CN110643071A - Preparation method of microcapsule-coated phytate epoxy resin flame retardant - Google Patents
Preparation method of microcapsule-coated phytate epoxy resin flame retardant Download PDFInfo
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- CN110643071A CN110643071A CN201911043886.7A CN201911043886A CN110643071A CN 110643071 A CN110643071 A CN 110643071A CN 201911043886 A CN201911043886 A CN 201911043886A CN 110643071 A CN110643071 A CN 110643071A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
According to the preparation method of the microcapsule-coated phytate epoxy resin flame retardant, the phytate which is a renewable resource is taken as a raw material or prepared according to needs, and the phytate is coated by the microcapsule, so that the dispersibility of the phytate in epoxy resin is improved, and the flame retardant effect is improved. The microcapsule coating raw materials comprise: epoxy resin (E51), 2-methyl-4-ethylimidazole, ethanol and sodium dodecyl benzene sulfonate. Reacting sodium phytate with magnesium chloride for a period of time under a certain condition, and washing, filtering and drying a product to obtain a product A; mixing epoxy resin and ethanol, adding the product A and sodium dodecyl benzene sulfonate, fully stirring for a period of time, adding 2-methyl-4-ethylimidazole, reacting under a certain condition, and performing suction filtration, washing and drying on a product to obtain a product B. The product B can be fully dispersed in the epoxy resin, has small influence on the mechanical property of the cured epoxy resin, and can effectively improve the flame retardant property of the epoxy resin.
Description
The technical field is as follows:
the invention belongs to the technical field of materials, and particularly relates to a preparation method of a microcapsule-coated phytate epoxy resin flame retardant.
Background art:
epoxy resin is a thermosetting polymer material, has excellent properties of adhesion, corrosion resistance, insulation, strength and the like, and is widely applied to the fields of aerospace, electronics and electricity and other industries. However, the application of the epoxy resin is greatly limited due to the inflammability of the epoxy resin, so that the flame retardance of the epoxy resin is enhanced, the occurrence and the spread of fire can be effectively reduced, and the research on the flame retardant of the epoxy resin has important significance.
In recent years, since halogen-containing materials cause a series of environmental problems, research and development of halogen-free materials have become a key issue, and a high-efficiency, low-toxicity, low-smoke halogen-free flame retardant is also a research focus. The development of highly effective flame retardants while maintaining or improving their mechanical properties remains a challenge. In recent years, phytic acid extracted from soybeans and cereals (such as corn, wheat and sorghum) is found to have great potential as a polymer flame retardant and has little influence on mechanical properties, the application of phytic acid as a flame retardant has been widely researched, but the application of metal phytate as a flame retardant of epoxy resin is less, and the microcapsule-coated metal phytate as an epoxy resin flame retardant can further enhance the dispersibility of the metal phytate in the epoxy resin and is beneficial to maintaining the original mechanical properties of the epoxy resin, so that the research on the microcapsule-coated metal phytate flame retardant has practical significance.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provide a method for preparing a microcapsule-coated phytate epoxy resin flame retardant, which comprises the steps of taking renewable resource sodium phytate as a raw material, reacting metal chloride with sodium phytate to synthesize a biological flame retardant phytate (substance A), carrying out microcapsule coating on the substance A to obtain a flame retardant (substance B), and dispersing the substance B into epoxy resin to improve the fire resistance of the epoxy resin and have little influence on the mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a microcapsule-coated phytate epoxy resin flame retardant comprises the following steps:
step 1, according to the mass ratio, epoxy resin: ethanol (1-1.5): 20, mixing the epoxy resin with ethanol, and fully stirring to obtain a product C;
step 2, adding a phytate solid powder A and an emulsifier into a product C, and fully stirring under a heating condition to obtain a product D, wherein the mass ratio of the substance A to the epoxy resin in the step (3) is 1 (7-5), the mass ratio of sodium dodecyl benzene sulfonate to the substance A is 1 (120-90), and the heating temperature is 50-80 ℃;
and 3, adding 2-methyl-4-ethylimidazole into the product D, fully stirring under a heating condition, carrying out suction filtration, washing and drying on the product to obtain the microcapsule coated phytate epoxy resin flame retardant, wherein the mass ratio of the 2-methyl-4-ethylimidazole to the epoxy resin used in the step (3) is 1 (20-25), and the heating temperature is 70-90 ℃.
In the step 1, the epoxy resin is e51, e55 or e 44.
In the step 1, the stirring time is 1-2 h.
In the step 2, the heating mode is water bath heating, and the stirring time is 0.5-1 h.
In the step 2, the emulsifier is sodium dodecyl benzene sulfonate.
In the step 2, the phytate solid powder A is one of sodium phytate, magnesium phytate or aluminum phytate powder, wherein the phytate solid powder A is purchased from the market when being sodium phytate powder, and is prepared by adopting the following method when being magnesium phytate or aluminum phytate powder:
(1) adding a sodium phytate solution and a magnesium chloride/aluminum chloride solution into a flask with a condenser, heating under the stirring condition, wherein the heating temperature is 80-100 ℃, the heating time is 1-2 hours, uniformly stirring, condensing and refluxing to obtain a colloid, and the feeding molar ratio of the sodium phytate to the magnesium chloride/aluminum chloride solute is 1 (4-7);
(2) washing, filtering and drying the colloid to obtain a substance A;
in the step (1), the sodium phytate solution and the magnesium chloride/aluminum chloride solution are respectively prepared from sodium phytate and magnesium chloride/aluminum chloride, wherein the concentration of the sodium phytate solution is 0.1-1 mol/L, and the concentration of the magnesium chloride/aluminum chloride solution is 0.5-1 mol/L.
In the step (1), heating is carried out in a water bath manner, and the stirring time is 1-2 h.
In the step (2), the drying mode is heating drying, the drying temperature is 70 ℃, and the drying time is 24 hours.
In the step 3, the heating mode is water bath heating, the heating temperature is 70-100 ℃, and the stirring and condensing reflux time is 3-4 h.
In the step 3, the drying mode is heating drying, the drying temperature is 70 ℃, and the drying time is 24 hours.
The application method of the microcapsule-coated phytate flame retardant comprises the following steps of: an epoxy resin system (5-10): (90-95) dispersing the microcapsule-coated phytate flame retardant into an epoxy resin system. Tests prove that compared with pure epoxy resin, the epoxy resin added with the microcapsule coated phytate has the peak value reduction amplitude of heat release rate of 30.6-36.22%, the peak value reduction amplitude of smoke release rate of 7.13-28.05%, the total heat release reduction amplitude of 13.7-23.04%, the peak value reduction amplitude of total smoke release rate of 13.36-27.06%, the peak value reduction amplitude of CO release rate of 21.73-49.02%, and CO2The peak value reduction amplitude of the release rate is 15.49-39.3%, and the strength of the release rate is 80-95% of that of pure epoxy resin.
The epoxy resin system comprises epoxy resin and a curing agent.
The invention has the beneficial effects that:
1. the epoxy resin flame retardant is prepared from renewable raw materials, has a flame retardant effect, and has small influence on mechanical properties.
2. The epoxy resin flame retardant prepared by the invention has the advantages of low toxicity, high efficiency and environmental protection, takes renewable resources as raw materials, and is beneficial to sustainable development.
3. The preparation method provided by the invention is simple, the conditions are mild, and the purity of the generated flame retardant is higher.
Description of the drawings:
FIG. 1 is a graph of heat release rate for a neat epoxy and an epoxy added with microencapsulated magnesium phytate prepared in example 1;
FIG. 2 is a graph of smoke release rate for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 1;
FIG. 3 is a total heat release profile of a neat epoxy and an epoxy added with microencapsulated magnesium phytate prepared in example 1;
FIG. 4 is a graph of the total smoke release curve for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 1;
FIG. 5 is a CO release rate profile for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 1;
FIG. 6 is CO of pure epoxy resin and epoxy resin added with microencapsulated magnesium phytate prepared in example 12A release rate profile;
FIG. 7 is a graph of heat release rate for neat epoxy and for epoxy with the addition of microencapsulated sodium phytate prepared in example 2;
FIG. 8 is a graph of smoke release rate for neat epoxy and for epoxy added with microencapsulated sodium phytate prepared in example 2;
FIG. 9 is a total heat release profile of neat epoxy and an epoxy added with microencapsulated sodium phytate prepared in example 2;
FIG. 10 is a graph of the total smoke release profile of neat epoxy and epoxy added with microencapsulated sodium phytate prepared in example 2;
FIG. 11 is a CO release rate profile for neat epoxy and epoxy added with microencapsulated sodium phytate prepared in example 2;
FIG. 12 is CO of pure epoxy resin and epoxy resin added with sodium phytate microcapsule prepared in example 22A release rate profile;
FIG. 13 is a graph of the heat release rate of a neat epoxy and an epoxy added with microencapsulated magnesium phytate prepared in example 3;
FIG. 14 is a graph of smoke release rate for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 3;
FIG. 15 is a total heat release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 3;
FIG. 16 is a graph of the total smoke release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 3;
FIG. 17 is a CO release rate profile for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 3;
FIG. 18 is CO of pure epoxy resin and epoxy resin added with microencapsulated magnesium phytate prepared in example 32A release rate profile;
FIG. 19 is a graph of the heat release rate of a neat epoxy and an epoxy added with microencapsulated magnesium phytate prepared in example 4;
FIG. 20 is a graph of smoke release rate for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 4;
FIG. 21 is a total heat release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 4;
FIG. 22 is a graph of the total smoke release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 4;
FIG. 23 is a CO release rate profile for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 4;
FIG. 24 is CO of pure epoxy resin and epoxy resin added with microencapsulated magnesium phytate prepared in example 42A release rate profile;
FIG. 25 is a graph showing heat release rate curves of a pure epoxy resin having a peak value of 992.8KW/m and an epoxy resin to which the microencapsulated magnesium phytate prepared in example 5 was added2The peak value of the heat release rate of the epoxy resin added with the flame retardant is 646.0KW/m2。
FIG. 26 is a graph of smoke release rate for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 5;
FIG. 27 is a total heat release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 5;
FIG. 28 is a graph of the total smoke release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 5;
FIG. 29 is a CO release rate profile for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 5;
FIG. 30 is CO of pure epoxy resin and epoxy resin added with microencapsulated magnesium phytate prepared in example 52A release rate profile;
FIG. 31 is a graph of the heat release rate of a neat epoxy and an epoxy added with microencapsulated magnesium phytate prepared in example 6;
FIG. 32 is a graph of smoke release rate for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 6;
FIG. 33 is a total heat release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 6;
FIG. 34 is a graph of the total smoke release profile of neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 6;
FIG. 35 is a CO release rate profile for neat epoxy and epoxy added with microencapsulated magnesium phytate prepared in example 6;
FIG. 36 is CO of pure epoxy resin and epoxy resin added with microencapsulated magnesium phytate prepared in example 62Release rate profile.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
In the following examples, the epoxy resin used as a raw material in the preparation of the flame retardant and the epoxy resin used for flame retardation after the preparation are all e51, i.e., pure epoxy resin. The peak value of the heat release rate of the pure epoxy resin is 992.8KW/m2The peak value of the smoke release rate is 0.18179m2/m2Total heat release of 80.3MJ/m2Total smoke release was 1530.3m2/m2The peak value of the CO release rate is 0.03125g/s, and the CO content is2The peak release rate was 0.49535 g/s.
After the preparation of the microcapsule-coated phytate epoxy resin flame retardant is finished, dispersing the microcapsule-coated phytate epoxy resin flame retardant into an epoxy resin system, wherein the epoxy resin system comprises epoxy resin and a curing agent, and the curing agent is 2-methyl-4-ethylimidazole with the ratio of 100: 4.
Example 1
Preparing sodium phytate and magnesium chloride into 0.1mol/L and 0.5mol/L aqueous solutions respectively, adding 100ml of sodium phytate solution and 100ml of magnesium chloride solution into a conical flask with a condenser tube, stirring for 1h in a water bath at the constant temperature of 100 ℃, performing suction filtration on the obtained product, washing to be neutral, and drying for 24h to obtain white powder A.
According to the mass ratio, the epoxy resin: ethanol 1.1: 20, adding 110g of ethanol and 6g of epoxy resin into a conical flask, mixing and stirring for 15 minutes, then adding 40g of powder A and 0.4g of sodium dodecyl benzene sulfonate, wherein the mass ratio of the powder A to the epoxy resin is 20:3, the mass ratio of the sodium dodecyl benzene sulfonate to the powder A is 1:100, stirring for 0.5 hour in a water bath at 60 ℃, adding 0.3g of 2-methyl-4-ethylimidazole, and the mass ratio of 2-methyl-4-ethylimidazole to the epoxy resin is 1:20, heating and stirring in the water bath at 80 ℃, carrying out condensation reflux for 3 hours, collecting cooling water to a reaction system through condensation reflux, carrying out suction filtration and washing to neutrality on the obtained product, and drying for 24 hours at 70 ℃ to obtain the microcapsule coated phytate epoxy resin flame retardant. Dispersing the microcapsule-coated phytate epoxy resin flame retardant into an epoxy resin system, wherein the flame retardant comprises the following components in percentage by weight: epoxy systems are 5: 95. The epoxy resin added with the microcapsule-coated phytate is subjected to flame retardant property test, and fig. 1 is a heat release rate curve of pure epoxy resin and the epoxy resin added with the microcapsule-coated magnesium phytate prepared in the embodiment, wherein the peak value of the heat release rate of the pure epoxy resin is 992.8KW/m2The peak value of the heat release rate of the epoxy resin added with the flame retardant is 643.1KW/m2. FIG. 2 is a smoke release rate curve of pure epoxy resin and epoxy resin added with microencapsulated magnesium phytate, the peak value of smoke release rate of pure epoxy resin is 0.18179m2/m2The peak value of the smoke release rate of the epoxy resin added with the flame retardant is 0.13115m2/s. FIG. 3 is a graph showing the total heat release curve of pure epoxy resin and epoxy resin with added microencapsulated magnesium phytate, the total heat release of pure epoxy resin is 80.3MJ/m2The total heat release of the epoxy resin with the flame retardant added is 68.2MJ/m2. FIG. 4 is a graph showing the total smoke release curve of pure epoxy resin with 1530.3m total smoke release and epoxy resin with added microencapsulated magnesium phytate2/m2The total smoke emission of the flame-retardant-added epoxy resin was 1282.5m2/m2. FIG. 5 is a CO release rate curve of pure epoxy resin and epoxy resin added with microcapsule-coated magnesium phytate, the peak value of CO release rate of the pure epoxy resin is 0.03125g/s, and the peak value of CO release rate of the epoxy resin added with flame retardant is 0.0164 g/s. FIG. 6 is CO of pure epoxy resin and epoxy resin with added microcapsule coated magnesium phytate2Release Rate Profile, CO of pure epoxy2The peak release rate was 0.7707g/s, CO of epoxy resin with flame retardant added2The peak release rate was 0.49535 g/s. The tensile strength of the pure epoxy resin is 10.2MPa, and the tensile strength of the epoxy resin added with the microcapsule coated magnesium phytate is 9.7MPa which is 95 percent of the original tensile strength.
Example 2
According to the mass ratio, the epoxy resin: ethanol 1.1: 20, adding 110g of ethanol and 6g of epoxy resin into a conical flask, mixing and stirring for 15 minutes, then adding 40g of powder A and 0.4g of sodium dodecyl benzene sulfonate, wherein the mass ratio of sodium phytate to epoxy resin is 20:3, the mass ratio of sodium dodecyl benzene sulfonate to powder A is 1:100, stirring for 0.5 hour in a water bath at 60 ℃, adding 0.3g of 2-methyl-4-ethylimidazole, and the mass ratio of 2-methyl-4-ethylimidazole to epoxy resin is 1:20, heating and stirring in a water bath at 80 ℃, carrying out condensation reflux for 3 hours, carrying out suction filtration and washing on the obtained product to be neutral, and drying for 24 hours at 70 ℃ to obtain the microcapsule-coated phytate epoxy resin flame retardant. Dispersing the microcapsule-coated phytate epoxy resin flame retardant into an epoxy resin system, wherein the flame retardant comprises the following components in percentage by weight: epoxy systems are 5: 95. Flame retardant performance test was performed on epoxy resin added with microencapsulated phytate, and FIG. 7 is heat release of pure epoxy resin and epoxy resin added with microencapsulated sodium phytate prepared in this exampleRate curve, peak value of heat release rate of pure epoxy resin 992.8KW/m2The peak value of the heat release rate of the epoxy resin added with the flame retardant is 689.0KW/m2. FIG. 8 is a smoke release rate curve of pure epoxy resin and the epoxy resin added with sodium phytate coated with microcapsules, wherein the peak value of the smoke release rate of the pure epoxy resin is 0.18179m2(s) the peak smoke release rate of the epoxy resin added with the flame retardant is 0.15175m2And s. FIG. 9 is the total heat release curve of pure epoxy resin and the epoxy resin with sodium phytate microcapsule added, the total heat release of pure epoxy resin is 80.3MJ/m2The total heat release of the epoxy resin added with the flame retardant is 61.8MJ/m2. FIG. 10 is a graph showing the total smoke release curve for neat epoxy and an epoxy with added microencapsulated sodium phytate, the total smoke release for neat epoxy being 1530.3m2/m2The total smoke emission of the flame-retardant-added epoxy resin was 1116.2m2/m2. FIG. 11 is a CO release rate curve of pure epoxy resin and epoxy resin added with microcapsule coated sodium phytate, the peak value of the CO release rate of the pure epoxy resin is 0.03125g/s, and the peak value of the CO release rate of the epoxy resin added with flame retardant is 0.01977 g/s. FIG. 12 is CO of pure epoxy resin and epoxy resin with added microcapsule coated sodium phytate2Release Rate Profile, CO of pure epoxy2The peak release rate was 0.7707g/s, CO of epoxy resin with flame retardant added2The peak release rate was 0.54446 g/s. The tensile strength of the pure epoxy resin is 10.2MPa, and the tensile strength of the epoxy resin added with the microcapsule coated sodium phytate is 9.2MPa which is 90.2 percent of the original tensile strength.
Example 3
Preparing sodium phytate and aluminum chloride into 0.1mol/L and 0.5mol/L aqueous solutions respectively, adding 100ml of sodium phytate solution and 100ml of aluminum chloride solution into a conical flask with a condensation tube, stirring for 1h in a water bath at 100 ℃, performing suction filtration on the obtained product, washing to be neutral, and drying for 24h to obtain white powder A.
According to the mass ratio, the epoxy resin: ethanol 1.1: 20, 110g of ethanol and 6g of epoxy resin are added to an erlenmeyer flask and mixed for 15 minutes, then 40g of powder A and 0 are added.4g of sodium dodecyl benzene sulfonate, wherein the mass ratio of the powder A to the epoxy resin is 20:3, the mass ratio of the sodium dodecyl benzene sulfonate to the powder A is 1:100, the mixture is stirred for 0.5 hour in a water bath at the temperature of 60 ℃, 0.3g of 2-methyl-4-ethylimidazole is added, the mass ratio of the 2-methyl-4-ethylimidazole to the epoxy resin is 1:20, the mixture is heated and stirred in a water bath at the temperature of 80 ℃, the mixture is condensed and refluxed for 3 hours, and the obtained product is filtered, washed to be neutral and dried for 24 hours at the temperature of 70 ℃ to obtain the microcapsule-coated phytate epoxy resin flame retardant. Dispersing the microcapsule-coated phytate epoxy resin flame retardant into an epoxy resin system, wherein the flame retardant comprises the following components in percentage by weight: epoxy systems are 5: 95. The epoxy resin added with the microcapsule-coated phytate is subjected to a flame retardant performance test, and fig. 13 is a heat release rate curve of the pure epoxy resin and the epoxy resin added with the microcapsule-coated magnesium phytate prepared in the embodiment, wherein the peak value of the heat release rate of the pure epoxy resin is 992.8KW/m2The peak value of the heat release rate of the epoxy resin added with the flame retardant is 673.5KW/m2. FIG. 14 is a graph showing the smoke release rate of pure epoxy resin with a peak smoke release rate of 0.18179m and the epoxy resin with added microencapsulated magnesium phytate2/m2The peak value of the smoke release rate of the epoxy resin added with the flame retardant is 0.16882m2And s. FIG. 15 is a graph showing the total heat release curve of pure epoxy resin and epoxy resin with added microencapsulated magnesium phytate, the total heat release of pure epoxy resin is 80.3MJ/m2The total heat release of the epoxy resin added with the flame retardant is 68.1MJ/m2. FIG. 16 is a graph showing the total smoke release curve for neat epoxy and epoxy with added microencapsulated magnesium phytate, the total smoke release for neat epoxy being 1530.3m2/m2The total smoke emission of the flame-retardant-added epoxy resin was 1325.8m2/m2. FIG. 17 is a CO release rate curve of pure epoxy resin and epoxy resin added with microcapsule-coated magnesium phytate, the peak value of CO release rate of the pure epoxy resin is 0.03125g/s, and the peak value of CO release rate of the epoxy resin added with flame retardant is 0.02446 g/s. FIG. 18 is CO of pure epoxy resin and epoxy resin with added microencapsulated magnesium phytate2Release Rate Profile, CO of pure epoxy2The peak release rate was 0.7707g/s, rings with added flame retardantCO of oxygen resin2The peak release rate was 0.65133 g/s. The tensile strength of the pure epoxy resin is 10.2MPa, and the tensile strength of the epoxy resin added with the microcapsule coated magnesium phytate is 9.1MPa and is 89 percent of the original tensile strength.
It can be seen that magnesium phytate has better flame retardant effect than other two salts.
Example 4
Preparing sodium phytate and magnesium chloride into 0.1mol/L and 0.5mol/L aqueous solutions respectively, adding 100ml of sodium phytate solution and 100ml of magnesium chloride solution into a conical flask with a condenser tube, stirring for 1h in a water bath at the constant temperature of 100 ℃, performing suction filtration on the obtained product, washing to be neutral, and drying for 24h to obtain white powder A.
Adding 110g of ethanol and 6g of epoxy resin into a conical flask, mixing and stirring for 15 minutes, then adding 30g of powder A and 0.3g of sodium dodecyl benzene sulfonate, wherein the mass ratio of the powder A to the epoxy resin is 1:5, the mass ratio of the sodium dodecyl benzene sulfonate to the powder A is 1:100, stirring for 0.5 hour in a water bath at 60 ℃, adding 0.3g of 2-methyl-4-ethylimidazole, and the mass ratio of 2-methyl-4-ethylimidazole to the epoxy resin is 1:20, heating and stirring in the water bath at 80 ℃, carrying out condensation reflux for 3 hours, carrying out suction filtration and washing on the obtained product to be neutral, and drying for 24 hours at 70 ℃ to obtain the microcapsule-coated phytate epoxy resin flame retardant. Dispersing the microcapsule-coated phytate epoxy resin flame retardant into an epoxy resin system, wherein the flame retardant comprises the following components in percentage by weight: epoxy systems are 5: 95. The epoxy resin added with the microcapsule-coated phytate is subjected to flame retardant property test, and fig. 19 is a heat release rate curve of the pure epoxy resin and the epoxy resin added with the microcapsule-coated magnesium phytate prepared in the embodiment, wherein the peak value of the heat release rate of the pure epoxy resin is 992.8KW/m2The peak value of the heat release rate of the epoxy resin added with the flame retardant is 648.5KW/m2. FIG. 20 is a graph showing the smoke release rate of pure epoxy resin with a peak smoke release rate of 0.18179m and the epoxy resin with added microencapsulated magnesium phytate2/m2The peak value of the smoke release rate of the epoxy resin added with the flame retardant is 0.13522m2And s. FIG. 21 is a graph of the total heat release profile of neat epoxy and epoxy with added microencapsulated magnesium phytateTotal heat release of pure epoxy resin is 80.3MJ/m2The total heat release of the flame retardant-added epoxy resin was 69.2MJ/m2. FIG. 22 is a graph showing the total smoke release curve for neat epoxy and epoxy with added microencapsulated magnesium phytate, the total smoke release for neat epoxy being 1530.3m2/m2The total smoke emission of the flame-retardant-added epoxy resin was 1321.4m2/m2. FIG. 23 is a CO release rate curve of pure epoxy resin and epoxy resin added with microcapsule-coated magnesium phytate, the peak value of CO release rate of the pure epoxy resin is 0.03125g/s, and the peak value of CO release rate of the epoxy resin added with flame retardant is 0.01921 g/s. FIG. 24 is CO of pure epoxy resin and epoxy resin with added microencapsulated magnesium phytate2Release Rate Profile, CO of pure epoxy2The peak release rate was 0.7707g/s, CO of epoxy resin with flame retardant added2The peak release rate was 0.54224 g/s. The tensile strength of the pure epoxy resin is 10.2MPa, and the tensile strength of the epoxy resin added with the microcapsule coated magnesium phytate is 9.2MPa which is 90 percent of the original tensile strength.
Example 5
Preparing sodium phytate and magnesium chloride into 0.1mol/L and 0.5mol/L aqueous solutions respectively, adding 100ml of sodium phytate solution and 100ml of magnesium chloride solution into a conical flask with a condenser tube, stirring for 1h in a water bath at the constant temperature of 100 ℃, performing suction filtration on the obtained product, washing to be neutral, and drying for 24h to obtain white powder A.
According to the mass ratio, the epoxy resin: ethanol 1.1: 20, adding 110g of ethanol and 6g of epoxy resin into a conical flask, mixing and stirring for 15 minutes, then adding 40g of powder A and 0.4g of sodium dodecyl benzene sulfonate, wherein the mass ratio of the powder A to the epoxy resin is 20:3, the mass ratio of the sodium dodecyl benzene sulfonate to the powder A is 1:100, stirring for 0.5 hour in a water bath at 60 ℃, adding 0.3g of 2-methyl-4-ethylimidazole, and the mass ratio of 2-methyl-4-ethylimidazole to the epoxy resin is 1:20, heating and stirring in the water bath at 90 ℃, carrying out condensation reflux for 3 hours, carrying out suction filtration and washing on the obtained product to be neutral, and drying for 24 hours at 70 ℃ to obtain the microcapsule-coated phytate epoxy resin flame retardant. Dispersing the microcapsule-coated phytate epoxy resin flame retardant into an epoxy resin system,flame retardant: epoxy systems are 5: 95. The epoxy resin added with the microcapsule-coated phytate is subjected to flame retardant property test, and fig. 25 is a heat release rate curve of the pure epoxy resin and the epoxy resin added with the microcapsule-coated magnesium phytate prepared in the embodiment, and the peak value of the heat release rate of the pure epoxy resin is 992.8KW/m2The peak value of the heat release rate of the epoxy resin added with the flame retardant is 646.0KW/m2. FIG. 26 is a graph showing the smoke release rate of pure epoxy resin with a peak smoke release rate of 0.18179m and the epoxy resin with added microencapsulated magnesium phytate2/m2The peak value of the smoke release rate of the epoxy resin added with the flame retardant is 0.13079m2And s. FIG. 27 is a graph of the total heat release profile of neat epoxy and epoxy with added microencapsulated magnesium phytate, the total heat release of neat epoxy being 80.3MJ/m2The total heat release of the flame retardant-added epoxy resin was 69.3MJ/m2. FIG. 28 is a graph showing the total smoke release curve for neat epoxy and epoxy with added microencapsulated magnesium phytate, the total smoke release for neat epoxy being 1530.3m2/m2The total smoke emission of the epoxy resin added with the flame retardant is 1295.6m2/m2. FIG. 29 is a CO release rate curve of pure epoxy resin and epoxy resin added with microcapsule-coated magnesium phytate, the peak value of CO release rate of the pure epoxy resin is 0.03125g/s, and the peak value of CO release rate of the epoxy resin added with flame retardant is 0.01923 g/s. FIG. 30 is CO of pure epoxy resin and epoxy resin with added microencapsulated magnesium phytate2Release Rate Profile, CO of pure epoxy2The peak release rate was 0.7707g/s, CO of epoxy resin with flame retardant added2The peak release rate was 0.52998 g/s. The tensile strength of the pure epoxy resin is 10.2MPa, and the tensile strength of the epoxy resin added with the microcapsule coated magnesium phytate is 9.1MPa and is 89 percent of the original tensile strength.
Example 6
Preparing sodium phytate and aluminum chloride into 0.1mol/L and 0.5mol/L aqueous solutions respectively, adding 100ml of sodium phytate solution and 100ml of aluminum chloride solution into a conical flask with a condensation tube, stirring for 1h in a water bath at 100 ℃, performing suction filtration on the obtained product, washing to be neutral, and drying for 24h to obtain white powder A.
According to the mass ratio, the epoxy resin: ethanol 1.1: 20, adding 110g of ethanol and 6g of epoxy resin into a conical flask, mixing and stirring for 15 minutes, then adding 40g of powder A and 0.4g of sodium dodecyl benzene sulfonate, wherein the mass ratio of the powder A to the epoxy resin is 20:3, the mass ratio of the sodium dodecyl benzene sulfonate to the powder A is 1:100, stirring for 0.5 hour in a water bath at 60 ℃, adding 0.3g of 2-methyl-4-ethylimidazole, and the mass ratio of 2-methyl-4-ethylimidazole to the epoxy resin is 1:20, heating and stirring in the water bath at 80 ℃, carrying out condensation reflux for 3 hours, carrying out suction filtration and washing on the obtained product to be neutral, and drying for 24 hours at 70 ℃ to obtain the microcapsule-coated phytate epoxy resin flame retardant. Dispersing the microcapsule-coated phytate epoxy resin flame retardant into the epoxy resin, wherein the dispersion amount is 10% of the total mass of the material. The epoxy resin added with the microcapsule-coated phytate is subjected to flame retardant property test, and fig. 31 is a heat release rate curve of the pure epoxy resin and the epoxy resin added with the microcapsule-coated magnesium phytate prepared in the embodiment, and the peak value of the heat release rate of the pure epoxy resin is 992.8KW/m2The peak value of the heat release rate of the epoxy resin added with the flame retardant is 646.8KW/m2. FIG. 32 is a graph showing the smoke release rate of pure epoxy resin with a peak smoke release rate of 0.18179m and the epoxy resin with added microencapsulated magnesium phytate2/m2The peak value of the smoke release rate of the epoxy resin added with the flame retardant is 0.13116m2And s. FIG. 33 is a graph showing the total heat release curves of neat epoxy and epoxy with added microencapsulated magnesium phytate, the total heat release of neat epoxy being 80.3MJ/m2The total heat release of the epoxy resin added with the flame retardant is 61.9MJ/m2. FIG. 34 is a graph showing the total smoke release curve for neat epoxy and epoxy with added microencapsulated magnesium phytate, the total smoke release for neat epoxy being 1530.3m2/m2The total smoke emission of the flame-retardant-added epoxy resin was 1260.0m2/m2. FIG. 35 is a CO release rate curve of pure epoxy resin and epoxy resin with added microcapsule-coated magnesium phytate, the peak value of CO release rate of pure epoxy resin is 0.03125g/s, and CO release rate of epoxy resin with added flame retardant is 0.03125g/sThe peak rate was 0.01593 g/s. FIG. 36 is CO of pure epoxy resin and epoxy resin with added microencapsulated magnesium phytate2Release Rate Profile, CO of pure epoxy2The peak release rate was 0.7707g/s, CO of epoxy resin with flame retardant added2The peak release rate was 0.47555 g/s. The tensile strength of the pure epoxy resin is 10.2MPa, and the tensile strength of the epoxy resin added with the microcapsule coated magnesium phytate is 8.2MPa and is 80 percent of the original tensile strength.
Claims (10)
1. A preparation method of a microcapsule-coated phytate epoxy resin flame retardant is characterized by comprising the following steps:
step 1, according to the mass ratio, epoxy resin: ethanol (1-1.5): 20, mixing the epoxy resin with ethanol, and fully stirring to obtain a product C;
step 2, adding a phytate solid powder A and an emulsifier into a product C, and fully stirring under a heating condition to obtain a product D, wherein the mass ratio of the substance A to the epoxy resin in the step (3) is 1 (7-5), the mass ratio of sodium dodecyl benzene sulfonate to the substance A is 1 (120-90), and the heating temperature is 50-80 ℃;
and 3, adding 2-methyl-4-ethylimidazole into the product D, fully stirring under a heating condition, carrying out suction filtration, washing and drying on the product to obtain the microcapsule coated phytate epoxy resin flame retardant, wherein the mass ratio of the 2-methyl-4-ethylimidazole to the epoxy resin used in the step (3) is 1 (20-25), and the heating temperature is 70-90 ℃.
2. The method for preparing the microencapsulated phytate epoxy resin flame retardant of claim 1, wherein in the step 1, the epoxy resin is e51, e55 or e 44.
3. The preparation method of the microcapsule-coated phytate epoxy resin flame retardant according to claim 1, wherein in the step 1, the stirring time is 1-2 h.
4. The preparation method of the microcapsule-coated phytate epoxy resin flame retardant of claim 1, wherein in the step 2, the heating mode is water bath heating, and the stirring time is 0.5-1 h.
5. The method for preparing the microcapsule-coated phytate epoxy resin flame retardant of claim 1, wherein in the step 2, the emulsifier is sodium dodecyl benzene sulfonate.
6. The method for preparing the microencapsulated phytate epoxy resin flame retardant according to claim 1, wherein in the step 2, the phytate solid powder A is one of sodium phytate, magnesium phytate and aluminum phytate powder, wherein the phytate solid powder A is commercially available in the case of sodium phytate powder, and the phytate solid powder A is prepared in the following manner in the case of magnesium phytate or aluminum phytate:
(1) adding a sodium phytate solution and a magnesium chloride/aluminum chloride solution into a flask with a condenser, heating under the stirring condition, wherein the heating temperature is 80-100 ℃, the heating time is 1-2 hours, uniformly stirring, condensing and refluxing to obtain a colloid, and the feeding molar ratio of the sodium phytate to the magnesium chloride/aluminum chloride solute is 1 (4-7);
(2) and washing, filtering and drying the colloid to obtain a substance A.
7. The preparation method of the microcapsule coated phytate epoxy resin flame retardant according to claim 6, wherein in the step (1), the heating mode is water bath heating, and the stirring time is 1-2 h.
8. The method for preparing the microcapsule-coated phytate epoxy resin flame retardant according to claim 6, wherein in the step (2), the drying manner is heating drying, the drying temperature is 70 ℃, and the drying time is 24 h.
9. The method for preparing the microcapsule-coated phytate epoxy resin flame retardant according to claim 1, wherein in the step 3, the drying manner is heating drying, the drying temperature is 70 ℃, and the drying time is 24 h.
10. The preparation method of the microcapsule-coated phytate epoxy resin flame retardant according to claim 1, wherein the microcapsule-coated phytate epoxy resin flame retardant prepared in the step 3 is used as follows, and the flame retardant is prepared from the following components in percentage by mass: an epoxy resin system (5-10): (90-95), dispersing the flame retardant into an epoxy resin system, and testing shows that compared with pure epoxy resin, the epoxy resin added with the microcapsule coated phytate has the heat release rate peak value reduction amplitude of 30.6-36.22%, the smoke release rate peak value reduction amplitude of 7.13-28.05%, the total heat release reduction amplitude of 13.7-23.04%, the total smoke release rate peak value reduction amplitude of 13.36-27.06%, the CO release rate peak value reduction amplitude of 21.73-49.02%, and CO2The peak value reduction amplitude of the release rate is 15.49-39.3%, and the strength of the release rate is 80-95% of that of pure epoxy resin.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010070695A (en) * | 2008-09-22 | 2010-04-02 | National Institute Of Advanced Industrial Science & Technology | Flame-retardant epoxy resin and method for producing the same |
| CN104264467A (en) * | 2014-09-15 | 2015-01-07 | 河南工程学院 | Preparation method of flame-retardant cotton fabric |
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| CN108047494A (en) * | 2017-11-15 | 2018-05-18 | 四川大学 | Phytic acid ammonium salt fire retardant and preparation method thereof and the fire-retardant toughened poly-lactic acid material to prepare |
| CN108559062A (en) * | 2018-05-14 | 2018-09-21 | 武汉工程大学 | A kind of epoxy resin biology base flame retardant curing agent and preparation method thereof, application |
| CN109320548A (en) * | 2018-09-14 | 2019-02-12 | 浙江工业大学 | A kind of biology base three-source-in-one expansion type fire retardant and preparation method thereof, application |
-
2019
- 2019-10-30 CN CN201911043886.7A patent/CN110643071B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010070695A (en) * | 2008-09-22 | 2010-04-02 | National Institute Of Advanced Industrial Science & Technology | Flame-retardant epoxy resin and method for producing the same |
| CN104264467A (en) * | 2014-09-15 | 2015-01-07 | 河南工程学院 | Preparation method of flame-retardant cotton fabric |
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| CN108047494A (en) * | 2017-11-15 | 2018-05-18 | 四川大学 | Phytic acid ammonium salt fire retardant and preparation method thereof and the fire-retardant toughened poly-lactic acid material to prepare |
| CN108559062A (en) * | 2018-05-14 | 2018-09-21 | 武汉工程大学 | A kind of epoxy resin biology base flame retardant curing agent and preparation method thereof, application |
| CN109320548A (en) * | 2018-09-14 | 2019-02-12 | 浙江工业大学 | A kind of biology base three-source-in-one expansion type fire retardant and preparation method thereof, application |
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