Preparation and application of high temperature resistant epoxy resin

Abstract

The present invention relates to the technical field of polymer materials, and discloses a kind of preparation and application of high temperature resistant epoxy resin, the present invention is by adding bisphenol A type epoxy resin, triazine-based polybenzimidazole into a reactor, stirring, continuing to add diaminodiphenylmethane curing agent, reacting, stirring, standing, obtaining high temperature resistant epoxy resin. The triazine-based polybenzimidazole of the present invention contains polybenzimidazole group, triazine group, zinc phytate group, phosphorus element, wherein the phosphorus element can be heated to produce phosphoric acid strong dehydration material, can promote material dehydration into carbon, achieve flame retardant effect, wherein zinc phytate can constitute organic-inorganic hybrid flame retardant system with phosphorus element; wherein the polybenzimidazole group, the triazine group itself just have good high temperature resistant effect, are added to epoxy resin, improve the high temperature resistance of epoxy resin.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to the preparation and application of a high temperature resistant epoxy resin. Background Art

[0002] Epoxy resin contains two or more active epoxy groups. Epoxy resin has good reactivity and bonding properties. Before curing, it is in liquid state with low molecular weight and cured under certain conditions with curing agent and auxiliary agent. At the same time, epoxy resin has good mechanical properties, but its flame retardant and high temperature resistance have not been improved. For example, patent CN105778419A discloses a modified high temperature resistant epoxy resin and a preparation method thereof. The invention first modifies polyether sulfone, and then modifies the epoxy resin twice. The finally obtained modified high temperature resistant epoxy resin is resistant to high temperature, has low curing shrinkage, small internal stress, and is not easy to crack. However, its flame retardant effect has not been improved. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In view of the deficiencies in the prior art, the present invention provides a preparation and application of a high temperature resistant epoxy resin, which has good flame retardant and high temperature resistance effects.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a preparation of a high temperature resistant epoxy resin, wherein the preparation method of the high temperature resistant epoxy resin is:

[0007] (1) adding 8-11 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75-90° C., adding 10-13 parts by weight of phytic acid thereto, mechanically stirring, and reacting under reflux at 85-95° C., washing after the reaction, and drying at 90-100° C. to obtain zinc phytate;

[0008] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline, and reacting under reflux at 75-90° C. for 1-3 h, then adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and continuing to stir for 8-10 h. After completion, filtering, washing, and drying to obtain nitrated zinc phytate;

[0009] (3) adding nitrated zinc phytate to N,N-dimethylformamide solvent, then adding ferric chloride and activated carbon, stirring and mixing, and then adding hydrazine hydrate solution, stirring and reacting at 70-90° C. for 10-20 hours, precipitating with deionized water after the reaction, filtering, and washing to obtain aminated zinc phytate;

[0010] (4) adding 4-hydroxy-5-methyl-1,3-phthalic acid and 3,3-diaminobenzidine to a reactor, and then continuing to add polyphosphoric acid, introducing nitrogen for protection, mechanically stirring, reacting at 180-210° C. for 20-24 hours, cooling after completion, washing with deionized water, filtering, neutralizing with 8-12% ammonia water, filtering, washing with water until neutral, and drying to obtain hydroxylated polybenzimidazole;

[0011] (5) In an ice bath, cyanuric chloride and hydroxylated polybenzimidazole are added to an acetone solvent, and refluxed at 75-80° C. for 2-3 h, and then amino phytic acid zinc is added thereto, and reacted at 90-110° C. for 6-10 h. After the reaction, the mixture is cooled to room temperature, concentrated to remove the solvent, and washed with petroleum ether to obtain triazine-based polybenzimidazole;

[0012] (6) Add 80-100 parts by weight of bisphenol A epoxy resin and 4-6 parts by weight of triazine polybenzimidazole into a reactor, stir, and continue to add 1-2 parts by weight of diaminodiphenylmethane curing agent, react for 2-4 hours, stir, and stand to obtain a high temperature resistant epoxy resin.

[0013] Preferably, the reflux reaction time in (1) is 3-5 h.

[0014] Preferably, the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in (2) is 1:0.9-1.1:0.4-0.6:1.4-1.6.

[0015] Preferably, the mass ratio of nitrated zinc phytate, ferric chloride, activated carbon and hydrazine hydrate solution in (3) is 1:1.3-1.6:2.1-2.4:1.5-2.2.

[0016] Preferably, the mass ratio of 4-hydroxy-5-methyl-1,3-phthalic acid, 3,3-diaminobenzidine and polyphosphoric acid in (4) is 1.3-1.4:1:0.01-0.02.

[0017] Preferably, the mass ratio of cyanuric chloride, hydroxylated polybenzimidazole and amino phytic acid zinc in (5) is 1:0.3-0.6:1.2-1.5.

[0018] Preferably, the high temperature resistant epoxy resin is used in the fields of adhesives, coatings, electronics, water conservancy and transportation.

[0019] (III) Beneficial technical effects

[0020] The invention prepares the high temperature resistant epoxy resin by adding bisphenol A epoxy resin and triazine polybenzimidazole into a reactor, stirring, continuously adding diaminodiphenylmethane curing agent, reacting, stirring and standing.

[0021] The triazine-based polybenzimidazole of the present invention contains a polybenzimidazole group, a triazine group, a zinc phytate group and a phosphorus element, wherein the phosphorus element can generate a phosphoric acid strong dehydrating substance when heated, can promote the dehydration of the material into carbon, and achieve a flame retardant effect, wherein the zinc phytate and the phosphorus element form an organic-inorganic hybrid flame retardant system; wherein the polybenzimidazole group and the triazine group themselves have a good high temperature resistance effect, and are added to the epoxy resin to improve the high temperature resistance of the epoxy resin, and the imidazole group in the polybenzimidazole group and the diaminodiphenylmethane curing agent form a curing system, which has a better curing effect. DETAILED DESCRIPTION

[0022] The mass fraction of phytic acid is 50%.

[0023] Example 1

[0024] (1) adding 8 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75° C., adding 10 parts by weight of phytic acid thereto, mechanically stirring, and reflux reacting at 85° C. for 3 h, washing after the reaction, and drying at 90° C. to obtain zinc phytate;

[0025] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, and reacting under reflux at 75° C. for 1 h, and then continuing to add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.9:0.4:1.4, and continuing to stir for 8 h. After the end, filtering, washing, and drying are performed to obtain nitrated zinc phytate;

[0026] (3) adding nitrated zinc phytate to N,N-dimethylformamide solvent, and then adding ferric chloride and activated carbon, stirring and mixing, and then adding hydrazine hydrate solution, wherein the mass ratio of nitrated zinc phytate, ferric chloride, activated carbon, and hydrazine hydrate solution is 1:1.3:2.1:1.5, stirring and reacting at 70° C. for 10 hours, and after the reaction, precipitating with deionized water, filtering, and washing to obtain aminated zinc phytate;

[0027] (4) adding 4-hydroxy-5-methyl-1,3-phthalic acid and 3,3-diaminobenzidine to a reactor, and then continuing to add polyphosphoric acid, wherein the mass ratio of 4-hydroxy-5-methyl-1,3-phthalic acid, 3,3-diaminobenzidine, and polyphosphoric acid is 1.3:1:0.01, introducing nitrogen for protection, mechanically stirring, reacting at 180° C. for 20 hours, cooling after completion, washing with deionized water, filtering, neutralizing with 8% ammonia water, filtering, washing with water until neutral, and drying to obtain hydroxylated polybenzimidazole;

[0028] (5) In an ice bath, cyanuric chloride and hydroxylated polybenzimidazole are added to an acetone solvent, refluxed at 75° C. for 2 h, and then amino-phytic acid zinc is added thereto, wherein the mass ratio of cyanuric chloride, hydroxylated polybenzimidazole, and amino-phytic acid zinc is 1:0.3:1.2, and the reaction is carried out at 90° C. for 6 h. After the reaction, the mixture is cooled to room temperature, concentrated to remove the solvent, and washed with petroleum ether to obtain triazine-based polybenzimidazole;

[0029] (6) 80 parts by weight of bisphenol A epoxy resin and 4 parts by weight of triazine polybenzimidazole are added to a reactor and stirred. 1 part by weight of diaminodiphenylmethane curing agent is added and reacted for 2 hours. The mixture is stirred and allowed to stand to obtain a high temperature resistant epoxy resin.

[0030] Example 2

[0031] (1) adding 11 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 90° C., adding 13 parts by weight of phytic acid thereto, mechanically stirring, and reflux reacting at 95° C. for 5 h, washing the solvent after reaction, and drying the solvent at 100° C. to obtain zinc phytate;

[0032] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, reflux reacting at 90° C. for 3 h, then continuing to add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.1:0.6:1.6, continuing to stir for 10 h, filtering and washing after the end, and drying to obtain nitrated zinc phytate;

[0033] (3) adding nitrated zinc phytate to N,N-dimethylformamide solvent, then adding ferric chloride and activated carbon, stirring and mixing, and then adding hydrazine hydrate solution, wherein the mass ratio of nitrated zinc phytate, ferric chloride, activated carbon, and hydrazine hydrate solution is 1:1.3:2.1:1.5, stirring and reacting at 70° C. for 10-20 hours, precipitating with deionized water after the reaction, filtering, and washing to obtain aminated zinc phytate;

[0034] (4) adding 4-hydroxy-5-methyl-1,3-phthalic acid and 3,3-diaminobenzidine to a reactor, and then continuing to add polyphosphoric acid, wherein the mass ratio of 4-hydroxy-5-methyl-1,3-phthalic acid, 3,3-diaminobenzidine, and polyphosphoric acid is 1.3:1:0.01, introducing nitrogen for protection, mechanically stirring, reacting at 180° C. for 20 hours, cooling after completion, washing with deionized water, filtering, neutralizing with 8% ammonia water, filtering, washing with water until neutral, and drying to obtain hydroxylated polybenzimidazole;

[0035] (5) In an ice bath, cyanuric chloride and hydroxylated polybenzimidazole are added to an acetone solvent, refluxed at 75° C. for 2 h, and then amino-phytic acid zinc is added thereto, wherein the mass ratio of cyanuric chloride, hydroxylated polybenzimidazole, and amino-phytic acid zinc is 1:0.3:1.2, and the reaction is carried out at 90° C. for 6 h. After the reaction, the mixture is cooled to room temperature, concentrated to remove the solvent, and washed with petroleum ether to obtain triazine-based polybenzimidazole;

[0036] (6) 80 parts by weight of bisphenol A epoxy resin and 4 parts by weight of triazine polybenzimidazole are added to a reactor and stirred. 1 part by weight of diaminodiphenylmethane curing agent is added and reacted for 2 hours. The mixture is stirred and allowed to stand to obtain a high temperature resistant epoxy resin.

[0037] Example 3

[0038] (1) adding 9.5 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 82° C., adding 11.5 parts by weight of phytic acid thereto, mechanically stirring, reflux reacting at 90° C. for 4 h, washing after completion, and drying at 95° C. to obtain zinc phytate;

[0039] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, reflux reacting at 83° C. for 2 h, and then continuing to add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.0:0.5:1.5, continuing to stir for 9 h, filtering, washing, and drying after the end to obtain nitrated zinc phytate;

[0040] (3) adding nitrated zinc phytate to N,N-dimethylformamide solvent, and then adding ferric chloride and activated carbon, stirring and mixing, and then adding hydrazine hydrate solution, wherein the mass ratio of nitrated zinc phytate, ferric chloride, activated carbon, and hydrazine hydrate solution is 1:1.45:2.25:1.85, stirring and reacting at 80° C. for 15 hours, and after the reaction, precipitating with deionized water, filtering, and washing to obtain aminated zinc phytate;

[0041] (4) adding 4-hydroxy-5-methyl-1,3-phthalic acid and 3,3-diaminobenzidine to a reactor, and then continuing to add polyphosphoric acid, wherein the mass ratio of 4-hydroxy-5-methyl-1,3-phthalic acid, 3,3-diaminobenzidine, and polyphosphoric acid is 1.35:1:0.015, introducing nitrogen for protection, mechanically stirring, reacting at 195° C. for 22 hours, cooling after completion, washing with deionized water, filtering, neutralizing with 10% ammonia water, filtering, washing with water until neutral, and drying to obtain hydroxylated polybenzimidazole;

[0042] (5) In an ice bath, cyanuric chloride and hydroxylated polybenzimidazole are added to an acetone solvent, and the mixture is refluxed at 77° C. for 2.5 h, and then amino-phytic acid zinc is added thereto, wherein the mass ratio of cyanuric chloride, hydroxylated polybenzimidazole, and amino-phytic acid zinc is 1:0.45:1.35, and the mixture is reacted at 100° C. for 8 h. After the reaction, the mixture is cooled to room temperature, concentrated to remove the solvent, and washed with petroleum ether to obtain triazine-based polybenzimidazole;

[0043] (6) 90 parts by weight of bisphenol A epoxy resin and 5 parts by weight of triazine polybenzimidazole are added to a reactor and stirred. 1.5 parts by weight of diaminodiphenylmethane curing agent are added and reacted for 3 hours. The mixture is stirred and allowed to stand to obtain a high temperature resistant epoxy resin.

[0044] Example 4

[0045] (1) adding 8 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75° C., adding 10 parts by weight of phytic acid thereto, mechanically stirring, and reflux reacting at 85° C. for 3 h, washing after the reaction, and drying at 90° C. to obtain zinc phytate;

[0046] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, and reacting under reflux at 75° C. for 1 h, and then continuing to add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.9:0.4:1.4, and continuing to stir for 8 h. After the end, filtering, washing, and drying are performed to obtain nitrated zinc phytate;

[0047] (3) adding nitrated zinc phytate to N,N-dimethylformamide solvent, then adding ferric chloride and activated carbon, stirring and mixing, and then adding hydrazine hydrate solution, wherein the mass ratio of nitrated zinc phytate, ferric chloride, activated carbon, and hydrazine hydrate solution is 1:1.3:2.1:1.5, stirring and reacting at 70° C. for 10-20 hours, precipitating with deionized water after the reaction, filtering, and washing to obtain aminated zinc phytate;

[0048] (4) adding 4-hydroxy-5-methyl-1,3-phthalic acid and 3,3-diaminobenzidine to a reactor, and then continuing to add polyphosphoric acid, wherein the mass ratio of 4-hydroxy-5-methyl-1,3-phthalic acid, 3,3-diaminobenzidine, and polyphosphoric acid is 1.3:1:0.01, introducing nitrogen for protection, mechanically stirring, reacting at 180° C. for 20 hours, cooling after completion, washing with deionized water, filtering, neutralizing with 8% ammonia water, filtering, washing with water until neutral, and drying to obtain hydroxylated polybenzimidazole;

[0049] (5) In an ice bath, cyanuric chloride and hydroxylated polybenzimidazole are added to an acetone solvent, and the mixture is refluxed at 77° C. for 2.5 h, and then amino-phytic acid zinc is added thereto, wherein the mass ratio of cyanuric chloride, hydroxylated polybenzimidazole, and amino-phytic acid zinc is 1:0.45:1.35, and the mixture is reacted at 100° C. for 8 h. After the reaction, the mixture is cooled to room temperature, concentrated to remove the solvent, and washed with petroleum ether to obtain triazine-based polybenzimidazole;

[0050] (6) 90 parts by weight of bisphenol A epoxy resin and 5 parts by weight of triazine polybenzimidazole are added to a reactor and stirred. 1.5 parts by weight of diaminodiphenylmethane curing agent are added and reacted for 3 hours. The mixture is stirred and allowed to stand to obtain a high temperature resistant epoxy resin.

[0051] Comparative Example 1

[0052] The difference between this comparative example and Example 4 is that no triazine-based polybenzimidazole is added.

[0053] The thermal properties of the high temperature resistant epoxy resin were tested by a thermogravimetric analyzer in a nitrogen atmosphere, with a heating rate of 25°C / min and a maximum temperature of 800°C. The limiting oxygen index of the material was tested using an oxygen index meter, and the combustion grade of the material was tested using a horizontal and vertical combustion instrument. The test results are shown in Table 1.

[0054] Table 1: High temperature resistance test and flame retardancy test.

[0055]

[0056] It can be seen from Table 1 that Examples 1-4 of the present invention have better flame retardancy than Comparative Example 1, and the temperatures of 20% and 50% mass loss in Comparative Example 1 are lower than those in Examples 1-4, indicating that the epoxy resin of the present invention has better high temperature resistance.

[0057] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a high temperature resistant epoxy resin, characterized in that: The preparation method of the high temperature resistant epoxy resin is: (1) adding 8-11 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75-90° C., adding 10-13 parts by weight of phytic acid, mechanically stirring the solvent, and performing a reflux reaction at 85-95° C., washing the solvent after reaction, and drying the solvent at 90-100° C. to obtain zinc phytate; (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline, and reacting under reflux at 75-90° C. for 1-3 h, then adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and continuing to stir for 8-10 h. After completion, filtering, washing, and drying to obtain nitrated zinc phytate; (3) adding nitrated zinc phytate to N,N-dimethylformamide solvent, and then adding ferric chloride and activated carbon, stirring and mixing, and then adding hydrazine hydrate solution, stirring and reacting at 70-90° C. for 10-20 hours, and after the reaction, precipitating with deionized water, filtering, and washing to obtain amino zinc phytate; (4) Add 4-hydroxy-5-methyl-1,3-phthalic acid and 3,3-diaminobenzidine into a reactor, then continue to add polyphosphoric acid, introduce nitrogen for protection, mechanically stir, react at 180-210° C. for 20-24 hours, cool after reaction, wash with deionized water, filter, neutralize with 8-12% ammonia water, filter, wash with water until neutral, and dry to obtain hydroxylated polybenzimidazole; (5) In an ice bath, cyanuric chloride and hydroxylated polybenzimidazole are added to an acetone solvent, and refluxed at 75-80°C for 2-3 hours, and then amino phytic acid zinc is added thereto, and the reaction is carried out at 90-110°C for 6-10 hours. After the reaction, the mixture is cooled to room temperature, concentrated to remove the solvent, and washed with petroleum ether to obtain triazine-based polybenzimidazole; (6) Add 80-100 parts by weight of bisphenol A epoxy resin and 4-6 parts by weight of triazine polybenzimidazole into a reactor, stir, and continue to add 1-2 parts by weight of diaminodiphenylmethane curing agent, react for 2-4 hours, stir, and stand to obtain a high temperature resistant epoxy resin.

2. The method for preparing a high temperature resistant epoxy resin according to claim 1, characterized in that: The reflux reaction time in (1) is 3-5h.

3. The method for preparing a high temperature resistant epoxy resin according to claim 1, characterized in that: The mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in (2) is 1:0.9-1.1:0.4-0.6:1.4-1.

6.

4. The method for preparing a high temperature resistant epoxy resin according to claim 1, characterized in that: The mass ratio of nitrated zinc phytate, ferric chloride, activated carbon and hydrazine hydrate solution in (3) is 1:1.3-1.6:2.1-2.4:1.5-2.

2.

5. The method for preparing a high temperature resistant epoxy resin according to claim 1, characterized in that: The mass ratio of 4-hydroxy-5-methyl-1,3-phthalic acid, 3,3-diaminobenzidine and polyphosphoric acid in (4) is 1.3-1.4:1:0.01-0.

02.

6. The method for preparing a high temperature resistant epoxy resin according to claim 1, characterized in that: The mass ratio of cyanuric chloride, hydroxylated polybenzimidazole and amino phytic acid zinc in (5) is 1:0.3-0.6:1.2-1.

5.

7. An application of an epoxy resin prepared by the method for preparing a high temperature resistant epoxy resin according to any one of claims 1 to 6, characterized in that: The high temperature resistant epoxy resin is used in the fields of adhesives, coatings, electronics, and water conservancy and transportation.

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