CN101629062A - Polyimide-epoxy resin adhesive and preparation method and application thereof - Google Patents
Polyimide-epoxy resin adhesive and preparation method and application thereof Download PDFInfo
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- CN101629062A CN101629062A CN200910056751A CN200910056751A CN101629062A CN 101629062 A CN101629062 A CN 101629062A CN 200910056751 A CN200910056751 A CN 200910056751A CN 200910056751 A CN200910056751 A CN 200910056751A CN 101629062 A CN101629062 A CN 101629062A
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Abstract
The invention relates to a polyimide-epoxy resin adhesive and a preparation method and an application thereof; the adhesive comprises the following components: maleimidopolyimide, polyfunctional epoxy resin, curing agent, promoter and organic solvent; the preparation method comprises the following steps: adding maleimidopolyimide powder and polyfunctional epoxy resin in a reaction rank to react for 1-2h, cooling, adding organic solvent, stirring the solution for dissolving, obtaining component A; mixing curing agent, promoter and organic solvent, stirring the solution for dissolving, obtaining component B; mixing the component A and component B, stirring evenly and obtaining the finished product. The adhesive has good adhesive property, the tensile shear strength is up to 30MPa; the preparation process is simple, the cost is low, the operation is simple, the reaction raw materials are accessible so that the method is applicable to industrialized production; and the adhesive can be used in high-tech fields such as electronics and microelectronics, flexible clad-copper laminates, flexible printed wiring boards, hard clad-copper laminates, automobiles, motors, aviation and aerospace and the like, and has broad application prospect.
Description
Technical field
The invention belongs to organic polymer binder and preparation thereof and Application Areas, particularly relate to a kind of polyimide-epoxy resin adhesive and preparation thereof and application.
Background technology
As everyone knows, Resins, epoxy has many good performances: the adhesiveproperties that (1) is good: the bonding strength height, 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, intensity that have even glue material itself above quilt, therefore can be used in many stress members, is one of main component of structure-type tackiness agent; (2) good processing properties: the diversity of the handiness of Formulaion of epoxy resin, complete processing and product properties is the most outstanding in the macromolecular material; (3) satisfactory stability performance: the curing of Resins, epoxy mainly is the ring opening polyaddition that relies on epoxy group(ing), therefore do not produce low-molecular material in the solidification process, its cure shrinkage is one of kind minimum in the thermosetting resin, be generally 1%-2%, if select suitable filler that shrinking percentage is reduced to about 0.2%; Resins, epoxy main chain after the curing is ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore has excellent resistance to acids and bases.
Therefore, Resins, epoxy is widely used in the every field of national economy: no matter be high-technology field or current techique field, no matter be defence and military or civilian industry, and even all can see its trace in the daily life.
At present, also there are some problems in the epoxy resin binder system, lower as thermotolerance, not as good as fragrant heterocyclic polymeric system (as polyimide, polybenzimidazole, polybenzoxazole, polyphenylene quinoxaline, polybenzothiozole etc.), can not satisfy the application under the hot conditions far away.
Relevant fire resistant epoxy adhesive composition is reported to some extent: Chinese patent CN101148656A discloses a kind of preparation method of heat-resistant solvent-free epoxy adhesive, be primarily characterized in that: TGDDM Resins, epoxy, Hydrogenated Bisphenol A, solidifying agent, promotor mix, and have made the heat-resistant solvent-free epoxy adhesive.But its resistance to elevated temperatures still has bigger limitation, fails to satisfy the practical application under many hot environments.
Chinese patent CN101397486A discloses a kind of preparation method of two-pack solvent-free epoxy resin tackiness agent, be primarily characterized in that: it comprises A component and B component, and wherein the A component contains novolac epoxy, alicyclic type epoxy resin and nbr carboxyl terminal; The B component is 1, two (2, the 4-diamino phenoxy) the benzene aromatic polyamine solidifying agent of 4-.The addition of alicyclic type epoxy resin and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy.1, the addition of two (2, the 4-diamino phenoxy) the benzene aromatic polyamine solidifying agent of 4-is the 15-20% (mass percent) of novolac epoxy, gained adhesive system good manufacturability, and tensile shear strength is up to 25MPa.But its resistance toheat is desirable not enough.
Polyimide resin is to have an extremely family macromolecule material of excellent heat resistance.Conventional polyimide structures, its heat decomposition temperature is general all more than 500 ℃, also has obdurability simultaneously.Therefore, also usually be used for thermosetting resin, as the heat-resisting plasticized modifier of Resins, epoxy, bimaleimide resin etc.But the consistency of polyimide system and Resins, epoxy is relatively poor, is difficult to make have polyimide high temperature-resistant concurrently and have the cohesiveness and the technological adhesive composition of Resins, epoxy excellence again.So, use conventional polyimide resin to come modified epoxy resin system, to obtain the tackiness agent of excellent combination property, be the comparison difficulty.
Therefore, the consistency that how to improve thermoplastic polyether imide resin and Resins, epoxy is a very significant problem.The scientific worker of this area has done number of research projects, and has obtained certain technique effect.
Chinese patent CN1927908A discloses a kind of preparation method of phenolic hydroxy group polyimide powder, because the existence of phenolic hydroxyl group, its polyimide powder can with epoxy reaction, form covalent linkage, thereby can improve the consistency of thermoplastic polyimide resin and Resins, epoxy, and can further make epoxy-resin systems reach good toughening effect.
People such as Yu Xinhai [development of high-temperature resistant single-component epoxy tackiness agent [J]. 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) is end-capping reagent, with 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa (BAHPFP), 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP), 2 of 2-, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides (BPADA) of 2-have obtained phenolic hydroxy group polyetherimide resin (HPEI) for main raw material is synthetic; The HPEI that obtains is resistant, toughened dose with synthesized, with N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent etc., preparation has obtained the high-temperature resistant single-component epoxy tackiness agent of excellent combination property.
Though this method has been carried out toughening modifying to Resins, epoxy, and has been obtained better technical effect by the synthetic polyetherimide resin (HPEI) that contains active reactive group (hydroxyl, unsaturated double-bond); But also have 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 seldom; (2) polyetherimide resin (HPEI) content in system (≤10%) on the low side causes the improved heat resistance of adhesive composition limited.
Summary of the invention
Technical problem to be solved by this invention provides a kind of polyimide-epoxy resin adhesive and preparation and application, the consistency of this adhesive composition own is good, the reactive group controllability is good, excellent combination property, has good adhesiveproperties, its tensile shear strength (base material: iron and steel) up to 30MPa; And preparation technology is simple, cost is low, easy to operate, reaction raw materials is easy to get, and can finish preparation process in general-purpose equipment, helps realizing suitability for industrialized production; Can be applicable to high-tech areas such as electronics microelectronics, flexible copper clad foil plate (FCCL), flexible printed circuit board (FPC), rigid copper coated foil plate (PCB), automobile, motor, aerospace, have broad application prospects.
A kind of polyimide-epoxy resin adhesive of the present invention, its component comprises: dimaleoyl imino polyimide (MHPI) powder of mass percent 5%-35%, the polyfunctional epoxy resin of mass percent 5%-35%, the solidifying agent of mass percent 5%-10% and the organic solvent of promotor and mass percent 45%-65%;
The weight ratio of described solidifying agent and promotor is 20-50: 1.
The preparation method of a kind of polyimide-epoxy resin adhesive of the present invention comprises:
According to aforementioned proportion dimaleoyl imino polyimide (MHPI) powder and polyfunctional epoxy resin are added in the reactor, after 1～2 hour, cool off in 80 ℃～120 ℃ reactions, add organic solvent, under the room temperature, stirring and dissolving, be homogeneous phase transparent solution, obtain the A component; Solidifying agent, promotor and organic solvent are mixed stirring and dissolving, the B component solution of acquisition homogeneous phase transparent; A, B component are mixed, stir, promptly get polyimide-epoxy resin adhesive.
The molecular structural formula of described dimaleoyl imino polyimide (MHPI) powder is:
Described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane, N, N, N ', N '-four glycidyl group-4,4, N, N, N ', the mixture of one or more in N '-four glycidyl group-3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, the thermoplastic phenolic Resins, epoxy;
Described organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), methylene dichloride, ethylene dichloride, trichloromethane, toluene, acetone, tetrahydrofuran (THF), methyltetrahydrofuran, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, the ethylene glycol diethyl ether;
Described solidifying agent is selected from pyromellitic acid anhydride, oxygen supports two phthalic anhydrides, 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride, biphenyl dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, phthalic anhydride, methyl tetrahydro phthalic anhydride, maleic anhydride, the Nai Dike acid anhydrides, methyl Nai Dike acid anhydrides, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 4,4 '-the diamino biphenyl, 3,3 '-diaminodiphenylsulfone(DDS), 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 1, two (3-amino-benzene oxygen) benzene of 4-, 2, two (4-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (3-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (4-amino-benzene oxygen) toluene of 6-, 2, two (4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (4-amino-benzene oxygen) toluene of 5-, 2, two (4-amino-benzene oxygen) tert-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) toluene of 5-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) tert.-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (3-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-diamino-4 " the hydroxyl tritane; 3,3 '-diamino-4; 4 '-dihydroxybiphenyl; 3; 3 '-dihydroxyl-4,4 '-benzidine; 2, two (the 3-amino-4-hydroxy phenyl) propane of 2-, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 3, the mixture of one or more in the 5-diaminobenzoic acid;
Described promotor is selected from 2-ethyl-4-methylimidazole, glyoxal ethyline, 2,4-methylimidazole, 2-ethyl imidazol(e), 2,4,6-three (dimethylamino methyl) phenol, benzyldimethylamine, triethylamine, tripropyl amine, Tributylamine, 1,8-diaza-dicyclo [5.4.0] hendecene-7, to certain herbaceous plants with big flowers diacid two hydrazides, m-phthalic acid hydrazides, Whitfield's ointment hydrazides, hexanodioic acid hydrazides, boron trifluoride-2, one or more mixtures in the 4-dimethyl benzene amine complex.
Polyimide-epoxy resin adhesive of the present invention can be applicable to high-tech areas such as electronics microelectronics, flexible copper clad foil plate (FCCL), flexible printed circuit board (FPC), rigid copper coated foil plate (PCB), automobile, motor, aerospace, has broad application prospects.
Get an amount of polyimide-epoxy resin adhesive of the present invention, and evenly be coated in the test piece of standard iron and steel, be cured: be heated to 100 ℃ from room temperature, insulation 1h continues to be warming up to 160 ℃, insulation 2h, continue to be warming up to 180 ℃, insulation 1h naturally cools to room temperature.
Beneficial effect
(1) the viscosity controllability of this polyimide-epoxy resin adhesive is good, can in broad scope, regulate, good manufacturability, and to metal base (comprising iron, copper, aluminium alloy etc.) adhesiveproperties excellence, its tensile shear strength (base material: iron and steel) up to 30Mpa;
(2) preparation technology of the present invention is simple, cost is low, easy to operate, the reaction raw materials convenient sources can be finished preparation process in general-purpose equipment, help realizing suitability for industrialized production.
Description of drawings
Fig. 1 is the molecular structural formula of dimaleoyl imino polyimide powder.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 10.0 gram dimaleoyl imino polyimide (MHPI) powder, 10.0 gram N, N, N ', N '-four glycidyl group-3,3 '-dimethyl-4,4 '-diaminodiphenylmethane and 60.0 gram thermoplastic phenolic Resins, epoxy add in the reactor, in 80 ℃～120 ℃ the reaction 1～2 hour after, cooling adds 65.5 gram N,N-dimethylacetamide organic solvents, under the room temperature, stirring and dissolving is homogeneous phase transparent solution, obtains the A component.
Restrain 2, two [4-(4-amino-benzene oxygen) phenyl] the HFC-236fa solidifying agent of 2-, 0.9 gram 2-ethyl-4-methylimidazole promotor and 34.5 gram N,N-dimethylacetamide organic solvents mixing, stirring and dissolving, the B component solution of acquisition homogeneous phase transparent with 19.1.
A, B component are mixed, stir, promptly get polyimide-epoxy resin adhesive, note is made PIEP-1.
Get an amount of PIEP-1 polyimide-epoxy resin adhesive, and evenly be coated in the test piece of standard iron and steel, superimposed, clamp, put into convection oven and be cured: be heated to 100 ℃ from room temperature, insulation 1h, continue to be warming up to 160 ℃, insulation 2h continues to be warming up to 180 ℃, insulation 1h naturally cools to room temperature.
This PIEP-1 polyimide-epoxy resin adhesive system viscosity controllability is good, can in broad scope, regulate, and good manufacturability, and to the adhesiveproperties excellence of metal base (as iron and steel etc.), its tensile shear strength is 30MPa (iron and steel a--iron and steel).
Embodiment 2
With 70.0 gram dimaleoyl imino polyimide (MHPI) powder and 10.0 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane adds in the reactor, in 80 ℃～120 ℃ reactions after 1～2 hour, and cooling, add 45.5 gram trichloromethanes and 20.0 gram N, the dinethylformamide organic solvent, under the room temperature, stirring and dissolving, be homogeneous phase transparent solution, obtain the A component.
With 9.8 grams 2, two (3-amino-4-hydroxy phenyl) the HFC-236fa solidifying agent of 2-, 0.2 gram 1,8-diaza-dicyclo [5.4.0] hendecene-7 promotor and 44.5 gram N,N-dimethylacetamide organic solvents mix, stirring and dissolving, the B component solution of acquisition homogeneous phase transparent.
A, B component are mixed, stir, promptly get polyimide-epoxy resin adhesive, note is made PIEP-2.
Get an amount of PIEP-2 polyimide-epoxy resin adhesive, and evenly be coated in the test piece of standard iron and steel, superimposed, clamp, put into convection oven and be cured: be heated to 100 ℃ from room temperature, insulation 1h, continue to be warming up to 160 ℃, insulation 2h continues to be warming up to 180 ℃, insulation 1h naturally cools to room temperature.
This PIEP-2 polyimide-epoxy resin adhesive system viscosity controllability is good, can in broad scope, regulate, and good manufacturability, and to the adhesiveproperties excellence of metal base (as iron and steel etc.), its tensile shear strength is 23MPa (iron and steel a--iron and steel).
Embodiment 3
With 24.0 gram dimaleoyl imino polyimide (MHPI) powder, 40.0 gram thermoplastic phenolic Resins, epoxy and 20.0 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane adds in the reactor, after 1～2 hour, cooling adds 50.0 gram methylene dichloride and 10.0 gram N-N-methyl-2-2-pyrrolidone N-organic solvents in 80 ℃～120 ℃ reactions, under the room temperature, stirring and dissolving is homogeneous phase transparent solution, obtains the A component.
With 15.5 grams 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane two anhydride curing agents of 2-, 0.5 gram 1,8-diaza-dicyclo [5.4.0] hendecene-7 promotor and 40.0 gram N-N-methyl-2-2-pyrrolidone N-organic solvents mix, stirring and dissolving, the B component solution of acquisition homogeneous phase transparent.
A, B component are mixed, stir, promptly get polyimide-epoxy resin adhesive, note is made PIEP-3.
Get an amount of PIEP-3 polyimide-epoxy resin adhesive, and evenly be coated in the test piece of standard iron and steel, superimposed, clamp, put into convection oven and be cured: be heated to 100 ℃ from room temperature, insulation 1h, continue to be warming up to 160 ℃, insulation 2h continues to be warming up to 180 ℃, insulation 1h naturally cools to room temperature.
This PIEP-3 polyimide-epoxy resin adhesive system viscosity controllability is good, can in broad scope, regulate, and good manufacturability, and to the adhesiveproperties excellence of metal base (as iron and steel etc.), its tensile shear strength is 24MPa (iron and steel a--iron and steel).
Claims (10)
1. polyimide-epoxy resin adhesive, its component comprises: the dimaleoyl imino polyimide MHPI powder of mass percent 5%-35%, the polyfunctional epoxy resin of mass percent 5%-35%, the solidifying agent of mass percent 5%-10% and the organic solvent of promotor and mass percent 45%-65%.
2. a kind of polyimide-epoxy resin adhesive according to claim 1 is characterized in that: the molecular structural formula of described dimaleoyl imino polyimide MHPI powder is:
Described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane, N, N, N ', N '-four glycidyl group-4,4, N, N, N ', the mixture of one or more in N '-four glycidyl group-3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, the thermoplastic phenolic Resins, epoxy; Organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), methylene dichloride, ethylene dichloride, trichloromethane, toluene, acetone, tetrahydrofuran (THF), methyltetrahydrofuran, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, the ethylene glycol diethyl ether; Solidifying agent is selected from pyromellitic acid anhydride, oxygen supports two phthalic anhydrides, 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride, biphenyl dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, phthalic anhydride, methyl tetrahydro phthalic anhydride, maleic anhydride, the Nai Dike acid anhydrides, methyl Nai Dike acid anhydrides, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 4,4 '-the diamino biphenyl, 3,3 '-diaminodiphenylsulfone(DDS), 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 1, two (3-amino-benzene oxygen) benzene of 4-, 2, two (4-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (3-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (4-amino-benzene oxygen) toluene of 6-, 2, two (4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (4-amino-benzene oxygen) toluene of 5-, 2, two (4-amino-benzene oxygen) tert-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) toluene of 5-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) tert.-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (3-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-diamino-4 " the hydroxyl tritane; 3,3 '-diamino-4; 4 '-dihydroxybiphenyl; 3; 3 '-dihydroxyl-4,4 '-benzidine; 2, two (the 3-amino-4-hydroxy phenyl) propane of 2-, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 3, the mixture of one or more in the 5-diaminobenzoic acid; Promotor is selected from 2-ethyl-4-methylimidazole, glyoxal ethyline, 2,4-methylimidazole, 2-ethyl imidazol(e), 2,4,6-three (dimethylamino methyl) phenol, benzyldimethylamine, triethylamine, tripropyl amine, Tributylamine, 1,8-diaza-dicyclo [5.4.0] hendecene-7, to certain herbaceous plants with big flowers diacid two hydrazides, m-phthalic acid hydrazides, Whitfield's ointment hydrazides, hexanodioic acid hydrazides, boron trifluoride-2, one or more mixtures in the 4-dimethyl benzene amine complex.
3. a kind of polyimide-epoxy resin adhesive according to claim 1 is characterized in that: the weight ratio of described solidifying agent and promotor is 20-50: 1.
4. the preparation method of a polyimide-epoxy resin adhesive comprises:
According to aforementioned proportion dimaleoyl imino polyimide MHPI powder and polyfunctional epoxy resin are added in the reactor, after 1～2 hour, cooling adds organic solvent in 80 ℃～120 ℃ reactions, and under the room temperature, stirring and dissolving is homogeneous phase transparent solution, obtains the A component; Solidifying agent, promotor and organic solvent are mixed stirring and dissolving, the B component solution of acquisition homogeneous phase transparent; A, B component are mixed, stir, promptly get polyimide-epoxy resin adhesive.
5. the preparation method of a kind of polyimide-epoxy resin adhesive according to claim 4, it is characterized in that: the molecular structural formula of described dimaleoyl imino polyimide MHPI powder is:
6. the preparation method of a kind of polyimide-epoxy resin adhesive according to claim 4, it is characterized in that: described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylsulfone(DDS), N, N, N ', N '-four glycidyl group-3,3 '-dimethyl-4,4 '-one or more mixture in the diaminodiphenylmethane, thermoplastic phenolic Resins, epoxy.
7. the preparation method of a kind of polyimide-epoxy resin adhesive according to claim 4, it is characterized in that: described organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), methylene dichloride, ethylene dichloride, trichloromethane, toluene, acetone, tetrahydrofuran (THF), methyltetrahydrofuran, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, the ethylene glycol diethyl ether.
8. the preparation method of a kind of polyimide-epoxy resin adhesive according to claim 4, it is characterized in that: described solidifying agent is selected from pyromellitic acid anhydride, oxygen supports two phthalic anhydrides, 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride, biphenyl dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, phthalic anhydride, methyl tetrahydro phthalic anhydride, maleic anhydride, the Nai Dike acid anhydrides, methyl Nai Dike acid anhydrides, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane, 4,4 '-the diamino biphenyl, 3,3 '-diaminodiphenylsulfone(DDS), 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 1, two (3-amino-benzene oxygen) benzene of 4-, 2, two (4-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (3-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (4-amino-benzene oxygen) toluene of 6-, 2, two (4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (4-amino-benzene oxygen) toluene of 5-, 2, two (4-amino-benzene oxygen) tert-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) toluene of 5-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) tert.-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (3-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-diamino-4 " hydroxyl tritane; 3; 3 '-diamino-4,4 '-dihydroxybiphenyl; 3,3 '-dihydroxyl-4; 4 '-benzidine; 2, two (the 3-amino-4-hydroxy phenyl) propane of 2-, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 3, the mixture of one or more in the 5-diaminobenzoic acid.
9. the preparation method of a kind of polyimide-epoxy resin adhesive according to claim 4, it is characterized in that: described promotor is selected from 2-ethyl-4-methylimidazole, glyoxal ethyline, 2, the 4-methylimidazole, the 2-ethyl imidazol(e), 2,4,6-three (dimethylamino methyl) phenol, benzyldimethylamine, triethylamine, tripropyl amine, Tributylamine, 1,8-diaza-dicyclo [5.4.0] hendecene-7, to certain herbaceous plants with big flowers diacid two hydrazides, the m-phthalic acid hydrazides, the Whitfield's ointment hydrazides, the hexanodioic acid hydrazides, boron trifluoride-2, one or more mixtures in the 4-dimethyl benzene amine complex.
10. polyimide-epoxy resin adhesive of the present invention is applied to electronics microelectronics, flexible copper clad foil plate FCCL, flexible printed circuit board FPC, rigid copper coated foil plate PCB, automobile, motor, aerospace high-tech area.
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| CN102643602A (en) * | 2012-04-19 | 2012-08-22 | 东华大学 | Polyimide-epoxy type electrical insulating paint and preparation method thereof |
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