaminobenzene. Epoxy resin, N, N, O- triglycidyl group para-aminophenol epoxy resin, N, N, O- triglycidyl meta-aminophenol ring Oxygen tree fat, N, N, N ', N '-four glycidyl group -4,4 '-MDA epoxy resin, N, N, N ', N '-four shrinks sweet Oil base -3,3 '-dimethyl -4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-diethyl Base -4,4 '-MDA epoxy resin, 3,3 '-two chloro- N, N, N ', N '-four glycidyl group -4,4 '-diaminourea two Phenylmethane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four Glycidyl -4,4 '-DADPS epoxy resin, N, N, N ', N '-four glycidyl group -3,4 '-diaminodiphenyl ether Epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-DADPS epoxy resin, N, N, N ', N '-four shrinks sweet Oil base -4,4 '-benzidine epoxy resin, N, N, N ', double (4- amino-benzene oxygens) phenyl ring of N '-four glycidyl group -1,4- Oxygen tree fat, N, N, N ', N '-four glycidyl group -1,4- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four shrinks Glyceryl -1,3- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', double (the 3- aminobenzenes of N '-four glycidyl group -1,3- Epoxide) benzene epoxy resin, N, N, N ', double (2- trifluoromethyl-4-aminophenoxyls) the phenyl ring oxygen of N '-four glycidyl group -1,4- Resin, N, N, N ', N '-four glycidyl group -1,3- double (2- trifluoromethyl-4-aminophenoxyls) benzene epoxy resin, N, N, N ', The glycidyl -4,4 of N ', O- five '-diaminourea -4 "-hydroxyl tritan. epoxy resin, N, N, N ', N '-four glycidyl group - 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', the double [4- (4- of N '-four glycidyl group -2,2- Amino-benzene oxygen) phenyl] HFC-236fa epoxy resin, N, N, N ', double [4- (the 3- aminobenzene oxygen of N '-four glycidyl group -2,2- Base) phenyl] propane epoxy resin, N, N, N ', the double [4- (2- trifluoromethyl -4- aminobenzene oxygen of N '-four glycidyl group -2,2- Base) phenyl] propane epoxy resin, N, N, N ', double [4- (3- amino-benzene oxygens) phenyl] hexafluoros of N '-four glycidyl group -2,2- Propane epoxy resin, N, N, N ', double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] six of N '-four glycidyl group -2,2- Fluoro-propane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4, 4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl -4- ammonia Phenoxyl) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) hexichol first Alkane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl-methane ring Oxygen tree fat, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone epoxy resin, N, N, N ', N '-four Glycidyl -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resins, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resin, N, N, N ', double (the 3- ammonia of N ', O, the O glycidyl of '-six -2,2- Base -4- hydroxy phenyls) one or more in HFC-236fa epoxy resin.

3. a kind of high temperature resistant BAHPFP type adhesive according to claim 1, it is characterised in that：It is described nitrogenous to organise Compound is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine, picoline, lutidines, 2-methylimidazole, 2- ethyl -4- first Base imidazoles, N, accelerine, N, N- dimethyl open-chain crown ethers, benzyl dimethylamine, 2,4,6- tri- (dimethylamino methyl) One or more in phenol, 1,8- diazabicyclos [5.4.0] hendecene -7.

4. a kind of high temperature resistant BAHPFP type adhesive according to claim 1, it is characterised in that：Described organometallic One or more of compound in aluminium acetylacetonate, dibutyl tin laurate, lead benzoate.

5. a kind of high temperature resistant BAHPFP type adhesive according to claim 1, it is characterised in that：Described isocyanates choosing From hexamethylene diisocyanate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, triphenylmethane triisocyanate, different Fluorine that ketone diisocyanate, hexamethylene diisocyanate trimer, toluene diisocyanate trimer, the isocyanide of diphenyl-methane two One or more in acid esters trimer, isoflurane chalcone diisocyanate trimer.

6. a kind of high temperature resistant BAHPFP type adhesive according to claim 1, it is characterised in that：Described aromatic diamine Selected from p-phenylenediamine, m-diaminobenzene., o-phenylenediamine, 4,4 '-MDA, 3,3 '-dimethyl -4,4 ' diaminourea hexichol Methane, 4,4 '-diaminodiphenyl ether, 4,4 '-benzidine, 3,3 '-dimethyl -4,4 ' benzidine, 2,2 '-diformazan Base -4,4 ' benzidine, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 4,4 '-DADPS, 3,3 ' - Double (3- amino-benzene oxygens) benzene of DADPS, 1,3-, double (3- amino-benzene oxygens) benzene of 1,4-, double (the 4- aminobenzene oxygen of 1,3- Base) benzene, double (4- amino-benzene oxygens) benzene of 1,4-, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,3-, double (the 2- trifluoros of 1,4- Methyl -4- amino-benzene oxygens) benzene, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS)s, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl ether, 4,4 '-bis- (3- Amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether, 4,4 '-bis- (4- aminobenzene oxygen Base) diphenyl sulfide, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) two Diphenyl sulfide, 4,4 '-bis- (4- amino-benzene oxygens) benzophenone, 4,4 '-bis- (3- amino-benzene oxygens) benzophenone, 4,4 '-bis- (2- Trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, 4,4 '-bis- (3- aminobenzene oxygen Base) biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl-methanes, 4, 4 '-bis- (3- amino-benzene oxygens) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl-methanes, 2,2- are double Double [4- (3- amino-benzene oxygens) phenyl] HFC-236fa of [4- (4- amino-benzene oxygens) phenyl] HFC-236fa, 2,2-, the double [4- of 2,2- (2- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fa, 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane, 2,2- Double [4- (3- amino-benzene oxygens) phenyl] propane, 2,2- double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane, 2,2- One or more in double (4- aminophenyls) HFC-236fa.

7. a kind of high temperature resistant BAHPFP type adhesive according to claim 1, it is characterised in that：Described organic solvent choosing From benzene,toluene,xylene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, methyltetrahydrofuran, butyl acetate, vinegar Acetoacetic ester, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, One or more in dimethyl sulfoxide, glycol monoethyl ether, ethylene glycol monoethyl ether.

8. a kind of preparation method of high temperature resistant BAHPFP type adhesive as claimed in claim 1, comprises the steps：

(1) double (3- amino-4-hydroxylphenyls) HFC-236fa of 2,2- and highly polar aprotic organic solvent are put in reactor, After stirring and dissolving, less than 5 DEG C are cooled to, add 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction -2 hours 1 hour, Aromatic diamine is added, continues stirring reaction -2 hours 1 hour, add dehydrant and catalyst, be heated to 80 DEG C -100 DEG C dehydration imidization -5 hours 2 hours, after being cooled to room temperature, adds precipitating agent, stirring to separate out hard resin, filters, third Ketone drip washing 2-3 time, is vacuum dried -4 hours 3 hours at 90 DEG C, and BAHPFP type phenolic hydroxy group polyimide resins are obtained；

(2) BAHPFP type phenolic hydroxy group polyimide resins and organic solvent are added in reactor, is heated to reflux, stirring and dissolving Afterwards, less than 60 DEG C are cooled to, isocyanates are added, backflow is heated to, stirring reaction -3 hours 1 hour is cooled to 60 DEG C Hereinafter, polyfunctional epoxy resin is added, stirring reaction 0.5 hour, obtains component A at being heated to 80 DEG C -90 DEG C；

(3) polyphenylene oxide resin and organic solvent are added in reactor, are heated to reflux, after stirring and dissolving, be cooled to less than 60 DEG C, Isocyanates are added, backflow is heated to, stirring reaction -3 hours 1 hour is cooled to less than 60 DEG C, adds multi-functional epoxy Resin, stirring reaction 0.5 hour, obtains B component at being heated to 80 DEG C -90 DEG C；

(4) under room temperature, by component A, B component mix homogeneously, organo-metallic compound and organic compounds containing nitrogen are added, stirring is mixed Close uniform.

9. the preparation method of a kind of high temperature resistant BAHPFP type adhesive according to claim 8, it is characterised in that：The step Suddenly the highly polar aprotic organic solvent in (1) is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2- One or more in ketopyrrolidine, N- ethyl-2-pyrrolidones, dimethyl sulfoxide；Wherein, highly polar aprotic organic solvent It is 4-6 with the mass ratio of reactant:1；The quality of reactant refers to 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa, virtues Fragrant race's diamidogen and 3,3 ', the quality sum of 4,4 '-tetracarboxylic diphenyl ether dianhydride.

10. the preparation method of a kind of high temperature resistant BAHPFP type adhesive according to claim 8, it is characterised in that：It is described One or more of dehydrant in step (1) in acetic anhydride, propionic andydride, chloracetic acid acid anhydride, trifluoroacetic anhydride (TFAA)；Wherein, take off Water preparation is 3-6 with the mass ratio of reactant:1；The quality of reactant refers to double (3- amino-4-hydroxylphenyls) hexafluoros third of 2,2- Alkane, aromatic diamine and 3,3 ', the quality sum of 4,4 '-tetracarboxylic diphenyl ether dianhydride.

A kind of 11. preparation methoies of high temperature resistant BAHPFP type adhesive according to claim 8, it is characterised in that：It is described One kind in triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine, picoline, the lutidines of catalyst in step (1) or It is several；Wherein, catalyst and the mass ratio of reactant are 0.01-0.1：1；The quality of reactant refers to the double (3- amino -4- of 2,2- Hydroxy phenyl) HFC-236fa, aromatic diamine and 3,3 ', the quality sum of 4,4 '-tetracarboxylic diphenyl ether dianhydride.

A kind of 12. preparation methoies of high temperature resistant BAHPFP type adhesive according to claim 8, it is characterised in that：It is described Precipitating agent in step (1) is selected from methanol, ethanol, propanol, ethylene glycol, Propylene Glycol, tetrahydrofuran, methyltetrahydrofuran, second two One or more in alcohol monomethyl ether, ethylene glycol monoethyl ether；Wherein, the mass ratio of precipitating agent and highly polar aprotic organic solvent For 2-5:1.

A kind of 13. preparation methoies of high temperature resistant BAHPFP type adhesive according to claim 8, it is characterised in that：It is described Acetone in step (1) is 1-2 with the mass ratio of highly polar aprotic organic solvent:1.