Processing technology of high-temperature-resistant cyano resin composite material

Abstract

The invention relates to the technical field of materials, and discloses a processing technology of a high-temperature-resistant cyano resin composite material, which comprises the following steps: adding bisphenol A type epoxy resin, epoxy zinc phytate and epoxy nano silicon dioxide into a reactor, stirring, continuously adding a 3, 6-dihydroxyphthalonitrile curing agent, carrying out curing reaction, stirring, standing, and carrying out heat preservation to obtain the high-temperature-resistant cyano resin composite material. The high-temperature-resistant cyano resin composite material is obtained. In the curing process, hydroxyl in the 3, 6-dihydroxyphthalonitrile curing agent and epoxy groups in the bisphenol A epoxy resin, the epoxy zinc phytate and the epoxy nano silicon dioxide are subjected to ring opening and cross-linking to form a tight cross-linked network, and the tensile strength is good. Zinc phytate and nano silicon dioxide in the cyano resin composite material have good high-temperature-resistant and flame-retardant effects.

Description

Technical Field

[0001] The invention relates to the technical field of materials, and in particular to a processing technology of a high-temperature resistant cyano resin composite material. Background Art

[0002] Ordinary bisphenol A epoxy resin has poor performance at high temperature, usually thermal deformation occurs at about 100°C, and thermal oxidation decomposition occurs at 180-200°C, and the flame retardant effect is not ideal. Nano-silicon dioxide has certain high temperature resistance and flame retardancy, but it is easy to agglomerate. The present invention improves its performance by modifying nano-silicon dioxide and introducing it into epoxy resin.

[0003] For example, the patent document "Bismadiazole resin toughened with phenolphthalein thermoplastic cyano resin and its composite material properties" prepared a series of high-temperature resistant BMI toughened and modified with phenolphthalein thermoplastic cyano resin, which also had good mechanical properties, but its flame retardant effect was not improved. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies in the prior art, the present invention provides a processing technology for a high-temperature resistant cyano resin composite material, which has good flame retardant, stretchable and high-temperature resistant effects.

[0006] (II) Technical solution

[0007] To achieve the above object, the present invention provides the following technical solution: a processing technology of a high temperature resistant cyano resin composite material, the processing technology of the high temperature resistant cyano resin composite material is:

[0008] (1) adding 9-12 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75-90° C., adding phytic acid thereto, mechanically stirring, and reflux reacting at 85-92° C. for 2-4 hours, washing after the reaction, and drying at 90-100° C. to obtain zinc phytate;

[0009] (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 hours, then adding diethyl phosphite, and continuing to stir for 8-10 hours. After the reaction is completed, filtering, washing, and drying to obtain nitrated zinc phytate;

[0010] (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;

[0011] (4) adding 2,5-divinyl-1,4-benzenedicarbaldehyde and amino phytate zinc to an ethanol solvent, stirring evenly, heating to 96-110° C., stirring and refluxing for 5-8 hours, and after the reaction is completed, filtering and drying to obtain olefinated phytate zinc;

[0012] (5) dissolving the olefinated zinc phytate in a reactor filled with N,N-dimethylformamide, adding m-chloroperbenzoic acid oxidant thereto at 3-4° C., stirring and mixing, raising the temperature to 20-25° C. for reaction, filtering, washing, and drying after the reaction is completed to obtain epoxy zinc phytate;

[0013] In the above reaction process, zinc phytate is added to an ethanol solvent, and then 3,4-dihydroxybenzaldehyde and p-nitroaniline are added to carry out a condensation reaction, thereby introducing a hydroxyl group, chelating the zinc phytate, and also introducing a nitro group, thereby obtaining nitrated zinc phytate; then, under the action of ferric chloride, activated carbon, and hydrazine hydrate solution, reduction is carried out to obtain aminated zinc phytate; the aldehyde group in 2,5-divinyl-1,4-benzenedicarbaldehyde and the amine group in the aminated zinc phytate are subjected to a condensation reaction to introduce an olefin group, thereby obtaining olefinated zinc phytate; then, under the action of an oxidant of meta-chloroperoxybenzoic acid, the olefin group is oxidized to an epoxy group, thereby obtaining epoxy zinc phytate;

[0014] (6) Add 50-75 parts by weight of bisphenol A epoxy resin, 0.4-0.5 parts by weight of epoxy phytate zinc, and 0.1-0.3 parts by weight of epoxy nano-silica into a reactor, stir, and continue to add 3-5 parts by weight of 3,6-dihydroxyphthalonitrile curing agent, react at 120-135° C. for 2-4 hours, stir, and stand to obtain a high-temperature resistant cyano resin composite material.

[0015] Preferably, the weight proportion of phytic acid in (1) is 10-12.

[0016] Preferably, the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline and diethyl phosphite in (2) is 1:0.8-1.03:0.64-0.75:1.21-1.24.

[0017] Preferably, the mass ratio of nitrated zinc phytate, ferric chloride, activated carbon and hydrazine hydrate solution in (3) is 1:1.22-1.51:2.31-2.36:1.43-1.64.

[0018] Preferably, the mass ratio of 2,5-divinyl-1,4-benzenedicarbaldehyde to amino-phytate zinc in (4) is 1:2.25-2.54.

[0019] Preferably, the mass ratio of olefinated zinc phytate to meta-chloroperbenzoic acid oxidant in (5) is 1:0.9-1.1.

[0020] Preferably, the reaction time in (5) is 8-12 hours.

[0021] (III) Beneficial technical effects

[0022] The invention provides a high temperature resistant cyano resin composite material by adding bisphenol A epoxy resin, epoxy zinc phytate and epoxy nano silicon dioxide into a reactor, stirring, continuously adding 3,6-dihydroxyphthalonitrile curing agent, performing curing reaction, stirring and standing.

[0023] During the curing process, the hydroxyl groups in the 3,6-dihydroxyphthalonitrile curing agent will open the ring with the epoxy groups in bisphenol A epoxy resin, epoxy zinc phytate, and epoxy nano-silica, and produce cross-linking, forming a tight cross-linking network with good tensile resistance. Both the zinc phytate and nano-silica in the cyano resin composite material have good high temperature resistance and flame retardant effects. The aldehyde group in 2,5-divinyl-1,4-benzenedialdehyde and the amine group in the amino zinc phytate are condensed to introduce an olefin group, thereby obtaining olefin zinc phytate; at the same time, the degree of substitution of zinc phytate is also increased, making the flame retardant effect of the material better. DETAILED DESCRIPTION

[0024] Preparation of epoxy nano-silica: Referring to the literature "Nano-silica modified with silane coupling agent KH-560", a certain amount of nano-silica was weighed and added to 20 mL of toluene. Ultrasonic dispersion was performed for 30 min at room temperature using a KQ-300E ultrasonic cleaner (300 W) to obtain a uniform suspension. Silane coupling agent KH-560 was then added and ultrasonic dispersion was continued for 3-4 min. The suspension was transferred to a 100 mL four-necked flask equipped with a reflux condenser and a power-enhanced electric stirrer and stirred in an oil bath at a set temperature for reaction. The slurry after the reaction was centrifuged at room temperature at a speed of 12000 r / min using a CT15RT desktop high-speed refrigerated centrifuge to obtain epoxy nano-silica.

[0025] Example 1

[0026] (1) adding 9 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75° C., and continuously adding phytic acid thereto, wherein the weight portion of phytic acid is 10 parts, mechanically stirring, and reflux reacting at 85° C. for 2 hours, washing after completion, and drying at 90° C. to obtain zinc phytate;

[0027] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, and reflux reacting at 75° C. for 1 hour, and then continuing to add diethyl phosphite thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline, and diethyl phosphite is 1:0.8:0.64:1.21, and continuing to stir for 8 hours. After the end, filtering, washing, and drying are performed to obtain nitrated zinc phytate;

[0028] (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 1:1.22:2.31:1.43, 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;

[0029] (4) adding 2,5-divinyl-1,4-benzenedicarbaldehyde and amino-phytic acid zinc to an ethanol solvent, wherein the mass ratio of 2,5-divinyl-1,4-benzenedicarbaldehyde to amino-phytic acid zinc is 1:2.25, stirring evenly, heating to 96° C., stirring and refluxing for 5 hours, and after the reaction is completed, filtering and drying to obtain olefin-phytic acid zinc;

[0030] (5) dissolving the olefinated zinc phytate in a reactor filled with N,N-dimethylformamide, adding meta-chloroperbenzoic acid oxidant thereto at 3°C, wherein the mass ratio of the olefinated zinc phytate to the meta-chloroperbenzoic acid oxidant is 1:0.9, stirring and mixing, heating to 20°C for reaction, wherein the reaction time is 8 hours, and after the reaction is completed, filtering, washing, and drying to obtain epoxy phytate zinc;

[0031] (6) Add 50 parts by weight of bisphenol A epoxy resin, 0.4 parts by weight of epoxy phytate zinc, and 0.1 parts by weight of epoxy nano-silica into a reactor, stir, and continue to add 3 parts by weight of 3,6-dihydroxyphthalonitrile curing agent, react at 120° C. for 2 hours, stir, and stand to obtain a high-temperature resistant cyano resin composite material.

[0032] Example 2

[0033] (1) adding 12 parts by weight of zinc acetate to a deionized water solvent, heating to 90° C., and continuously adding phytic acid thereto, wherein the weight portion of phytic acid is 12, mechanically stirring, and reflux reacting at 92° C. for 4 hours, washing after completion, and drying at 100° C. to obtain zinc phytate;

[0034] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, and reflux reacting at 90° C. for 3 hours, and then continuing to add diethyl phosphite thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline, and diethyl phosphite is 1:1.03:0.75:1.24, and continuing to stir for 10 hours. After the end, filtering, washing, and drying are performed to obtain nitrated zinc phytate;

[0035] (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 1:1.51:2.36:1.64, stirring and reacting at 90° C. for 20 hours, and after the reaction, precipitating with deionized water, filtering, and washing to obtain aminated zinc phytate;

[0036] (4) adding 2,5-divinyl-1,4-benzenedicarbaldehyde and amino-phytic acid zinc to an ethanol solvent, wherein the mass ratio of 2,5-divinyl-1,4-benzenedicarbaldehyde to amino-phytic acid zinc is 1:2.54, stirring evenly, heating to 110° C., stirring and refluxing for 8 hours, and after the reaction is completed, filtering and drying to obtain olefin-phytic acid zinc;

[0037] (5) dissolving the olefinated zinc phytate in a reactor filled with N,N-dimethylformamide, adding meta-chloroperbenzoic acid oxidant thereto at 4°C, wherein the mass ratio of the olefinated zinc phytate to the meta-chloroperbenzoic acid oxidant is 1:1.1, stirring and mixing, heating to 25°C for reaction, wherein the reaction time is 12 hours, and after the reaction is completed, filtering, washing, and drying to obtain epoxy phytate zinc;

[0038] (6) Add 75 parts by weight of bisphenol A epoxy resin, 0.5 parts by weight of epoxy phytate zinc, and 0.3 parts by weight of epoxy nano-silica into a reactor, stir, and continue to add 5 parts by weight of 3,6-dihydroxyphthalonitrile curing agent, react at 135° C. for 4 hours, stir, and stand to obtain a high-temperature resistant cyano resin composite material.

[0039] Example 3

[0040] (1) adding 10 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 82° C., and continuously adding phytic acid, wherein the weight portion of phytic acid is 11, mechanically stirring, and reflux reacting at 88° C. for 3 h. After completion, washing is performed, and drying is performed at 95° C. to obtain zinc phytate;

[0041] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, and reflux reacting at 82° C. for 2 h, and then continuing to add diethyl phosphite thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline, and diethyl phosphite is 1:1:0.7:1.22, and continuing to stir for 9 h. After the end, filtering, washing, and drying are performed to obtain nitrated zinc phytate;

[0042] (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 1:1.35:2.33:1.53, 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;

[0043] (4) adding 2,5-divinyl-1,4-benzenedicarbaldehyde and amino-phytic acid zinc to an ethanol solvent, wherein the mass ratio of 2,5-divinyl-1,4-benzenedicarbaldehyde to amino-phytic acid zinc is 1:2.4, stirring evenly, heating to 103° C., stirring and reflux reaction for 7 hours, and after the reaction is completed, filtering and drying to obtain olefin-phytic acid zinc;

[0044] (5) dissolving the olefinated zinc phytate in a reactor filled with N,N-dimethylformamide, adding meta-chloroperbenzoic acid oxidant thereto at 4°C, wherein the mass ratio of the olefinated zinc phytate to the meta-chloroperbenzoic acid oxidant is 1:1, stirring and mixing, heating to 22°C for reaction, wherein the reaction time is 10 hours, and after the reaction is completed, filtering, washing, and drying to obtain epoxy phytate zinc;

[0045] (6) Add 62 parts by weight of bisphenol A epoxy resin, 0.45 parts by weight of epoxy phytate zinc, and 0.2 parts by weight of epoxy nano-silica into a reactor, stir, and continue to add 4 parts by weight of 3,6-dihydroxyphthalonitrile curing agent, react at 127°C for 3 hours, stir, and stand to obtain a high-temperature resistant cyano resin composite material.

[0046] Example 4

[0047] (1) adding 9 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75° C., and continuously adding phytic acid thereto, wherein the weight portion of phytic acid is 10 parts, mechanically stirring, and reflux reacting at 85° C. for 2 hours, washing after completion, and drying at 90° C. to obtain zinc phytate;

[0048] (2) adding zinc phytate to an ethanol solvent, stirring and dispersing, then adding 3,4-dihydroxybenzaldehyde and p-nitroaniline thereto, and reflux reacting at 75° C. for 1 hour, and then continuing to add diethyl phosphite thereto, wherein the mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline, and diethyl phosphite is 1:0.8:0.64:1.21, and continuing to stir for 8 hours. After the end, filtering, washing, and drying are performed to obtain nitrated zinc phytate;

[0049] (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 1:1.51:2.36:1.64, stirring and reacting at 90° C. for 20 hours, and after the reaction, precipitating with deionized water, filtering, and washing to obtain aminated zinc phytate;

[0050] (4) adding 2,5-divinyl-1,4-benzenedicarbaldehyde and amino-phytic acid zinc to an ethanol solvent, wherein the mass ratio of 2,5-divinyl-1,4-benzenedicarbaldehyde to amino-phytic acid zinc is 1:2.54, stirring evenly, heating to 110° C., stirring and refluxing for 8 hours, and after the reaction is completed, filtering and drying to obtain olefin-phytic acid zinc;

[0051] (5) dissolving the olefinated zinc phytate in a reactor filled with N,N-dimethylformamide, adding meta-chloroperbenzoic acid oxidant thereto at 4°C, wherein the mass ratio of the olefinated zinc phytate to the meta-chloroperbenzoic acid oxidant is 1:1, stirring and mixing, heating to 22°C for reaction, wherein the reaction time is 10 hours, and after the reaction is completed, filtering, washing, and drying to obtain epoxy phytate zinc;

[0052] (6) Add 62 parts by weight of bisphenol A epoxy resin, 0.45 parts by weight of epoxy phytate zinc, and 0.1 parts by weight of epoxy nano-silica into a reactor, stir, and continue to add 4 parts by weight of 3,6-dihydroxyphthalonitrile curing agent, react at 127°C for 3 hours, stir, and stand to obtain a high-temperature resistant cyano resin composite material.

[0053] Comparative Example 1

[0054] The difference between this comparative example and Example 4 is that no epoxy phytate zinc is added.

[0055] Comparative Example 2

[0056] The difference between this comparative example and Example 4 is that no epoxy nano-silica is added.

[0057] Thermogravimetric analysis test of high temperature resistant cyano resin composite materials: TG thermogravimetric analyzer, nitrogen atmosphere, heating rate of 10℃ / min, test temperature 20-800℃, sample size of 20mm×20mm×2mm.

[0058] Table 1: High temperature resistance test.

[0059]

[0060] As can be seen from Table 1, the high temperature resistant cyano resin composite material embodiments 1-4 of the present invention have better initial decomposition temperature and residual carbon rate than the comparative examples 1-2, indicating that the high temperature resistance is better.

[0061] Combustion performance test: oxygen index tester, test method according to GB / T 2406.1-2008 standard.

[0062] Table 2: Flame retardancy test.

[0063]

[0064]

[0065] It can be seen from Table 2 that the high temperature resistant cyano resin composite material embodiments 1-4 of the present invention have better flame retardant effects than the comparative examples 1-2.

[0066] The tensile test was carried out in accordance with GB / T 1040.1-2018. The test results are shown in Table 3.

[0067] Table 3: Tensile strength test.

[0068] project Tensile strength(MPa) Example 1 54.6 Example 2 57.1 Example 3 56.5 Example 4 55.3 Comparative Example 1 40.6 Comparative Example 2 38.2

[0069] It can be seen from Table 3 that the high temperature resistant cyano resin composite material embodiments 1-4 of the present invention have better tensile properties than the comparative examples 1-2.

[0070] 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 processing technology for a high temperature resistant cyano resin composite material, characterized in that: The processing technology of the high temperature resistant cyano resin composite material is as follows: (1) adding 9-12 parts by weight of zinc acetate to a deionized water solvent, heating the solvent to 75-90° C., adding phytic acid thereto, mechanically stirring, and reflux reacting at 85-92° C. for 2-4 hours, washing after the reaction, and drying 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 hours, then adding diethyl phosphite, and continuing to stir for 8-10 hours. After the reaction is completed, filtering, washing, and drying to obtain nitrated zinc phytate; (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; (4) adding 2,5-divinyl-1,4-benzenedicarbaldehyde and amino phytate zinc to an ethanol solvent, stirring evenly, heating to 96-110° C., stirring and refluxing for 5-8 hours, and after the reaction is completed, filtering and drying to obtain olefinated phytate zinc; (5) dissolving the olefinated zinc phytate in a reactor filled with N,N-dimethylformamide, adding m-chloroperbenzoic acid oxidant thereto at 3-4° C., stirring and mixing, raising the temperature to 20-25° C. for reaction, filtering, washing, and drying after the reaction is completed to obtain epoxy zinc phytate; (6) Add 50-75 parts by weight of bisphenol A epoxy resin, 0.4-0.5 parts by weight of epoxy phytate zinc, and 0.1-0.3 parts by weight of epoxy nano-silica into a reactor, stir, and continue to add 3-5 parts by weight of 3,6-dihydroxyphthalonitrile curing agent, react at 120-135° C. for 2-4 hours, stir, and stand to obtain a high-temperature resistant cyano resin composite material.

2. The processing technology of the high temperature resistant cyano resin composite material according to claim 1, characterized in that: The weight proportion of phytic acid in (1) is 10-12.

3. The processing technology of the high temperature resistant cyano resin composite material according to claim 1, characterized in that: The mass ratio of zinc phytate, 3,4-dihydroxybenzaldehyde, p-nitroaniline and diethyl phosphite in (2) is 1:0.8-1.03:0.64-0.75:1.21-1.

24.

4. The processing technology of the high temperature resistant cyano resin composite material 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 1:1.22-1.51:2.31-2.36:1.43-1.

64.

5. The processing technology of the high temperature resistant cyano resin composite material according to claim 1, characterized in that: The mass ratio of 2,5-divinyl-1,4-benzenedicarbaldehyde to amino-phytate zinc in (4) is 1:2.25-2.

54.

6. The processing technology of the high temperature resistant cyano resin composite material according to claim 1, characterized in that: The mass ratio of olefinated zinc phytate to meta-chloroperbenzoic acid oxidant in (5) is 1:0.9-1.

1.

7. The processing technology of the high temperature resistant cyano resin composite material according to claim 1, characterized in that: The reaction time in (5) is 8-12 hours.

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