Multifunctional epoxy resin TGTHEIC, adhesive and preparation and application of multifunctional epoxy resin TGTHEIC

Abstract

The invention relates to multifunctional epoxy resin TGTHEIC, an adhesive and a preparation method and application of the multifunctional epoxy resin TGTHEIC. According to the multifunctional epoxy resin TGTHEIC, THEIC and ECH serve as main raw materials, an epoxy resin intermediate is obtained after a ring-opening addition reaction is carried out under a Lewis acid catalyst, after the epoxy resin intermediate is dissolved through an alcohol solvent, a mixture of TGTHEIC and salt is obtained under the action of an alkali metal hydroxide aqueous solution, after the epoxy resin is dissolved in a ketone solvent, the mixture is subjected to ring closing, filtering and vacuum devolatilization, and the multifunctional epoxy resin TGTHEIC is obtained. And filtering and carrying out vacuum devolatilization to prepare the light yellow sticky TGTHEIC. The multifunctional epoxy adhesive prepared from the TGTHEIC resin has excellent high temperature resistance (the tensile shear strength at 100 DEG C is greater than or equal to 12.18 MPa, and the tensile strength retention rate is greater than or equal to 10%), low dielectric loss (less than or equal to 2.9%), high mechanical strength (the impact strength is greater than or equal to 16.3 kJ / m < 2 >) and low water absorption (less than or equal to 1.48%), and is suitable for the fields of electronic packaging, aerospace high-temperature parts and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of epoxy resin adhesives, and particularly relates to a polyfunctional epoxy resin TGTHEIC, an adhesive, and a preparation method and application thereof. Background Art

[0002] Polyfunctional epoxy resins refer to organic compounds containing three or more epoxy groups in their structures. Due to their high crosslinking density, polyfunctional epoxy resins have better heat resistance, so they are widely used in high-temperature fields such as electronics and electrical (PCB printed circuit boards), aerospace, etc.

[0003] Triglycidyl tris(2-hydroxyethyl) isocyanurate (TGTHEIC), its molecular structure is as follows:

[0004]

[0005] A novel multifunctional epoxy resin - triglycidyl tris(2-hydroxyethyl) isocyanurate (TGTHEIC), due to its symmetric structure of triazine ring in the molecular structure, has a stable molecular structure, good thermal stability and chemical stability, low dipole moment, can improve the dielectric properties of the resin system, and increase heat resistance. Thus, the comprehensive performance of the final product can be greatly improved. It can be applied in fields such as liquid crystal encapsulants, insulating coatings, carbon nanotube composites, printed circuit boards, etc.

[0006] Chinese invention patent CN117487134A discloses a modified epoxy resin and a liquid crystal encapsulation sealant prepared by compounding it. Triglycidyl tris(2-hydroxyethyl) isocyanurate is modified with methacrylic acid to obtain a modified epoxy resin, and then fillers, photoinitiators, and curing agents are added to the epoxy resin system to obtain a liquid crystal encapsulant. This encapsulant has excellent moisture permeability resistance and anti-pollution performance, but its strength is not high.

[0007] The present invention successfully prepared an adhesive with both high strength and low water absorption by exploring and optimizing its synthesis process and combining specific formula design, filling the gap in the prior art. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to provide a polyfunctional epoxy resin TGTHEIC, an adhesive, and a preparation method and application thereof. The polyfunctional epoxy adhesive of the present invention has excellent high-temperature resistance (tensile shear strength at 100 °C ≥ 12.18 MPa, tensile strength retention rate ≥ 10%), low dielectric loss (≤ 2.9%), high mechanical strength (impact strength ≥ 16.3 kJ / m 2 ), and low water absorption rate (≤ 1.48%), and is suitable for fields such as electronic packaging, high-temperature components in aerospace, etc.

[0009] In the first aspect of the present invention, a multifunctional epoxy resin TGTHEIC is provided. The multifunctional epoxy resin TGTHEIC is a light yellow viscous liquid obtained by a ring-opening reaction of 1,3,5-tris(2-hydroxyethyl)isocyanurate and epichlorohydrin with a molar ratio of 1:10 - 30 under the action of a catalyst, and then a ring-closure reaction under alkaline conditions; wherein, the weight ratio of the catalyst to 1,3,5-tris(2-hydroxyethyl)isocyanurate is 1:0.01 - 0.1.

[0010] Further, the catalyst is a Lewis acid catalyst, specifically selected from one of boron trifluoride and tin tetrachloride.

[0011] Further, the molar ratio of 1,3,5-tris(2-hydroxyethyl)isocyanurate to epichlorohydrin is 1:15 - 25.

[0012] Further, the weight ratio of the catalyst to 1,3,5-tris(2-hydroxyethyl)isocyanurate is 1:0.02.

[0013] Further, the alkaline condition refers to an environment of a strong base aqueous solution; the strong base is selected from one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide; the molar ratio of the strong base to the diethylmethyl-m-phenylenediamine is 1 - 5:1; the mass percentage of the strong base aqueous solution is 30% - 50%.

[0014] In the second aspect of the present invention, a preparation method of the above multifunctional epoxy resin TGTHEIC is provided, including the following steps:

[0015] (1) 1,3,5-tris(2-hydroxyethyl)isocyanurate and epichlorohydrin with a molar ratio of 1:10 - 30 react at 90 - 100 °C for 3 - 6 h under the action of a catalyst, and the excessive epichlorohydrin is removed by rotary evaporation to obtain an epoxy resin intermediate;

[0016] (2) The intermediate obtained in step (1) is dissolved in an alcohol solvent, and a desalting ring-closure reaction is carried out under alkaline conditions at 60 °C, and then filtered and rotary evaporated to obtain a mixture of TGTHEIC and salt;

[0017] (3) After dissolving the epoxy resin in a ketone solvent, it is filtered and vacuum devolatilized to prepare a light yellow viscous TGTHEIC.

[0018] Further, the catalyst in step (1) is a Lewis acid catalyst, specifically selected from one of boron trifluoride and tin tetrachloride; the weight ratio of the catalyst to 1,3,5-tris(2-hydroxyethyl)isocyanurate is 1:0.01 - 0.1; preferably, the weight ratio of the catalyst to 1,3,5-tris(2-hydroxyethyl)isocyanurate is 1:0.02.

[0019] Further, the alkaline condition in step (1) refers to an environment of a strong alkali aqueous solution; the strong alkali is selected from one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide; the molar ratio of the strong alkali to N,N-diethyl-m-toluidine is 1-5:1; the mass percentage of the strong alkali aqueous solution is 30%-50%; preferably, the mass percentage of the strong alkali aqueous solution is 30%-35%.

[0020] Further, the alcohol solvent in step (2) is one of methanol, ethanol, propanol, ethylene glycol, propylene glycol, and glycerol; the mass ratio of the alcohol solvent to the intermediate is 1:0.5-2.

[0021] Further, in step (2), after the intermediate is prepared, a phase transfer catalyst is added, and the mass ratio of the phase transfer catalyst to the intermediate is 1:0.015-0.02; the phase transfer catalyst is selected from one of tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, benzyltriethylammonium bromide, or dodecyltrimethylammonium bromide.

[0022] Further, the ketone solvent in step (3) is selected from one of acetone, methyl isobutyl ketone, butanone, and pentanone.

[0023] The third aspect of the present invention provides a multifunctional epoxy resin TGTHEIC adhesive, comprising the following components in parts by weight: 40-140 parts of TGTHEIC epoxy resin, 100-140 parts of bisphenol A epoxy resin, 5-15 parts of silicone epoxy resin, 1-3 parts of reactive diluent, 1-60 parts of curing agent, and 1-5 parts of chain extender.

[0024] Further, the multifunctional epoxy resin TGTHEIC adhesive comprises the following components in parts by weight: 40-60 parts of TGTHEIC epoxy resin, 100-120 parts of bisphenol A epoxy resin, 5-10 parts of silicone epoxy resin, 2-3 parts of reactive diluent, 40-60 parts of curing agent, and 1-3 parts of chain extender.

[0025] Further, the multifunctional epoxy resin TGTHEIC adhesive comprises the following components in parts by weight: 40.4 parts of TGTHEIC epoxy resin, 100 parts of E-51 epoxy resin, 8.5 parts of silicone epoxy resin SE362, 3 parts of TGS-563, 46.9 parts of DMDAC238-1.68, and 3 parts of BAPP.

[0026] Further, the epoxy value of the triglycidyl isocyanurate (TGTHEIC) is 0.33-0.36, the volatile matter ≤1.6%, and the viscosity is 1500-1800 mPa·s.

[0027] Further, the bisphenol A epoxy resin is E-51 epoxy resin (Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.).

[0028] Further, the silicone epoxy resin is SE362 (Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.).

[0029] Further, the reactive diluent is one or more of TGS-563 (purchased from Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.), CE-793 (purchased from Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.), and resorcinol diglycidyl ether.

[0030] Further, the chain extender is selected from one or more of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BAPFP), 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane (BAPP-2TF), 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane (BAPFP-2TF), and SD-248 (purchased from Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.).

[0031] Further, the curing agent is selected from one or more of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, DMDAC238-1.68 (purchased from Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.), methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, tung oil anhydride, m-xylenediamine, DMP-30, 4,4'-diaminodiphenyl sulfone, and 2-ethyl-4-methylimidazole.

[0032] The fourth aspect of the present invention provides a preparation method of the above-mentioned multifunctional epoxy resin TGTHEIC adhesive, comprising the following steps:

[0033] By weight, the TGTHEIC epoxy resin, bisphenol A epoxy resin, silicone epoxy resin, TGS-563 (purchased from Zhejiang Yingrui Cloud New Materials Technology Co., Ltd.), and reactive diluent are placed in an oven at 100 °C to be fully fused, stirred and mixed. After being homogeneous and transparent, it is cooled to room temperature; a curing agent is added to the mixture, and it is stirred and mixed evenly at room temperature to obtain the adhesive. The adhesive is cured by heating and then subjected to a series of tests.

[0034] The fifth aspect of the present invention provides an application of the above-mentioned multifunctional epoxy resin TGTHEIC adhesive, including: adopting a low-temperature curing process. During curing, the temperature is raised to 60 °C, held for 30 min, then the temperature is further raised to 90 °C, held for 30 min, and then the temperature is further raised to 120 °C, held for 1 h, and then naturally cooled to room temperature.

[0035] The present invention uses 1,3,5-tris(2-hydroxyethyl)isocyanurate (THEIC) and epichlorohydrin (ECH) as the main raw materials. After ring-opening addition reaction under a Lewis acid catalyst, vacuum devolatilization is carried out to obtain an epoxy resin intermediate. After being dissolved in an alcohol solvent, desalting and ring-closing, filtration, and vacuum devolatilization are carried out under the action of an aqueous solution of an alkali metal hydroxide to obtain a mixture of TGTHEIC and salt. After dissolving the epoxy resin in a ketone solvent, filtration and vacuum devolatilization are carried out to prepare light yellow viscous TGTHEIC.

[0036] Beneficial effects

[0037] The operation steps of the present invention are simple, the working environment is friendly, and the production cost is relatively low. There are no special requirements for equipment (i.e., no high temperature, high pressure, anti-corrosion measures, etc.); the excessive epichlorohydrin in the reaction system is easy to recover and can be recycled, with less three wastes and environmental friendliness.

[0038] The multi-functional epoxy resin adhesive of the present invention has high tensile strength, and the preparation process is simple, low in cost, and convenient to operate, which is conducive to realizing industrial production. Especially in the fields of electronics and microelectronics, flexible copper-clad laminate (FCCL), flexible printed circuit board (FPC), motors, aerospace, etc., it has broad application prospects. Description of the Drawings

[0039] Figure 1 is the viscosity-temperature curve of Adhesive Examples 4 - 9;

[0040] Figure 2 is the relationship between the relative dielectric constant and frequency of Adhesive Examples 4 - 9 (100 kHz - 1000 kHz);

[0041] Figure 3 is the relationship between the dielectric loss and frequency of Adhesive Examples 4 - 9 (100 kHz - 1000 kHz). Detailed Embodiments

[0042] The following will further illustrate the present invention in conjunction with specific embodiments. 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.

[0043] All the raw material reagents used in the following examples can be obtained through commercial channels.

[0044] Example 1:

[0045] 26.1 g (0.1 mol) of 1,3,5-tris(2-hydroxyethyl) isocyanurate (THEIC) and 176 g (1.9 mol) of epichlorohydrin (ECH) were added to a four-necked flask and stirred at 105 °C to make the system homogeneous and transparent. 0.68 g (2.6% of THEIC) of tin tetrachloride was dissolved in 30 g of toluene, and the tin tetrachloride-toluene solution was slowly added dropwise to the flask over 5 min. After reacting at 100 °C for 2 h, the reaction temperature was lowered, and the reaction was carried out at 90 °C for 2.5 h. After the reaction was completed, the excess ECH and toluene were removed by rotary evaporation, and the recovery rates of toluene and epichlorohydrin were calculated. After dissolving the intermediate in 60 g of absolute ethanol, it was transferred to a flask, 0.860 g of tetrabutylammonium bromide was added, the temperature was raised to 60 °C, and 14 g (0.35 mol) of 32% aqueous sodium hydroxide solution was added dropwise over 1.5 h. After the addition was completed, the reaction was continued at 60 °C for 1 h. Stirring was stopped, the insoluble matter was removed by filtration, the filtrate was subjected to vacuum devolatilization at 60 °C, and when the absolute ethanol and water were almost completely removed, the temperature was raised to 105 °C and vacuum devolatilization was continued until completely removed. The product was dissolved in an equal weight of acetone and filtered by suction, and the filtrate was subjected to vacuum devolatilization at room temperature to 70 °C; the residue after devolatilization was a pale yellow viscous substance, namely TGTHEIC. After measuring the feed amount of THEIC and the product amount, the yield was 85.3%.

[0046] Example 2:

[0047] 104.4 g (0.4 mol) of 1,3,5-tris(2-hydroxyethyl) isocyanurate (THEIC) and 703 g (7.6 mol) of epichlorohydrin (ECH) were added to a four-necked flask and stirred at 105 °C to make the system homogeneous and transparent. 2.71 g (2.6% of THEIC) of tin tetrachloride was dissolved in a mixed solvent of 120 g of xylene and ethylbenzene, and the tin tetrachloride-xylene / ethylbenzene solution was slowly added dropwise to the flask over 5 min. After reacting at 100 °C for 2 h, the reaction temperature was lowered, and the reaction was carried out at 90 °C for 2.5 h. After the reaction was completed, the excess ECH and toluene were removed by rotary evaporation, and the recovery rates of xylene, ethylbenzene and epichlorohydrin were calculated. After dissolving the intermediate in 200 g of absolute ethanol, it was transferred to a flask, 3.4 g of tetrabutylammonium chloride was added, the temperature was raised to 60 °C, and 56 g (1.4 mol) of 32% aqueous sodium hydroxide solution was added dropwise over 1.5 h. After the addition was completed, the reaction was continued at 60 °C for 1 h. Stirring was stopped, the insoluble matter was removed by filtration, the filtrate was subjected to vacuum devolatilization at 60 °C, and when the absolute ethanol and water were almost completely removed, the temperature was raised to 105 °C and vacuum devolatilization was continued until completely removed. The product was dissolved in an equal weight of acetone and filtered by suction, and the filtrate was subjected to vacuum devolatilization at room temperature to 70 °C; the residue after devolatilization was a pale yellow viscous substance, namely TGTHEIC. After measuring the feed amount of THEIC and the product amount, the yield was 93.2%.

[0048] Example 3:

[0049] Except that the added epichlorohydrin (ECH) is recycled material (here the recycled epichlorohydrin comes from Example 2), other process steps, material quantities and reaction parameters are the same as those in Example 1. As a result, TGTHEIC was obtained. By measuring the feeding amount of THEIC and the product amount, the yield was 69.9%.

[0050] Example 4:

[0051] Put the TGTHEIC epoxy resin and SE362 into a disposable plastic cup, and let them fully fuse in an oven at 60 °C, stir and mix. After being homogeneous and transparent, cool to room temperature. Add DMDAC238-1.68 (purchased from Zhejiang Yingrui Yun New Material Technology Co., Ltd.) to this mixture and stir and mix evenly at room temperature. The specific formula is as follows:

[0052] TGTHEIC epoxy resin: 140 grams

[0053] SE362: 8.4 grams

[0054] DMDAC238-1.68: 46.7 grams

[0055] Example 5:

[0056] Put the E-51 epoxy resin and SE362 into a disposable plastic cup, and let them fully fuse in an oven at 60 °C, stir and mix. After being homogeneous and transparent, cool to room temperature. Add DMDAC238-1.68 to this mixture and stir and mix evenly at room temperature. The specific formula is as follows:

[0057] E-51 epoxy resin: 140 grams

[0058] SE362: 8.4 grams

[0059] DMDAC238-1.68: 46.7 grams

[0060] Example 6:

[0061] Put the TGTHEIC epoxy resin, E-51 epoxy resin, SE362, and BAPP into a disposable plastic cup, and let them fully fuse in an oven at 100 °C, stir and mix. After being homogeneous and transparent, cool to room temperature. Add DMDAC238-1.68 to this mixture and stir and mix evenly at room temperature. The specific formula is as follows:

[0062] TGTHEIC epoxy resin: 40.4 grams

[0063] E-51 epoxy resin: 100 grams

[0064] SE362: 8.6 grams

[0065] BAPP: 1.0 gram

[0066] DMDAC238 - 1.68: 46.7 grams

[0067] Example 7:

[0068] Add TGTHEIC epoxy resin, E - 51 epoxy resin, SE362, BAPP, and TGS - 563 into a disposable plastic cup, and let them fully blend in an oven at 100°C, stir and mix. After it becomes homogeneous and transparent, cool it to room temperature. Then add DMDAC238 - 1.68 to this mixture and stir and mix evenly at room temperature. The specific formulation is as follows:

[0069] TGTHEIC epoxy resin: 40.4 grams

[0070] E - 51 epoxy resin: 100 grams

[0071] SE362: 8.6 grams

[0072] BAPP: 2.0 grams

[0073] TGS - 563: 3.0 grams

[0074] DMDAC238 - 1.68: 46.7 grams

[0075] Example 8:

[0076] Add TGTHEIC epoxy resin, E - 51 epoxy resin, SE362, BAPP, and TGS - 563 into a disposable plastic cup, and let them fully blend in an oven at 100°C, stir and mix. After it becomes homogeneous and transparent, cool it to room temperature. Then add DMDAC238 - 1.68 to this mixture and stir and mix evenly at room temperature. The specific formulation is as follows:

[0077] TGTHEIC epoxy resin: 40.4 grams

[0078] E - 51 epoxy resin: 100 grams

[0079] SE362: 8.6 grams

[0080] BAPP: 3.0 grams

[0081] TGS - 563: 3.0 grams

[0082] DMDAC238 - 1.68: 46.7 grams

[0083] Example 9:

[0084] Put TGTHEIC epoxy resin, E-51 epoxy resin, SE362, and BAPP into a disposable plastic cup, and let them fully fuse in an oven at 100 °C. Stir and mix them. After they become homogeneous and transparent, cool them to room temperature. Then add DMDAC238-1.68 to this mixture and stir and mix evenly at room temperature. The specific formula is as follows:

[0085] TGTHEIC epoxy resin: 40.4 g

[0086] E-51 epoxy resin: 100 g

[0087] SE362: 8.6 g

[0088] BAPP: 3.0 g

[0089] DMDAC238-1.68: 46.7 g

[0090] Take an appropriate amount of the epoxy resin adhesive from Examples 4-9 above, evenly apply it on a polished standard iron sheet, stack and clamp it, and then put it into a forced-air oven for curing: heat up to 60 °C, keep warm for 30 min, continue to heat up to 90 °C, keep warm for 30 min, continue to heat up to 120 °C, keep warm for 1 h, and then cool it naturally to room temperature. The tensile shear strength is measured as shown in Table 1.

[0091] Take an appropriate amount of the epoxy resin adhesive from Examples 4-9 above, pour it into a mold of a certain specification, and put it into a forced-air oven for curing: heat up to 60 °C, keep warm for 30 min, continue to heat up to 90 °C, keep warm for 30 min, continue to heat up to 120 °C, keep warm for 1 h, and then cool it naturally to room temperature. The tensile strength, impact strength, and flexural strength are measured as shown in Table 1.

[0092] Grind the cured spline into a thin sheet of 15 mm × 15 mm × 1 mm, dry it in an oven at 100 °C for 1 h, weigh the dry weight G1, then soak it in pure water for 24 h, dry the surface and weigh the wet weight G2. The water absorption rate is measured as shown in Table 1.

[0093] Table 1 Performance test of samples in Examples 4-9

[0094] Specimen Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Tensile shear strength, MPa 14.48 12.88 11.22 14.29 14.55 14.11 Tensile strength, MPa 67.85 65.90 71.36 76.55 78.99 74.15 Flexural strength, MPa 73.2 81.34 92.61 94.89 94.25 85.82 <![CDATA[Impact strength, kJ / m 2 > 16.309 21.139 16.302 24.813 26.03 22.243 Water absorption rate, % 1.26 1.26 1.29 1.00 1.19 1.48

[0095] According to Table 1 and Figures 1-3As can be seen, the adhesives formulated in the present invention have excellent mechanical and electrical properties. In terms of mechanical properties, the room temperature tensile strength of all six adhesives is ≥60 MPa. At 100 °C, the tensile strength of Example 7 can still reach 12.18 MPa, and that of Example 8 can even reach 15.04 MPa, which are significantly higher than those of traditional epoxy adhesives. In terms of electrical properties, the water absorption rate of all formulations is ≤1.5%. The low water absorption rate is beneficial to maintaining the good dielectric properties and intermolecular bonding strength of the epoxy resin adhesive system, and is suitable for storage and use in humid environments. At the same time, the dielectric loss of all formulations at 100 kHz is ≤2.9%, and the relative dielectric constant is stable at 3.49 - 4.78. Figures 2-3 It can be seen that in the frequency range of 100 - 1000 KHz, as the frequency increases, the capacitance of the cured products of the three adhesives shows a weak decreasing trend and generally remains stable, indicating that all adhesives have good capacitance stability and electrical insulation properties. By adding TGS-563, the impact strength of Example 7 and Example 8 is increased to 24.813 kJ / m 2 、26.03 kJ / m 2 , which is a 52.1% and 59.6% increase compared to the basic formulation. At the same time, the two amino groups of BAPP can further form a dense cross-linked structure with the epoxy adhesive. This cross-linking effect improves the mechanical properties while reducing its water absorption rate, showing more obvious advantages compared to other formulations. Example 8 with 3 parts of BAPP added has more prominent mechanical properties. In addition, Figure 1 It can be seen that adding BAPP can reduce the viscosity of the adhesive and obtain better processing performance. In summary, due to its high tensile shear strength, excellent flexural strength and low dielectric loss characteristics, the adhesive exhibits a significant multi-functional synergistic effect, providing a material basis for its engineering applications in fields such as high-precision electronic packaging and lightweight spacecraft structure bonding.

[0096] In this paper, the compounds of the present invention, their preparation methods and applications are described in combination with some specific embodiments and examples, and many details are also stated and explained. However, it should be understood that the specific embodiments and examples provided herein are only exemplary and do not limit the protection scope of the present invention. In fact, for those skilled in the art, the present invention can also be implemented in other specific ways, and the corresponding modifications, changes or adjustments do not depart from the spirit and main idea of the present invention, and thus should all be regarded as being included within the scope of the present invention.

Claims

1. A multifunctional epoxy resin TGTHEIC, characterized in that: The multifunctional epoxy resin TGTHEIC is a light yellow viscous liquid obtained by a ring-opening reaction of 1,3,5-tris(2-hydroxyethyl)isocyanurate and epichlorohydrin with a molar ratio of 1:10 - 30 under the action of a catalyst, and then a ring-closing reaction under alkaline conditions; wherein, the weight ratio of the catalyst to 1,3,5-tris(2-hydroxyethyl)isocyanurate is 1:0.01 - 0.

1.

2. The multifunctional epoxy resin TGTHEIC according to claim 1, characterized in that: The catalyst is selected from one of boron trifluoride and tin tetrachloride.

3. The multifunctional epoxy resin TGTHEIC 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, and potassium hydroxide; the molar ratio of the strong alkali to the diethylmethyl-m-phenylenediamine is 1 - 5:1; the mass percentage of the strong alkali aqueous solution is 30% - 50%.

4. The preparation method of the multifunctional epoxy resin TGTHEIC according to any one of claims 1 - 3, comprising the following steps: (1) 1,3,5-tris(2-hydroxyethyl)isocyanurate and epichlorohydrin with a molar ratio of 1:10 - 30 react at 90 - 100 °C for 3 - 6 h under the action of a catalyst, and the excessive epichlorohydrin is removed by rotary evaporation to obtain an epoxy resin intermediate; (2) The intermediate obtained in step (1) is dissolved in an alcohol solvent, and a desalting ring-closing reaction is carried out under alkaline conditions at 60 °C, and then filtered and rotary evaporated to obtain a mixture of TGTHEIC and salt; (3) After dissolving the epoxy resin in a ketone solvent, it is filtered and vacuum devolatilized to prepare the light yellow viscous TGTHEIC.

5. A multifunctional epoxy resin TGTHEIC adhesive, comprising the following components in parts by weight: 40 - 140 parts of TGTHEIC epoxy resin, 100 - 140 parts of bisphenol A epoxy resin, 5 - 15 parts of silicone epoxy resin, 1 - 3 parts of reactive diluent, 1 - 60 parts of curing agent, and 1 - 5 parts of chain extender.

6. The multifunctional epoxy resin TGTHEIC adhesive according to claim 5, wherein: The multifunctional epoxy resin TGTHEIC adhesive comprises the following components in parts by weight: 40 - 60 parts of TGTHEIC epoxy resin, 100 - 120 parts of bisphenol A epoxy resin, 5 - 10 parts of silicone epoxy resin, 2 - 3 parts of reactive diluent, 40 - 60 parts of curing agent, and 1 - 3 parts of chain extender.

7. A multifunctional epoxy resin TGTHEIC adhesive according to claim 5, characterized in that: The epoxy value of the tris-glycidyl-tris(2-hydroxyethyl)isocyanurate TGTHEIC is 0.33 - 0.36, the volatile content ≤ 1.6%, and the viscosity is 1500 - 1800 mPa·s.

8. A multifunctional epoxy resin TGTHEIC adhesive according to claim 5, characterized in that: The bisphenol A epoxy resin is E-51 epoxy resin, purchased from Zhejiang Yingrui Cloud New Material Technology Co., Ltd.; the silicone epoxy resin is SE362, purchased from Zhejiang Yingrui Cloud New Material Technology Co., Ltd.

9. The preparation method of a multifunctional epoxy resin TGTHEIC adhesive according to any one of claims 5 - 8, comprising the following steps: By weight parts, TGTHEIC epoxy resin, bisphenol A epoxy resin, silicone epoxy resin, TGS-563, and active diluent are placed in an oven at 100 °C to allow them to fully blend, stirred and mixed. After becoming homogeneous and transparent, it is cooled to room temperature. A curing agent is added to this mixture, and it is stirred and mixed evenly at room temperature to obtain an adhesive. After the adhesive is cured by heating, a series of tests are carried out.

10. Use of a multifunctional epoxy resin TGTHEIC adhesive according to any one of claims 5-8, comprising: Using a low-temperature curing process, during curing, the temperature is raised to 60 °C, held for 30 min, then the temperature is further raised to 90 °C, held for 30 min, and then the temperature is further raised to 120 °C, held for 1 h, and then naturally cooled to room temperature.

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