CN101914357A - Epoxy-organic silicon polyimide adhesive and preparation method thereof - Google Patents
Epoxy-organic silicon polyimide adhesive and preparation method thereof Download PDFInfo
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- CN101914357A CN101914357A CN2010102476673A CN201010247667A CN101914357A CN 101914357 A CN101914357 A CN 101914357A CN 2010102476673 A CN2010102476673 A CN 2010102476673A CN 201010247667 A CN201010247667 A CN 201010247667A CN 101914357 A CN101914357 A CN 101914357A
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Abstract
The invention relates to an epoxy-organic silicon polyimide adhesive comprising the following components: organic silicon polyimide (SPI) resin, multifunctional epoxy resin, a curing agent, an accelerating agent and an organic solvent. The preparation method of the epoxy-organic silicon polyimide adhesive comprises the following steps of: adding the SPI resin to a reactor for reacting for 0.5 hours at 130 DEG C, then cooling, adding the organic solvent, and stirring for dissolution to obtain a component A; stirring the curing agent, the accelerating agent and the organic solvent for dissolution to obtain a component solution B; and when in use, uniformly mixing and stirring the components A, B to obtain the epoxy-organic silicon polyimide adhesive. The tensile sheering strength of the epoxy-organic silicon polyimide adhesive reaches 25.4 MPa at the room temperature, and the epoxy-organic silicon polyimide adhesive also has the advantages of excellent heat resistance, strong hydrophobicity, simple preparation process and low cost, is beneficial to realizing industrial production and has extensive application prospects in the fields of electronics, microelectronics, flexible copper--clad laminates, flexible printed circuit boards, hard copper-clad laminates, motors, aerospace and the like.
Description
Technical field
The invention belongs to the organic polymer binder preparation field, particularly relate to a kind of epoxy-organic silicon polyimide adhesive and preparation method thereof.
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, toughner, 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.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.
Present method is though by the synthetic polyetherimide resin (HPEI) that contains active reactive group (hydroxyl, unsaturated double-bond), carried out toughening modifying to Resins, epoxy, and obtained better technical effect.But, also there are some shortcomings:
(1) the 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.
Two (3-amino-4-hydroxy phenyl) the HFC-236fa monomers such as (BAHPFP) of (2) 2,2-cost an arm and a leg, and cause the cost of polyetherimide resin (HPEI) and tackiness agent very high, are unfavorable for large-scale promotion application, can only be confined to some special dimension.
Summary of the invention
Technical problem to be solved by this invention provides a kind of epoxy-organic silicon polyimide adhesive and preparation method thereof, and the consistency of this adhesive composition own is good, and the reactive group controllability is good, toughness and excellent heat resistance, strong (rate of moisture absorption≤0.05% of hydrophobicity; Water-intake rate≤0.2%), anti-atomic oxygen, excellent combination property, the room temperature tensile shearing resistance of this epoxy-organic silicon polyimide adhesive also has excellent thermotolerance up to 25.4MPa, and the tensile shear strength in the time of 120 ℃ is up to 12.6MPa; 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; In fields such as electronics microelectronics, flexible copper clad foil plate (FCCL), flexible printed circuit board (FPC), rigid copper coated foil plate (PCB), motor, aerospace, have broad application prospects.
A kind of epoxy-organic silicon polyimide adhesive of the present invention, its component comprises: the organic solvent of the solidifying agent of the organic silicon polyimide SPI resin of 10wt%-15wt%, the polyfunctional epoxy resin of 15wt%-35wt%, 5wt%-10wt% and promotor (being that both content sums are 5wt%-10wt%), 45wt%-65wt%.
Described organic silicon polyimide resin is provided by Shanghai EMST Electron Material Co., Ltd, and its molecular structural formula 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, the mixture of one or more 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, the mixture of one or more in the 4-dimethyl benzene amine complex.
The preparation method of a kind of epoxy-organic silicon polyimide adhesive of the present invention comprises:
(1) according to the said components ratio organic silicon polyimide SPI resin and polyfunctional epoxy resin are added in the reactor, after 0.5 hour, cooling adds organic solvent in 130 ℃ of reactions, and under the room temperature, stirring and dissolving is the homogeneous phase transparent viscous liquid, obtains the A component;
(2) with solidifying agent, promotor and organic solvent, stirring and dissolving under room temperature, the B component solution of acquisition homogeneous phase transparent;
When (3) using, A, B component are mixed, under room temperature, stir, promptly get epoxy-organic silicon polyimide adhesive.
Beneficial effect
(1) the viscosity controllability of epoxy-organic silicon polyimide adhesive provided by the invention is good, can in broad scope, regulate, good manufacturability, and to metal base (comprising iron, copper, aluminium alloy, glass, pottery etc.) adhesiveproperties excellence, stainless steel) and 17.5MPa (base material: glass) its room temperature tensile shearing resistance 25.4MPa (base material:, also has excellent thermotolerance, (base material: stainless steel), hydrophobicity is (rate of moisture absorption≤0.05% by force up to 12.6MPa for tensile shear strength in the time of 120 ℃; Water-intake rate≤0.2%), anti-atomic oxygen, excellent combination property 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;
(2) this preparation technology 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 organic silicon polyimide resin.
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 20.0 gram organic silicon polyimide (SPI) resins, 30.0 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane and 30.0 gram thermoplastic phenolic Resins, epoxy add in the reactors, in 130 ℃ of reactions after 0.5 hour, and cooling, add 40.0 gram N, N-N,N-DIMETHYLACETAMIDE organic solvent, under the room temperature, stirring and dissolving, be the homogeneous phase transparent viscous liquid, obtain the A component.
With 2.1 grams 4,4 '-diaminodiphenylsulfone(DDS) and 17.0 grams 4,4 '-two (3-amino-benzene oxygen) sulfobenzide solidifying agent, 0.9 gram 2-ethyl-4-methylimidazole promotor and 60.0 gram N,N-dimethylacetamide organic solvents mix, stirring and dissolving under room temperature, the B component solution of acquisition homogeneous phase transparent.
A, B component are mixed, stir under room temperature, promptly get epoxy-organic silicon polyimide adhesive, note is made ESPIA-1.
Get an amount of ESPIA-1 epoxy-organic silicon polyimide adhesive, and evenly be coated in the normal glass test piece, superimposed, clamp, put into convection oven and be cured: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour, continue to be warming up to 120 ℃, insulation reaction 2 hours continues to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
This ESPIA-1 epoxy-organic silicon polyimide adhesive system viscosity controllability is good, can in broad scope, regulate, good manufacturability, and to the adhesiveproperties excellence of glass baseplate, its room temperature (25 ℃) tensile shear strength is a 17.5MPa (base material: glass); Tensile shear strength in the time of 120 ℃ is a 12.6MPa (base material: stainless steel).
Replace above-mentioned glass coupon, revision test with stainless steel test piece, aluminium alloy test piece and copper test piece.The result shows: room temperature (25 ℃) tensile shear strength is: 25.4MPa (base material: stainless steel); 23.1MPa (base material: copper); 15.2MPa (base material: aluminium alloy).
Get an amount of ESPIA-1 epoxy-organic silicon polyimide adhesive, on polytetrafluoroethylene film, push away film, place vacuum drying oven, in 30 ℃-40 ℃ temperature range, vacuumize, remove organic solvent, subsequently, the solventfree resin tackiness agent is made the square sample that is of a size of 5mm * 5mm * 1mm, curing process is: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour continues to be warming up to 120 ℃, insulation reaction 2 hours, continue to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
The square sample of above-mentioned exsiccant is weighed after (W1), be soaked in the deionized water (25 ℃), after 72 hours, take out, dry the surface with filter paper, weigh (W2), calculating water-intake rate is 0.12%.
The square sample of above-mentioned exsiccant is weighed after (G1), be positioned over climatic chamber (85 ℃, RH85%) in, after 72 hours, take out, dry the surface with filter paper, weigh (G2), calculating rate of moisture absorption is 0.03%.
Embodiment 2
With 30.0 gram organic silicon polyimide (SPI) resins, 20.0 gram N, N, N ', N '-four glycidyl group-3,3 '-dimethyl-4,4 '-diaminodiphenylmethane and 40.0 gram thermoplastic phenolic Resins, epoxy add in the reactor, in 130 ℃ the reaction 0.5 hour after, cooling adds 20.0 gram N, dinethylformamide and 20.0 gram ethylene dichloride organic solvents, under the room temperature, stirring and dissolving is the homogeneous phase transparent viscous liquid, obtains the A component.
With 3.0 grams 4,4 '-diaminodiphenylsulfone(DDS) and 6.0 grams 2, two (2-trifluoromethyl-4-amino-benzene oxygen) the tert.-butylbenzene solidifying agent of 5-, 1.0 gram 2-ethyl imidazol(e) promotor and 60.0 gram N, the dinethylformamide organic solvent mixes, stirring and dissolving under room temperature, the B component solution of acquisition homogeneous phase transparent.
A, B component are mixed, stir under room temperature, promptly get epoxy-organic silicon polyimide adhesive, note is made ESPIA-2.
Get an amount of ESPIA-2 epoxy-organic silicon polyimide adhesive, and evenly be coated in the normal glass test piece, superimposed, clamp, put into convection oven and be cured: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour, continue to be warming up to 120 ℃, insulation reaction 2 hours continues to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
This ESPIA-2 epoxy-organic silicon polyimide adhesive system viscosity controllability is good, can in broad scope, regulate, good manufacturability, and to the adhesiveproperties excellence of glass baseplate, its room temperature (25 ℃) tensile shear strength is a 16.2MPa (base material: glass); Tensile shear strength in the time of 120 ℃ is a 11.5MPa (base material: stainless steel).
Replace above-mentioned glass coupon, revision test with stainless steel test piece, aluminium alloy test piece and copper test piece.The result shows: room temperature (25 ℃) tensile shear strength is: 22.1MPa (base material: stainless steel); 21.7MPa (base material: copper); 11.7MPa (base material: aluminium alloy).
Get an amount of ESPIA-2 epoxy-organic silicon polyimide adhesive, on polytetrafluoroethylene film, push away film, place vacuum drying oven, in 30 ℃-40 ℃ temperature range, vacuumize, remove organic solvent, subsequently, the solventfree resin tackiness agent is made the square sample that is of a size of 5mm * 5mm * 1mm, curing process is: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour continues to be warming up to 120 ℃, insulation reaction 2 hours, continue to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
The square sample of above-mentioned exsiccant is weighed after (W1), be soaked in the deionized water (25 ℃), after 72 hours, take out, dry the surface with filter paper, weigh (W2), calculating water-intake rate is 0.10%.
The square sample of above-mentioned exsiccant is weighed after (G1), be positioned over climatic chamber (85 ℃, RH85%) in, after 72 hours, take out, dry the surface with filter paper, weigh (G2), calculating rate of moisture absorption is 0.02%.
Embodiment 3
With 20.0 gram organic silicon polyimide (SPI) resins, 40.0 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane and 30.0 gram thermoplastic phenolic Resins, epoxy add in the reactors, in 130 ℃ of reactions after 0.5 hour, and cooling, add 35.0 gram N, N-N,N-DIMETHYLACETAMIDE organic solvent, under the room temperature, stirring and dissolving, be the homogeneous phase transparent viscous liquid, obtain the A component.
With 2.0 grams 4,4 '-diamino bismethane and 7.0 gram methyl tetrahydro phthalic anhydride solidifying agent, 1.0 gram 2-ethyl-4-methylimidazole promotor and 65.0 gram N,N-dimethylacetamide organic solvents mix, stirring and dissolving under room temperature obtains the B component solution of homogeneous phase transparent.
A, B component are mixed, stir under room temperature, promptly get epoxy-organic silicon polyimide adhesive, note is made ESPIA-3.
Get an amount of ESPIA-3 epoxy-organic silicon polyimide adhesive, and evenly be coated in the normal glass test piece, superimposed, clamp, put into convection oven and be cured: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour, continue to be warming up to 120 ℃, insulation reaction 2 hours continues to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
This ESPIA-3 epoxy-organic silicon polyimide adhesive system viscosity controllability is good, can in broad scope, regulate, good manufacturability, and to the adhesiveproperties excellence of glass baseplate, its room temperature (25 ℃) tensile shear strength is a 17.2MPa (base material: glass); Tensile shear strength in the time of 120 ℃ is a 12.0MPa (base material: stainless steel).
Replace above-mentioned glass coupon, revision test with stainless steel test piece, aluminium alloy test piece and copper test piece.The result shows: room temperature (25 ℃) tensile shear strength is: 24.1MPa (base material: stainless steel); 25.3MPa (base material: copper); 14.7MPa (base material: aluminium alloy).
Get an amount of ESPIA-3 epoxy-organic silicon polyimide adhesive, on polytetrafluoroethylene film, push away film, place vacuum drying oven, in 30 ℃-40 ℃ temperature range, vacuumize, remove organic solvent, subsequently, the solventfree resin tackiness agent is made the square sample that is of a size of 5mm * 5mm * 1mm, curing process is: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour continues to be warming up to 120 ℃, insulation reaction 2 hours, continue to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
The square sample of above-mentioned exsiccant is weighed after (W1), be soaked in the deionized water (25 ℃), after 72 hours, take out, dry the surface with filter paper, weigh (W2), calculating water-intake rate is 0.2%.
The square sample of above-mentioned exsiccant is weighed after (G1), be positioned over climatic chamber (85 ℃, RH85%) in, after 72 hours, take out, dry the surface with filter paper, weigh (G2), calculating rate of moisture absorption is 0.05%.
Embodiment 4
With 10.0 gram organic silicon polyimide (SPI) resins, 10.0 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane and 5.0 gram thermoplastic phenolic Resins, epoxy add in the reactors, in 130 ℃ of reactions after 0.5 hour, and cooling, add 10.0 gram N, N-N,N-DIMETHYLACETAMIDE organic solvent, under the room temperature, stirring and dissolving, be the homogeneous phase transparent viscous liquid, obtain the A component.
With 9.5 grams 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa solidifying agent of 2-, 0.5 gram 2-ethyl-4-methylimidazole promotor and 55.0 gram N, N-N,N-DIMETHYLACETAMIDE organic solvent mixes, stirring and dissolving under room temperature, the B component solution of acquisition homogeneous phase transparent.
A, B component are mixed, stir under room temperature, promptly get epoxy-organic silicon polyimide adhesive, note is made ESPIA-4.
Get an amount of ESPIA-4 epoxy-organic silicon polyimide adhesive, and evenly be coated in the normal glass test piece, superimposed, clamp, put into convection oven and be cured: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour, continue to be warming up to 120 ℃, insulation reaction 2 hours continues to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
This ESPIA-4 epoxy-organic silicon polyimide adhesive system viscosity controllability is good, can in broad scope, regulate, good manufacturability, and to the adhesiveproperties excellence of glass baseplate, its room temperature (25 ℃) tensile shear strength is a 14.3MPa (base material: glass); Tensile shear strength in the time of 120 ℃ is a 11.5MPa (base material: stainless steel).
Replace above-mentioned glass coupon, revision test with stainless steel test piece, aluminium alloy test piece and copper test piece.The result shows: room temperature (25 ℃) tensile shear strength is: 24.9MPa (base material: stainless steel); 25.1MPa (base material: copper); 11.3MPa (base material: aluminium alloy).
Get an amount of ESPIA-4 epoxy-organic silicon polyimide adhesive, on polytetrafluoroethylene film, push away film, place vacuum drying oven, in 30 ℃-40 ℃ temperature range, vacuumize, remove organic solvent, subsequently, the solventfree resin tackiness agent is made the square sample that is of a size of 5mm * 5mm * 1mm, curing process is: begin to be warming up to 80 ℃ from room temperature, insulation reaction 1 hour continues to be warming up to 120 ℃, insulation reaction 2 hours, continue to be warming up to 150 ℃, insulation reaction 0.5 hour naturally cools to room temperature.
The square sample of above-mentioned exsiccant is weighed after (W1), be soaked in the deionized water (25 ℃), after 72 hours, take out, dry the surface with filter paper, weigh (W2), calculating water-intake rate is 0.2%.
The square sample of above-mentioned exsiccant is weighed after (G1), be positioned over climatic chamber (85 ℃, RH85%) in, after 72 hours, take out, dry the surface with filter paper, weigh (G2), calculating rate of moisture absorption is 0.04%.
Claims (7)
1. epoxy-organic silicon polyimide adhesive, its component comprises: the organic solvent of the solidifying agent of the organic silicon polyimide SPI resin of 10wt%-15wt%, the polyfunctional epoxy resin of 15wt%-35wt%, 5wt%-10wt% and promotor, 45wt%-65wt%.
2. a kind of epoxy-organic silicon polyimide adhesive according to claim 1 is characterized in that: described organic silicon polyimide resin, and its molecular structural formula is:
3. a kind of epoxy-organic silicon polyimide adhesive according to claim 1 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.
4. a kind of epoxy-organic silicon polyimide adhesive according to claim 1, it is characterized in that: described organic solvent is selected from N, the mixture of one or more 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.
5. a kind of epoxy-organic silicon polyimide adhesive according to claim 1, 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.
6. a kind of epoxy-organic silicon polyimide adhesive according to claim 1, it is characterized in that: 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, the mixture of one or more in the 4-dimethyl benzene amine complex.
7. the preparation method of an epoxy-organic silicon polyimide adhesive comprises:
(1) according to the said components ratio organic silicon polyimide SPI resin and polyfunctional epoxy resin are added in the reactor, after 0.5 hour, cooling adds organic solvent in 130 ℃ of reactions, and under the room temperature, stirring and dissolving is the homogeneous phase transparent viscous liquid, obtains the A component;
(2) with solidifying agent, promotor and organic solvent, stirring and dissolving under room temperature, the B component solution of acquisition homogeneous phase transparent;
When (3) using, A, B component are mixed, under room temperature, stir, promptly get epoxy-organic silicon polyimide adhesive.
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