A high-efficiency non-halogen flame retardant additive for plastics and its preparation method

Abstract

The invention discloses a kind of high-efficiency non-halogen plastic flame retardant additive and preparation method thereof, relate to the technical field of plastic additives, be made up of the following raw materials by weight: modified porous nano-scale flame retardant oxide / expanded graphite composite 35-45 parts, organic phosphinate metal salt 8-10 parts, phosphorus system synergist 10-12 parts, nitrogen system synergist 10-12 parts, coupling agent 3-5 parts;Described modified porous nano-scale flame retardant oxide / expanded graphite composite is 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide co-modified porous nano-scale flame retardant oxide / expanded graphite composite.This additive is environmentally friendly, has remarkable flame retardant effect, is added in small amount, has good compatibility with plastic matrix, and has little negative impact on plastic mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of plastic additives, and in particular to a high-efficiency non-halogen plastic flame retardant additive and a preparation method thereof. Background Art

[0002] Plastics are increasingly used in all aspects of life and production, and are indispensable materials for human production. However, many plastics are highly flammable due to their chemical composition. Once a fire occurs, the consequences are severe. The combustion process produces large amounts of toxic and harmful gases, posing a significant threat to humans and the surrounding environment. Therefore, to improve the fire resistance of plastic products, it is often necessary to add a certain amount of flame retardant additives during their processing and molding.

[0003] At present, the flame retardants for plastics on the market mainly include halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants and inorganic flame retardants. When plastic products containing halogen flame retardants burn, they will release a large amount of highly toxic and carcinogenic gases such as dioxins. These gases will not only cause serious pollution to the atmospheric environment, but will also accumulate in organisms, posing a long-term threat to the ecosystem and human health. Although pure phosphorus flame retardants can improve the flame retardant properties of plastics to a certain extent, their flame retardant efficiency is still lower than that of halogen flame retardants, and when added in large amounts, it will affect the processing properties of plastics, resulting in a decrease in the surface quality of plastic products, such as flow marks, reduced gloss and other problems. Nitrogen flame retardants usually need to be used in combination with other flame retardants. When used alone, the flame retardant effect is poor, and they may decompose at high temperatures to produce a pungent odor, affecting the user experience of the product. Inorganic flame retardant additives have the advantages of low cost, non-toxicity and smokelessness, but their addition amount is large. Due to compatibility and other issues, they will significantly reduce the mechanical properties and performance stability of plastics, making plastic products brittle and significantly reducing impact strength, making it difficult to meet application scenarios with high requirements for the comprehensive performance of materials.

[0004] For example, the Chinese invention patent with authorization announcement number CN112724468B discloses a composite environmentally friendly flame retardant for PP and PP flame-retardant plastic, which is obtained by mixing dimethyl trimethylsilylmethylphosphonate, pentaerythritol melamine phosphate, magnesium hydroxide, aluminum hydroxide, antimony trioxide, magnesium sulfate whisker halogen-free flame retardant, and graphene. However, the addition amount of this composite environmentally friendly flame retardant is large, requiring 20% ​​to achieve a good flame retardant effect. In addition, antimony trioxide is expensive and has poor environmental performance.

[0005] It can be seen that this field still needs an efficient non-halogen plastic flame retardant additive and its preparation method with good environmental protection, significant flame retardant effect, small addition amount, good compatibility with plastic matrix, and small negative impact on the mechanical properties of the plastic matrix. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide an efficient non-halogen plastic flame retardant additive and its preparation method with good environmental protection, significant flame retardant effect, small addition amount, good compatibility with plastic matrix, and little negative impact on the mechanical properties of the plastic matrix.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] A high-efficiency non-halogen flame retardant additive for plastics is prepared from the following raw materials in parts by weight: 35-45 parts of a modified porous nanoscale flame retardant oxide / expanded graphite composite, 8-10 parts of an organic phosphinate metal salt, 10-12 parts of a phosphorus-based synergist, 10-12 parts of a nitrogen-based synergist, and 3-5 parts of a coupling agent; the modified porous nanoscale flame retardant oxide / expanded graphite composite is a composite co-modified with 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, and diphenyl (4-vinylphenyl) phosphine oxide.

[0009] Preferably, the coupling agent is any one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570, or a combination of several of them.

[0010] Preferably, the nitrogen-based synergist is one or more of melamine, melamine cyanurate, and ammonium polyphosphate.

[0011] Preferably, the phosphorus-based synergist is one or more of tricresyl phosphate, triphenyl phosphate, and resorcinol bis(diphenyl phosphate).

[0012] Preferably, the organic metal phosphinate is aluminum phosphinate.

[0013] Preferably, the preparation method of the modified porous nanoscale flame retardant oxide / expanded graphite composite comprises the following steps:

[0014] Step I: Dispersing a zinc source, a silicon source, a magnesium source, a copper source, and a molybdenum source in an alcohol solvent, stirring uniformly, slowly adding sodium acetate, transferring the mixture to a polytetrafluoroethylene-lined hydrothermal reactor, and reacting at 195-220° C. for 15-20 hours; removing the reactor, and after the reaction system is cooled to room temperature, repeatedly washing with anhydrous ethanol and deionized water, followed by drying in a vacuum drying oven at 85-95° C. for 10-20 hours, and finally calcining to obtain a porous nanoscale flame retardant oxide;

[0015] Step II: After the porous nano-scale flame retardant oxide and expanded graphite are uniformly mixed, they are dispersed in N,N-dimethylformamide, and then 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide and initiator are added thereto. The mixture is stirred and reacted at 60-70° C. in an inert gas atmosphere for 3-5 hours, and then the solvent is removed by rotary evaporation to obtain a modified porous nano-scale flame retardant oxide / expanded graphite composite.

[0016] Preferably, in step I, the zinc source is zinc nitrate; the silicon source is at least one of sodium silicate and silicon tetrachloride; the magnesium source is magnesium nitrate; the copper source is copper chloride; and the molybdenum source is molybdenum chloride.

[0017] Preferably, the mass ratio of the zinc source, silicon source, magnesium source, copper source, molybdenum source, alcohol solvent and sodium acetate in step I is (0.1-0.3):1:0.2:(0.1-0.3):0.1:(10-20):3.

[0018] Preferably, the alcohol solvent in step I is at least one of ethanol, ethylene glycol, and n-butanol.

[0019] Preferably, the calcination temperature in step I is 600-800° C. and the calcination time is 4-6 hours.

[0020] Preferably, the mass ratio of the porous nanoscale flame retardant oxide, expanded graphite, N,N-dimethylformamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide, and initiator in step II is 3:1:(15-25):0.6:0.3:(0.3-0.5):(0.01-0.03).

[0021] Preferably, the initiator in step II is azobisisobutyronitrile.

[0022] Preferably, the expanded graphite in step II has a particle size of 100 mesh, model 8080200, and is provided by Qingdao Baixing Graphite Co., Ltd.

[0023] Preferably, the inert gas in step II is any one of nitrogen, helium, neon and argon.

[0024] Another object of the present invention is to provide a method for preparing the high-efficiency non-halogen plastic flame retardant additive, comprising the following steps: mixing the raw materials by weight, ball milling and mixing, to obtain the high-efficiency non-halogen plastic flame retardant additive.

[0025] The beneficial effects of adopting the above technical solution are:

[0026] (1) The preparation method of the high-efficiency non-halogen plastic flame retardant provided by the present invention only requires mixing the raw materials. The process is simple, no special equipment is required, the preparation efficiency is high, and it is suitable for continuous industrial production. It has high promotion and application value.

[0027] (2) The high-efficiency non-halogen plastic flame retardant additive provided by the present invention is made of the following raw materials in parts by weight: 35-45 parts of a modified porous nano-scale flame retardant oxide / expanded graphite composite, 8-10 parts of an organic phosphinate metal salt, 10-12 parts of a phosphorus-based synergist, 10-12 parts of a nitrogen-based synergist, and 3-5 parts of a coupling agent; the modified porous nano-scale flame retardant oxide / expanded graphite composite is a porous nano-scale flame retardant oxide / expanded graphite composite co-modified with 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, and diphenyl (4-vinylphenyl) phosphine oxide. Through the synergistic effect of various raw materials, the flame retardant additive is environmentally friendly, has a significant flame retardant effect, requires minimal addition, exhibits excellent compatibility with the plastic matrix, and has minimal negative impact on the mechanical properties of the plastic matrix. It forms a stable carbonaceous layer on the plastic surface, effectively preventing the transfer of heat and oxygen, thereby significantly improving the plastic's flame retardancy. The high specific surface area of ​​the modified porous nano-scale flame retardant oxide / expanded graphite composite further enhances the flame retardant effect. Through the rational selection of raw materials and modifiers, the flame retardant additive not only combines the advantages of multiple flame retardant active ingredients, but also improves its compatibility with plastics, preventing agglomeration or delamination during use, thereby ensuring the plastic's processing performance and product quality.

[0028] (3) The high-efficiency non-halogen flame retardant additive for plastics provided by the present invention does not contain halogen and is safer and more environmentally friendly to use; the modified porous nano-scale flame retardant oxide / expanded graphite composite uses zinc source, silicon source, magnesium source, copper source, molybdenum source and expanded graphite as raw materials, and uses 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl cycloboroxine, and diphenyl (4-vinylphenyl) phosphine oxide as modifiers, so that the prepared flame retardant contains not only inorganic flame retardant active ingredients, but also flame retardant active ingredients such as amphoteric organic ion salts, cycloboroxine and phenylphosphine oxide structures. These structures can effectively improve the flame retardant effect under the effects of electronic effect, steric effect and conjugation effect, and at the same time improve the compatibility with plastics, so that it can still achieve good flame retardant effect when used in a smaller amount, and further reduce the negative impact on the mechanical properties of plastics. DETAILED DESCRIPTION

[0029] In order to enable those skilled in the art to better understand the technical solution of the present invention and to make the above-mentioned features, purposes and advantages of the present invention more clearly understood, the present invention is further described below in conjunction with examples. The examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0030] Example 1

[0031] A high-efficiency non-halogen flame retardant additive for plastics is prepared from the following raw materials in parts by weight: 35 parts of a modified porous nanoscale flame retardant oxide / expanded graphite composite, 8 parts of an organic phosphinate metal salt, 10 parts of a phosphorus-based synergist, 10 parts of a nitrogen-based synergist, and 3 parts of a coupling agent; the modified porous nanoscale flame retardant oxide / expanded graphite composite is a composite co-modified with 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, and diphenyl (4-vinylphenyl) phosphine oxide.

[0032] The coupling agent is silane coupling agent KH550; the nitrogen-based synergist is melamine; the phosphorus-based synergist is tricresyl phosphate; and the organic phosphinate metal salt is aluminum phosphinate.

[0033] The preparation method of the modified porous nano-scale flame-retardant oxide / expanded graphite composite comprises the following steps:

[0034] Step I: Disperse a zinc source, a silicon source, a magnesium source, a copper source, and a molybdenum source in an alcohol solvent, stir evenly, slowly add sodium acetate, transfer the mixture to a polytetrafluoroethylene-lined hydrothermal reactor, and react at 195°C for 15 hours; remove the reactor, wait for the reaction system to cool to room temperature, repeatedly wash with anhydrous ethanol and deionized water, then dry in a vacuum drying oven at 85°C for 10 hours, and finally calcine to obtain a porous nanoscale flame retardant oxide;

[0035] Step II: After the porous nano-scale flame retardant oxide and expanded graphite are uniformly mixed, they are dispersed in N,N-dimethylformamide, and then 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide and initiator are added thereto. The mixture is stirred and reacted at 60°C in an inert gas atmosphere for 3 hours, and then the solvent is removed by rotary evaporation to obtain a modified porous nano-scale flame retardant oxide / expanded graphite composite.

[0036] The zinc source in step I is zinc nitrate; the silicon source is sodium silicate; the magnesium source is magnesium nitrate; the copper source is copper chloride; and the molybdenum source is molybdenum chloride; the mass ratio of the zinc source, silicon source, magnesium source, copper source, molybdenum source, alcohol solvent, and sodium acetate in step I is 0.1:1:0.2:0.1:0.1:10:3; the alcohol solvent in step I is ethanol; the calcination temperature in step I is 600°C and the time is 4 hours.

[0037] The mass ratio of the porous nanoscale flame retardant oxide, expanded graphite, N,N-dimethylformamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide, and initiator in step II is 3:1:15:0.6:0.3:0.3:0.01; the initiator in step II is azobisisobutyronitrile; the particle size of the expanded graphite in step II is 100 mesh, model 8080200, and is provided by Qingdao Baixing Graphite Co., Ltd.; the inert gas in step II is nitrogen.

[0038] A preparation method of the high-efficiency non-halogen flame retardant additive for plastics comprises the following steps: mixing raw materials in parts by weight, and ball milling to uniformly mix the raw materials to obtain the high-efficiency non-halogen flame retardant additive for plastics.

[0039] Example 2

[0040] A high-efficiency non-halogen plastic flame retardant additive is prepared from the following raw materials in parts by weight: 37 parts of a modified porous nanoscale flame retardant oxide / expanded graphite composite, 8.5 parts of an organic phosphinate metal salt, 10.5 parts of a phosphorus-based synergist, 10.5 parts of a nitrogen-based synergist, and 3.5 parts of a coupling agent; the modified porous nanoscale flame retardant oxide / expanded graphite composite is a composite co-modified with 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, and diphenyl (4-vinylphenyl) phosphine oxide.

[0041] The coupling agent is silane coupling agent KH560; the nitrogen-based synergist is melamine cyanurate; the phosphorus-based synergist is triphenyl phosphate; and the organic phosphinate metal salt is aluminum phosphinate.

[0042] The preparation method of the modified porous nano-scale flame-retardant oxide / expanded graphite composite comprises the following steps:

[0043] Step I: Dispersing a zinc source, a silicon source, a magnesium source, a copper source, and a molybdenum source in an alcohol solvent, stirring uniformly, slowly adding sodium acetate, and transferring the mixture to a polytetrafluoroethylene-lined hydrothermal reactor for reaction at 200°C for 16 hours; removing the reactor, and after the reaction system is cooled to room temperature, repeatedly washing with anhydrous ethanol and deionized water, followed by drying in a vacuum drying oven at 87°C for 13 hours, and finally calcining to obtain a porous nanoscale flame retardant oxide;

[0044] Step II: After the porous nano-scale flame retardant oxide and expanded graphite are uniformly mixed, they are dispersed in N,N-dimethylformamide, and then 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, diphenyl (4-vinylphenyl) phosphine oxide and initiator are added thereto. The mixture is stirred and reacted at 63°C in an inert gas atmosphere for 3.5 hours, and then the solvent is removed by rotary evaporation to obtain a modified porous nano-scale flame retardant oxide / expanded graphite composite.

[0045] The zinc source in step I is zinc nitrate; the silicon source is silicon tetrachloride; the magnesium source is magnesium nitrate; the copper source is copper chloride; and the molybdenum source is molybdenum chloride; the mass ratio of the zinc source, silicon source, magnesium source, copper source, molybdenum source, alcohol solvent, and sodium acetate in step I is 0.15:1:0.2:0.15:0.1:13:3; the alcohol solvent in step I is ethylene glycol; the calcination temperature in step I is 650°C and the time is 4.5h.

[0046] The mass ratio of the porous nanoscale flame retardant oxide, expanded graphite, N,N-dimethylformamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide, and initiator in step II is 3:1:17:0.6:0.3:0.35:0.015; the initiator in step II is azobisisobutyronitrile; the particle size of the expanded graphite in step II is 100 mesh, model 8080200, and is provided by Qingdao Baixing Graphite Co., Ltd.; the inert gas in step II is helium.

[0047] A preparation method of the high-efficiency non-halogen flame retardant additive for plastics comprises the following steps: mixing raw materials in parts by weight, and ball milling to uniformly mix the raw materials to obtain the high-efficiency non-halogen flame retardant additive for plastics.

[0048] Example 3

[0049] A high-efficiency non-halogen plastic flame retardant additive is prepared from the following raw materials in parts by weight: 40 parts of a modified porous nanoscale flame retardant oxide / expanded graphite composite, 9 parts of an organic phosphinate metal salt, 11 parts of a phosphorus-based synergist, 11 parts of a nitrogen-based synergist, and 4 parts of a coupling agent; the modified porous nanoscale flame retardant oxide / expanded graphite composite is a composite co-modified with 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, and diphenyl (4-vinylphenyl) phosphine oxide.

[0050] The coupling agent is silane coupling agent KH570; the nitrogen-based synergist is ammonium polyphosphate; the phosphorus-based synergist is resorcinol bis(diphenyl phosphate); and the organic phosphinate metal salt is aluminum phosphinate.

[0051] The preparation method of the modified porous nano-scale flame-retardant oxide / expanded graphite composite comprises the following steps:

[0052] Step I: Disperse a zinc source, a silicon source, a magnesium source, a copper source, and a molybdenum source in an alcohol solvent, stir evenly, slowly add sodium acetate, transfer the mixture to a polytetrafluoroethylene-lined hydrothermal reactor, and react at 210°C for 18 hours; remove the reactor, wait for the reaction system to cool to room temperature, repeatedly wash with anhydrous ethanol and deionized water, then dry in a vacuum drying oven at 90°C for 15 hours, and finally calcine to obtain a porous nanoscale flame retardant oxide;

[0053] Step II: After the porous nano-scale flame retardant oxide and expanded graphite are uniformly mixed, they are dispersed in N,N-dimethylformamide, and then 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, diphenyl (4-vinylphenyl) phosphine oxide and initiator are added thereto. The mixture is stirred and reacted at 65°C in an inert gas atmosphere for 4 hours, and then the solvent is removed by rotary evaporation to obtain a modified porous nano-scale flame retardant oxide / expanded graphite composite.

[0054] The zinc source in step I is zinc nitrate; the silicon source is sodium silicate; the magnesium source is magnesium nitrate; the copper source is copper chloride; and the molybdenum source is molybdenum chloride; the mass ratio of the zinc source, silicon source, magnesium source, copper source, molybdenum source, alcohol solvent, and sodium acetate in step I is 0.2:1:0.2:0.2:0.1:15:3; the alcohol solvent in step I is n-butanol; the calcination temperature in step I is 700°C and the time is 5h.

[0055] The mass ratio of the porous nanoscale flame retardant oxide, expanded graphite, N,N-dimethylformamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide, and initiator in step II is 3:1:20:0.6:0.3:0.4:0.02; the initiator in step II is azobisisobutyronitrile; the particle size of the expanded graphite in step II is 100 mesh, model 8080200, and is provided by Qingdao Baixing Graphite Co., Ltd.; the inert gas in step II is neon.

[0056] A preparation method of the high-efficiency non-halogen flame retardant additive for plastics comprises the following steps: mixing raw materials in parts by weight, and ball milling to uniformly mix the raw materials to obtain the high-efficiency non-halogen flame retardant additive for plastics.

[0057] Example 4

[0058] A high-efficiency non-halogen flame retardant additive for plastics is prepared from the following raw materials in parts by weight: 43 parts of a modified porous nanoscale flame retardant oxide / expanded graphite composite, 9.5 parts of an organic phosphinate metal salt, 11.5 parts of a phosphorus-based synergist, 11.5 parts of a nitrogen-based synergist, and 4.5 parts of a coupling agent; the modified porous nanoscale flame retardant oxide / expanded graphite composite is a composite co-modified with 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, and diphenyl (4-vinylphenyl) phosphine oxide.

[0059] The coupling agent is a mixture of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570 in a mass ratio of 1:2:3; the nitrogen-based synergist is a mixture of melamine, melamine cyanurate, and ammonium polyphosphate in a mass ratio of 1:3:5; the phosphorus-based synergist is a mixture of tricresyl phosphate, triphenyl phosphate, and resorcinol bis(diphenyl phosphate) in a mass ratio of 1:1:2; and the organic phosphinate metal salt is aluminum phosphinate.

[0060] The preparation method of the modified porous nano-scale flame-retardant oxide / expanded graphite composite comprises the following steps:

[0061] Step I: Disperse a zinc source, a silicon source, a magnesium source, a copper source, and a molybdenum source in an alcohol solvent, stir evenly, slowly add sodium acetate, transfer the mixture to a polytetrafluoroethylene-lined hydrothermal reactor, and react at 215°C for 19 hours; remove the reactor, wait for the reaction system to cool to room temperature, repeatedly wash with anhydrous ethanol and deionized water, then dry in a vacuum drying oven at 93°C for 18 hours, and finally calcine to obtain a porous nanoscale flame retardant oxide;

[0062] Step II: After the porous nano-scale flame retardant oxide and expanded graphite are uniformly mixed, they are dispersed in N,N-dimethylformamide, and then 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide and initiator are added thereto. The mixture is stirred and reacted at 68° C. in an inert gas atmosphere for 4.5 hours, and then the solvent is removed by rotary evaporation to obtain a modified porous nano-scale flame retardant oxide / expanded graphite composite.

[0063] The zinc source in step I is zinc nitrate; the silicon source is sodium silicate; the magnesium source is magnesium nitrate; the copper source is copper chloride; and the molybdenum source is molybdenum chloride; the mass ratio of the zinc source, silicon source, magnesium source, copper source, molybdenum source, alcohol solvent, and sodium acetate in step I is 0.25:1:0.2:0.25:0.1:18:3; the alcohol solvent in step I is a mixture of ethanol, ethylene glycol, and n-butanol in a mass ratio of 2:1:1; the calcination temperature in step I is 750°C and the time is 5.5h.

[0064] The mass ratio of the porous nanoscale flame retardant oxide, expanded graphite, N,N-dimethylformamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide, and initiator in step II is 3:1:23:0.6:0.3:0.45:0.025; the initiator in step II is azobisisobutyronitrile; the particle size of the expanded graphite in step II is 100 mesh, model 8080200, and is provided by Qingdao Baixing Graphite Co., Ltd.; the inert gas in step II is argon.

[0065] A preparation method of the high-efficiency non-halogen flame retardant additive for plastics comprises the following steps: mixing raw materials in parts by weight, and ball milling to uniformly mix the raw materials to obtain the high-efficiency non-halogen flame retardant additive for plastics.

[0066] Example 5

[0067] A high-efficiency non-halogen flame retardant additive for plastics is prepared from the following raw materials in parts by weight: 45 parts of a modified porous nanoscale flame retardant oxide / expanded graphite composite, 10 parts of an organic phosphinate metal salt, 12 parts of a phosphorus-based synergist, 12 parts of a nitrogen-based synergist, and 5 parts of a coupling agent; the modified porous nanoscale flame retardant oxide / expanded graphite composite is a composite co-modified with 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinylboroxine, and diphenyl (4-vinylphenyl) phosphine oxide.

[0068] The coupling agent is silane coupling agent KH550; the nitrogen-based synergist is melamine; the phosphorus-based synergist is tricresyl phosphate; and the organic phosphinate metal salt is aluminum phosphinate.

[0069] The preparation method of the modified porous nano-scale flame-retardant oxide / expanded graphite composite comprises the following steps:

[0070] Step I: Disperse a zinc source, a silicon source, a magnesium source, a copper source, and a molybdenum source in an alcohol solvent, stir evenly, slowly add sodium acetate, transfer the mixture to a polytetrafluoroethylene-lined hydrothermal reactor, and react at 220°C for 20 hours; remove the reactor, wait for the reaction system to cool to room temperature, repeatedly wash with anhydrous ethanol and deionized water, then dry in a vacuum drying oven at 95°C for 20 hours, and finally calcine to obtain a porous nanoscale flame retardant oxide;

[0071] Step II: After the porous nano-scale flame retardant oxide and expanded graphite are uniformly mixed, they are dispersed in N,N-dimethylformamide, and then 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide and initiator are added thereto. The mixture is stirred and reacted at 70°C in an inert gas atmosphere for 5 hours, and then the solvent is removed by rotary evaporation to obtain a modified porous nano-scale flame retardant oxide / expanded graphite composite.

[0072] The zinc source in step I is zinc nitrate; the silicon source is silicon tetrachloride; the magnesium source is magnesium nitrate; the copper source is copper chloride; and the molybdenum source is molybdenum chloride; the mass ratio of the zinc source, silicon source, magnesium source, copper source, molybdenum source, alcohol solvent, and sodium acetate in step I is 0.3:1:0.2:0.3:0.1:20:3; the alcohol solvent in step I is ethanol; the calcination temperature in step I is 800°C and the time is 6 hours.

[0073] The mass ratio of the porous nanoscale flame retardant oxide, expanded graphite, N,N-dimethylformamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide, and initiator in step II is 3:1:25:0.6:0.3:0.5:0.03; the initiator in step II is azobisisobutyronitrile; the particle size of the expanded graphite in step II is 100 mesh, model 8080200, and is provided by Qingdao Baixing Graphite Co., Ltd.; the inert gas in step II is argon.

[0074] A preparation method of the high-efficiency non-halogen flame retardant additive for plastics comprises the following steps: mixing raw materials in parts by weight, and ball milling to uniformly mix the raw materials to obtain the high-efficiency non-halogen flame retardant additive for plastics.

[0075] Comparative Example 1

[0076] A high-efficiency non-halogen plastic flame retardant additive and a preparation method thereof are basically the same as Example 1, except that an equal amount of a silicon source is used instead of a molybdenum source; and an equal amount of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt is used instead of 2,4,6-trivinyl cycloboroxine.

[0077] Comparative Example 2

[0078] A high-efficiency non-halogen plastic flame retardant additive and a preparation method thereof, which are basically the same as Example 1, except that an equal amount of a silicon source is used instead of a copper source; and an equal amount of 2,4,6-trivinyl cycloboroxine is used instead of 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt.

[0079] The high-efficiency non-halogen plastic flame retardant additives prepared in Examples 1-5 and Comparative Examples 1-2 were respectively subjected to performance tests. The test results are shown in Table 1. The test method is as follows: the high-efficiency non-halogen plastic flame retardant additives prepared in each example were added to polypropylene resin (PP). The mass ratio of the high-efficiency non-halogen plastic flame retardant additive to PP was 10:90. The PP was a general-purpose homopolymer polypropylene with a grade of T30S. The limiting oxygen index test was performed in accordance with GB / T 2406.2-2009 "Determination of Combustion Behavior by Oxygen Index Method for Plastics - Part 2: Room Temperature Test". The flame retardant grade was evaluated with reference to UL94-2023; the tensile property test was performed with reference to GB / T1040.2-2006.

[0080] As can be seen from Table 1, the high-efficiency non-halogen plastic flame retardant additive disclosed in the embodiment of the present invention has better flame retardant effect and less negative impact on the mechanical properties of the plastic than the comparative example; the combined use of a molybdenum source, a copper source, a silicon source, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt and 2,4,6-trivinyl cycloboroxine is beneficial to improving the above-mentioned properties.

[0081] Table 1

[0082] Test items Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Tensile strength (MPa) 39.1 39.4 39.6 40.1 40.5 38.5 38.9 Limiting oxygen index (%) 35.2 35.6 36.3 36.6 37.1 29.4 28.9 Flame retardant grade V-0 V-0 V-0 V-0 V-0 V-1 V-1

[0083] The above shows and describes the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions merely illustrate the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and modifications are intended to fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. A high-efficiency non-halogen flame retardant additive for plastics, characterized in that: The invention is prepared from the following raw materials in parts by weight: 35-45 parts of modified porous nano-scale flame retardant oxide / expanded graphite composite, 8-10 parts of aluminum phosphinate, 10-12 parts of phosphorus synergist, 10-12 parts of nitrogen synergist, and 3-5 parts of coupling agent; The preparation method of the modified porous nano-scale flame-retardant oxide / expanded graphite composite comprises the following steps: Step I: Dispersing a zinc source, a silicon source, a magnesium source, a copper source, and a molybdenum source in an alcohol solvent, stirring evenly, slowly adding sodium acetate, transferring the mixture to a polytetrafluoroethylene-lined hydrothermal reactor, and reacting at 195-220° C. for 15-20 hours; removing the reactor, and after the reaction system is cooled to room temperature, repeatedly washing with anhydrous ethanol and deionized water, then drying in a vacuum drying oven at 85-95° C. for 10-20 hours, and finally calcining to obtain a porous nanoscale flame retardant oxide; the mass ratio of the zinc source, silicon source, magnesium source, copper source, molybdenum source, alcohol solvent, and sodium acetate is (0.1-0.3):1:0.2:(0.1-0.3):0.1:(10-20):3; Step II: After the porous nano-scale flame retardant oxide and expanded graphite are uniformly mixed, they are dispersed in N,N-dimethylformamide, and then 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide and initiator are added thereto. The mixture is stirred and reacted at 60-70° C. in an inert gas atmosphere for 3-5 hours, and then the solvent is removed by rotary evaporation to obtain a modified porous nano-scale flame retardant oxide / expanded graphite composite.

2. The high-efficiency non-halogen flame retardant additive for plastics according to claim 1, characterized in that: The coupling agent is any one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570, or a combination of several thereof; the nitrogen-based synergist is one or more of melamine, melamine cyanurate, and ammonium polyphosphate.

3. The high-efficiency non-halogen flame retardant additive for plastics according to claim 1, characterized in that: The phosphorus-based synergist is one or more of tricresyl phosphate, triphenyl phosphate, and resorcinol bis(diphenyl phosphate).

4. The high-efficiency non-halogen flame retardant additive for plastics according to claim 1, characterized in that: The zinc source is zinc nitrate; the silicon source is at least one of sodium silicate and silicon tetrachloride; the magnesium source is magnesium nitrate; the copper source is copper chloride; and the molybdenum source is molybdenum chloride.

5. The high-efficiency non-halogen flame retardant additive for plastics according to claim 1, characterized in that: The alcohol solvent in step I is at least one of ethanol, ethylene glycol, and n-butanol; the calcination temperature in step I is 600-800° C., and the calcination time is 4-6 hours.

6. The high-efficiency non-halogen flame retardant additive for plastics according to claim 1, characterized in that: The mass ratio of the porous nanoscale flame retardant oxide, expanded graphite, N,N-dimethylformamide, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, 2,4,6-trivinyl boroxine, diphenyl (4-vinylphenyl) phosphine oxide, and initiator in step II is 3:1:(15-25):0.6:0.3:(0.3-0.5):(0.01-0.03).

7. The high-efficiency non-halogen flame retardant additive for plastics according to claim 1, characterized in that: The initiator in step II is azobisisobutyronitrile; the particle size of the expanded graphite in step II is 100 mesh, and the model is 8080200.

8. The high-efficiency non-halogen flame retardant additive for plastics according to claim 1, characterized in that: The inert gas in step II is any one of nitrogen, helium, neon and argon.

9. A method for preparing a high-efficiency non-halogen flame retardant additive for plastics according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing raw materials according to weight parts, and evenly mixing them through ball milling to obtain a high-efficiency non-halogen plastic flame retardant additive.