CN103131368A - 4,4'-bis(2,4-diamidophenoxy)diphenyl ether high-temperature-resistant epoxy adhesive and preparation method thereof - Google Patents
4,4'-bis(2,4-diamidophenoxy)diphenyl ether high-temperature-resistant epoxy adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a 4,4'-bis(2,4-diamidophenoxy)diphenyl ether high-temperature-resistant epoxy adhesive and a preparation method thereof. The 4,4'-bis(2,4-diamidophenoxy)diphenyl ether high-temperature-resistant epoxy adhesive is composed of a component A and a component B in a mass ratio of 1:(1-2), wherein the component A is a copolymer prepared by reacting 4,4'-bis(2,4-diamido phenoxy)diphenyl ether and epoxy resin; and the component B is a homogeneous-phase transparent solution with the solid content of 15-30%, which is prepared by reacting 4,4'-bis(2,4-diamidophenoxy)diphenyl ether and aromatic dibasic acid anhydride in a strong-polarity non-proton organic solvent and toluene. The preparation method comprises the following step: evenly mixing the component A and the component B in a mass ratio of 1:(1-2) at room temperature. The preparation technique is simple; and the adhesive has excellent comprehensive properties, can be widely used for bonding steel, copper, aluminum or any other metal with ceramic, glass, resin-base composite material or any other substrate, and has favorable industrialization prospects.
Description
Technical field
The invention belongs to epoxyn and preparation field thereof, particularly a kind of 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive and preparation method thereof.
Background technology
As everyone knows, epoxy resin has many good 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, polymer matrix composites, timber, plastics etc.) is very high, what have even surpasses by the intensity of sticking material itself, therefore can be used in many stress members, is one of main component of structure-type tackiness agent; (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 curing of epoxy resin is mainly the ring opening polyaddition that relies on epoxy group(ing), therefore do not produce low-molecular material in solidification process, its cure shrinkage is one of kind minimum in thermosetting resin, be generally 1%-2%, if select suitable filler can make shrinking percentage be down to 0.2% left and right; Epoxy resin main chain after curing 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: be no matter high-technology field or current techique field, no matter be defence and military or civilian industry, and even all can see its trace in daily life.
Relevant epoxyn system has had a lot of research reports, and a lot of patents of invention are also arranged:
Yan Rui, and the people such as Yu Xinhai [preparation of novel epoxy tackiness agent and performance study, insulating material, 2012,45(2): 12-14,18] a kind of neo-epoxy resin tackiness agent and preparation method thereof is disclosed, and its performance has been carried out systematic research.
The people such as Yu Xinhai [preparation and the performance study of organosilicon epoxy systems tackiness agent, insulating material, 2012,45(2): 1-3,11] disclose a kind of adhesive composition of silicone resin modified epoxy, and its performance has been studied, obtained simultaneously the superior tackiness agent of over-all properties.
Chinese invention patent CN101503608B discloses a kind of preparation method of phenolic epoxy resin system conductive adhesive, and has obtained the superior electro-conductive adhesive product of over-all properties.
The people such as Yu Xinhai have applied for Chinese invention patent CN102220102A, disclose a kind of high-temperature-resistant adhesive and preparation method thereof.
Chinese invention patent CN102260480A discloses a kind of high-temperature-resistant modified epoxy resin adhesive and preparation method thereof.
Chinese invention patent CN102181251A discloses epoxyn of a kind of unsaturated polyimides modification and preparation method thereof.
Chinese invention patent CN102031082A discloses a kind of benzimidazole diamine curing type epoxy adhesive and preparation method thereof.
Chinese invention patent CN101649174A discloses a kind of high temperature resistant one-component solvent-free epoxy adhesive and preparation method thereof.
Chinese invention patent CN101544879A discloses a kind of preparation method of high strength solventless epoxy adhesive.
The people such as Wu Min [development of novel high-strength one-component epoxy resin adhesive, bonding, 2009,30(9): 54-57] and a kind of epoxy binder in monocomponent in is disclosed, excellent combination property particularly has very high tensile shear strength.
The people such as Chen Hongjiang [the cure kinetics research of neo-epoxy resin adhesive system, bonding, 2009,30(8): 43-45] a kind of epoxyn system is disclosed, and its cure kinetics is studied.
The people such as Fei Fei [preparation of high temperature resistant epoxy binder in monocomponent in, bonding, 2009,30(12): 34-37] disclose a kind of one-component thermostable epoxy adhesive.
The people such as Xu Meifang [the cure kinetics research of polyimide-epoxy resin tackiness agent, chemical and bonding, 2011,33(2): 17-20] a kind of polyimide-epoxy resin tackiness agent is disclosed, and it has been carried out cure kinetics research.
The people such as Li En [preparation of high strength epoxy binder in monocomponent in and performance study thereof, insulating material, 2012,45(1): 12-14] a kind of high strength epoxy binder in monocomponent in is disclosed, and its performance has been carried out systematic research.
Chinese invention patent CN101148656A, a kind of preparation method of heat-resistant solvent-free epoxy adhesive is disclosed, be primarily characterized in that: TGDDM epoxy resin, 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 larger limitation, fails to satisfy the practical application under many hot environments.
Chinese invention patent CN101397486A, a kind of preparation method of two-pack solvent-free epoxy resin tackiness agent is disclosed, 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 4,4 '-two (2,4-diamino phenoxy) phenyl ether aromatic polyamine solidifying agent.The addition of alicyclic type epoxy resin and nbr carboxyl terminal is respectively 20-35% and the 12%(mass percent of novolac epoxy).The addition of 4,4 '-two (2,4-diamino phenoxy) phenyl ether aromatic polyamine solidifying agent is the 15-20%(mass percent of novolac epoxy), gained adhesive system good manufacturability.But its resistance toheat is desirable not enough.
Chinese invention patent CN1927908A, a kind of preparation method of phenolic hydroxyl group containing polyimide powder is disclosed, existence due to phenolic hydroxyl group, its polyimide powder can with epoxy reaction, form covalent linkage, thereby can improve the consistency of thermoplastic polyimide resin and epoxy resin, and can further make epoxy-resin systems reach good toughening effect.
the 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: take maleic anhydride (MA) as 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-, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) obtained phenolic hydroxy group polyetherimide resin (HPEI) for main raw material is synthetic, take synthesized the HPEI that obtains as resistant, toughened dose, with N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl oxide (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.
The method is although by the synthetic polyetherimide resin (HPEI) that contains active reactive group (hydroxyl, unsaturated double-bond), carried out toughening modifying to epoxy resin, and obtained technique effect preferably.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.
The monomers such as two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of (2) 2,2-are expensive, 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 is to provide a kind of 4,4 '-two (2, the 4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive and preparation method thereof, this adhesive system bonding strength is high, excellent combination property, can be applicable to the bonding of the base materials such as metal, glass, pottery, polymer matrix composites, have a good application prospect.
Of the present invention a kind of 4,4 '-two (2, the 4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive, the A component and the B component that are 1:1-2 by mass ratio form, wherein, the A component is by 4, the multipolymer that 4 '-two (2,4-diamino phenoxy) phenyl ether and epoxy resin reaction form; The B component is by 4, and 4 '-two (2,4-diamino phenoxy) phenyl ether and the aromatic dicarboxylic anhydride solid content that reaction forms in strong polar non-proton organic solvent and toluene is the homogeneous phase transparent solution of 15%-30%.
The preparation method of a kind of 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive of the present invention comprises:
(1) with epoxy resin and 4,4 '-two (2,4-diamino phenoxy) phenyl ether is put into reactor, is heated to 50 ℃-90 ℃, stirring reaction 0.5-2 hour, obtains the multipolymer of homogeneous phase transparent, i.e. the A component; Wherein, the epoxy group(ing) mole number and 4 of epoxy resin, the ratio of the mole number of 4 '-two (2,4-diamino phenoxy) phenyl ether is 16-20:1;
(2) under room temperature, with 4,4 '-two (2,4-diamino phenoxy) phenyl ether and strong polar non-proton organic solvent add in reactor, after stirring and dissolving is complete, add aromatic dicarboxylic anhydride, stirring reaction 0.5-1 hour, obtain homogeneous phase transparent solution; Wherein, 4,4 '-two (2,4-diamino phenoxy) phenyl ether is 1:3.5-4.2 with the ratio of the mole number of aromatic dicarboxylic anhydride; The quality and 4 of strong polar non-proton organic solvent, the ratio of the total mass of 4 '-two (2,4-diamino phenoxy) phenyl ether and aromatic dicarboxylic anhydride is 2-4:1; Add toluene, be heated to backflow, the reflux water-dividing range of reaction temperature is 100 ℃-130 ℃, reaction times 2-5 hour, after reaction is completed, tell the part organic solvent, and the solution solid content is in the scope of 15%-30%, get the B component; Wherein, toluene is 0.2-2:1 with the mass ratio of strong polar non-proton organic solvent;
(3) under room temperature, with A component, B component in mass ratio 1:1-2 mix and get final product.
Epoxy resin in described step (1) is selected from one or more in bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, glycidyl amine type epoxy resin, Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin.
Described bisphenol A type epoxy resin is selected from one or more in E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin.
described glycidyl amine type epoxy resin is selected from N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-dimethyl-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group 3, 3 '-diethyl-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group 3, 3 '-two chloro-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-diaminodiphenyl oxide 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 glycidyls-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 '-two (4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) biphenyl epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, N, N ', N ', O, O '-six glycidyl-2, two (3-amino-4-hydroxylphenyl) the HFC-236fa epoxy resin of 2-, N, N, O – triglycidyl group p-aminophenol epoxy resin, N, N, one or more in O – triglycidyl group Metha Amino Phenon epoxy resin.
Described Racemic glycidol ether type epoxy is selected from 1,3-diglycidyl Resorcinol, 1,4-diglycidyl Resorcinol, 4,4 '-diglycidyl bisphenol S, 2, one or more in two (the 4-glycidyl phenyl) HFC-236fa of 2-.
Described glycidyl ester type epoxy resin is selected from terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methyne tetrahydrophthalic acid 2-glycidyl ester epoxy resin, 4,5-epoxy cyclohexane-1, one or more in 2-dioctyl phthalate 2-glycidyl ester epoxy resin, the sad diglycidyl ether epoxy resin of adjacent benzene two.
aromatic dicarboxylic anhydride in described step (2) is selected from pyromellitic acid anhydride, 3, 3 ', 4, 4 '-tetracarboxylic phenyl ether dianhydride, 3, 3 ', 4, 4 '-tetracarboxylic phenyl ether dianhydride, 3, 3 ', 4, 4 '-tetracarboxylic biphenyl dianhydride, 3, 3 ', 4, 4 '-tetracarboxylic benzophenone dianhydride, 2, 2-two (3, 4-dicarboxyl phenyl) hexafluoropropane 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] the propane dianhydride, 4, 4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride, 4, 4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride, 4, 4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride, 4, 4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dianhydride, 4, 4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride, 1, 3-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 1, 4-two (3, the 4-di carboxyl phenyloxy) one or more in benzene dianhydride.
Strong polar non-proton organic solvent in described step (2) is selected from one or more in DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO).
Obtain in described step (3) 4,4 '-two (2, the 4-diamino phenoxy) curing process of diphenyl ether type high temperature resistant epoxy adhesive is: begin to be warming up to 80 ℃ from room temperature, keep after 1 hour, continue to be warming up to 120 ℃, keep continuing to be warming up to 150 ℃ after 2 hours, keep naturally cooling to room temperature after 2 hours.
Beneficial effect
(1) viscosity controllability of the present invention is good, can regulate in broader scope, good manufacturability, and excellent to metal base (comprising iron, copper, aluminium, aluminium alloy etc.) and non-metallic substrate (comprising polymer matrix composites, glass, pottery etc.) adhesiveproperties, hydrophobicity is strong, excellent combination property can be applicable to the bonding of the base materials such as metal, glass, pottery, polymer matrix composites, has a good application prospect;
(2) preparation technology of the present invention is simple, cost is low, easy to operate, the reaction raw materials convenient sources can be completed preparation process in general-purpose equipment, be conducive to realize suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention 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 limited range equally.
Embodiment 1
The preparation of A component
With 100 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane epoxy resin (oxirane value is 0.8) and 20.7 grams (0.05 mole) 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether is put into reactor, is heated to 50 ℃, stirring reaction 2 hours, obtain the multipolymer of 120.7 gram homogeneous phase transparent, be denoted as A1.
With 100 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane epoxy resin (oxirane value is 0.8) and 16.6 grams (0.04 mole) 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether is put into reactor, is heated to 60 ℃, stirring reaction 1 hour, obtain the multipolymer of 116.6 gram homogeneous phase transparent, be denoted as A2.
With 100 grams 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester epoxy resin (oxirane value is 0.85) and 19.5 grams (0.047 mole) 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether is put into reactor, is heated to 70 ℃, stirring reaction 1 hour, obtain the multipolymer of 119.5 gram homogeneous phase transparent, be denoted as A3.
With 100 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane epoxy resin (oxirane value is 0.8), 100 gram ES216 epoxy resin (oxirane value is 0.2), 150 gram ECC202 epoxy resin (oxirane value is 0.2) and 31.9 grams (0.077 mole) 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether is put into reactor, is heated to 80 ℃, stirring reaction 1 hour, obtain the multipolymer of 381.9 gram homogeneous phase transparent, be denoted as A4.
With 120 gram N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenylmethane epoxy resin (oxirane value is 0.8), 80 grams 1,3-diglycidyl Resorcinol (oxirane value is 0.8) is put into reactor with 33.1 grams (0.08 mole) 4,4 '-two (2,4-diamino phenoxy) phenyl ether, be heated to 90 ℃, stirring reaction 0.5 hour obtains the multipolymer of 233.1 gram homogeneous phase transparent, is denoted as A5.
Embodiment 2
The preparation of B component
under room temperature, with 41.4 grams (0.1 mole) 4, 4 '-two (2, the 4-diamino phenoxy) phenyl ether and 839 gram N, the N-N,N-DIMETHYLACETAMIDE adds in reactor, after stirring and dissolving is complete, add 104 grams (0.2 mole) 2, 2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride and 64.4 grams (0.2 mole) 3, 3 ', 4, 4 '-tetracarboxylic benzophenone dianhydride, stirring reaction 0.5 hour, obtain 1048.8 gram homogeneous phase transparent solution, add 170 gram toluene, be heated to backflow, carry out the reflux water-dividing reaction, its temperature is 100 ℃, 5 hours reaction times, after reaction is completed, tell the part organic solvent, its solid content is in the scope of 15%-30%, be denoted as B1.
under room temperature, with 41.4 grams (0.1 mole) 4, 4 '-two (2, the 4-diamino phenoxy) phenyl ether and 200 gram N, N-N,N-DIMETHYLACETAMIDE and 450 gram METHYLPYRROLIDONEs add in reactor, after stirring and dissolving is complete, add 104 grams (0.2 mole) 2, 2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride and 68.2 grams (0.22 mole) 3, 3 ', 4, 4 '-tetracarboxylic phenyl ether dianhydride, stirring reaction 1 hour, obtain 863.6 gram homogeneous phase transparent solution, add 650 gram toluene, be heated to backflow, carry out the reflux water-dividing reaction, its temperature is 120 ℃, 2 hours reaction times, after reaction is completed, tell the part organic solvent, its solid content is in the scope of 15%-30%, be denoted as B2.
under room temperature, with 41.4 grams (0.1 mole) 4, 4 '-two (2, the 4-diamino phenoxy) phenyl ether and 540 gram METHYLPYRROLIDONEs add in reactor, after stirring and dissolving is complete, add 83.2 grams (0.16 mole) 2, 2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride and 68.2 grams (0.22 mole) 3, 3 ', 4, 4 '-tetracarboxylic phenyl ether dianhydride, stirring reaction 0.5 hour, obtain 732.8 gram homogeneous phase transparent solution, add 1000 gram toluene, be heated to backflow, carry out the reflux water-dividing reaction, its temperature is 110 ℃, 3 hours reaction times, after reaction is completed, tell the part organic solvent, its solid content is in the scope of 15%-30%, be denoted as B3.
Embodiment 3
The preparation of 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive
Under room temperature, with A component, B component in mass ratio 1:1-2 mix, can obtain series 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive, be denoted as HTEA-p, p is natural number, specifically fills a prescription as shown in table 1.
Table 14,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive formula table unit: gram
| Component | A1 | A2 | A3 | A4 | A5 | B1 | B2 | B3 |
| HTEA-1 | 50.0 | 0 | 10.0 | 0 | 0 | 30.0 | 20.0 | 10.0 |
| HTEA-2 | 10.0 | 40.0 | 0 | 10.0 | 0 | 30.0 | 40.0 | 0 |
| HTEA-3 | 10.0 | 30.0 | 10.0 | 0 | 10.0 | 40.0 | 20.0 | 10.0 |
| HTEA-4 | 25.0 | 10.0 | 0 | 15.0 | 0 | 0 | 30.0 | 40.0 |
| HTEA-5 | 0 | 0 | 0 | 40.0 | 30.0 | 50.0 | 0 | 50.0 |
| HTEA-6 | 20.0 | 10.0 | 0 | 10.0 | 20.0 | 30.0 | 10.0 | 40.0 |
| HTEA-7 | 0 | 25.0 | 20.0 | 0 | 15.0 | 0 | 20.0 | 60.0 |
| HTEA-8 | 20.0 | 0 | 20.0 | 0 | 50.0 | 30.0 | 30.0 | 70.0 |
Embodiment 4
Get respectively appropriate 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive as shown in table 1, be HTEA-1～HTEA-8, and be coated on equably respectively in the test piece of standard stainless steel, superimposed, clamp, putting into convection oven is cured: begin to be warming up to 80 ℃ from room temperature, keep continuing to be warming up to 120 ℃ after 1 hour, keep after 2 hours, continue to be warming up to 150 ℃, keep naturally cooling to room temperature after 2 hours.Utilize electronic tensile machine, respectively its tensile shear strength that carries out under room temperature (25 ℃) and high temperature (150 ℃) condition is tested, result is as shown in table 2.
Get respectively appropriate 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive as shown in table 1, be HTEA-1～HTEA-8, and be coated on equably respectively in the standard copper test piece, superimposed, clamp, putting into convection oven is cured: begin to be warming up to 80 ℃ from room temperature, keep continuing to be warming up to 120 ℃ after 1 hour, keep after 2 hours, continue to be warming up to 150 ℃, keep naturally cooling to room temperature after 2 hours.Utilize electronic tensile machine, respectively its tensile shear strength that carries out under room temperature (25 ℃) and high temperature (150 ℃) condition is tested, result is as shown in table 2.
Get respectively appropriate 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive as shown in table 1, be HTEA-1～HTEA-8, and be coated on equably respectively in the test piece of standard epoxy resin bonded fiber, superimposed, clamp, putting into convection oven is cured: begin to be warming up to 80 ℃ from room temperature, keep continuing to be warming up to 120 ℃ after 1 hour, keep after 2 hours, continue to be warming up to 150 ℃, keep naturally cooling to room temperature after 2 hours.Utilize electronic tensile machine, respectively its tensile shear strength that carries out under room temperature (25 ℃) and high temperature (150 ℃) condition is tested, result is as shown in table 2.
Get respectively appropriate 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive as shown in table 1, be HTEA-1～HTEA-8, and be coated on equably respectively on standard tempering glass coupon, superimposed, clamp, putting into convection oven is cured: begin to be warming up to 80 ℃ from room temperature, keep continuing to be warming up to 120 ℃ after 1 hour, keep after 2 hours, continue to be warming up to 150 ℃, keep naturally cooling to room temperature after 2 hours.Utilize electronic tensile machine, respectively its tensile shear strength that carries out under room temperature (25 ℃) and high temperature (150 ℃) condition is tested, result is as shown in table 2.
Table 2 tensile shear strength, unit: MPa
Claims (10)
1. one kind 4,4 '-two (2, the 4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive, it is characterized in that: the A component and the B component that are 1:1-2 by mass ratio form, wherein, the A component is by 4, the multipolymer that 4 '-two (2,4-diamino phenoxy) phenyl ether and epoxy resin reaction form; The B component is by 4, and 4 '-two (2,4-diamino phenoxy) phenyl ether and the aromatic dicarboxylic anhydride solid content that reaction forms in strong polar non-proton organic solvent and toluene is the homogeneous phase transparent solution of 15%-30%.
2. one kind 4, the preparation method of 4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive comprises:
(1) with epoxy resin and 4,4 '-two (2,4-diamino phenoxy) phenyl ether is put into reactor, is heated to 50 ℃-90 ℃, stirring reaction 0.5-2 hour, obtains the multipolymer of homogeneous phase transparent, i.e. the A component; Wherein, the epoxy group(ing) mole number and 4 of epoxy resin, the ratio of the mole number of 4 '-two (2,4-diamino phenoxy) phenyl ether is 16-20:1;
(2) under room temperature, with 4,4 '-two (2,4-diamino phenoxy) phenyl ether and strong polar non-proton organic solvent add in reactor, after stirring and dissolving is complete, add aromatic dicarboxylic anhydride, stirring reaction 0.5-1 hour, obtain homogeneous phase transparent solution; Wherein, 4,4 '-two (2,4-diamino phenoxy) phenyl ether is 1:3.5-4.2 with the ratio of the mole number of aromatic dicarboxylic anhydride; The quality and 4 of strong polar non-proton organic solvent, the ratio of the total mass of 4 '-two (2,4-diamino phenoxy) phenyl ether and aromatic dicarboxylic anhydride is 2-4:1; Add toluene, be heated to backflow, the reflux water-dividing range of reaction temperature is 100 ℃-130 ℃, reaction times 2-5 hour, after reaction is completed, tell the part organic solvent, and the solution solid content is in the scope of 15%-30%, get the B component; Wherein, toluene is 0.2-2:1 with the mass ratio of strong polar non-proton organic solvent;
(3) under room temperature, with A component, B component in mass ratio 1:1-2 mix and get final product.
3. according to claim 2 a kind of 4,4 '-two (2, the 4-diamino phenoxy) preparation method of diphenyl ether type high temperature resistant epoxy adhesive is characterized in that: the epoxy resin in described step (1) is selected from one or more in bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, glycidyl amine type epoxy resin, Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin.
4. according to claim 3 a kind of 4,4 '-two (2, the 4-diamino phenoxy) preparation method of diphenyl ether type high temperature resistant epoxy adhesive is characterized in that: described bisphenol A type epoxy resin is selected from one or more in E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin.
5. according to claim 3 a kind of 4, 4 '-two (2, the 4-diamino phenoxy) preparation method of diphenyl ether type high temperature resistant epoxy adhesive, it is characterized in that: described glycidyl amine type epoxy resin is selected from N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-dimethyl-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group 3, 3 '-diethyl-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group 3, 3 '-two chloro-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 4 '-diaminodiphenyl oxide epoxy resin, N, N, N ', N '-four glycidyl group-3, 3 '-diaminodiphenyl oxide 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 glycidyls-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 '-two (4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) benzophenone epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (4-amino-benzene oxygen) biphenyl epoxy resin, N, N, N ', N '-four glycidyl group-4, 4 '-two (2-trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, N, N ', N ', O, O '-six glycidyl-2, two (3-amino-4-hydroxylphenyl) the HFC-236fa epoxy resin of 2-, N, N, O – triglycidyl group p-aminophenol epoxy resin, N, N, one or more in O – triglycidyl group Metha Amino Phenon epoxy resin.
6. according to claim 3 a kind of 4,4 '-two (2, the 4-diamino phenoxy) preparation method of diphenyl ether type high temperature resistant epoxy adhesive, it is characterized in that: described Racemic glycidol ether type epoxy is selected from 1,3-diglycidyl Resorcinol, 1,4-diglycidyl Resorcinol, 4,4 '-diglycidyl bisphenol S, 2, one or more in two (the 4-glycidyl phenyl) HFC-236fa of 2-.
7. according to claim 3 a kind of 4, 4 '-two (2, the 4-diamino phenoxy) preparation method of diphenyl ether type high temperature resistant epoxy adhesive, it is characterized in that: described glycidyl ester type epoxy resin is selected from terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methyne tetrahydrophthalic acid 2-glycidyl ester epoxy resin, 4, 5-epoxy cyclohexane-1, 2-dioctyl phthalate 2-glycidyl ester epoxy resin, one or more in the sad diglycidyl ether epoxy resin of adjacent benzene two.
8. the preparation method of a kind of 4,4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive according to claim 2, it is characterized in that: the aromatic dicarboxylic anhydride in described step (2) is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic phenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic phenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2,2-, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, 4,4 '-two (3,4-di carboxyl phenyloxy) phenyl ether dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) phenyl ether dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) phenyl ether dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) benzophenone dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) biphenyl dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 1,3-, one or more in Isosorbide-5-Nitrae-two (3,4-di carboxyl phenyloxy) benzene dianhydride.
9. according to claim 2 a kind of 4,4 '-two (2, the 4-diamino phenoxy) preparation method of diphenyl ether type high temperature resistant epoxy adhesive, it is characterized in that: the strong polar non-proton organic solvent in described step (2) is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO).
10. according to claim 2 a kind of 4, the preparation method of 4 '-two (2,4-diamino phenoxy) diphenyl ether type high temperature resistant epoxy adhesive is characterized in that: obtain in described step (3) 4,4 '-two (2, the 4-diamino phenoxy) curing process of diphenyl ether type high temperature resistant epoxy adhesive is: begin to be warming up to 80 ℃ from room temperature, keep continuing to be warming up to 120 ℃ after 1 hour, keep after 2 hours, continue to be warming up to 150 ℃, keep naturally cooling to room temperature after 2 hours.
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| CN114686157A (en) * | 2022-03-09 | 2022-07-01 | 江苏环峰电工材料有限公司广州分公司 | Three-dimensional reticular polymer for adhesive and preparation method thereof |
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