CN105112002A - High-temperature-resistant BAHPFP (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) adhesive and preparation method thereof - Google Patents
High-temperature-resistant BAHPFP (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) adhesive and preparation method thereof Download PDFInfo
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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
Technical field
The invention belongs to polymeric material field, particularly one high temperature resistant BAHPFP type tackiness agent and preparation method thereof.
Background technology
Epoxy resin has the mechanical property etc. of excellent cohesiveness, moulding processability, electrical insulation properties and excellence, is widely used in the fields such as aerospace, electronic apparatus, automobile, naval vessel.But also there are some shortcomings in epoxy resin, as thermotolerance is on the low side, far away not as good as aromatic heterocyclic polymer systems such as such as polyimide, polybenzimidazole, polybenzoxazoles, epoxy-resin systems mechanical property in high temperature environments, electric property etc. decline significantly, are difficult to meet practical application request.Therefore, carrying out resistant, toughened modification to epoxy resin, is the focus of the outer scientific and technical personnel's research of Present Domestic.
As everyone knows, epoxy resin has many excellent performances: the adhesiveproperties that (1) is good: bonding strength is high, bonding wide, the bonding strength of it and many metals (as iron, steel, copper, aluminium, metal alloy etc.) or non-metallic material (as glass, pottery, timber, plastics etc.) is very high, what have even exceedes by the intensity of sticky material itself, therefore can be used in many stress members, is one of main component of structural adhesive; (2) good processing characteristics: the diversity of the handiness of Formulaion of epoxy resin, complete processing and product properties is the most outstanding in macromolecular material; (3) satisfactory stability performance: the solidification of epoxy resin mainly relies on the ring opening polyaddition of epoxy group(ing), therefore low-molecular material is not produced in solidification process, its cure shrinkage is one of kind minimum in thermosetting resin, be generally 1%-2%, if select suitable filler that shrinking percentage can be made to be down to about 0.2%; Epoxy main chains after solidification is ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore has excellent resistance to acids and bases.
Therefore, epoxy resin is widely used in the every field of national economy: no matter no matter is high-technology field or field of general technology, be defence and military or civilian industry, and even all can see its trace in daily life.
Chinese invention patent CN103146330A discloses a kind of 2, two [the 4-(2 of 2-, 4-diamino phenoxy) phenyl] HFC-236fa type high temperature resistant epoxy adhesive and preparation method thereof, be that the component A of 1:1-2 and B component form by mass ratio, wherein, component A is the multipolymer reacted by two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa of 2,2-and epoxy resin; The homogeneous phase transparent solution of B component to be the solid content reacted in strong polar non-proton organic solvent and toluene by two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa of 2,2-and aromatic dicarboxylic anhydride be 15%-30%.Preparation method comprises: under room temperature, by A, B component in mass ratio 1:1-2 be uniformly mixed.
Chinese invention patent CN103131369A discloses a kind of 4,4'-two (2,4-diamino phenoxy) sulfobenzide type high temperature resistant epoxy adhesive and preparation method thereof, be that the component A of 1:1-2 and B component form by mass ratio, wherein component A is by 4, the multipolymer that 4 '-bis-(2,4-diamino phenoxy) sulfobenzide and epoxy resin react; The homogeneous phase transparent solution of B component to be the solid content reacted in strong polar non-proton organic solvent and toluene by 4,4 '-bis-(2,4-diamino phenoxy) sulfobenzide and aromatic dicarboxylic anhydride be 15%-30%.Preparation method comprises: under room temperature, by A, B component in mass ratio 1:1-2 be uniformly mixed.
Chinese invention patent CN103146331A discloses a kind of 4,4'-two (2,4-diamino phenoxy) biphenyl type high temperature resistant epoxy adhesive and preparation method thereof, be that the component A of 1:1-2 and B component form by mass ratio, wherein component A is by 4, the multipolymer that 4 '-bis-(2,4-diamino phenoxy) biphenyl and epoxy resin react; The homogeneous phase transparent solution of B component to be the solid content reacted in strong polar non-proton organic solvent and toluene by 4,4 '-bis-(2,4-diamino phenoxy) biphenyl and aromatic dicarboxylic anhydride be 15%-30%.Preparation method comprises: under room temperature, by A, B component in mass ratio 1:1-2 be uniformly mixed.
Chinese invention patent CN103030787A discloses a kind of benzoglyoxaline-epoxy matrix resin and preparation method thereof, resin by A, B two component form.Preparation method, comprise the steps: that (1) is by N, N, N ', N ' two [4-(4-amino-benzene oxygen) phenyl] propane of-four glycidyl group-2,2-and 2-(4-aminophenyl)-5-aminobenzimidazole put into reactor, after being heated to 70-80 DEG C of stirring reaction 15min-30min, add reactive thinner and organic solvent, stir, obtain component A; (2) by solidifying agent and organic solvent mixing, stirring and dissolving is even, namely obtains B component; (3), when using, by A, B component mixing, stir.
Chinese invention patent CN103013414A discloses a kind of alpha-cyano-β-ethoxy ethyl acrylate modified epoxide resin adhesive and preparation method thereof, consisting of of tackiness agent: mass ratio is the epoxy resin of 100:100 ~ 50:60 ~ 30:5 ~ 20:30 ~ 80, epoxy ester resin, endurable active toughener, alpha-cyano-β-ethoxy ethyl acrylate and solidifying agent.Preparation method, comprises the steps: epoxy resin to mix with endurable active toughener, after 60 DEG C-80 DEG C reaction 15-20min, adds epoxy ester resin and alpha-cyano-β-ethoxy ethyl acrylate, is uniformly mixed, obtains component A; Solidifying agent is B component; During use, A, B component are mixed, to obtain final product.
Polyimide resin is a family macromolecule material with extremely excellent heat resistance.Conventional polyimide structures, its heat decomposition temperature, generally all more than 500 DEG C, also has obdurability simultaneously.Therefore, also usually for thermosetting resin, as the heat-resisting plasticized modifier of epoxy resin, bimaleimide resin etc.But the consistency of polyimide system and epoxy resin is poor, is difficult to the obtained polyimide high temperature-resistant that has concurrently and has again the cohesiveness of epoxy resin excellence and a technological adhesive composition.So using conventional polyimide resin to carry out modified epoxy resin system, to obtain the tackiness agent of excellent combination property, is more difficult.
Chinese patent CN1927908A discloses a kind of preparation method of phenolic hydroxyl group containing polyimide powder, due to the existence of phenolic hydroxyl group, its polyimide powder can with epoxy reaction, form covalent linkage, thus the consistency of thermoplastic polyimide resin and epoxy resin can be improved, and the toughening effect that epoxy-resin systems reaches good can be made further.
Chinese invention patent CN101962436A discloses a kind of heat resist modification multi-functional epoxy matrix resin used for advanced composite material and preparation method thereof, be primarily characterized in that: adopt 1,4-two (2,4-dimaleimide phenoxyl) four maleimide resins of benzene and polyfunctional epoxy resin, nbr carboxyl terminal CTBN be obtained by reacting the novel fire resistant resin of high tenacity, add organic solvent, stirring and dissolving is even, obtains the viscous liquid of homogeneous phase transparent, i.e. component A; Solidifying agent mixes with organic solvent, and stirring and dissolving is even, obtains B component; A, B component are mixed, stirs, obtain heat resist modification multi-functional epoxy substrate resin solution used for advanced composite material.
The people such as Yu Xinhai [development [J] of high-temperature resistant single-component epoxy tackiness agent. bonding, 2008, 29 (12): 16-19] a kind of preparation method of high-temperature resistant single-component epoxy tackiness agent is disclosed, be primarily characterized in that: with maleic anhydride (MA) for end-capping reagent, with 2, two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP) of 2-, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) for main raw material synthesis obtain phenolic hydroxy group polyetherimide resin (HPEI), it is resistant, toughened dose with the synthesized HPEI obtained, with N, N, N', N'-four glycidyl group-4,4'-diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent etc., preparation obtains the high-temperature resistant single-component epoxy tackiness agent of excellent combination property.
The method, although by the polyetherimide resin (HPEI) of synthesis containing active reactive group (hydroxyl, unsaturated double-bond), carried out toughening modifying to epoxy resin, and achieved good technique effect.But, also there are some shortcomings:
(1) reactable group is limited, and particularly the content of unsaturated double-bond is on the low side.Because maleic anhydride uses as end-capping reagent, the consumption of maleic anhydride is little.
(2) 2, the monomers such as 2-two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) are expensive, cause the cost of polyetherimide resin (HPEI) and tackiness agent very high, be unfavorable for large-scale promotion application, some special dimension can only be confined to.
Chinese invention patent CN103483552A discloses a kind of carbon-fibre composite matrix resin and preparation method thereof, this carbon-fibre composite matrix resin is by N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl oxide (TGDADPE) epoxy resin, ES216 epoxy resin, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane, 3 of 2-, 3 '-dimethyl-4,4 '-bis-(4-carboxyl phthalimide group) ditane, solidifying agent and organic solvent form, its preparation method, comprise the steps: that (1) is by N, N, N ', N '-four glycidyl group-4, 4 ' diaminodiphenyl oxide (TGDADPE) epoxy resin and 3, 3 '-dimethyl-4, reactor put into by 4 '-bis-(4-carboxyl phthalimide group) ditane, in 80 DEG C of-100 DEG C of temperature ranges, stirring reaction is after 0.5 hour-1 hour, add ES216 epoxy resin and 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane of 2-, continue stirring reaction 0.5 hour-1 hour, add organic solvent, stir, obtain component A, (2) by solidifying agent and organic solvent mixing, stirring and dissolving is homogeneous phase, obtains B component, (3), when using, component A, B component are mixed.
Chinese invention patent CN103408727A discloses a kind of TGBAPOPP mold base resin used for advanced composite material and preparation method thereof, this matrix resin is by N, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (TGBAPOPP), o-cresol formaldehyde epoxy resin, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, 2,2,4-trimethylammonium-1,2-diamino quinoline, 2,2-two [4-(4-maleimide phenoxyl) phenyl] propane, solidifying agent and organic solvent compositions; Preparation method comprises the steps: N, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, o-cresol formaldehyde epoxy resin, 2, two [4-(4-maleimide phenoxyl) phenyl] propane of 2-puts into reactor, react certain hour in the temperature range of 90 DEG C-100 DEG C after, N-sec.-propyl-N '-diphenyl-para-phenylene diamine solution, 2,2,4-trimethylammoniums-1 are added under room temperature, 2-dihyaroquinoline solution, be uniformly mixed, add curing agent solution, be uniformly mixed.
Chinese invention patent CN103483553A discloses a kind of TGDADPE type epoxy matrix resin used for advanced composite material and preparation method thereof, this matrix resin is the N of 100:5-10:10-20:1-5:80-200 by mass ratio, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl oxide epoxy resin (TGDADPE), aromatic diamine, aromatic dicarboxylic anhydride, solidifying agent and organic solvent composition; Its preparation method comprises the steps: N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl oxide epoxy resin (TGDADPE) and aromatic diamine put into reactor, after reacting 30min-40min, are cooled to room temperature in the temperature range of 50 DEG C-90 DEG C, add the homogeneous phase solution of aromatic dicarboxylic anhydride, solidifying agent and organic solvent, be uniformly mixed.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of high temperature resistant BAHPFP type tackiness agent and preparation method thereof, the preparation technology of this tackiness agent is easy to operate, raw material sources are convenient, production cost is low, can complete preparation, good manufacturability on general-purpose equipment, under products obtained therefrom is hot, there is good over-all properties, there is low dielectric loss and excellent high-temperature stability, can be applicable to insulating material, high temperature resistant mechanism material etc., there is good market application foreground.
One of the present invention is high temperature resistant BAHPFP type tackiness agent, BAHPFP type phenolic hydroxy group polyimide resin, polyphenylene oxide resin, polyfunctional epoxy resin, isocyanic ester, organic compounds containing nitrogen, organometallic compound and organic solvent that described tackiness agent is 100:20-100:10-30:20-50:1-5:1-3:480-1000 by mass ratio form; BAHPFP type phenolic hydroxy group polyimide resin is 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, the aromatic diamines and 3 of 2:1-3:4-6 by mol ratio, 3 ', 4, and the reaction of 4 '-tetracarboxylic diphenyl ether dianhydride forms.
Described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group Ursol D epoxy resin, N, N, N ', N '-four glycidyl group mphenylenediamine epoxy resin, N, N, O-triglycidyl group p-aminophenol epoxy resin, N, N, O-triglycidyl group Metha Amino Phenon epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-dimethyl-4, 4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-diethyl-4, 4 '-diaminodiphenylmethane epoxy resin, 3, 3 '-two chloro-N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenylsulfone(DDS) epoxy resin, N, N, N ', N '-four glycidyl group-3, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-diaminodiphenylsulfone(DDS) epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group Ursol D epoxy resin, N, N, N ', N '-four glycidyl group mphenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group-1, two (4-amino-benzene oxygen) the phenyl ring epoxy resins of 4-, N, N, N ', N '-four glycidyl group-1, two (3-amino-benzene oxygen) the phenyl ring epoxy resins of 4-, N, N, N ', N '-four glycidyl group-1, two (4-amino-benzene oxygen) the phenyl ring epoxy resins of 3-, N, N, N ', N '-four glycidyl group-1, two (3-amino-benzene oxygen) the phenyl ring epoxy resins of 3-, N, N, N ', N '-four glycidyl group-1, two (2-trifluoromethyl-4-aminophenoxyl) the phenyl ring epoxy resins of 4-, N, N, N ', N '-four glycidyl group-1, two (2-trifluoromethyl-4-aminophenoxyl) the phenyl ring epoxy resins of 3-, N, N, N ', N ', O-five glycidyl-4, 4 '-diamino-4 "-hydroxyl tritane epoxy resin, N, N, N ', N '-four glycidyl group-2, two [4-(4-amino-benzene oxygen) phenyl] the propane epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(4-amino-benzene oxygen) phenyl] the HFC-236fa epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(3-amino-benzene oxygen) phenyl] the propane epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] the propane epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(3-amino-benzene oxygen) phenyl] the HFC-236fa epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] the HFC-236fa epoxy resin of 2-, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) sulfobenzide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) ditane epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) ditane epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) biphenyl epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, N, N ', N ', O, O '-six glycidyl-2, one or more in two (3-amino-4-hydroxylphenyl) the HFC-236fa epoxy resin of 2-.
Described organic compounds containing nitrogen is selected from triethylamine, tripropyl amine, Tributylamine, pyridine, picoline, lutidine, glyoxal ethyline, 2-ethyl-4-methylimidazole, N, accelerine, N, N-dimethyl open-chain crown ether, DMP-30, benzyldimethylamine, 2,4, one or more in 6-tri-(dimethylamino methyl) phenol, DBU, 1,8-diazabicyclo [5.4.0] hendecene-7.
Described organometallic compound is selected from one or more in aluminium acetylacetonate, dibutyl tin laurate, lead benzoate.
Described isocyanic ester is selected from one or more in hexamethylene diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate, triphenylmethane triisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate trimer, toluene diisocyanate trimer, '-diphenylmethane diisocyanate tripolymer, isoflurane chalcone diisocyanate tripolymer.
Described aromatic diamine is selected from Ursol D, mphenylenediamine, O-Phenylene Diamine, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 ' diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 ' benzidine, 2,2 '-dimethyl-4,4 ' benzidine, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, DDS, 3,3 '-diaminodiphenylsulfone(DDS), two (3-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(4-amino-benzene oxygen) phenyl ether, 4,4 '-bis-(3-amino-benzene oxygen) phenyl ether, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) phenyl ether, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide, 4,4 '-bis-(4-amino-benzene oxygen) benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, 4,4 '-bis-(4-amino-benzene oxygen) ditane, 4,4 '-bis-(3-amino-benzene oxygen) ditane, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) ditane, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, one or more in two (4-aminophenyl) HFC-236fa of 2,2-.
Described organic solvent is selected from benzene,toluene,xylene, methylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), methyltetrahydrofuran, N-BUTYL ACETATE, vinyl acetic monomer, N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether.
The preparation method of a kind of high temperature resistant BAHPFP type tackiness agent of the present invention, comprises the steps:
(1) by 2, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and strong polar non-proton organic solvent put into reactor, after stirring and dissolving, be cooled to less than 5 DEG C, add 3, 3 ', 4, 4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction 1 hour-2 hours, add aromatic diamine, continue stirring reaction 1 hour-2 hours, add dewatering agent and catalyzer, be heated to 80 DEG C-100 DEG C dehydration imidizations 2 hours-5 hours, after cool to room temperature, add precipitating agent, stir and separate out solid resin, filter, acetone drip washing 2-3 time, vacuum-drying 3 hours-4 hours at 90 DEG C, obtained BAHPFP type phenolic hydroxy group polyimide resin,
(2) BAHPFP type phenolic hydroxy group polyimide resin and organic solvent are added in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add isocyanic ester, be heated to backflow, stirring reaction 1 hour-3 hours, is cooled to less than 60 DEG C, adds polyfunctional epoxy resin, at being heated to 80 DEG C-90 DEG C, stirring reaction 0.5 hour, obtains component A;
(3) polyphenylene oxide resin and organic solvent are added in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add isocyanic ester, be heated to backflow, stirring reaction 1 hour-3 hours, is cooled to less than 60 DEG C, adds polyfunctional epoxy resin, at being heated to 80 DEG C-90 DEG C, stirring reaction 0.5 hour, obtains B component;
(4) under room temperature, component A, B component are mixed, add organometallic compound and organic compounds containing nitrogen, be uniformly mixed.
Strong polar non-proton organic solvent in described step (1) is selected from one or more in DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO); Wherein, the mass ratio of strong polar non-proton organic solvent and reactant is 4-6:1; The quality of reactant refers to 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and 3,3 ', 4, the quality sum of 4 '-tetracarboxylic diphenyl ether dianhydride.
Dewatering agent in described step (1) is selected from one or more in diacetyl oxide, propionic anhydride, chloracetic acid acid anhydride, trifluoroacetic anhydride (TFAA); Wherein, the mass ratio of dewatering agent and reactant is 3-6:1; The quality of reactant refers to 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and 3,3 ', 4, the quality sum of 4 '-tetracarboxylic diphenyl ether dianhydride.
Catalyzer in described step (1) is selected from one or more in triethylamine, tripropyl amine, Tributylamine, pyridine, picoline, lutidine; Wherein, the mass ratio of catalyzer and reactant is 0.01-0.1:1; The quality of reactant refers to 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and 3,3 ', 4, the quality sum of 4 '-tetracarboxylic diphenyl ether dianhydride.
Precipitating agent in described step (1) is selected from one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), methyltetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; Wherein, the mass ratio of precipitating agent and strong polar non-proton organic solvent is 2-5:1.
Acetone in described step (1) and the mass ratio of strong polar non-proton organic solvent are 1-2:1.
beneficial effect
(1) the present invention has good over-all properties, has low dielectric loss and excellent high-temperature stability;
(2) the present invention can be applicable to insulating material, high-temperature-resistant structure material etc., has good market application foreground;
(3) preparation technology of the present invention is simple, cost is low, easy to operate, reaction raw materials convenient sources, can complete preparation process in general-purpose equipment, is conducive to realizing suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By 73.2 grams of (0.2 moles) 2, two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-and 910 grams of N, N-N,N-DIMETHYLACETAMIDE puts into reactor, after stirring and dissolving, be cooled to less than 5 DEG C, add 124.0 grams of (0.4 moles) 3, 3 ', 4, 4 '-tetracarboxylic diphenyl ether dianhydride (ODPA), stirring reaction 2 hours, add 29.2 grams of (0.1 moles) 1, two (3-amino-benzene oxygen) benzene of 3-, continue stirring reaction 1 hour, add 680 grams of diacetyl oxides and 2.3 grams of pyridines, be heated to 100 DEG C of dehydration imidizations 2 hours, after cool to room temperature, add 1820 grams of methyl alcohol, stir and separate out solid resin, filter, 910 grams of acetone drip washing 2-3 time, vacuum-drying 3 hours at 90 DEG C, obtained 207.4 grams of BAHPFP type phenolic hydroxy group polyimide resins (theoretical yield 215.6 grams), be denoted as HFPI-1, yield 96.2%.
Embodiment 2
By 73.2 grams of (0.2 moles) 2, two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 2000 grams of METHYLPYRROLIDONEs and 200 grams of N, dinethylformamide puts into reactor, after stirring and dissolving, be cooled to less than 5 DEG C, add 186.0 grams of (0.6 moles) 3, 3 ', 4, 4 '-tetracarboxylic diphenyl ether dianhydride (ODPA), stirring reaction 1 hour, add 82.0 grams of (0.2 moles) 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-and 29.2 grams of (0.1 moles) 1, two (4-amino-benzene oxygen) benzene of 3-, continue stirring reaction 2 hours, add 2000 grams of diacetyl oxides and 37.0 grams of lutidine, be heated to 80 DEG C of dehydration imidizations 5 hours, after cool to room temperature, add 10000 grams of ethanol and 1000 grams of methyl alcohol, stir and separate out solid resin, filter, 4400 grams of acetone drip washing 2-3 time, vacuum-drying 4 hours at 90 DEG C, obtained 346.4 grams of BAHPFP type phenolic hydroxy group polyimide resins (theoretical yield 352.4 grams), be denoted as HFPI-2, yield 98.3%.
Embodiment 3
The BAHPFP type phenolic hydroxy group polyimide resin of 50.0 grams of HFPI-1 and 200 grams of N,N-dimethylacetamide are added in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add 4.0 grams of '-diphenylmethane diisocyanates (MDI), be heated to backflow, stirring reaction 1 hour, is cooled to less than 60 DEG C, adds 1.5 grams of N, N, O-triglycidyl group p-aminophenol epoxy resin, stirring reaction 0.5 hour at being heated to 80 DEG C, obtains 255.5 grams of component A.
Add in reactor by 10.0 grams of polyphenylene oxide resins and 40 grams of dimethylbenzene, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add 6.0 grams of toluene diisocyanate trimers, be heated to backflow, stirring reaction 1 hour, is cooled to less than 60 DEG C, adds 3.5 grams of N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane epoxy resin, stirring reaction 0.5 hour at being heated to 80 DEG C, obtains 59.5 grams of B component.
Under room temperature, component A, B component are mixed, add 0.5 gram of aluminium acetylacetonate and 0.5 gram 2,4,6-tri-(dimethylamino methyl) phenol, be uniformly mixed, obtain 316.0 grams of high temperature resistant BAHPFP type tackiness agent, be denoted as J-1.
Embodiment 4
By the BAHPFP type phenolic hydroxy group polyimide resin of 50.0 grams of HFPI-2, 150 grams of METHYLPYRROLIDONEs and 100 grams of N, dinethylformamide adds in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add 12.0 grams of toluene diisocyanate trimers and 8.0 grams of '-diphenylmethane diisocyanates (MDI), be heated to backflow, stirring reaction 3 hours, be cooled to less than 60 DEG C, add 10.0 grams of N, N, O-triglycidyl group p-aminophenol epoxy resin, stirring reaction 0.5 hour at being heated to 90 DEG C, obtain 330.0 grams of component A.
50.0 grams of polyphenylene oxide resins, 50 grams of tetrahydrofuran (THF)s and 200 grams of dimethylbenzene are added in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add 5.0 grams of isoflurane chalcone diisocyanates (IPDI), be heated to backflow, stirring reaction 3 hours, is cooled to less than 60 DEG C, add 5.0 grams of N, N, N ', N '-four glycidyl group-3,3 '-dimethyl-4,4 '-diaminodiphenylmethane epoxy resin, stirring reaction 0.5 hour at being heated to 80 DEG C, obtains 310.0 grams of B component.
Under room temperature, component A, B component are mixed, add 1.5 grams of dibutyl tin laurates and 2.5 gram of 1,8-diazabicyclo [5.4.0] hendecene-7, be uniformly mixed, obtain 644.0 grams of high temperature resistant BAHPFP type tackiness agent, be denoted as J-2.
Embodiment 5
The BAHPFP type phenolic hydroxy group polyimide resin of 30.0 grams of HFPI-1 and 20.0HFPI-2,220 grams of METHYLPYRROLIDONEs are added in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add 7.0 grams of isoflurane chalcone diisocyanates (IPDI) and 5.0 grams of '-diphenylmethane diisocyanates (MDI), be heated to backflow, stirring reaction 2 hours, be cooled to less than 60 DEG C, add 6.0 grams of N, N, O-triglycidyl group p-aminophenol epoxy resin, stirring reaction 0.5 hour at being heated to 85 DEG C, obtains 288.0 grams of component A.
Add in reactor by 40.0 grams of polyphenylene oxide resins, 80 grams of METHYLPYRROLIDONEs and 100 grams of dimethylbenzene, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add 8.0 grams of tolylene diisocyanates, be heated to backflow, stirring 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 '-diaminodiphenylmethane epoxy resin, stirring reaction 0.5 hour at being heated to 90 DEG C, obtains 232.0 grams of B component.
Under room temperature, component A, B component are mixed, add 0.5 gram of aluminium acetylacetonate and 0.5 gram of dibutyl tin laurate, 1.0 grams of N, N-dimethyl open-chain crown ether and 1.0 gram 2,4,6-tri-(dimethylamino methyl) phenol, is uniformly mixed, obtain 523.0 grams of high temperature resistant BAHPFP type tackiness agent, be denoted as J-3.
Embodiment 6
Get the high temperature resistant BAHPFP type tackiness agent of appropriate embodiment 3 ~ embodiment 5 respectively, i.e. J-1 ~ J-3, and be coated in the test piece of standard stainless steel respectively equably, after room temperature hangs 0.5 hour, superimposed, clamping, puts into convection oven and is cured: from room temperature, be warming up to 100 DEG C, insulation reaction 2 hours, continue to be warming up to 150 DEG C, insulation reaction 2 hours, continue to be warming up to 200 DEG C, insulation reaction 2 hours, naturally cools to room temperature.Utilize electronic tensile machine to carry out room temperature (25 DEG C) to it to test with the tensile shear strength (σ) under high temperature (240 DEG C) state, result is as shown in table 1.
Get the high temperature resistant BAHPFP type tackiness agent of appropriate embodiment 3 ~ embodiment 5 respectively, i.e. J-1 ~ J-3, polytetrafluoroethylene film pushes away film, is placed in vacuum drying oven, be made into the square coupons being of a size of 5mm × 5mm × 1mm, curing process is: from room temperature, be warming up to 100 DEG C, insulation reaction 2 hours, continues to be warming up to 150 DEG C, insulation reaction 2 hours, continue to be warming up to 200 DEG C, insulation reaction 2 hours, naturally cools to room temperature.
Its volume specific resistance ρ v (1MHz, 25 DEG C) tested by the megger utilizing Guilin Electro Scientific institute to produce, and the results are shown in Table 1.
Utilize the TH2828S tester of Changzhou Tong Hui Electron equipment Co., Ltd to test its dielectric loss (D) (1MHz, 25 DEG C), the results are shown in Table 1.
Utilize precision electronic balance, the square coupons of above-mentioned drying is weighed after (W1), be soaked in deionized water (25 DEG C), after 72 hours, take out, dry surface with filter paper, weigh (W2), and the data calculating water-intake rate (φ) are as shown in table 1.
Utilize precision electronic balance, the square coupons of above-mentioned drying is weighed after (G1), be positioned over climatic chamber (85 DEG C, RH85%) in, after 72 hours, take out, dry surface with filter paper, weigh (G2), and the data calculating rate of moisture absorption (ψ) are as shown in table 1.
The performance data of table 1 is high temperature resistant BAHPFP type tackiness agent
Claims (13)
1. a high temperature resistant BAHPFP type tackiness agent, is characterized in that: BAHPFP type phenolic hydroxy group polyimide resin, polyphenylene oxide resin, polyfunctional epoxy resin, isocyanic ester, organic compounds containing nitrogen, organometallic compound and organic solvent that described tackiness agent is 100:20-100:10-30:20-50:1-5:1-3:480-1000 by mass ratio form; BAHPFP type phenolic hydroxy group polyimide resin is 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, the aromatic diamines and 3 of 2:1-3:4-6 by mol ratio, 3 ', 4, and the reaction of 4 '-tetracarboxylic diphenyl ether dianhydride forms.
2. one according to claim 1 high temperature resistant BAHPFP type tackiness agent, it is characterized in that: described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group Ursol D epoxy resin, N, N, N ', N '-four glycidyl group mphenylenediamine epoxy resin, N, N, O-triglycidyl group p-aminophenol epoxy resin, N, N, O-triglycidyl group Metha Amino Phenon epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-dimethyl-4, 4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-diethyl-4, 4 '-diaminodiphenylmethane epoxy resin, 3, 3 '-two chloro-N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenylmethane epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenylsulfone(DDS) epoxy resin, N, N, N ', N '-four glycidyl group-3, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-diaminodiphenylsulfone(DDS) epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group Ursol D epoxy resin, N, N, N ', N '-four glycidyl group mphenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group-1, two (4-amino-benzene oxygen) the phenyl ring epoxy resins of 4-, N, N, N ', N '-four glycidyl group-1, two (3-amino-benzene oxygen) the phenyl ring epoxy resins of 4-, N, N, N ', N '-four glycidyl group-1, two (4-amino-benzene oxygen) the phenyl ring epoxy resins of 3-, N, N, N ', N '-four glycidyl group-1, two (3-amino-benzene oxygen) the phenyl ring epoxy resins of 3-, N, N, N ', N '-four glycidyl group-1, two (2-trifluoromethyl-4-aminophenoxyl) the phenyl ring epoxy resins of 4-, N, N, N ', N '-four glycidyl group-1, two (2-trifluoromethyl-4-aminophenoxyl) the phenyl ring epoxy resins of 3-, N, N, N ', N ', O-five glycidyl-4, 4 '-diamino-4 "-hydroxyl tritane epoxy resin, N, N, N ', N '-four glycidyl group-2, two [4-(4-amino-benzene oxygen) phenyl] the propane epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(4-amino-benzene oxygen) phenyl] the HFC-236fa epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(3-amino-benzene oxygen) phenyl] the propane epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] the propane epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(3-amino-benzene oxygen) phenyl] the HFC-236fa epoxy resin of 2-, N, N, N ', N '-four glycidyl group-2, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] the HFC-236fa epoxy resin of 2-, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) sulfobenzide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) ditane epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) ditane epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(4-amino-benzene oxygen) biphenyl epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, N, N ', N ', O, O '-six glycidyl-2, one or more in two (3-amino-4-hydroxylphenyl) the HFC-236fa epoxy resin of 2-.
3. one according to claim 1 high temperature resistant BAHPFP type tackiness agent, it is characterized in that: described organic compounds containing nitrogen is selected from triethylamine, tripropyl amine, Tributylamine, pyridine, picoline, lutidine, glyoxal ethyline, 2-ethyl-4-methylimidazole, N, accelerine, N, N-dimethyl open-chain crown ether, DMP-30, benzyldimethylamine, 2,4, one or more in 6-tri-(dimethylamino methyl) phenol, DBU, 1,8-diazabicyclo [5.4.0] hendecene-7.
4. one according to claim 1 high temperature resistant BAHPFP type tackiness agent, is characterized in that: described organometallic compound is selected from one or more in aluminium acetylacetonate, dibutyl tin laurate, lead benzoate.
5. one according to claim 1 high temperature resistant BAHPFP type tackiness agent, is characterized in that: described isocyanic ester is selected from one or more in hexamethylene diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate, triphenylmethane triisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate trimer, toluene diisocyanate trimer, '-diphenylmethane diisocyanate tripolymer, isoflurane chalcone diisocyanate tripolymer.
6. one according to claim 1 high temperature resistant BAHPFP type tackiness agent, is characterized in that: described aromatic diamine is selected from Ursol D, mphenylenediamine, O-Phenylene Diamine, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 ' diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 ' benzidine, 2,2 '-dimethyl-4,4 ' benzidine, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, DDS, 3,3 '-diaminodiphenylsulfone(DDS), two (3-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(4-amino-benzene oxygen) phenyl ether, 4,4 '-bis-(3-amino-benzene oxygen) phenyl ether, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) phenyl ether, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide, 4,4 '-bis-(4-amino-benzene oxygen) benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, 4,4 '-bis-(4-amino-benzene oxygen) ditane, 4,4 '-bis-(3-amino-benzene oxygen) ditane, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) ditane, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, one or more in two (4-aminophenyl) HFC-236fa of 2,2-.
7. one according to claim 1 high temperature resistant BAHPFP type tackiness agent, it is characterized in that: described organic solvent is selected from benzene,toluene,xylene, methylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), methyltetrahydrofuran, N-BUTYL ACETATE, vinyl acetic monomer, N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether.
8. a preparation method for high temperature resistant BAHPFP type tackiness agent as claimed in claim 1, comprises the steps:
(1) by 2, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and strong polar non-proton organic solvent put into reactor, after stirring and dissolving, be cooled to less than 5 DEG C, add 3, 3 ', 4, 4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction 1 hour-2 hours, add aromatic diamine, continue stirring reaction 1 hour-2 hours, add dewatering agent and catalyzer, be heated to 80 DEG C-100 DEG C dehydration imidizations 2 hours-5 hours, after cool to room temperature, add precipitating agent, stir and separate out solid resin, filter, acetone drip washing 2-3 time, vacuum-drying 3 hours-4 hours at 90 DEG C, obtained BAHPFP type phenolic hydroxy group polyimide resin,
(2) BAHPFP type phenolic hydroxy group polyimide resin and organic solvent are added in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add isocyanic ester, be heated to backflow, stirring reaction 1 hour-3 hours, is cooled to less than 60 DEG C, adds polyfunctional epoxy resin, at being heated to 80 DEG C-90 DEG C, stirring reaction 0.5 hour, obtains component A;
(3) polyphenylene oxide resin and organic solvent are added in reactor, reflux, after stirring and dissolving, be cooled to less than 60 DEG C, add isocyanic ester, be heated to backflow, stirring reaction 1 hour-3 hours, is cooled to less than 60 DEG C, adds polyfunctional epoxy resin, at being heated to 80 DEG C-90 DEG C, stirring reaction 0.5 hour, obtains B component;
(4) under room temperature, component A, B component are mixed, add organometallic compound and organic compounds containing nitrogen, be uniformly mixed.
9. the preparation method of a kind of high temperature resistant BAHPFP type tackiness agent according to claim 8, it is characterized in that: the strong polar non-proton organic solvent in described step (1) is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO); Wherein, the mass ratio of strong polar non-proton organic solvent and reactant is 4-6:1; The quality of reactant refers to 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and 3,3 ', 4, the quality sum of 4 '-tetracarboxylic diphenyl ether dianhydride.
10. the preparation method of a kind of high temperature resistant BAHPFP type tackiness agent according to claim 8, is characterized in that: the dewatering agent in described step (1) is selected from one or more in diacetyl oxide, propionic anhydride, chloracetic acid acid anhydride, trifluoroacetic anhydride (TFAA); Wherein, the mass ratio of dewatering agent and reactant is 3-6:1; The quality of reactant refers to 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and 3,3 ', 4, the quality sum of 4 '-tetracarboxylic diphenyl ether dianhydride.
The preparation method of 11. a kind of high temperature resistant BAHPFP type tackiness agent according to claim 8, is characterized in that: the catalyzer in described step (1) is selected from one or more in triethylamine, tripropyl amine, Tributylamine, pyridine, picoline, lutidine; Wherein, the mass ratio of catalyzer and reactant is 0.01-0.1:1; The quality of reactant refers to 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa, aromatic diamine and 3,3 ', 4, the quality sum of 4 '-tetracarboxylic diphenyl ether dianhydride.
The preparation method of 12. a kind of high temperature resistant BAHPFP type tackiness agent according to claim 8, is characterized in that: the precipitating agent in described step (1) is selected from one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, tetrahydrofuran (THF), methyltetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; Wherein, the mass ratio of precipitating agent and strong polar non-proton organic solvent is 2-5:1.
The preparation method of 13. a kind of high temperature resistant BAHPFP type tackiness agent according to claim 8, is characterized in that: the acetone in described step (1) and the mass ratio of strong polar non-proton organic solvent are 1-2:1.
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