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    • 专利摘要:
    The present disclosure provides a two—dimensional nanomaterial synergistic flame—retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification and a preparation method thereof, and belongs to the technical field of flame—retardant resin composite materials. In the present disclosure, two two—dimensional materials are subjected to stripping by using a microwave stripping method to obtain a two—dimensional nanostructure, the two—dimensional materials are subjected to intercalation organic modification during microwave stripping to form a laminated or mixed two— dimensional composite nanomaterial, and the two—dimensional composite nanomaterial is used as a nano synergistic flame retardant to achieve a synergistic flame—retardant effect with an intumescent flame retardant on epoxy resin; and the two two— dimensional nanomaterials and the intumescent flame retardant have a superhigh multiphase insulation advantage of the two—dimensional nanostructure, so that the heat and smoke release rate and other performance of the epoxy resin during combustion are greatly reduced, the esterified carbonization quality and rate of the intumescent flame retardant can be improved to the maximum extent, the flame retardant efficiency of the intumescent flame retardant is improved, and the flame retardancy of the intumescent flame retardant is comprehensively and greatly improved.
    公开号:NL2029694A
    申请号:NL2029694
    申请日:2021-11-09
    公开日:2021-12-21
    发明作者:Fan Qixiang；Du Jin；Guo Junxin；Wu Zhenghuan
    申请人:Guangdong Dongguan Quality Supervision Testing Center；
    IPC主号:
    专利说明:

    TWO-DIMENSIONAL NANOMATERIAL SYNERGISTIC FLAME-RETARDANT EPOXYRESIN COMPOSITE MATERIAL BASED ON SIMULTANEOUS MICROWAVE STRIPPINGAND INTERCALATION ORGANIC MODIFICATION AND PREPARATION METHODTHEREOF
    TECHNICAL FIELD The present disclosure relates to the technical field of flame-retardant resin composite materials, and in particular to a two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification and a preparation method thereof.
    BACKGROUND ART Epoxy resin is a polymer material with an aromatic, alicyclic or aliphatic main chain and a chain segment containing two or more epoxy groups. Due to strong adhesion, high rigidity, low shrink- age, solvent resistance, excellent electrical insulation and other characteristics, the epoxy resin is widely used in emerging fields such as smart electronics and aerospace. However, a limit oxygen index of the epoxy resin is only 21.7%, a large amount of heat and toxic black smoke are released during combustion of the epoxy res- in, and the safety of the human body is seriously endangered.
    Due to multiple functions such as thermal insulation, oxygen resistance, smoke suppression and drip prevention, intumescent flame retardants have become the most widely used additive-type environment-friendly flame retardants in China and other countries in recent 20 years. However, a material can reach level UL94-V0 when an added amount of the intumescent flame retardants is 30-40 wt3 of a mass of the epoxy resin, or the heat and black smoke re- leased during combustion of the epoxy resin and other factors more closely related to the environment and the human health are diffi- cult to suppress, so that expanded uses of the epoxy resin are se- verely restricted. The reason is that the intumescent flame re- tardants have a low esterified carbonization rate and low carboni-
    zation quality.
    In order to solve the problems above of the intumescent flame retardants, methods of using other types of flame retardants and the intumescent flame retardants for synergistic flame retardancy in the prior art include a synergistic flame retardant method, a catalytic method, a surface modification method, a ternary inte- gration method and the like. Where, the synergistic flame retard- ant method mainly includes achieving a synergistic flame-retardant effect of various flame-retardant elements, a flame-retardant mechanism is not clear, and in order to achieve the flame- retardant effect, the added amount of the intumescent flame re- tardants is still relatively high; the catalytic method generally includes using a strong acid or a strong oxidizing substance to accelerate intumescent carbonization of the intumescent flame re- tardants, and the method has a corrosion effect and is difficult to promote in a large scale; the surface modification method can improve the limit oxygen index and other performance to a certain extent, but cannot fully improve the flame-retardant effect of the intumescent flame retardants; and the ternary integration method includes synthesizing acid sources, gas sources and carbon sources in the intumescent flame retardants to form macromolecules, but the process is complicated, and mass production in a large scale is difficult.
    Therefore, in view of the disadvantages of low flame- retardant efficiency, insignificant effect, large added amount and the like of the existing intumescent flame retardants during use, it is urgent to provide a method that has a low added amount of a flame retardant and can significantly improve the flame retardancy of the intumescent flame retardants.
    SUMMARY An objective of the present disclosure is to provide a two- dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification and a preparation method there- of, and an excellent flame-retardant effect can be achieved with a low added amount.
    In order to achieve the objective of the present disclosure, the present disclosure has the following technical solutions.
    The present disclosure provides a preparation method of a two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification, and the method includes the following steps: mixing a two-dimensional material, sodium dodecyl benzene sulfonate and deionized water for dispersion to obtain a suspen- sion; sequentially conducting first microwave treatment and second microwave treatment on the suspension to obtain an intercalated organically modified two-dimensional nanomaterial; mixing an intumescent flame retardant and a silane coupling agent for surface modification to obtain a modified intumescent flame retardant; and mixing the intercalated organically modified two-dimensional nanomaterial, the modified intumescent flame retardant, epoxy res- in and a curing agent to obtain a two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic mod- ification; where the two-dimensional material includes any two selected from the group consisting of molybdenum disulfide, layered graph- ite, hexagonal boron nitride, graphene, a transition metal disul- fide, a transition metal carbide, a nitride, a carbonitride, black phosphorus, a layered double hydroxide, a two-dimensional metal organic framework material, a Pd nanosheet, an antimonene nanosheet and a boron nanosheet.
    Preferably, a mass ratio of the two-dimensional material to the sodium dodecyl benzene sulfonate is 100: (0.5-2). Preferably, a mass ratio of any two two-dimensional materials in the two-dimensional material is (1-7): (1-7). Preferably, the first microwave treatment is conducted at a constant power of 500-800 W for 5-20 minutes.
    Preferably, the second microwave treatment is conducted at a constant power of 200-260 W for 1-4 minutes.
    Preferably, the intumescent flame retardant is formed by mix- ing ammonium polyphosphate, pentaerythritol and melamine at a mass ratio of (20-40): (10-18): (10-15).
    Preferably, the silane coupling agent is A-172; and a mass of the silane coupling agent is 0.5% to 1.5% of a mass of the intu- mescent flame retardant.
    Preferably, the epoxy resin is bisphenol A epoxy resin, the curing agent is a polyamide €50 curing agent, and a mass ratio of the epoxy resin to the curing agent is (0.5-1.5):(0.5-1.5).
    Preferably, a mass ratio of the epoxy resin to the modified intumescent flame retardant to the intercalated organically modi- fied two-dimensional nanomaterial is (35-40): (6-12): (1-3).
    The present disclosure provides a two-dimensional nanomateri- al synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organ- ic modification prepared by using the preparation method according to the technical solution above.
    The present disclosure provides a preparation method of a two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification, and the method includes the following steps: mixing a two-dimensional material, sodium do- decyl benzene sulfonate and deionized water for dispersion to ob- tain a suspension; sequentially conducting first microwave treat- ment and second microwave treatment on the suspension to obtain an intercalated organically modified two-dimensional nanomaterial; mixing an intumescent flame retardant and a silane coupling agent for surface modification to obtain a modified intumescent flame retardant; and mixing the intercalated organically modified two- dimensional nanomaterial, the modified intumescent flame retard- ant, epoxy resin and a curing agent to obtain a two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite ma- terial based on simultaneous microwave stripping and intercalation organic modification; where the two-dimensional material includes any two selected from the group consisting of molybdenum disul- fide, layered graphite, hexagonal boron nitride, graphene, a tran- sition metal disulfide, a transition metal carbide, a nitride, a carbonitride, black phosphorus, a layered double hydroxide, a two- dimensional metal organic framework material, a Pd nanosheet, an antimonene nanosheet and a boron nanosheet. In the present disclo- sure, two two-dimensional materials are subjected to stripping by 5 using a microwave stripping method to obtain a two-dimensional nanostructure, and the two-dimensional materials are subjected to intercalation organic modification during microwave stripping to form a laminated or mixed two-dimensional composite nanomaterial so that a catalytic carbonization effect, an enhanced carboniza- tion effect, high thermal conductivity and high thermal stability of the two two-dimensional nanomaterials can be fully exerted, and the two-dimensional composite nanomaterial is used as a nano syn- ergistic flame retardant to achieve a synergistic flame-retardant effect with the intumescent flame retardant on the epoxy resin; and the two two-dimensional nanomaterials and the intumescent flame retardant have a superhigh multiphase insulation advantage of the two-dimensional nanostructure, so that the heat and smoke release rate and other performance of the epoxy resin during com- bustion are greatly reduced, the esterified carbonization quality and rate of the intumescent flame retardant can be improved to the maximum extent, the flame retardant efficiency of the intumescent flame retardant is improved, and the flame retardancy of the intu- mescent flame retardant is comprehensively and greatly improved. The method of the present disclosure can not only provide a new flame-retardant approach for the flame-retardant epoxy resin, but also provide a new reference for production of new flame retard- ants.
    The nano synergistic flame retardant of the present disclo- sure can achieve a synergistic flame-retardant effect with the in- tumescent flame retardant on the epoxy resin in a very small added amount, so that the added amount of the intumescent flame retard- ant is reduced, a better flame-retardant effect is achieved, and the flame retardancy of the synergistic flame retardant in a small amount is higher than the flame-retardant effect of an original single intumescent flame retardant on the epoxy resin in a high added amount. Results of examples and comparative examples show that the comprehensive flame-retardant effect of the "nano molyb-
    denum disulfide/nano layered graphite" synergistic intumescent flame retardant with an added amount of 20% (including 2% of the "nano molybdenum disulfide/nano layered graphite", 18% of the in- tumescent flame retardant and 80% of the epoxy resin) in the pre- sent disclosure is higher than the flame-retardant effect of a 20% pure intumescent flame retardant {including 20% of an intumescent flame retardant and 80% of epoxy resin) on the epoxy resin, and the added amount is reduced by 34%. The flame retardancy is un- changed or improved without reducing the added amount of the flame retardant, indicating that the mechanical performance of the epoxy resin composite material is reduced to the minimum extent, and a product has a wider range of uses.
    DETAILED DESCRIPTION OF THE EMBODIMENTS The present disclosure provides a preparation method of a two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification, and the method includes the following steps: mixing a two-dimensional material, sodium dodecyl benzene sulfonate and deionized water for dispersion to obtain a suspen- sion; sequentially conducting first microwave treatment and second microwave treatment on the suspension to obtain an intercalated organically modified two-dimensional nanomaterial; mixing an intumescent flame retardant and a silane coupling agent for surface modification to obtain a modified intumescent flame retardant; and mixing the intercalated organically modified two-dimensional nanomaterial, the modified intumescent flame retardant, epoxy res- in and a curing agent to obtain a two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic mod- ification; where the two-dimensional material includes any two selected from the group consisting of molybdenum disulfide, layered graph- ite, hexagonal boron nitride, graphene, a transition metal disul-
    fide, a transition metal carbide, a nitride, a carbonitride, black phosphorus, a layered double hydroxide, a two-dimensional metal organic framework material, a Pd nanosheet, an antimonene nanosheet and a boron nanosheet.
    In the present disclosure, unless otherwise specified, all raw materials required for preparation are commercially available products well known to persons skilled in the art.
    In the present disclosure, the two-dimensional material, the sodium dodecyl benzene sulfonate and the deionized water are mixed for dispersion to obtain the suspension. In the present disclo- sure, specific specifications of the two-dimensional material are not particularly limited, and the two-dimensional material is a commercially available product well known in the art. In the pre- sent disclosure, the two-dimensional material includes any two se- lected from the group consisting of molybdenum disulfide, layered graphite, hexagonal boron nitride, graphene, a transition metal disulfide, a transition metal carbide, a nitride, a carbonitride, black phosphorus, a layered double hydroxide, a two-dimensional metal organic framework material, a Pd nanosheet, an antimonene nanosheet and a boron nanosheet, and preferably includes molyb- denum disulfide and layered graphite, or hexagonal boron nitride and layered graphite. In the present disclosure, a mass ratio of any two two-dimensional materials in the two-dimensional material is preferably (1-7):(1-7), more preferably 1:7, 2:6, 3:5, 4:4, 5:3, 6:2 or 7:1.
    In the present disclosure, a purity of the sodium dodecyl benzene sulfonate is preferably equal to or greater than 90%; a mass ratio of the two-dimensional material to the sodium dodecyl benzene sulfonate is preferably 2:0.01; and a mass ratio of the deionized water to the sodium dodecyl benzene sulfonate is prefer- ably 50:0.01. The sodium dodecyl benzene sulfonate is used as an organic modifier to conduct intercalation organic modification on the two-dimensional material in the present disclosure, a surface of the obtained two-dimensional nanomaterial can be covered with organic small molecules, the compatibility between the two- dimensional nanomaterial and the epoxy resin is improved, and syn- ergy with the intumescent flame retardant is facilitated to im-
    prove the flame retardancy of the epoxy resin.
    The process of mixing the two-dimensional material, the sodi- um dodecylbenzene sulfonate and the deionized water is not partic- ularly limited in the present disclosure, and the materials can be uniformly mixed according to a process well known in the art.
    In the present disclosure, the dispersion is preferably con- ducted under conditions of high-speed stirring, the high-speed stirring is preferably conducted at a stirring speed of 1,000- 2,000 r/min, more preferably 1,500 r/min, and the dispersion time is preferably 10-30 minutes, more preferably 15-25 minutes.
    After the dispersion is completed, an obtained dispersion liquid is preferably subjected to standing to obtain the suspen- sion in the present disclosure; and the standing time is prefera- bly 12-24 hours, more preferably 15-20 hours.
    In the present disclosure, after the suspension is obtained, the suspension is sequentially subjected to the first microwave treatment and the second microwave treatment to obtain the inter- calated organically modified two-dimensional nanomaterial. In the present disclosure, the first microwave treatment and the second microwave treatment are preferably conducted in a microwave reac- tor, and the microwave reactor in the present disclosure is not particularly limited and can be a microwave reactor well known in the art.
    In the present disclosure, a constant power of the first mi- crowave treatment is preferably 500-800 W, more preferably 600-700 W; and the time is preferably 5-20 minutes, more preferably 10-15 minutes. In the present disclosure, after the first microwave treatment is completed, an obtained material is naturally cooled to room temperature and then subjected to the second microwave treatment.
    In the present disclosure, a constant power of the second mi- crowave treatment is preferably 200-260 W, more preferably 220-250 W; and the time is preferably 1-4 minutes, more preferably 2-3 minutes. In the present disclosure, after the second microwave treatment is completed, an obtained material is naturally cooled to room temperature and then placed into a freezer for freezing; after the material is completely frozen, an obtained material is placed into a vacuum freeze dryer for vacuum freeze-drying, and then an obtained material is ground into powder to obtain the in- tercalated organically modified two-dimensional nanomaterial. In the present disclosure, a particle size of the intercalated organ- ically modified two-dimensional nanomaterial obtained after grind- ing is not particularly limited, and the intercalated organically modified two-dimensional nanomaterial is ground powder well known in the art. In the present disclosure, a freezing temperature is preferably -20°C to -40°C, and the time is preferably 12 hours; and the vacuum freeze-drying time is preferably 12-24 hours, and a temperature is preferably -20°C to -40°C.
    During the first microwave treatment and the second microwave treatment, the two two-dimensional materials are simultaneously subjected to stripping under the action of microwaves to obtain a two-dimensional nanomaterial, and the two two-dimensional materi- als are subjected to intercalation organic modification by using the sodium dodecyl benzene sulfonate, so that not only are nano characteristics of the two two-dimensional materials exerted, but also the compatibility between the two-dimensional nanomaterial and the epoxy resin can be improved, the dispersibility of the two-dimensional nanomaterial in the epoxy resin is improved, and the two-dimensional nanomaterial achieves a synergistic flame- retardant effect with the intumescent flame retardant on the epoxy resin more effectively.
    In the present disclosure, the first microwave treatment is conducted at a larger microwave power to strip hard aggregates be- tween two-dimensional material layers, the second microwave treat- ment is conducted at a lower microwave power to strip soft aggre- gates between the two-dimensional material layers, and after a continuous two-step microwave process is conducted, a thinner two- dimensional nanomaterial can be stripped to the maximum extent, so that a large specific surface area of the two-dimensional nano- material is more effectively used when the synergistic flame- retardant effect is achieved, heat insulation, oxygen insulation, combustible insulation and other functions of the two-dimensional nanomaterial are more effectively exerted, and the flame retardan- cy of the epoxy resin is improved by synergy with the intumescent flame retardant.
    In the present disclosure, the intumescent flame retardant and the silane coupling agent are mixed for surface modification to obtain the modified intumescent flame retardant. In the present disclosure, the intumescent flame retardant is preferably formed by mixing ammonium polyphosphate, pentaerythritol and melamine, the mixing process is not particularly limited in the present dis- closure, and the raw materials are uniformly mixed according to a process well known in the art. In the present disclosure, a mass ratio of the ammonium polyphosphate to the pentaerythritol to the melamine is preferably (20-40): (10-18): (10-15), more preferably (25-35): (12-16): (12-14). In the present disclosure, the silane coupling agent is pref- erably A-172; and a purity of the silane coupling agent is prefer- ably equal to or greater than 99%. In the present disclosure, a mass of the silane coupling agent is preferably 0.5% to 1.5% of a mass of the intumescent flame retardant, more preferably 0.8% to
    1.2%, further more preferably 1.0%. In the present disclosure, the process of mixing the intumes- cent flame retardant and the silane coupling agent preferably in- cludes dissolving the silane coupling agent in absolute ethanol and then spraying an obtained solution onto the intumescent flame retardant. In the present disclosure, a purity of the absolute ethanol is preferably equal to or greater than 99.7%; and a mass ratio of the absolute ethancl to the silane coupling agent is preferably 3:1. The spraying process in the present disclosure is not particularly limited, and the solution can be sprayed by using a process well known in the art. In the present disclosure, the surface modification is pref- erably conducted at room temperature; a room temperature range is preferably 20°C to 35°C; and a surface modification process pref- erably includes conducting natural volatilization on a mixed mate- rial for 24-48 hours, more preferably 30-42 hours. The compatibil- ity between the intumescent flame retardant and the epoxy resin is improved by the surface modification in the present disclosure.
    In the present disclosure, after the intercalated organically modified two-dimensional nanomaterial and the modified intumescent flame retardant are obtained, the intercalated organically modi- fied two-dimensional nanomaterial, the modified intumescent flame retardant, the epoxy resin and the curing agent are mixed to ob- tain the two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification. In the present disclosure, the epoxy resin is preferably bisphenol A epoxy resin; and in examples of the present disclosure, the bisphenol A epoxy resin is specifically model 6101, the curing agent is preferably a polyamide 650 curing agent, and a mass ratio of the epoxy resin to the curing agent is (0.5-1.5):(0.5-1.5), more preferably (0.8-
    1.2):{0.8-1.2).
    In the present disclosure, a mass ratio of the epoxy resin to the modified intumescent flame retardant to the intercalated or- ganically modified two-dimensional nanomaterial is preferably (35- 40) :(e-12): (1-3), more preferably (36-38):{(8-10):{(1.5-2.5).
    In the present disclosure, the process of mixing the interca- lated organically modified two-dimensional nanomaterial, the modi- fied intumescent flame retardant, the epoxy resin and the curing agent is preferably conducted under conditions of stirring, and the stirring is preferably conducted at a rotation speed of 50 r/min. After the mixing is completed, the two-dimensional nano- material synergistic flame-retardant epoxy resin composite materi- al based on simultaneous microwave stripping and intercalation or- ganic modification is obtained.
    The present disclosure provides a two-dimensional nanomateri- al synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organ- ic modification prepared by using the preparation method according to the technical solution above. In the present disclosure, in the two-dimensional nanomaterial synergistic flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation organic modification, a part of the two- dimensional nanomaterial is physically mixed, and a part of the two-dimensional nanomaterial is laminated under the action of a van der waals force, and at the same time, the organically modi- fied two-dimensional nanomaterial is compatible with the surface modified intumescent flame retardant and the epoxy resin to form the composite material.
    The technical solutions in the present disclosure are clearly and completely described below in conjunction with the examples of the present disclosure. Apparently, the described examples are merely some rather than all of the examples of the present disclo- sure. All other examples obtained by a person of ordinary skill in the art based on the examples of the present disclosure without creative efforts shall fall within the protection scope of the present disclosure.
    In the following examples and comparative examples, the puri- ty of the sodium dodecyl benzene sulfonate is equal to or greater than 90%; the purity of the absolute ethanol is equal to or great- er than 99.7%; the purity of the silane coupling agent is equal to or greater than 99%; the epoxy resin used is bisphenol A epoxy resin 6101; and the curing agent is a polyamide 650 curing agent.
    Example 1
    7.5 g of molybdenum disulfide, 2.5 g of layered graphite and
    0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 600 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 260 W for 2 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Example 2 5 g of molybdenum disulfide, 5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 500 W for 10 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 260 W for 3 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Example 3 5 g of molybdenum disulfide, 5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 500 W for 5 minutes and then naturally cooled to room temperature; in the second stage, the suspension was subjected to second micro- wave treatment at a constant power of 200 W for 1 minute and then naturally cooled to room temperature, and an obtained mixed mate- rial was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vac- uum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Example 4 5 g of molybdenum disulfide, 5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 800 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 260 W for 4 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Example 5 5 g of molybdenum disulfide, 5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 700 W for 10 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 260 W for 1 minute and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Example 6 5 g of molybdenum disulfide, 5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 500 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 220 W for 3 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Example 7 5 g of molybdenum disulfide, 5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 600 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 260 W for 2 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Example 8 5 g of molybdenum disulfide, 5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 700 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 220 W for 1 minute and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material. Example 9
    3.75 g of molybdenum disulfide, €.25 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a suspension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 600 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 260 W for 2 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano molybdenum disulfide/nano layered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano molybdenum disulfide/nano lay- ered graphite material and a mixture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano molybdenum di- sulfide/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material. Example 10
    3.75 g of hexagonal boron nitride, 6.25 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a suspension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 800 W for 5 minutes and then naturally cooled to room temperature; in the second stage, the suspension was subjected to second micro- wave treatment at a constant power of 240 W for 2 minutes and then naturally cooled to room temperature, and an obtained mixed mate- rial was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vac- uum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano hexagonal boron nitride/nano lay- ered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano hexagonal boron nitride/nano layered graphite material and a mixture of epoxy resin and a cur- ing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano hexagonal boron nitride/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material. Example 11 5 g of hexagonal boron nitride, 5 g of layered graphite and
    0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 800 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 260 W for 4 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano hexagonal boron nitride/nano lay- ered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano hexagonal boron nitride/nano layered graphite material and a mixture of epoxy resin and a cur- ing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano hexagonal boron nitride/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material. Example 12 5 g of hexagonal boron nitride, 5 g of layered graphite and
    0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 800 W for 15 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 200 W for 2 minutes and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano hexagonal boron nitride/nano lay- ered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano hexagonal boron nitride/nano layered graphite material and a mixture of epoxy resin and a cur- ing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano hexagonal boron nitride/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material. Example 13 5 g of hexagonal boron nitride, 5 g of layered graphite and
    0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 800 W for 5 minutes and then naturally cooled to room temperature; in the second stage, the suspension was subjected to second micro- wave treatment at a constant power of 240 W for 2 minutes and then naturally cooled to room temperature, and an obtained mixed mate- rial was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vac- uum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano hexagonal boron nitride/nano lay- ered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano hexagonal boron nitride/nano layered graphite material and a mixture of epoxy resin and a cur- ing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano hexagonal boron nitride/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material. Example 14 5 g of hexagonal boron nitride, 5 g of layered graphite and
    0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a sus- pension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 700 W for 20 minutes and then naturally cooled to room tempera- ture; in the second stage, the suspension was subjected to second microwave treatment at a constant power of 220 W for 1 minute and then naturally cooled to room temperature, and an obtained mixed material was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vacuum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano hexagonal boron nitride/nano lay- ered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano hexagonal boron nitride/nano layered graphite material and a mixture of epoxy resin and a cur- ing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano hexagonal boron nitride/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material. Example 15
    2.5 g of hexagonal boron nitride, 7.5 g of layered graphite and 0.05 g of sodium dodecyl benzene sulfonate were dispersed in 250 g of deionized water and stirred at a high speed of 1,500 r/min for dispersion for 15 minutes; and after standing for 24 hours, a suspension was obtained; the suspension was placed in a microwave reactor for micro- wave treatment in two stages: in the first stage, the suspension was subjected to first microwave treatment at a constant power of 800 W for 5 minutes and then naturally cooled to room temperature; in the second stage, the suspension was subjected to second micro- wave treatment at a constant power of 240 W for 2 minutes and then naturally cooled to room temperature, and an obtained mixed mate- rial was placed into a freezer for freezing at -40°C for 12 hours; after being completely frozen, the material was placed into a vac- uum freeze dryer for vacuum freeze-drying at -20°C for 12-24 hours, and after the freeze-drying was completed, the material was taken out and ground into powder in a mortar to obtain an interca- lated organically modified nano hexagonal boron nitride/nano lay- ered graphite material; ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant, the inter- calated organically modified nano hexagonal boron nitride/nano layered graphite material and a mixture of epoxy resin and a cur- ing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly mixed and stirred at a mass ratio of 9:1:40 and a rotation speed of 50 r/min to obtain a nano hexagonal boron nitride/nano layered graphite synergistic intumescent flame- retardant epoxy resin composite material.
    Comparative Example 1 Epoxy resin and a curing agent were uniformly stirred at a mass ratio of 1:1 to obtain an epoxy resin substrate material.
    Comparative Example 2 Ammonium polyphosphate, pentaerythritol and melamine were mixed at a mass ratio of 23:14:13 to obtain an intumescent flame retardant, absolute ethanol and a silane coupling agent A-172 (at a mass ratio of 3:1) were prepared into a solution, the solution was sprayed onto the intumescent flame retardant (a mass of the silane coupling agent was 0.5% of a mass of the intumescent flame retardant), and then the intumescent flame retardant was subjected to natural volatilization at 25°C for 24 hours to obtain a surface modified intumescent flame retardant; and the surface modified intumescent flame retardant and a mix- ture of epoxy resin and a curing agent (a mass ratio of the epoxy resin to the curing agent was 20:20) were uniformly stirred at a mass ratio of 20:80 and a rotation speed of 50 r/min to obtain an intumescent flame-retardant epoxy resin composite material.
    Performance tests 1) The thermal stability, vertical combustion grade, limit oxygen index and cone calorimetry of the epoxy resin composite ma-
    terials prepared in Examples 1 to 15 were tested, where the ther- mal stability was tested according to GB/T 27761-2011, the verti- cal combustion grade was tested according to UL-94, the limit oxy- gen index was tested according to UL-94, the cone calorimetry was tested with a cone calorimeter according to IS05660, and results were shown in Tables 1 to 3. Table 1 Test results of thermal stability of epoxy resin com- posite materials prepared in Examples 1 to 15 Exam o Q Orr o 3
    0.5297 355.81 17.07
    0.6659 380.22 14.37
    0.5896 370.07 14.97
    0.5511 367.48 13.58
    0.6070 369.72 15.57 6 299.73 0.5357 369.50 14.07
    0.5382 366.74 14.83 [8 25209 0.5761 369.83 14.22 9 Jae 0.5478 357.67 15.36
    0.5739 376.28 14.00
    0.5853 371.24 14.3
    0.6031 373.89 14.68
    0.6215 371.34 19.24 ee HE
    0.6007 379.97 14.5 Note: Ts: referred to an initial decomposition temperature of a material; Ta: referred to a temperature corresponding to a maxi- mum thermal degradation rate of a material; Vs. referred to a max- imum thermal degradation rate of a material, and a smaller Vrax value was better; and C. referred to a residue content of a materi- al at 800°C. When a temperature difference between T and Tua: was smaller, less heat was released, and the performance was better; when Vua: was smaller, the thermal decomposition degree was lower;
    and when C, was larger, combustion of a substrate was less suffi- cient, and the protection performance of a flame retardant was better.
    Table 2 Vertical combustion and limit oxygen index values of epoxy resin composite materials prepared in Examples 1 to 15 Vertical combustion grade Limit oxygen index Example (UL-94) (%) Ee EN Kn Note: The vertical combustion grade (UL-94) included no grade, a grade V-2, a grade V-1 and a grade V-0, and the grades became better from left to right; when the limit oxygen index was equal to or greater than 27%, a material was considered as a flame-retardant material, and a higher limit oxygen index value was better.
    Table 3 Test results of cone calorimetry of epoxy resin com- posite materials prepared in Examples 1, 2 and 10 MHRR THR TSP CO/CO: EHC Example . , (KW/M") (MJ /m*) {m°) (kg/kg) (MJ/kg)
    0.01/ 1 51.2 86.8 17.0 4.8
    0.25
    0.0006/ 2 59.8 102.0 20.3 6.4
    0.02
    0.02/ 3 66.7 99.6 21.0 6.4
    0.35 Note: MHRR referred to a mean heat release rate, and a lower MHRR value was better; THR referred to total heat release, and a lower THR value was better; TSP referred to total smoke produc- tion, and a lower TSP value was better; "CO/CO:" referred to a to- tal emission of "carbon monoxide/carbon dioxide", and a lower CO/CO.: value was better; and EHC referred to effective heat combus- tion, and a lower EHC value was better.
    2) Performance tests were conducted on the composite materi- als prepared in Comparative Examples 1 to 2 according to the meth- od in 1) above, and test results of thermal stability, vertical combustion grade, limit oxygen index and cone calorimetry of the composite materials were shown in Tables 4 to 6. Table 4 Test results of thermal stability of composite mate- rials prepared in Comparative Examples 1 to 2 Comparative os Te: (°C) Vax (5 oc =) Trax (°C) Ct (%) Example
    338.52 0.94049 374.18 2.759
    235.62 0.5894 370.59 13.10
    Table 5 Vertical combustion and limit oxygen index values of composite materials prepared in Comparative Examples 1 to 2 Comparative Ex- Vertical combustion Limit oxygen index ample grade (UL-984) (%)
    I Table 6 Test results of cone calorimetry of composite materi- als prepared in Comparative Examples 1 to 2 Comparative MHRR THR TSP CO/CO: EHC Example (kW/M*) (MJ /m*) (m*) (kg/kg) (MJ/kg)
    0.03/ 1 352.1 163.5 31.0 23.0
    1.73
    0.02/ 2 75.8 103.7 26.9 6.8
    0.35 From comparison between Tables 4 to 6 and Tables 1 to 3, it can be seen that unique characteristics such as thermal resistance and thermal conductivity of the two-dimensional nanomaterial were exerted; and due to a two-dimensional insulation function of the two-dimensional nanomaterial, characteristics of oxygen insula- tion, heat insulation and combustible insulation of an intumescent carbon layer produced by an intumescent flame retardant could be improved. It can be seen from Tables 1 to 6 that release of heat, smoke and the like was greatly reduced, and a pure intumescent flame retardant could not achieve the flame-retardant effect. Therefore, the epoxy resin composite material prepared in the pre- sent disclosure has excellent flame retardancy. The above descriptions are merely preferred embodiments of the present disclosure. It should be noted that a person of ordi- nary skill in the art may further make several improvements and modifications without departing from the principle of the present disclosure, but such improvements and modifications should be deemed as falling within the protection scope of the present dis- closure.
    权利要求:
    Claims (10)
    [1]
    A process for preparing a two-dimensional synergistic nanomaterial flame-retardant epoxy resin composite material based on simultaneous microwave stripping and intercalation of organic modification, comprising the steps of: mixing a two-dimensional material, sodium dodecylbenzene sulfonate and deionized water for dispersion to obtain a suspension; sequentially performing a first microwave treatment and a second microwave treatment on the slurry to obtain an intercalated organically modified two-dimensional nanomaterial; mixing an intumescent flame retardant and a silane coupling agent for surface modification to obtain a modified intumescent flame retardant; and mixing the intercalated organically modified two-dimensional nanomaterial, the modified intumescent flame retardant, epoxy resin and a curing agent to obtain a two-dimensional synergistic flame-retardant epoxy resin composite nanomaterial based on simultaneous microwave stripping and intercalation of organic modification; wherein the two-dimensional material comprises any two selected from the group consisting of molybdenum disulfide, layered graphite, hexagonal boron nitride, graphene, a transition metal disulfide, a transition metal carbide, a nitride, a carbonitride, black phosphor, a layered double hydroxide, a two-dimensional metal - organic framework material, a Pd nanoleaf, an antimony nanoleaf and a boron nanoleaf.
    [2]
    The preparation method of claim 1, wherein a mass ratio of the two-dimensional material to the sodium dodecyl benzene sulfonate is 100:{0.5-2).
    [3]
    The preparation method according to claim 1 or 2, wherein a mass
    sa ratio of any two two-dimensional materials in the two-dimensional material is (1-7): (1-7).
    [4]
    The preparation method according to claim 1, wherein the first microwave treatment is carried out at a constant power of 500-800 W for 5-20 minutes.
    [5]
    The production method according to claim 1, wherein the second microwave treatment is carried out at a constant power of 200-260 W for 1-4 minutes.
    [6]
    The production method according to claim 1, wherein the intumescent flame retardant is formed by mixing ammonium polyphosphate, pentaerythritol and melamine in a mass ratio of (20-40): (10-18): (10-15).
    [7]
    Production method according to claim 1 or 6, wherein the silane coupling agent is A-172; and a mass of the silane coupling agent is 0.5% to 1.5% of a mass of the intumescent flame retardant.
    [8]
    The preparation method according to claim 1, wherein the epoxy resin is bisphenol A epoxy resin, the curing agent is a polyamide 650 curing agent, and a mass ratio of the epoxy resin to the curing agent (0.5-1.5): (0.5-1.5) is.
    [9]
    The production method according to claim 1 or 8, wherein a mass ratio of the epoxy resin to the modified intumescent flame retardant to the intercalated organically modified two-dimensional nanomaterial is (35-40): (6-12): (1-3).
    [10]
    A two-dimensional synergistic flame-retardant epoxy resin composite nanomaterial based on simultaneous microwave stripping and intercalation of organic modification prepared by the preparation method according to any one of claims 1 to 9.
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    同族专利:
    公开号 | 公开日
    CN112662136A|2021-04-16|
    引用文献:
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    CN202011460624.3A|CN112662136A|2020-12-11|2020-12-11|Microwave simultaneous stripping and intercalation organic modified nano two-dimensional material synergistic flame-retardant epoxy resin composite material and preparation method thereof|
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