CN103030787B - Benzimidazole-epoxy matrix resin and preparation method thereof - Google Patents
Benzimidazole-epoxy matrix resin and preparation method thereof Download PDFInfo
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- CN103030787B CN103030787B CN201210585965.2A CN201210585965A CN103030787B CN 103030787 B CN103030787 B CN 103030787B CN 201210585965 A CN201210585965 A CN 201210585965A CN 103030787 B CN103030787 B CN 103030787B
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Abstract
The invention relates to benzimidazole-epoxy matrix resin and a preparation method thereof. The resin consists of an A component and a B component. The preparation method comprises the following steps of (1) putting N,N,N',N'-tetraglycidyl-2,2-di-[4-(4-amino phenoxyl) phenyl] propane and 2-(4-amino phenyl)-5-amino benzimidazole into a reaction kettle, heating and raising the temperature to 70-80 DEG C, stirring and reacting for 15min-30min, adding a reactive diluent and an organic solvent, stirring uniformly, obtaining the A component, (2) mixing a curing agent with the organic solvent, stirring and dissolving uniformly, obtaining the B component, and (3) mixing the A component with the B component and stirring uniformly in a use process. The preparation method is simple; and the obtained matrix resin is excellent in comprehensive performance, can be applied to glass fiber or carbon fiber reinforced advanced composites, and can also be applied to adhesive agents of substrates such as metal, glass and ceramics.
Description
Technical field
The invention belongs to organic polymer resin and preparation field thereof, particularly a kind of benzoglyoxaline-epoxy matrix resin and preparation method thereof.
Background technology
Polybenzimidazole is the polymkeric substance that a class over-all properties is very excellent, has very excellent thermotolerance, lower temperature resistance, solvent resistance, self lubricity and the characteristic such as fire-retardant, meanwhile, also has very excellent mechanical property and dielectric properties.Therefore, it is widely used in the high temperature material of refractory fibrous material and spaceship, satellite or space craft etc.; The advanced configuration matrix material of the aspects such as aerospace, automobile, electromechanics, C level or 200 higher level insulating materials, high-temperature resistance adhesive etc.; And the body material of FPC or PCB of electronics microelectronic, the interlayer dielectic of IC, super large-scale integration passivating coating and alpha-particle blocking layer coating material etc.
Xu Jun, Yu Xinhai, wait people [3; the synthesis of 3', 4,4'-tetramino phenyl ether and the preparation [J] of polybenzimidazole resin thereof. insulating material; 2009,42(3): 31-35] disclose the preparation method of polybenzimidazole resin, it is characterized in that: with 4; 4'-diaminodiphenyl oxide is raw material, through acetylize, nitrated, alkaline hydrolysis, reduction, neutralization five step Reactive Synthesis 3,3'; 4; 4'-tetramino phenyl ether, total recovery is 52.8%, and characterizes it by FT-IR and fusing point measuring technology.In addition, based on 3,3', 4,4'-tetramino phenyl ether monomer, under the system of polyphosphoric acid and Vanadium Pentoxide in FLAKES, be polymerized the polybenzimidazole obtaining high molecular further with diacid, its molecular structural formula is:
Chinese invention patent CN101456964A discloses a kind of preparation method of aromatic series polybenzimidazole resin film, be primarily characterized in that: the aromatic series quaternary amine and the aromatic dicarboxylic acid that adopt specific molecular structure, under the effect of polyphosphoric acid/Vanadium Pentoxide in FLAKES system, in nitrogen atmosphere, solution polycondensation reaction is carried out, obtained garnet rubber elastomer shaped polymer in room temperature-200 DEG C of temperature ranges.Cooling in resin pulper, blends powdered in falling back, and alkali cleaning is to neutral, and select suitable solvent to be dissolved after drying, casting film-forming, heat temperature raising, desolvation, obtain aromatic polybenzimidazole film, its molecular structural formula is as follows:
As everyone knows, epoxy resin has many excellent performances: the adhesiveproperties that (1) is good: bonding strength is high, bonding wide, the bonding strength of it and many metals (as iron, steel, copper, aluminium, metal alloy etc.) or non-metallic material (as glass, pottery, timber, plastics etc.) is very high, what have even exceedes by the intensity of sticky material itself, therefore can be used in many stress members, is one of main component of structural adhesive; (2) good processing characteristics: the diversity of the handiness of Formulaion of epoxy resin, complete processing and product properties is the most outstanding in macromolecular material; (3) satisfactory stability performance: the solidification of epoxy resin mainly relies on the ring opening polyaddition of epoxy group(ing), therefore low-molecular material is not produced in solidification process, its cure shrinkage is one of kind minimum in thermosetting resin, be generally 1%-2%, if select suitable filler that shrinking percentage can be made to be down to about 0.2%; Epoxy main chains after solidification is ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore has excellent resistance to acids and bases.
Therefore, epoxy resin is widely used in the every field of national economy: no matter no matter is high-technology field or field of general technology, be defence and military or civilian industry, and even all can see its trace in daily life.
Chinese invention patent 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, obtained heat-resistant solvent-free epoxy adhesive.But its resistance to elevated temperatures still has larger limitation, fail to meet the practical application under many hot environments.
Chinese invention patent CN101397486A, disclose a kind of preparation method of two-pack solvent-free epoxy resin tackiness agent, be primarily characterized in that: it comprises component A and B component, wherein component A contains novolac epoxy, alicyclic type epoxy resin and nbr carboxyl terminal; B component is Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene aromatic polyvalent amine hardener.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 Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene aromatic polyvalent amine hardener is the 15-20%(mass percent of novolac epoxy), gained adhesive system good manufacturability.But its resistance toheat is desirable not enough.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of benzoglyoxaline-epoxy matrix resin and preparation method thereof, this matrix resin excellent combination property, can be applicable to glass fibre or carbon fiber reinforced advanced composite material, in addition, also can be applicable to the caking agent of the base materials such as metal, glass, pottery.
A kind of benzoglyoxaline-epoxy matrix resin of the present invention, described resin by mass ratio be 1:0.2-0.5 A, B two component form; Wherein, consisting of of component A: mass ratio is the N of 100:5-10:20-30:140-200, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2-(4-aminophenyl)-5-aminobenzimidazole, reactive thinner and organic solvent; Consisting of of B component: mass ratio is solidifying agent and the organic solvent of 1:1-2.
Described 2-(4-aminophenyl) molecular structural formula of-5-aminobenzimidazole is:
Described reactive thinner is selected from resorcinol diglycidyl ether, 3,4-epoxycyclohexyethylSiOi formic acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4-epoxy group(ing)-6-methyl cyclohexane formic acid-3 ', 4 '-epoxy group(ing)-6 '-methyl cyclohexane methyl esters, tetrahydrophthalic acid 2-glycidyl ester, phthalic acid two shrink in two glyceryl ester, the sad diglycidyl ether of adjacent benzene two one or more.
Described organic solvent is selected from toluene, dimethylbenzene, acetone, methylethylketone, tetrahydrofuran (THF), methyltetrahydrofuran, methylene dichloride, trichloromethane, 1,4-dioxane, N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
Described solidifying agent is selected from 2-ethyl-4-methylimidazole, 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4，4′-diaminodicyclohexylmethane, 2,2-pair [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-pair [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-pair [4-(3-amino-benzene oxygen) phenyl] propane, 2,2-pair [4-(3-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-bis-(4-amino-benzene oxygen) benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, two (3-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 2,2-pair [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane, 2,2-pair [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene, two (2, the 4-diamino phenoxy) benzene of 1,3-, 2,2-pair [4-(2,4-diamino phenoxy) phenyl] propane, 2,2-pair [4-(2,4-diamino phenoxy) phenyl] HFC-236fa, 4,4 '-bis-(2,4-diamino phenoxy) sulfobenzide, 4,4 '-bis-(2,4-diamino phenoxy) biphenyl, one or more in 4,4 '-bis-(2,4-diamino phenoxy) diphenyl sulfide.
The preparation method of a kind of benzoglyoxaline-epoxy matrix resin of the present invention, comprises the steps:
(1) by N, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane and 2-(4-aminophenyl)-5-aminobenzimidazole puts into reactor, after being heated to 70-80 DEG C of stirring reaction 15min-30min, adds reactive thinner and organic solvent, stir, obtain component A;
(2) by solidifying agent and organic solvent mixing, stirring and dissolving is even, namely obtains B component;
(3), when using, by A, B component mixing, stir.
The present invention adopts the benzoglyoxaline group of resistance to elevated temperatures excellence to be incorporated in the high temperature resistant polyfunctional epoxy resin system of adhesive property brilliance, with novel benzimidazole-epoxy matrix resin that obtained over-all properties is superior, meet the actual needs in high temperature resistant advanced composite material and high-temperature-resistant adhesive field.
beneficial effect
(1) the present invention synthesizes the reaction conditions gentleness of matrix resin, and simple to operate, reaction process is carried out at ambient pressure, does not relate to and does not also produce corrosives, and to equipment without particular requirement, less investment, is conducive to reducing production cost;
(2) gained benzoglyoxaline-epoxy matrix resin product of the present invention has the premium properties of benzoglyoxaline and epoxy concurrently, has excellent dimensional stability, mechanical property and thermotolerance;
(3) the present invention synthesizes the reaction raw materials convenient sources of matrix resin, and cost is lower, is convenient to further genralrlization application;
(4) the synthesis technique equipment that the present invention is used is universal, the suite of equipment of existing production resin or epoxy adhesive can be utilized completely to implement the present invention, be very beneficial for the industrialization of product.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By 100.0 grams of N, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (TGBAPP) and 5.0 grams of 2-(4-aminophenyls)-5-aminobenzimidazole (APABI) puts into reactor, after being heated to 70 DEG C of stirring reaction 15min, add 21.5 grams of resorcinol diglycidyl ethers, 100.0 grams of methylethylketones and 40.0 grams of Isosorbide-5-Nitrae-dioxane, stir, obtain 266.5 grams of component A, be denoted as A1, resin quality degree is 47.5%;
By 100.0 grams of N, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (TGBAPP) and 8.0 grams of 2-(4-aminophenyls)-5-aminobenzimidazole (APABI) puts into reactor, after being heated to 80 DEG C of stirring reaction 30min, add 5.0 grams of resorcinol diglycidyl ethers and 15.0 gram 3,4-epoxycyclohexyethylSiOi formic acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 120.0 grams of methylethylketones and 60.0 grams of trichloromethanes, stir, and obtains 308.0 grams of component A, be denoted as A2, resin quality degree is 41.6%;
By 100.0 grams of N, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (TGBAPP) and 10.0 grams of 2-(4-aminophenyls)-5-aminobenzimidazole (APABI) puts into reactor, after being heated to 75 DEG C of stirring reaction 20min, add 30.0 gram 3,4-epoxycyclohexyethylSiOi formic acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 80.0 grams of toluene and 100.0 grams of trichloromethanes, stir, and obtains 320.0 grams of component A, be denoted as A3, resin quality degree is 43.8%;
By 100.0 gram 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa and 30.0 grams of 2-ethyl-4-methylimidazoles and 60.0 gram 1,4-dioxane and 70.0 grams of N, dinethylformamide mixes, stirring and dissolving is even, namely obtain 260.0 grams of B component, be denoted as B1, solidifying agent mass percentage content is 50.0%;
By 50.0 gram 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 50.0 gram 4,4 '-diamino-dicyclohexyl methane and 20.0 grams of 2-ethyl-4-methylimidazoles and 80.0 grams of acetone and 120.0 grams of N, N-N,N-DIMETHYLACETAMIDE mixes, stirring and dissolving is even, namely obtain 320.0 grams of B component, be denoted as B2, solidifying agent mass percentage content is 37.5%;
By 30.0 gram 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane and 120.0 gram 2,2-two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa and 160.0 grams of trichloromethanes and 140.0 grams of N, dinethylformamide mixes, and stirring and dissolving is even, namely obtains 450.0 grams of B component, be denoted as B3, solidifying agent mass percentage content is 25.0%.
Embodiment 2
By the component A of embodiment 1, namely A1, A2, A3 and B component, i.e. B1, B2, B3, mix in proportion, stirs, and obtains the benzoglyoxaline-epoxy matrix resin of series, be denoted as BIE-1 ~ BIE-9, as shown in table 1.
The formula of the serial benzoglyoxaline-epoxy matrix resin (BIE) of table 1
| BIE | BIE-1 | BIE-2 | BIE-3 | BIE-4 | BIE-5 | BIE-6 | BIE-7 | BIE-8 | BIE-9 |
| A1, gram | 10.0 | 0 | 0 | 5.0 | 0 | 2.0 | 3.5 | 4.0 | 2.0 |
| A2, gram | 0 | 10.0 | 0 | 5.0 | 5.0 | 0 | 1.5 | 0 | 3.0 |
| A3, gram | 0 | 0 | 10.0 | 0 | 5.0 | 8.0 | 5.0 | 6.0 | 5.0 |
| B1, gram | 2.0 | 0 | 0 | 3.0 | 2.0 | 0 | 2.0 | 1.0 | 3.0 |
| B2, gram | 0 | 3.5 | 0 | 1.5 | 2.0 | 3.5 | 0 | 4.0 | 1.0 |
| B3, gram | 0 | 0 | 5.0 | 0 | 1.0 | 1.2 | 2.0 | 0 | 1.0 |
Embodiment 3
Get appropriate benzoglyoxaline-epoxy matrix resin (BIE) respectively, i.e. BIE-1 ~ BIE-9, and be coated in the test piece of standard stainless steel respectively equably, after room temperature hangs 0.5 hour, superimposed, clamping, put into convection oven to be cured: from room temperature, be warming up to 70 DEG C, insulation reaction 1 hour, continue to be warming up to 100 DEG C, insulation reaction 1 hour, naturally cools to room temperature.Utilize electronic tensile machine to carry out room temperature (25 DEG C) to it to test with the tensile shear strength (σ) under high temperature (150 DEG C) state, result is as shown in table 2.
Get appropriate benzoglyoxaline-epoxy matrix resin (BIE) respectively, i.e. BIE-1 ~ BIE-9, polytetrafluoroethylene film pushes away film, be placed in vacuum drying oven, be made into the square coupons being of a size of 5mm × 5mm × 1mm, curing process is: from room temperature, be warming up to 70 DEG C, insulation reaction 1 hour, continue to be warming up to 100 DEG C, insulation reaction 1 hour, naturally cools to room temperature.
Its volume specific resistance ρ v(1MHz tested by the megger utilizing Guilin Electro Scientific institute to produce, 25 DEG C), the results are shown in Table 2.
Utilize the TH2828S tester of Changzhou Tong Hui Electron equipment Co., Ltd to test its dielectric loss (D) (1MHz, 25 DEG C), the results are shown in Table 2.
Utilize precision electronic balance, after weighed by the square coupons of above-mentioned drying (W1), be soaked in deionized water (25 DEG C), after 72 hours, take out, dry surface with filter paper, weigh (W2), calculates water-intake rate
data as shown in table 2.
Utilize precision electronic balance, after weighed by the square coupons of above-mentioned drying (G1), be positioned over climatic chamber (85 DEG C, RH85%), in, after 72 hours, take out, dry surface with filter paper, weigh (G2), and the data calculating rate of moisture absorption (ψ) are as shown in table 2.
The performance data of the serial benzoglyoxaline-epoxy matrix resin (BIE) of table 2
Claims (5)
1. benzoglyoxaline-epoxy matrix resin, is characterized in that: described resin by mass ratio be 1:0.2-0.5 A, B two component form; Wherein, consisting of of component A: mass ratio is the N of 100:5-10:20-30:140-200, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2-(4-aminophenyl)-5-aminobenzimidazole, reactive thinner and organic solvent; Consisting of of B component: mass ratio is solidifying agent and the organic solvent of 1:1-2.
2. a kind of benzoglyoxaline-epoxy matrix resin according to claim 1, it is characterized in that: described reactive thinner is selected from resorcinol diglycidyl ether, 3,4-epoxycyclohexyethylSiOi formic acid-3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4-epoxy group(ing)-6-methyl cyclohexane formic acid-3 ', 4 '-epoxy group(ing)-6 '-methyl cyclohexane methyl esters, tetrahydrophthalic acid 2-glycidyl ester, phthalic acid two shrink in two glyceryl ester, the sad diglycidyl ether of adjacent benzene two one or more.
3. a kind of benzoglyoxaline-epoxy matrix resin according to claim 1, it is characterized in that: described organic solvent is selected from toluene, dimethylbenzene, acetone, methylethylketone, tetrahydrofuran (THF), methyltetrahydrofuran, methylene dichloride, trichloromethane, 1,4-dioxane, N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
4. a kind of benzoglyoxaline-epoxy matrix resin according to claim 1, is characterized in that: described solidifying agent is selected from 2-ethyl-4-methylimidazole, 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4，4′-diaminodicyclohexylmethane, 2,2-pair [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-pair [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-pair [4-(3-amino-benzene oxygen) phenyl] propane, 2,2-pair [4-(3-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-bis-(4-amino-benzene oxygen) benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, two (3-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 2,2-pair [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane, 2,2-pair [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) benzophenone, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) diphenyl sulfide, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) biphenyl, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene, two (2, the 4-diamino phenoxy) benzene of 1,3-, 2,2-pair [4-(2,4-diamino phenoxy) phenyl] propane, 2,2-pair [4-(2,4-diamino phenoxy) phenyl] HFC-236fa, 4,4 '-bis-(2,4-diamino phenoxy) sulfobenzide, 4,4 '-bis-(2,4-diamino phenoxy) biphenyl, one or more in 4,4 '-bis-(2,4-diamino phenoxy) diphenyl sulfide.
5. a preparation method for benzoglyoxaline-epoxy matrix resin as claimed in claim 1, comprises the steps:
(1) by N, N, N ', N '-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane and 2-(4-aminophenyl)-5-aminobenzimidazole puts into reactor, after being heated to 70-80 DEG C of stirring reaction 15min-30min, adds reactive thinner and organic solvent, stir, obtain component A;
(2) by solidifying agent and organic solvent mixing, stirring and dissolving is even, namely obtains B component;
(3), when using, by A, B component mixing, stir.
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