Glycidyl amine type multifunctional epoxy resin, adhesive and preparation method of glycidyl amine type multifunctional epoxy resin

Abstract

The invention relates to glycidyl amine type multifunctional epoxy resin, an adhesive and a preparation method of the glycidyl amine type multifunctional epoxy resin. The glycidyl amine type multifunctional epoxy resin of diethylmethyl m-phenylenediamine is viscous transparent liquid obtained by carrying out ring-opening reaction on diethylmethyl m-phenylenediamine and epoxy chloropropane under the action of a catalyst and then carrying out ring-closing reaction under an alkaline condition. The multifunctional epoxy resin is adopted as a raw material and reacts with a flexibilizer, a curing agent, maleimide resin and an epoxy chain extender to obtain the adhesive with excellent comprehensive performance. The multifunctional epoxy resin disclosed by the invention is simple in preparation process and can be manufactured in general equipment, and an adhesive prepared by taking the multifunctional epoxy resin as a main raw material has good interface performance and bonding strength with materials such as metal, ceramic, glass, liquid crystal polyester, carbon fiber and aramid fiber in high and low temperature environments; the resin can be applied to matrix resin systems of various high and low temperature resistant adhesives, pouring sealants, castable, high and low temperature resistant advanced composite materials and the like, and has good potential market and application prospects.

Description

Technical Field

[0001] The present invention belongs to the field of adhesives, and particularly relates to a glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine, an adhesive, and a preparation method thereof. Background Art

[0002] Epoxy resins have a wide range of applications in the fields of adhesives, composite materials, encapsulation materials, etc., and have excellent electrical insulation properties, processing and forming properties, mechanical properties, etc.

[0003] There are many types of epoxy resins, mainly including glycidyl ether type epoxy resins, glycidylamine type epoxy resins, alicyclic epoxy resins, etc. Among them, glycidyl ether type epoxy resins are typically represented by bisphenol A epoxy resins prepared by reacting bisphenol A with epichlorohydrin, and the annual output has reached a scale of tens of millions of tons, with quite extensive uses. In recent years, the research and development of glycidylamine type epoxy resins have also been very active, and they have very unique advantages:

[0004] (1) It is liquid at room temperature, and is easy to prepare solvent-free adhesives, casting materials, encapsulation adhesives, RTM resins, vacuum infusion resins, VPI insulating paints, pultrusion matrix resins, etc., which is environmentally friendly;

[0005] (2) It has good interfacial properties with the surface of carbon fibers and is suitable for preparing matrix resins of carbon fiber reinforced advanced composite materials, etc.;

[0006] (3) Since multiple epoxy groups are contained in the same molecular structure, the heat resistance and rigidity of its cured product system are greatly improved, and it has good applications in the preparation of high-Tg PCB boards and other fields.

[0007] Chinese Patent CN1900135A discloses a preparation method of a glycidylamine type polyfunctional epoxy resin, which includes the following steps:

[0008] (1) 4,4'-methylenedi-o-toluidine and epichlorohydrin with a molar ratio of 1:4 to 20 react in water and an alcohol solvent with a volume ratio of 1:2 to 18 at 40 to 90 °C for 3 to 10 hours; the weight ratio of water to 4,4'-methylenedi-o-toluidine is 1:2 to 10; (2) A 20% aqueous solution of alkali metal hydroxide is dropped in at 60 °C, and after carrying out a desalting and ring-closing reaction at 60 to 80 °C, it is prepared into amber viscous N,N,N',N'-tetraglycidyl-4,4'-methylenedi-o-toluidine through extraction with an extractant, washing, liquid separation, and vacuum devolatilization; the molar ratio of 4,4'-methylenedi-o-toluidine to alkali metal hydroxide is 1:4 to 6.

[0009] The product of this invention has good quality and high yield by itself, but the reaction time in the preparation process is relatively long and the production efficiency is low; the concentration of the aqueous solution of alkali metal hydroxide used is only 20%, and the amount of wastewater is relatively high, resulting in relatively high post-treatment and wastewater treatment costs; in addition, specific performance data and application examples of the application effect of the product of this invention have not been disclosed.

[0010] Chinese Patent for Invention CN103409093B discloses a solvent-free TGDADPE type multi-functional epoxy resin adhesive and its preparation method, the main features of which are: composed of component A and component B with a mass ratio of 10:3 - 9; wherein, component A is composed of N,N,N’,N’-tetraglycidyl-4,4’-diaminodiphenyl ether epoxy resin, hydrogenated bisphenol A epoxy resin and amino silicone resin with a mass ratio of 100:85 - 120:5 - 20; component B is composed of m-xylene diamine, N,N,N’,N’-tetraglycidyl-4,4’-diaminodiphenyl ether epoxy resin and 2-ethyl-4-methylimidazole with a mass ratio of 100:15 - 30:10 - 30.

[0011] The product of this invention has excellent room temperature bonding strength and low water absorption, but the high temperature performance data has not been disclosed. From the formulation composition of this invention, hydrogenated bisphenol A epoxy resin is used and the usage amount is relatively large. It is not difficult to speculate that although N,N,N’,N’-tetraglycidyl-4,4’-diaminodiphenyl ether epoxy resin itself should have the potential for high temperature resistance and the contribution degree to the high temperature performance of the cured product, due to the relatively large amount of hydrogenated bisphenol A epoxy resin used, the heat resistance of the adhesive cured product will inevitably be greatly reduced.

[0012] Wu Feng, Yu Xinhai [Adhesion, 2014, 64 - 68] disclosed the synthesis of PPDA - type polyfunctional epoxy resin and the development of its adhesive. Its main features are as follows: The PPDA - type polyfunctional epoxy resin TGPPDA was synthesized by a two - step method, and its viscosity, epoxy value and volatile content were tested. The results showed that the synthesized epoxy resin TGPPDA was a transparent yellow - brown viscous liquid, with a yield of 90% - 92%, a viscosity of 259 mPa·s at 80 °C, an epoxy value of 0.89 - 0.95 mol / 100 g, and a volatile content of 0.91% - 0.95%. In addition, based on the polyfunctional epoxy resin TGPPDA, a new type of TPA epoxy resin adhesive was prepared using the reactive diluent CE793, 2,2 - bis[4 - (4 - aminophenoxy)phenyl]propane (BAPP), methyltetrahydrophthalic anhydride (MTHPA) and 2,4,6 - tris(dimethylaminomethyl)phenol (DMP - 30); in addition, using the commercial TGDDM polyfunctional epoxy resin to replace the TGPPDA polyfunctional epoxy resin, the TMA epoxy resin adhesive was prepared, and a comparative study was carried out on its viscosity, gelation time, contact angle, water absorption, dielectric properties and tensile shear strength at varying temperatures. The results showed that the viscosity of the adhesive TPA was smaller than that of TMA, with better fluidity, easier to apply glue, and better processability in applications; the gelation time of TPA was longer than that of TMA, and the curing reaction rate was appropriate; within the temperature range of RT - 220 °C, the bonding strength of TPA was higher than that of TMA; the cured products of the adhesives TPA and TMA both had good hydrophobicity and electrical properties.

[0013] In this article, the quality of the PPDA - type polyfunctional epoxy resin is good, and the epoxy value, volatile content and their yield data are disclosed, but the specific names of the synthetic reactants are not disclosed, such as the catalyst C - 50, the auxiliary agent A - 50, etc.; for the PPDA - type polyfunctional epoxy resin adhesive TPA, its formula, process and performance are disclosed, with a room - temperature tensile shear strength of 14.8 MPa, a 200 °C tensile shear strength of 4.8 MPa, and a 220 °C tensile shear strength of 3.5 MPa. It can be seen that the tensile shear strength of the TPA adhesive at room temperature and high temperature is not high and cannot meet the application requirements in the high - temperature and high - strength field.

[0014] Chinese invention patent CN101148656A discloses a preparation method of a high - temperature - resistant solvent - free epoxy adhesive, the main feature of which is that TGDDM epoxy resin, toughening agent, hydrogenated bisphenol A, curing agent and accelerator are mixed evenly to obtain a high - temperature - resistant solvent - free epoxy adhesive. However, its high - temperature resistance still has great limitations and fails to meet the actual applications in many high - temperature environments.

[0015] Chinese Patent CN101397486A discloses a preparation method of a two-component solvent-free epoxy resin adhesive, and its main features are as follows: It includes component A and component B. Component A contains phenolic epoxy resin, alicyclic epoxy resin and carboxyl-terminated nitrile rubber; component B is 1,4-bis(2,4-diaminophenoxy)benzene aromatic polyamine curing agent. The addition amounts of the alicyclic epoxy resin and the carboxyl-terminated nitrile rubber are 20-35% and 12% (mass percentage) of the phenolic epoxy resin respectively. The addition amount of the 1,4-bis(2,4-diaminophenoxy)benzene aromatic polyamine curing agent is 15-20% (mass percentage) of the phenolic epoxy resin, and the obtained adhesive system has good processability. However, its heat resistance is not yet ideal enough.

[0016] Yu Xinhai et al. [Research and Development of High-Temperature Resistant One-Component Epoxy Adhesive [J]. Adhesion, 2008, 29(12): 16-19] disclose a preparation method of a high-temperature resistant one-component epoxy adhesive, and its main features are as follows: Using maleic anhydride (MA) as a capping agent, and using 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHPFP), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPOPP), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) as main raw materials to synthesize a phenolic hydroxyl group-containing polyetherimide resin (HPEI); Using the synthesized HPEI as a high-temperature resistant toughening agent, and formulating with N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent, etc., to obtain a high-temperature resistant one-component epoxy adhesive with excellent comprehensive performance.

[0017] Although this method has carried out toughening modification on the epoxy resin by synthesizing a polyetherimide resin (HPEI) containing reactive functional groups (hydroxyl group, unsaturated double bond) and achieved good technical effects. However, there are also some disadvantages:

[0018] (1) The reactive functional groups are limited, especially the content of unsaturated double bonds is relatively low. Because maleic anhydride is used as a capping agent, the dosage of maleic anhydride is very small.

[0019] (2) Monomers such as 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHPFP) are expensive, resulting in high costs of the polyetherimide resin (HPEI) and the adhesive, which is not conducive to large-scale popularization and application and can only be limited to some special fields. Summary of the Invention

[0020] The technical problem to be solved by the present invention is to provide a glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine, an adhesive and a preparation method thereof. The polyfunctional epoxy resin of the present invention has a simple preparation process, can be manufactured in general equipment, and the adhesive prepared with it as the main raw material is environmentally friendly and has excellent comprehensive properties. It has good interfacial properties and bonding strength with materials such as metals, ceramics, glass, liquid crystal polyester, carbon fiber, and aramid fiber in high and low temperature environments. It can be applied to various high and low temperature resistant adhesives, potting adhesives, casting materials, matrix resin systems of high and low temperature resistant advanced composites, etc. It has good potential market and application prospects and is conducive to realizing industrial production.

[0021] In the first aspect of the present invention, there is provided a glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine. The glycidylamine type polyfunctional epoxy resin is a viscous transparent liquid obtained by ring-opening reaction of diethylmethyl-m-phenylenediamine and epichlorohydrin with a molar ratio of 1:4 - 30 under the action of a catalyst, and then carrying out a ring-closure reaction under alkaline conditions; wherein, the mass ratio of the catalyst to the diethylmethyl-m-phenylenediamine is 0.01 - 0.2:1.

[0022] Further, the catalyst is selected from one or more of ethanol, methanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol, water, tetrabutylammonium bromide, tetrabutylammonium chloride, trimethylbenzylammonium chloride, tributylbenzylammonium chloride, triethylbenzylammonium chloride, trimethylbenzylammonium bromide, tributylbenzylammonium bromide, triethylbenzylammonium bromide, 18-crown-6, and benzo crown ether; the mass ratio of the catalyst to the diethylmethyl-m-phenylenediamine is 0.06 - 0.12:1.

[0023] Further, the alkaline condition refers to an environment of a strong alkali aqueous solution; the strong alkali is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; the molar ratio of the strong alkali to the diethylmethyl-m-phenylenediamine is 4.0 - 4.5:1; the mass percentage of the strong alkali aqueous solution is 30% - 50%.

[0024] In the second aspect of the present invention, there is provided a preparation method of the above-mentioned glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine, including the following steps:

[0025] 1) At room temperature, add epichlorohydrin and the catalyst into the reaction kettle, add diethylmethyl-m-phenylenediamine in batches, each batch accounting for 1 / 4 of the total amount of diethylmethyl-m-phenylenediamine, stir and react, control the reaction temperature within the range of 50°C - 60°C, stir and react until homogeneous, then add the second batch of diethylmethyl-m-phenylenediamine, and so on. After the batch feeding is completed and the reaction becomes homogeneous, continue to stir and react for 1 hour - 2 hours, heat up to 70°C - 90°C, and keep the temperature for reaction for 1 hour - 2 hours;

[0026] 2) Cool the system to 50 °C, dropwise add an aqueous solution of strong base, stir the reaction while adding dropwise. After the addition is completed, stir the reaction at a temperature range of 50 °C - 60 °C for 1 - 2 hours, then filter to remove the solid salt (collect), let the mother liquor stand for liquid separation (aqueous layer + organic layer), wash the organic layer 2 - 3 times, perform liquid separation 2 - 3 times, concentrate the organic layer under reduced pressure, recover epichlorohydrin for recycling. The obtained concentrate is the target product, a light yellow viscous transparent glycidylamine-type polyfunctional epoxy resin of diethylmethyl-m-phenylenediamine.

[0027] The third aspect of the present invention provides an adhesive containing the above glycidylamine-type polyfunctional epoxy resin, which is composed of the glycidylamine-type polyfunctional epoxy resin, maleimide resin, epoxy chain extender, curing agent, and toughening agent;

[0028] Among them, the mass ratio of the toughening agent to the glycidylamine-type polyfunctional epoxy resin is 0.01 - 0.1:1; the mass ratio of the curing agent to the glycidylamine-type polyfunctional epoxy resin is 0.4 - 0.8:1; the mass ratio of the maleimide resin to the glycidylamine-type polyfunctional epoxy resin is 0.01 - 0.1:1; the mass ratio of the epoxy chain extender to the glycidylamine-type polyfunctional epoxy resin is 1 - 20:100.

[0029] Furthermore, the toughening agent is selected from one or more of CB-100 of Zhejiang Yingrui Cloud New Material Technology Co., Ltd., carboxy-terminated nitrile rubber, amino-terminated nitrile rubber, hydroxy-terminated nitrile rubber, hydroxyl-terminated polyethersulfone, epoxy-terminated polyethersulfone, maleimide-based polyimide, anhydride-terminated polyimide, and amino-terminated polyimide; among them, the mass ratio of the toughening agent to the glycidylamine-type polyfunctional epoxy resin is 0.04 - 0.07:1.

[0030] Furthermore, the curing agent is selected from one or more of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, tung oil anhydride, 2-ethyl-4-methylimidazole, N,N-dimethyl-p-toluidine, benzyldimethylamine, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undec-7-ene; among them, the mass ratio of the curing agent to the glycidylamine-type polyfunctional epoxy resin is 0.5 - 0.7:1.

[0031] Further, the maleimide resin is selected from one or more of N-phenyl maleimide resin, 4,4'-bismaleimide diphenylmethane, 4,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenyl sulfone, 1,4-bis(4-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,4-bis(3-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, 4,4'-bis(4-maleimidophenoxy)biphenyl, 4,4'-bis(3-maleimidophenoxy)biphenyl, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-3-maleimidophenoxy)phenyl]hexafluoropropane, 1,4-bis(2,4-dimaleimidophenoxy)benzene, 1,3-bis(2,4-dimaleimidophenoxy)benzene, 1,2-bis(2,4-dimaleimidophenoxy)benzene, 2,2-bis[4-(2,4-dimaleimidophenoxy)phenyl]propane, 2,2-bis[4-(2,4-dimaleimidophenoxy)phenyl]hexafluoropropane, 4,4'-bis(2,4-dimaleimidophenoxy)diphenyl ether, 4,4'-bis(2,4-dimaleimidophenoxy)diphenyl sulfide, 4,4'-bis(2,4-dimaleimidophenoxy)biphenyl, 4,4'-bis(2,4-dimaleimidophenoxy)diphenyl sulfone, 4,4'-bis(2,4-dimaleimidophenoxy)benzophenone, 4,4'-bis(2,4-dimaleimidophenoxy)diphenylmethane.

[0032] Among them, the preferred maleimide resin is selected from one or more of 4,4'-bismaleimide diphenylmethane, 1,3-bis(4-maleimidophenoxy)benzene, 2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane; the mass ratio of the maleimide resin to the glycidylamine type polyfunctional epoxy resin is 0.05-0.08:1.

[0033] Further, the epoxy chain extender is SD-248, a product of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.; wherein, the mass ratio of the epoxy chain extender to the glycidylamine type polyfunctional epoxy resin is 5-15:100.

[0034] The fourth aspect of the present invention provides a preparation method of the above-mentioned glycidylamine type polyfunctional epoxy resin adhesive, which includes the following steps:

[0035] By weight, add the glycidylamine type polyfunctional epoxy resin and the epoxy chain extender into a reaction kettle, and stir and react at a temperature range of 90°C - 100°C for 0.5 hour - 1.0 hour; add maleimide resin, and stir and react at a temperature range of 100°C - 110°C for 0.5 hour - 1.0 hour; then add a toughening agent, and stir and react at a temperature range of 90°C - 100°C for 10 minutes - 30 minutes, and cool to 60°C; add a curing agent, stir evenly at a temperature range of 20°C - 60°C, and cool to room temperature to obtain the glycidylamine type polyfunctional epoxy resin adhesive based on diethylmethyl-m-phenylenediamine.

[0036] Beneficial effects

[0037] (1) The preparation process of the present invention is simple, low-cost, and easy to operate. The reaction raw materials are easily available, and the preparation process can be completed in general equipment, which is conducive to industrial production;

[0038] (2) The present invention has excellent comprehensive performance, and has good interfacial properties and bonding strength with materials such as metals, ceramics, glass, liquid crystal polyester, carbon fiber, and aramid fiber in high and low temperature environments. It can be applied to various high and low temperature resistant adhesives, potting adhesives, casting materials, matrix resin systems of high and low temperature resistant advanced composite materials, etc., and has good potential market and application prospects. Description of the Drawings

[0039] Figure 1 is the infrared spectrum of the glycidylamine type polyfunctional epoxy resin of diethylmethyl-m-phenylenediamine in Example 1. Detailed Embodiments

[0040] The following specific embodiments are used to further illustrate the present invention. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0041] All raw material reagents used in the following examples can be obtained through commercial channels.

[0042] Example 1

[0043] At room temperature, 2775.0 g (30.0 mol) of epichlorohydrin, 15.0 g of ethanol, 10.0 g of water and 10.6 g of tetrabutylammonium bromide as a catalyst were added to a reaction kettle. 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added in batches, and the reaction was stirred. The reaction temperature was controlled within the range of 50 °C - 60 °C. After stirring the reaction until homogeneous, 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added. The reaction was stirred, the reaction temperature was controlled within the range of 50 °C - 60 °C. After stirring the reaction until homogeneous, 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added. The reaction was stirred, the reaction temperature was controlled within the range of 50 °C - 60 °C. After stirring the reaction until homogeneous, 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added. The reaction was stirred, the reaction temperature was controlled within the range of 50 °C - 60 °C. After stirring the reaction until homogeneous, the reaction was continued to stir for 2 hours, heated to 70 °C - 90 °C, and kept warm for 2 hours; the system was cooled to 50 °C, and 360.0 g (4.5 mol of sodium hydroxide) of a strong sodium hydroxide aqueous solution with a mass percentage concentration of 50% was added dropwise while stirring the reaction. After the addition was completed, the reaction was stirred for 2 hours within the temperature range of 50 °C - 60 °C, and then the solid salt was filtered off (collected). The mother liquor was allowed to stand for liquid separation (aqueous layer + organic layer). The organic layer was washed with water 2 - 3 times and separated 2 - 3 times. The organic layer was concentrated under reduced pressure to recover epichlorohydrin for recycling, and 382.7 g (theoretical yield 402 g) of a light yellow viscous transparent glycidylamine-type polyfunctional epoxy resin of diethylmethyl-m-phenylenediamine was obtained, denoted as TGDETDA-1. Its infrared spectrum is as Figure 1 shown, the yield was 95.2%, the epoxy value was 0.82 (hydrochloric acid-acetone method), and the volatile content was 0.21%.

[0044] Example 2

[0045] At room temperature, 370.0 g (4.0 mol) of epichlorohydrin and 1.78 g of tetrabutylammonium chloride catalyst were added to a reaction kettle. 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added in batches, and the mixture was stirred and reacted. The reaction temperature was controlled within the range of 50°C - 60°C. After stirring until homogeneous, 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added, and the mixture was stirred and reacted. The reaction temperature was controlled within the range of 50°C - 60°C. After stirring until homogeneous, 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added, and the mixture was stirred and reacted. The reaction temperature was controlled within the range of 50°C - 60°C. After stirring until homogeneous, 44.5 g (0.25 mol) of diethylmethyl-m-phenylenediamine was added, and the mixture was stirred and reacted. The reaction temperature was controlled within the range of 50°C - 60°C. After stirring until homogeneous, the mixture was continuously stirred and reacted for 1 hour, heated to 70°C - 90°C, and kept warm for 1 hour; the system was cooled to 50°C, and 746.7 g (4.0 mol of potassium hydroxide) of a strong potassium hydroxide aqueous solution with a mass percentage concentration of 30% was added dropwise while stirring and reacting. After the addition was completed, the mixture was stirred and reacted within the temperature range of 50°C - 60°C for 1 hour, then the solid salt was filtered off (collected), and the mother liquor was allowed to stand for liquid separation (aqueous layer + organic layer). The organic layer was washed with water 2 - 3 times and separated 2 - 3 times. The organic layer was concentrated under reduced pressure to recover epichlorohydrin for recycling, and 335.3 g (theoretical yield 402 g) of a light yellow viscous transparent glycidylamine-type polyfunctional epoxy resin of diethylmethyl-m-phenylenediamine was obtained, denoted as TGDETDA-2, with a yield of 83.4%, an epoxy value of 0.65 (hydrochloric acid-acetone method), and a volatile content of 0.53%.

[0046] Example 3

[0047] 100.0 g of the glycidylamine-type polyfunctional epoxy resin TGDETDA-1 of diethylmethyl-m-phenylenediamine and 10.0 g of the chain extender SD-248 (product of Zhejiang Yingrui Yun New Materials Technology Co., Ltd.) were added to a reaction kettle. After stirring and reacting within the temperature range of 90°C - 100°C for 0.5 hour, 5.0 g of the maleimide resin of 4,4'-bismaleimido diphenylmethane was added. After stirring and reacting within the temperature range of 100°C - 110°C for 1.0 hour, 8.0 g of the toughening agent CB-100 (product of Zhejiang Yingrui Yun New Materials Technology Co., Ltd.) was added, and the mixture was stirred and reacted within the temperature range of 90°C - 100°C for 10 minutes. After cooling to 60°C, 65.0 g of methyltetrahydrophthalic anhydride and 4.0 g of the curing agent 2-ethyl-4-methylimidazole were added, and the mixture was stirred evenly within the temperature range of 20°C - 60°C, then cooled to room temperature to obtain a glycidylamine-type polyfunctional epoxy resin adhesive based on diethylmethyl-m-phenylenediamine, denoted as JTD-1.

[0048] Example 4

[0049] 100.0 g of the glycidylamine-type polyfunctional epoxy resin TGDETDA-2 of diethylmethyl-m-phenylenediamine and 20.0 g of the chain extender SD-248 (product of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.) were added to a reaction kettle. After stirring and reacting for 1.0 h within the temperature range of 90°C - 100°C, 10.0 g of the maleimide resin of 2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane was added. After stirring and reacting for 0.5 h within the temperature range of 100°C - 110°C, 1.0 g of the toughening agent of terminal epoxy polyethersulfone was added, and then stirred and reacted for 30 minutes within the temperature range of 90°C - 100°C. After cooling to 60°C, 3.0 g of 2,4,6-tris(dimethylaminomethyl)phenol, 47.0 g of methylhexahydrophthalic anhydride, and 30.0 g of tung oil anhydride as curing agents were added, and stirred evenly within the temperature range of 20°C - 60°C, then cooled to room temperature to obtain the glycidylamine-type polyfunctional epoxy resin adhesive based on diethylmethyl-m-phenylenediamine, denoted as JTD-2.

[0050] Example 5

[0051] 100.0 g of the glycidylamine-type polyfunctional epoxy resin TGDETDA-1 of diethylmethyl-m-phenylenediamine and 1.0 g of the chain extender SD-248 (product of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.) were added to a reaction kettle. After stirring and reacting for 0.5 h within the temperature range of 90°C - 100°C, 1.0 g of the maleimide resin of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane was added. After stirring and reacting for 0.5 h within the temperature range of 100°C - 110°C, 7.0 g of carboxy nitrile rubber and 3.0 g of the toughening agent of terminal amino polyimide were added, and then stirred and reacted for 20 minutes within the temperature range of 90°C - 100°C. After cooling to 60°C, 10.0 g of 1,8-diazabicyclo[5.4.0]undec-7-ene, 20.0 g of methyltetrahydrophthalic anhydride, 4.0 g of 2-ethyl-4-methylimidazole, and 6.0 g of dodecenyl succinic anhydride as curing agents were added, and stirred evenly within the temperature range of 20°C - 60°C, then cooled to room temperature to obtain the glycidylamine-type polyfunctional epoxy resin adhesive based on diethylmethyl-m-phenylenediamine, denoted as JTD-3.

[0052] Comparative Example 1

[0053] 100.0 g of bisphenol A epoxy resin E-51 and 10.0 g of chain extender SD-248 (product of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.) were added to a reaction kettle. After stirring and reacting at a temperature range of 90°C - 100°C for 0.5 h, 5.0 g of maleimide resin of 4,4'-bismaleimidodiphenylmethane was added. After stirring and reacting at a temperature range of 100°C - 110°C for 1.0 h, 8.0 g of toughening agent CB-100 (product of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.) was added. After stirring and reacting at a temperature range of 90°C - 100°C for 10 minutes, it was cooled to 60°C. 65.0 g of methyltetrahydrophthalic anhydride and 4.0 g of curing agent of 2-ethyl-4-methylimidazole were added. After stirring evenly at a temperature range of 20°C - 60°C and cooling to room temperature, an adhesive was obtained, denoted as CJTD-1.

[0054] Comparative Example 2

[0055] 100.0 g of p-phenylenediamine glycidylamine type polyfunctional epoxy resin TGPPDA and 10.0 g of chain extender SD-248 (product of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.) were added to a reaction kettle. After stirring and reacting at a temperature range of 90°C - 100°C for 0.5 h, 5.0 g of maleimide resin of 4,4'-bismaleimidodiphenylmethane was added. After stirring and reacting at a temperature range of 100°C - 110°C for 1.0 h, 8.0 g of toughening agent CB-100 (product of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.) was added. After stirring and reacting at a temperature range of 90°C - 100°C for 10 minutes, it was cooled to 60°C. 65.0 g of methyltetrahydrophthalic anhydride and 4.0 g of curing agent of 2-ethyl-4-methylimidazole were added. After stirring evenly at a temperature range of 20°C - 60°C and cooling to room temperature, a glycidylamine type polyfunctional epoxy resin adhesive based on diethylmethyl-m-phenylenediamine was obtained, denoted as CJTD-2.

[0056] Example 6

[0057] The adhesives JTD-1, JTD-2, JTD-3, CJTD-1, and CJTD-2 of Examples 3 - 5 and Comparative Examples 1 - 2 were subjected to performance testing and characterization.

[0058] A BROOKFIELD CAP2000+ viscometer was used to test the relationship between viscosity and temperature, and the results are shown in Table 1; a gelation time tester was used to test the relationship between gelation time and temperature, and the results are shown in Table 2.

[0059] The adhesives JTD-1, JTD-2, JTD-3, CJTD-1, and CJTD-2 of the above Examples 3-5 and Comparative Examples 1-2 were respectively and evenly coated on standard stainless steel test pieces. After air-drying at room temperature for 10 min, they were laminated, clamped, and placed in a forced-air oven for curing: heated from room temperature to 80 °C, held for a reaction for 0.5 h, then continued to be heated to 120 °C, held for a reaction for 1 h, and naturally cooled to room temperature. The tensile shear strength (σ) was tested using an electronic tensile machine within the temperature range of low temperature (-60 °C) to high temperature (190 °C). The holding time at each test temperature point was 15 minutes, and the test results are shown in Table 3.

[0060] Appropriately take the adhesives JTD-1, JTD-2, JTD-3, CJTD-1, and CJTD-2 of the above Examples 3-5 and Comparative Examples 1-2, put them into a square groove with a polytetrafluoroethylene inner surface, place them in a vacuum drying oven for curing and forming, and make them into square specimens with a size of 50 mm × 50 mm × 1 mm. The curing process is as follows: heated from room temperature to 80 °C, held for a reaction for 0.5 h, then continued to be heated to 120 °C, held for a reaction for 1 h, and naturally cooled to room temperature.

[0061] Using a precision electronic balance, after weighing (W1) the above dried square specimens, soak them in deionized water (25 °C). After 72 h, take them out, dry the surface with filter paper, weigh (W2), and calculate the water absorption rate. The data are shown in Table 3.

[0062] Table 1 Viscosity performance data of adhesives: mPa·s

[0063] Sample JTD-1 JTD-2 JTD-3 CJTD-1 CJTD-2 50℃ 1720 1932 1875 1835 2346 55℃ 1185 1343 1210 1137 1562 60℃ 976 1024 983 887 1031 65℃ 792 876 801 785 941 70℃ 675 751 719 692 877

[0064] Table 2 Gelation time data of adhesives: s

[0065]

[0066]

[0067] Table 3 Performance data of adhesive cured products

[0068]

[0069] From the performance data in Tables 1-3, it can be seen that the adhesive prepared from the glycidylamine type polyfunctional epoxy resin of the present invention has more excellent high-temperature resistance and excellent hydrophobic properties compared with the adhesive (CJTD-1) prepared from bisphenol A type epoxy resin E-51; and has more excellent hydrophobic properties compared with the adhesive (CJTD-2) prepared from p-phenylenediamine glycidylamine type polyfunctional epoxy resin TGPPDA.

[0070] The present invention describes the compounds of the present invention, their preparation methods and applications in combination with some specific embodiments and examples, and also makes statements and explanations regarding many details. However, it should be understood that the specific embodiments and examples provided herein are only exemplary and do not limit the scope of protection of the present invention. In fact, for those skilled in the art, the present invention can also be implemented by adopting other specific methods, and the corresponding modifications, changes or adjustments do not depart from the spirit and gist of the present invention, and thus should all be regarded as being included within the scope of the present invention.

Claims

1. A glycidylamine-type multifunctional epoxy resin based on diethylmethyl-m-phenylenediamine, characterized in that: The glycidylamine type polyfunctional epoxy resin is a viscous transparent liquid obtained by ring-opening reaction of diethylmethyl-m-phenylenediamine and epichlorohydrin with a molar ratio of 1:4 - 30 under the action of a catalyst, and then carrying out a ring-closure reaction under alkaline conditions; wherein, the mass ratio of the catalyst to the diethylmethyl-m-phenylenediamine is 0.01 - 0.2:

1.

2. The glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine according to claim 1, characterized in that: The catalyst is selected from one or more of ethanol, methanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol, water, tetrabutylammonium bromide, tetrabutylammonium chloride, trimethylbenzylammonium chloride, tributylbenzylammonium chloride, triethylbenzylammonium chloride, trimethylbenzylammonium bromide, tributylbenzylammonium bromide, triethylbenzylammonium bromide, 18-crown-6, and benzo crown ether; the mass ratio of the catalyst to the diethylmethyl-m-phenylenediamine is 0.06 - 0.12:

1.

3. A glycidylamine-type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine according to claim 1, characterized in that: The alkaline condition refers to an environment of a strong alkali aqueous solution; the strong alkali is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; the molar ratio of the strong alkali to the diethylmethyl-m-phenylenediamine is 4.0 - 4.5:1; the mass percentage of the strong alkali aqueous solution is 30% - 50%.

4. A preparation method of a glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine according to any one of claims 1 - 3, comprising the following steps: 1) At room temperature, add epichlorohydrin and the catalyst into a reaction kettle, add diethylmethyl-m-phenylenediamine in batches, with each batch accounting for 1 / 4 of the total amount of the diethylmethyl-m-phenylenediamine, stir and react, control the reaction temperature within the range of 50°C - 60°C, after stirring and reacting until homogeneous, add the second batch of diethylmethyl-m-phenylenediamine, and so on. After the batch feeding is completed and the reaction becomes homogeneous, continue to stir and react for 1 hour - 2 hours, heat up to 70°C - 90°C, and keep the temperature for 1 hour - 2 hours. 2) Cool the system to 50°C, dropwise add the strong alkali aqueous solution, stir and react while dropping, after the dropping is completed, stir and react for 1 hour - 2 hours within the temperature range of 50°C - 60°C, filter to remove solid salts, let the mother liquor stand for liquid separation, wash the organic layer 2 - 3 times, carry out liquid separation 2 - 3 times, concentrate the organic layer under reduced pressure, recover epichlorohydrin for recycling, and the obtained concentrate is the target product, which is a light yellow viscous transparent glycidylamine type polyfunctional epoxy resin of diethylmethyl-m-phenylenediamine.

5. An adhesive containing a glycidylamine-type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine according to any one of claims 1-3, characterized in that: It is composed of the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine, maleimide resin, epoxy chain extender, curing agent, and toughening agent; wherein, the mass ratio of the toughening agent to the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine is 0.01 - 0.1:1; the mass ratio of the curing agent to the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine is 0.4 - 0.8:1; the mass ratio of the maleimide resin to the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine is 0.01 - 0.1:1; the mass ratio of the epoxy chain extender to the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine is 1 - 20:

100.

6. The adhesive according to claim 5, characterized in that: The toughening agent is selected from one or more of CB-100 of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd., carboxy-terminated nitrile rubber, amino-terminated nitrile rubber, hydroxy-terminated nitrile rubber, hydroxyl-terminated polyethersulfone, epoxy-terminated polyethersulfone, maleimide-based polyimide, anhydride-terminated polyimide, and amino-terminated polyimide; wherein, the mass ratio of the toughening agent to the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine is 0.04 - 0.07:

1.

7. The adhesive according to claim 5, characterized in that: The curing agent is selected from one or more of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, tung oil anhydride, 2-ethyl-4-methylimidazole, N,N-dimethyl-p-toluidine, benzyldimethylamine, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene-7; wherein, the mass ratio of the curing agent to the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine is 0.5 - 0.7:

1.

8. The adhesive according to claim 5, characterized in that: The maleimide resin is selected from one or more of N-phenylmaleimide resin, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimidodiphenyl ether, 4,4'-bismaleimidodiphenyl sulfone, 1,4-bis(4-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,4-bis(3-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, 4,4'-bis(4-maleimidophenoxy)biphenyl, 4,4'-bis(3-maleimidophenoxy)biphenyl, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-3-maleimidophenoxy)phenyl]hexafluoropropane, 1,4-bis(2,4-dimaleimidophenoxy)benzene, 1,3-bis(2,4-dimaleimidophenoxy)benzene, 1,2-bis(2,4-dimaleimidophenoxy)benzene, 2,2-bis[4-(2,4-dimaleimidophenoxy)phenyl]propane, 2,2-bis[4-(2,4-dimaleimidophenoxy)phenyl]hexafluoropropane, 4,4'-bis(2,4-dimaleimidophenoxy)diphenyl ether, 4,4'-bis(2,4-dimaleimidophenoxy)diphenyl sulfide, 4,4'-bis(2,4-dimaleimidophenoxy)biphenyl, 4,4'-bis(2,4-dimaleimidophenoxy)diphenyl sulfone, 4,4'-bis(2,4-dimaleimidophenoxy)benzophenone, 4,4'-bis(2,4-dimaleimidophenoxy)diphenylmethane.

9. The adhesive according to claim 5, characterized in that: The epoxy chain extender is product SD-248 of Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.; wherein, the mass ratio of the epoxy chain extender to the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine is 5-15:

100.

10. The preparation method of the adhesive according to any one of claims 5-9, comprising the following steps: By weight parts, add the glycidylamine type polyfunctional epoxy resin based on diethylmethyl-m-phenylenediamine and the epoxy chain extender into a reaction kettle, and stir and react within the temperature range of 90°C - 100°C for 0.5 hour - 1.0 hour; add maleimide resin, and stir and react within the temperature range of 100°C - 110°C for 0.5 hour - 1.0 hour; then add a toughening agent, and stir and react within the temperature range of 90°C - 100°C for 10 minutes - 30 minutes, and cool to 60°C; add a curing agent, stir evenly within the temperature range of 20°C - 60°C, and cool to room temperature to obtain the glycidylamine type polyfunctional epoxy resin adhesive based on diethylmethyl-m-phenylenediamine.

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