A biphenyl-type high-temperature resistant and toughened modified epoxy resin and its preparation method

Abstract

The present application discloses a biphenyl type high temperature resistant toughening modified epoxy resin and a preparation method thereof, and relates to the field of epoxy resin modification technology, comprising the following steps: 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, bisphenol A, phosphate, triglycidyl p-aminophenol, deionized water and solvent are added to the reaction vessel in sequence, fully stirred to make it uniformly mixed, and N2 protection is introduced for 30min at the same time. After heating to 95-105°C, tetrabutylammonium bromide is slowly added to the system and reacted for 3-5h. After the reaction is completed, methanol is removed by rotary evaporation, and then deionized water is added, washed to neutrality, and vacuum dried to obtain a biphenyl type high temperature resistant toughening modified epoxy resin. The reaction conditions of its experimental scheme are easy to control and the reaction process is simple. The synthesized biphenyl type high temperature resistant toughening modified epoxy resin can maintain considerable toughness and impact resistance while maintaining high temperature resistance, and can be used in epoxy packaging materials.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resin modification, and particularly relates to a biphenyl-type high-temperature resistant and toughened modified epoxy resin and a preparation method thereof. Background Art

[0002] Epoxy resins have excellent physical and mechanical properties and electrical properties, and are widely used as coatings, adhesives, resin matrices for composite materials, electronic packaging materials, etc. With the development of integrated circuits towards ultra-large scale, high density, high power, high precision, and multi-function, and the rapid development of electronic packaging technology, the development direction of epoxy packaging materials is towards high purity, high reliability, high thermal conductivity, high temperature resistance, high bonding strength, low stress, low viscosity, low environmental pollution, and easy processing.

[0003] 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether is a pale yellow crystal, solid at room temperature, easy to form powder, and has a very low viscosity in the molten state above the melting point. The high-rigidity heat-resistant biphenyl group contained in its main chain has an almost planar structure, which increases the chain regularity and intermolecular force, and increases the physical crosslinking density in the isotropic network. Its cured product has good heat resistance. And the tetramethyl groups it carries have a large steric hindrance, making the movement of the macromolecular chain segments in the cured product network relatively difficult, increasing the dynamic mechanical properties, and having good toughness.

[0004] Triglycidyl p-aminophenol is a trifunctional high-temperature resistant epoxy resin. This epoxy resin can form a relatively high crosslinking density and aromatic density during the curing process, making the cured product exhibit good heat resistance, high mechanical strength, low curing shrinkage rate, and good resistance to radiation, water, and chemicals. In addition, due to its low viscosity, it is easy to operate and can achieve solvent-free operation. It is used for electrical casting insulation products with higher heat resistance requirements, and composite products formed by carbon fiber and glass fiber winding, pultrusion, lamination, and prepreg processes.

[0005] High-temperature resistance and toughening of epoxy resins are important aspects of epoxy resin modification. Existing modified epoxy resins are brittle and easy to break, which seriously affects their application in high-toughness and high-temperature occasions. Therefore, providing a high-temperature resistant and toughened modified epoxy resin is an urgent problem for those skilled in the art. Summary of the Invention

[0006] The present application provides a biphenyl-type high-temperature resistant and toughened modified epoxy resin and a preparation method thereof, which solve the problems that existing modified epoxy resins have low toughness, are brittle and easy to break, or are not resistant to high temperatures, resulting in affecting their application in high-toughness and high-temperature occasions.

[0007] To solve the above problems, the present invention provides a method for preparing a biphenyl-type high-temperature resistant and toughened modified epoxy resin. The main reaction principle is to use a coupling agent and hydrolyzed phosphate ester to couple 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether and triglycidyl p-aminophenol, thereby modifying 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether to improve its toughness and high-temperature resistance.

[0008] To prepare the biphenyl-type high-temperature resistant and toughened modified epoxy resin according to the above reaction principle, the following reactions are included:

[0009]

[0010] In the compound II, the R1 and R2 groups are hydrogen or methyl;

[0011] The compound I is one of the following structural formulas:

[0012]

[0013] The end product is one of the following compound structural formulas:

[0014]

[0015] Among them, the R3, R4 and R5 groups are:

[0016] The above preparation method includes the following specific steps:

[0017] Add 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, compound II, compound I, triglycidyl p-aminophenol, deionized water and solvent into a reaction vessel, mix evenly, while introducing an inert gas for protection, and finally heat and slowly add tetrabutylammonium bromide to the system for reaction; after the reaction is completed, a biphenyl-type high-temperature resistant and toughened modified epoxy resin is obtained.

[0018] Preferably, the compound II is bisphenol A or bisphenol F.

[0019] Preferably, the molar ratio of 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, compound II, compound I and triglycidyl p-aminophenol is 1-1.5:1:1-1.2:1-1.5.

[0020] Preferably, the solvent is one or more of methanol, ethanol, ethyl acetate, and ether.

[0021] Preferably, the mass of tetrabutylammonium bromide accounts for 0.1% - 0.3% of the total mass of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, Compound II, Compound I, and triglycidyl p-aminophenol.

[0022] Preferably, the mass of deionized water accounts for 5% - 10% of the mass of Compound I.

[0023] In some embodiments, after the reaction is completed, a post-treatment step is carried out, including rotary evaporation to remove the solvent, washing with water until neutral, and vacuum drying.

[0024] Preferably, after introducing N2 protection, the temperature is raised to 95 - 105 °C, and tetrabutylammonium bromide is slowly added to the reaction system, and the reaction is carried out for 3 - 5 h.

[0025] Preferably, the mass of the solvent is 3 - 5 times the total mass of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, Compound II, Compound I, and triglycidyl p-aminophenol.

[0026] A biphenyl-type high-temperature resistant and toughened modified epoxy resin is prepared by the above preparation method.

[0027] The beneficial effects achieved by the present invention:

[0028] The present invention prepares and obtains a biphenyl-type high-temperature resistant and toughened modified epoxy resin, which is obtained by a ring-opening reaction using 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, bisphenol A, phosphate ester, and triglycidyl p-aminophenol as raw materials. The reaction conditions of the experimental scheme are easy to control, and the reaction process is simple. The synthesized biphenyl-type high-temperature resistant and toughened modified epoxy resin can maintain considerable toughness and impact resistance while maintaining high-temperature resistance, and can be used in epoxy encapsulation materials.

[0029] The present invention utilizes the combination of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether and triglycidyl p-aminophenol to further enhance the high-temperature resistance of the epoxy resin and significantly improve the disadvantage of the epoxy resin being brittle and easy to break. Description of the Drawings

[0030] Figure 1 It is a schematic diagram of the reaction principle of the biphenyl-type high-temperature resistant and toughened modified epoxy resin in Example 1. Detailed Description of the Invention

[0031] The following provides a detailed description of the specific embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present application.

[0032] Example 1

[0033] 18.6 g of 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, 10 g of bisphenol A (as a coupling agent), 8.8 g of [substance not specified], 15.7 g of triglycidyl p-aminophenol, 0.6 g of deionized water, and 190 g of methanol were successively added to a four-necked flask equipped with a stirring device, a dropping funnel, and a condenser. Stir well to mix evenly, and at the same time, introduce N2 for protection for 30 min. After heating to 100 °C, 0.11 g of tetrabutylammonium bromide was slowly added to the system, and the reaction was carried out for 4 h. After the reaction was completed, methanol was removed by rotary evaporation, then deionized water was added, washed until neutral, and dried under vacuum to obtain a biphenyl-type high-temperature resistant and toughness-modified epoxy resin.

[0034] The reaction formula is as follows:

[0035]

[0036] Since the phosphate ester hydrolyzes to form hydroxyl groups during the reaction, the substituents (such as ethyl, butyl, phenyl, etc.) on the phosphate ester are all removed as by-products. The hydroxyl groups then react with the epoxy groups, and each hydroxyl group can react with one epoxy group. Therefore, the resulting end product (biphenyl-type high-temperature resistant and toughness-modified epoxy resin) is a mixture, containing at least one of the following compounds:

[0037]

[0038] Example 2

[0039] 24.5 g of 3,3',5,5'-tetramethylbiphenyl bisphenol diglycidyl ether, 12 g of bisphenol A, 9.6 g of triethyl phosphite, 19 g of triglycidyl p-aminophenol, 0.5 g of deionized water, and 260 g of methanol were successively added to a four-necked flask equipped with a stirring device, a dropping funnel, and a condenser. Stir well to mix evenly, and at the same time, introduce N2 for protection for 30 min. After heating to 95 °C, 0.13 g of tetrabutylammonium bromide was slowly added to the system, and the reaction was carried out for 5 h. After the reaction was completed, methanol was removed by rotary evaporation, then deionized water was added, washed until neutral, and dried under vacuum to obtain a biphenyl-type high-temperature resistant and toughness-modified epoxy resin.

[0040] The end product contains at least one of the following compounds:

[0041]

[0042] Example 3

[0043] 46 g of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, 20 g of bisphenol A, 21.3 g of dibutyl phosphite, 36 g of triglycidyl p-aminophenol, 1.8 g of deionized water and 400 g of methanol were successively added to a four-necked flask equipped with a stirring device, a dropping funnel and a condenser, and stirred well to make them evenly mixed. At the same time, N2 was introduced for protection for 30 min. After the temperature was raised to 105 °C, 0.22 g of tetrabutylammonium bromide was slowly added to the system, and the reaction was carried out for 3 h. After the reaction was completed, methanol was removed by rotary evaporation, then deionized water was added, washed to neutral, and dried in vacuo to obtain a biphenyl-type high-temperature resistant and toughness-modified epoxy resin.

[0044] The final product contains at least one of the following compounds:

[0045]

[0046] Example 4

[0047] 18.5 g of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, 8 g of bisphenol A, 7.6 g of glycerol phosphate, 14.4 g of triglycidyl p-aminophenol, 0.5 g of deionized water and 190 g of methanol were successively added to a four-necked flask equipped with a stirring device, a dropping funnel and a condenser, and stirred well to make them evenly mixed. At the same time, N2 was introduced for protection for 30 min. After the temperature was raised to 100 °C, 0.1 g of tetrabutylammonium bromide was slowly added to the system, and the reaction was carried out for 5 h. After the reaction was completed, methanol was removed by rotary evaporation, then deionized water was added, washed to neutral, and dried in vacuo to obtain a biphenyl-type high-temperature resistant and toughness-modified epoxy resin.

[0048] The final product contains at least one of the following compounds:

[0049]

[0050] Example 5

[0051] 28.5 g of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, 14 g of bisphenol A, 22 g of triphenyl phosphate, 22 g of triglycidyl p-aminophenol, 1.5 g of deionized water and 340 g of methanol were successively added to a four-necked flask equipped with a stirring device, a dropping funnel and a condenser, and stirred well to make them evenly mixed. At the same time, N2 was introduced for protection for 30 min. After the temperature was raised to 95 °C, 0.17 g of tetrabutylammonium bromide was slowly added to the system, and the reaction was carried out for 3 h. After the reaction was completed, methanol was removed by rotary evaporation, then deionized water was added, washed to neutral, and dried in vacuo to obtain a biphenyl-type high-temperature resistant and toughness-modified epoxy resin.

[0052] The final product contains at least one of the following compounds:

[0053]

[0054] Example 6

[0055] 12 g of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, 6 g of bisphenol F, 6 g of triethyl diphosphate, 9.5 g of triglycidyl p-aminophenol, 0.4 g of deionized water and 130 g of methanol were successively added into a four-necked flask equipped with a stirring device, a dropping funnel and a condenser. Stir well to make them mix evenly. At the same time, introduce N2 to protect for 30 min. After heating to 100 °C, slowly add 0.05 g of tetrabutylammonium bromide into the system and react for 5 h. After the reaction is completed, remove methanol by rotary evaporation, then add deionized water, wash until neutral, and dry under vacuum to obtain a biphenyl-type high-temperature resistant and toughened modified epoxy resin.

[0056] The final product contains at least one of the following compounds:

[0057]

[0058] Example 7

[0059] 18.6 g of 3,3’,5,5’-tetramethylbiphenyl diglycidyl ether, 10 g of bisphenol A (as a linker), 8.8 g of triethyl phosphate, 15.7 g of triglycidyl p-aminophenol, 0.6 g of deionized water and 190 g of ethanol were successively added into a four-necked flask equipped with a stirring device, a dropping funnel and a condenser. Stir well to make them mix evenly. At the same time, introduce N2 to protect for 30 min. After heating to 100 °C, slowly add 0.11 g of tetrabutylammonium bromide into the system and react for 4 h. After the reaction is completed, remove methanol by rotary evaporation, then add deionized water, wash until neutral, and dry under vacuum to obtain a biphenyl-type high-temperature resistant and toughened modified epoxy resin.

[0060] The final product contains at least one of the following compounds:

[0061]

[0062] Characterization and testing:

[0063] To test the various properties of the biphenyl - type high - temperature resistant and toughness - enhanced modified epoxy resin, the viscosity of the synthesized modified epoxy resin was tested, and the heat distortion temperature and tensile strength of the cured modified epoxy resin were tested. The results are shown in Table 1. It can be seen from Table 1 that the synthesized modified epoxy resin has good high - temperature resistance and toughness - enhancing properties. The viscosity was tested with a rotational viscometer according to the GB / T10247 - 2008 standard; the heat distortion temperature was measured with a SWB - 300 vicat softening point & heat deflection temperature tester; the tensile strength was tested with a universal testing machine according to the GB / T2567 - 008 standard (tensile rate: 20 mm / min).

[0064] In the comparative example, the raw material tris - glycidyl - p - aminophenol in Example 1 was used as a sample for testing.

[0065] Table 1 Various properties of the modified epoxy resin

[0066] Viscosity, cps (90 °C) Heat distortion temperature, °C Tensile strength / MPa Example 1 1305 210 68.32 Example 2 1287 200 65.57 Example 3 1300 210 68.09 Example 4 1259 200 64.41 Example 5 1280 200 65.15 Example 6 1294 210 67.69 Comparative example 5731 150 48.94

[0067] The tensile strengths of Examples 1 - 6 are significantly higher than those of the comparative example, indicating that the modified epoxy resin effectively solves the technical problem of "brittleness and easy breakage".

[0068] The present application has been described in detail above in combination with specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present application. Those skilled in the art understand that without departing from the spirit and scope of the present application, various equivalent substitutions, modifications or improvements can be made to the technical solutions and their implementation manners of the present application, and all of these fall within the scope of the present application. The protection scope of the present application is subject to the appended claims.

Claims

1. A preparation method of a biphenyl-type high-temperature resistant and toughness-modified epoxy resin, characterized in that, It includes the following reactions: In the compound II, the R1 and R2 groups are hydrogen or methyl. The compound I is one of the following structural formulas: The end product is one of the following compound structural formulas: Among them, the R3, R4 and R5 groups are:

2. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 1, characterized in that, It includes the following specific steps: Add 3,3’,5,5’-tetramethylbiphenol diglycidyl ether, compound II, compound I, triglycidyl p-aminophenol, deionized water and a solvent into a reaction vessel, mix evenly, while introducing an inert gas for protection, and finally heat and slowly add tetrabutylammonium bromide to the system for reaction; after the reaction is completed, a biphenyl-type high-temperature resistant and toughness-modified epoxy resin is obtained.

3. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 2, characterized in that, The compound II is bisphenol A or bisphenol F.

4. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 2, characterized in that, The molar ratio of 3,3’,5,5’-tetramethylbiphenol diglycidyl ether, compound II, compound I and triglycidyl p-aminophenol is 1 - 1.5:1:1 - 1.2:1 - 1.

5.

5. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 2, characterized in that, The solvent is one or more of methanol, ethanol, ethyl acetate, and ether.

6. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 2, characterized in that, The mass of tetrabutylammonium bromide accounts for 0.1% - 0.3% of the total mass of 3,3’,5,5’-tetramethylbiphenol diglycidyl ether, compound II, compound I and triglycidyl p-aminophenol.

7. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 2, characterized in that, The mass of deionized water accounts for 5% - 10% of the mass of compound I.

8. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 2, characterized in that, After the reaction is completed, post-treatment steps are carried out, including rotary evaporation to remove the solvent, washing with water until neutral, and vacuum drying steps.

9. The preparation method of a biphenyl-type high-temperature resistant and toughness-enhanced modified epoxy resin according to claim 2, characterized in that, After introducing N2 for protection, heat up to 95 - 105 °C, slowly add tetrabutylammonium bromide to the reaction system, and react for 3 - 5 h.

10. The preparation method of a biphenyl-type high-temperature resistant and toughened modified epoxy resin according to claim 2, characterized in that, The mass of the solvent is 3 - 5 times the total mass of 3,3’,5,5’-tetramethylbiphenol diglycidyl ether, compound II, compound I and triglycidyl p-aminophenol.

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