CN116003923B - Low-smoke flame-retardant rubber compound and preparation method thereof - Google Patents
Low-smoke flame-retardant rubber compound and preparation method thereof Download PDFInfo
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- CN116003923B CN116003923B CN202310178373.7A CN202310178373A CN116003923B CN 116003923 B CN116003923 B CN 116003923B CN 202310178373 A CN202310178373 A CN 202310178373A CN 116003923 B CN116003923 B CN 116003923B
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The invention relates to a low-smoke flame-retardant rubber compound and a preparation method thereof, belonging to the technical field of rubber production. The low-smoke flame-retardant rubber compound consists of ethylene propylene diene monomer, fluororubber, chloroprene rubber, a white carbon black composite aluminum hydroxide modified flame retardant, a flame retardant microcapsule, an accelerator, a vulcanizing agent, a filler and a lubricant, wherein the combination of the white carbon black composite aluminum hydroxide modified flame retardant and the flame retardant microcapsule synergistically improves the flame retardant performance of a rubber compound formed by the ethylene propylene diene monomer, fluororubber and chloroprene rubber. The oxygen index can reach more than 30% according to GB/T10707 test.
Description
The present application claims priority from chinese patent application No. 202210947196.X filed on month 08 and 09 of 2022.
Technical Field
The invention belongs to the technical field of rubber preparation, and relates to a low-smoke flame-retardant rubber compound and a preparation method thereof.
Background
The rubber product is widely used in various fields such as road traffic, house construction, medical engineering, aerospace navigation and the like, and plays an important role in promoting urban construction and improving people's life. However, because the main constituent elements of the rubber are carbon and hydrogen, the rubber is extremely easy to burn, especially nitrile rubber and some rubber containing halogen are extremely flammable, and the generated dense smoke and toxic gas during combustion not only cause harm to the environment, but also form a great threat to the life and property safety of people. In the prior art, flame retardant properties of rubber are generally improved by adding flame retardants. The flame retardant is also called as flame retardant, fire retardant or fire retardant, is a functional material for endowing inflammable polymer with flame retardancy, and can effectively delay the ignition time of rubber when being attacked by external fire source, reduce the flame propagation speed and rapidly and automatically extinguish after leaving the fire source even if the rubber has flame retardancy and self-extinguishing property. The use of flame retardants has a great protective effect on the life and property safety of humans, and is therefore widely used in polymeric materials, rapidly developing.
Existing flame retardants mainly include two classes: most of the additive type and the reaction type are added flame retardants in rubber products, wherein halogen flame retardants are widely used due to good flame retardant effect, small influence on the performance of materials and high cost performance, and mainly comprise chlorinated paraffin, tetrabromobisphenol A and decabromodiphenyl ether, but the halogen flame retardants release corrosive gas, toxic substances and a large amount of harmful smog in the flame retardant process due to the defects of environmental protection, and developed countries such as Europe and the like are sequentially provided with regulations to restrict the use of the halogen flame retardants, so that the use amount of the halogen flame retardants is gradually reduced. The non-halogen flame retardant mainly comprises an organic phosphorus flame retardant, an inorganic flame retardant and the like. Among them, the organic phosphorus flame retardant has less influence on the physical and mechanical properties of the polymer and has better compatibility with the polymer, and is favored in recent years. However, most of the organic phosphorus flame retardants are liquid, and have the defects of strong volatility, large smoke generation amount and poor heat stability. Inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, red phosphorus, zinc borate, antimony oxide and the like, and have the advantages of good stability, non-volatility, rich raw material sources, environmental friendliness and the like, but the inorganic flame retardants generally need to have large filling quantity and poor compatibility with high polymer materials, so that the rubber has poor fluidity during mixing and molding, and the processing and mechanical properties of the synthetic materials are reduced, so that the application of the inorganic flame retardants is limited.
Patent publication number CN106188700a discloses a flame retardant rubber composition and a method for producing a flame retardant rubber, wherein the method for producing comprises: mixing styrene-butadiene rubber, natural rubber, methyl dimethyl phosphate, ethyl diethyl phosphate, a scorch retarder and an accelerator, and then mixing to obtain the flame-retardant rubber. The flame retardants in the patent are all common flame retardants and simply combined to have common flame retardant effect.
Patent CN102040779a discloses a flame retardant rubber and a preparation method thereof, the flame retardant rubber is obtained by mixing and vulcanizing a mixture containing ethylene-propylene-diene monomer, modified polybutadiene, a vulcanizing agent and a hydroxide flame retardant. According to the invention, the hydroxide flame retardant is modified by the modified polybutadiene, so that the compatibility of the hydroxide flame retardant in the ethylene propylene diene monomer is improved, and the flame retardant effect is enhanced.
Patent CN110128726a discloses a stepped flame retardant rubber material, which comprises the following components in parts by weight: 80-120 parts of rubber, 80-200 parts of flame retardant, 40-60 parts of filler and 0.3-2 parts of auxiliary agent, wherein the flame retardant is inorganic flame retardant powder coated with a high polymer modifier on the surface; the preparation method comprises the following steps: and (3) preparing and modifying inorganic flame retardant powder, and preparing a flame retardant rubber material. According to the invention, by adjusting the rubber formula, the flame retardant materials and different fillers are added into the rubber, so that different flame retardant shells can be formed on rubber products at different temperatures, and the multi-stage flame retardant effect is achieved.
Patent CN112592540a discloses a flame retardant rubber for coal mine, which is prepared from the following raw materials in parts by weight: 1-2 parts of triethylamine, 10-14 parts of tributyl citrate, 30-40 parts of zinc hydroxystannate, 3-4 parts of stearic acid, 5-7 parts of gamma-mercaptopropyl trimethoxy silane, 2-3 parts of N-phenylaniline, 60-70 parts of methyl methacrylate, 2-3 parts of ammonium persulfate, 190-210 parts of ethylene propylene diene monomer, 1-2 parts of accelerator and 1-2 parts of sulfur. The invention realizes further coating of the polyester on the coating filler, thereby improving the surface activity of zinc hydroxystannate, leading the polyester-coated filler to be well dispersed in the rubber substrate and improving the flame retardant effect.
Patent publication No. CN108641148A discloses a preparation method of a composite flame retardant rubber material, and belongs to the technical field of high polymer materials. According to the invention, aluminum sulfide hexahydrate, magnesium chloride hexahydrate and absolute ethyl alcohol are heated, stirred and mixed to obtain a mixed solution; stirring and mixing the mixed solution and the modified dispersing agent, dropwise adding acetic acid solution with the volume of 0.01-0.02 times of the mixed solution, dropwise adding ammonia water for precipitation, aging, filtering, washing and drying to obtain modified filter residues; plasticating the matrix rubber, adding modified filter residues, waste rubber powder, magnesium stearate, a vulcanizing agent, an anti-aging agent, an accelerator and pretreated carbonized rice hull powder, mixing, calendaring and vulcanizing to obtain the composite flame-retardant rubber material. According to the invention, the aluminum sulfide hexahydrate and the magnesium chloride hexahydrate are modified by the modified dispersing agent so as to improve the compatibility of the aluminum sulfide hexahydrate and the magnesium chloride hexahydrate in rubber materials and enhance the flame retardant effect of the aluminum sulfide hexahydrate and the magnesium chloride hexahydrate.
Patent publication No. CN111073289A discloses a sensitive plant element modified graphene oxide flame-retardant silicone rubber, which takes silicone rubber as base rubber, uses a pyridine structure in sensitive plant element for modifying graphene oxide to obtain a sensitive plant element modified graphene oxide flame retardant, and blends the sensitive plant element modified graphene oxide flame retardant with silicone rubber to obtain the flame-retardant silicone rubber with higher flame retardant property. Compared with the existing flame-retardant silicone rubber, the flame retardance of the silicone rubber obtained by blending the novel mimin modified graphene oxide flame retardant and the silicone rubber is effectively improved.
Patent publication No. CN114437580A discloses a graphene composite magnesium hydroxide modified flame retardant for fire control and a preparation method thereof, wherein each liter of the flame retardant is prepared from the following raw materials: 6-10 g of graphene, 290-320 g of magnesium hydroxide, 50-70 g of zinc borate, 4-6 mL of coupling agent, 162-190 g of surfactant and the balance of water; the preparation method comprises the steps of mixing graphene, magnesium hydroxide, zinc borate and a coupling agent in proportion and grinding to obtain a mixture; mixing the mixture with a surfactant, adding water, heating to 70-80 ℃ under stirring, and preserving heat for at least 1h to obtain the modified surfactant. The invention provides a novel emulsion flame retardant, which is characterized in that magnesium hydroxide and zinc borate coated by a coupling agent are fully dispersed on the surface of graphene, and then are stably dispersed into emulsion under the action of a surfactant.
Disclosure of Invention
The invention aims to provide a low-smoke flame-retardant rubber compound and a preparation method thereof, and belongs to the technical field of rubber production. The low-smoke flame-retardant rubber compound consists of ethylene propylene diene monomer, fluororubber, chloroprene rubber, a white carbon black composite aluminum hydroxide modified flame retardant, a flame retardant microcapsule, an accelerator, a vulcanizing agent, a filler and a lubricant, wherein the combination of the white carbon black composite aluminum hydroxide modified flame retardant and the flame retardant microcapsule synergistically improves the flame retardant performance of a rubber compound formed by the ethylene propylene diene monomer, fluororubber and chloroprene rubber. The oxygen index can reach more than 30% according to GB/T10707 test.
The aim of the invention can be achieved by the following technical scheme:
the low-smoke flame-retardant rubber compound consists of 50-60 parts by weight of ethylene propylene diene monomer rubber, 30-45 parts by weight of fluororubber, 25-35 parts by weight of chloroprene rubber, 40-50 parts by weight of filler, 5-9 parts by weight of white carbon black composite aluminum hydroxide modified flame retardant, 3-8 parts by weight of flame retardant microcapsule, 3-8 parts by weight of accelerator, 2-5 parts by weight of vulcanizing agent and 1-3 parts by weight of lubricant.
As a preferable technical scheme of the invention, the white carbon black composite aluminum hydroxide modified flame retardant is prepared by the following method: mixing the fumed silica and the aluminum hydroxide according to a proportion, grinding the mixture to the particle size of 10-20nm to obtain a mixture, adding the titanate coupling agent and the surfactant sodium stearyl sulfate, adding water, stirring and heating to 50-60 ℃ to obtain the white carbon black composite aluminum hydroxide modified flame retardant.
As a preferable technical scheme of the invention, the addition amounts of the fumed silica, the aluminum hydroxide, the titanate coupling agent and the surfactant sodium stearyl sulfate are respectively as follows: 20-35 parts of fumed silica, 30-40 parts of aluminum hydroxide, 10-15 parts of titanate coupling agent and 35-45 parts of surfactant sodium stearyl sulfate.
As a preferable technical scheme of the invention, the preparation method of the flame retardant microcapsule comprises the following steps:
(1) Iron oxide, zinc oxide and methyl methacrylate are put into water and stirred to form mixed solution;
(2) Dissolving styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding a styrene solution and an initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating in a water bath to 80-90 ℃, generating copolymerization reaction between styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin, depositing the copolymer resin on the surfaces of ferric oxide and zinc oxide, and wrapping the copolymer resin to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
As a preferable technical scheme of the invention, the addition amounts of the ferric oxide, the zinc oxide, the methyl methacrylate, the styrene and the initiator are respectively as follows: 12-20 parts of ferric oxide, 8-15 parts of zinc oxide, 40-50 parts of methyl methacrylate, 10-20 parts of styrene and 0.01-0.05 part of initiator t-butyl peroxyacetate.
As a preferable technical scheme of the invention, the accelerator is one of zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate and zinc dimethyl dithiocarbamate.
As a preferable technical scheme of the invention, the vulcanizing agent is one of sulfur, 4' -dimorpholine disulfide and 2,4, 6-trimercapto-s-triazine.
As a preferable technical scheme of the invention, the filler consists of talcum powder, silicon micropowder and calcium carbonate, and the mass ratio of the talcum powder to the silicon micropowder is 1-3:1-5:2-6.
As a preferable technical scheme of the invention, the lubricant is one of ethylene bis-stearamide and pentaerythritol stearate.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: and mixing ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
The invention has the beneficial effects that:
(1) According to the invention, methyl methacrylate is dissolved in water, styrene is dissolved in n-hexane, ferric oxide and zinc oxide are dispersed in water in advance, two completely mutually incompatible solvents of water and n-hexane are selected to respectively dissolve two polymerization monomers, when an initiator is added and the reaction temperature is heated, interfacial polymerization is carried out on the interface of the mutually incompatible solvents through styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin, the methyl methacrylate-styrene copolymer resin is deposited on the surfaces of the ferric oxide and the zinc oxide, the ferric oxide and the zinc oxide are wrapped to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores, the copolymerization product of the styrene and the methyl methacrylate can be uniformly dispersed on the surfaces of the ferric oxide and the zinc oxide and wrapped to take the styrene and the methyl methacrylate as comonomers, the compatibility between the styrene and the methyl methacrylate as comonomers is better than that between the styrene-ethylene propylene diene monomer, the fluororubber and the chloroprene rubber is finally, the zinc oxide and the ferric oxide serving as flame retardants are uniformly dispersed in the rubber, the structure greatly enhances the flame retardant property of the inorganic oxidizing agents in the ethylene-propylene diene rubber, the fluororubber and the formed rubber, and the formed rubber are further enhanced;
(2) The low-smoke flame-retardant rubber compound comprises a white carbon black composite aluminum hydroxide modified flame retardant, wherein white carbon black and aluminum hydroxide which are ground to have the particle size of 10-20nm are selected in the preparation process, so that the white carbon black and the aluminum hydroxide are uniformly dispersed in water, the dispersion property of octadecyl sodium sulfate is matched, the surface composite modification is carried out on the white carbon black and the aluminum hydroxide by a titanate coupling agent and a surfactant, namely octadecyl sodium sulfate, the compatibility of the obtained white carbon black composite aluminum hydroxide modified flame retardant in rubber compound formed by ethylene propylene diene monomer, fluororubber and chloroprene rubber is obviously improved, the compatibility between the white carbon black composite aluminum hydroxide modified flame retardant and the rubber compound is better, meanwhile, the white carbon black and the aluminum hydroxide can also synergistically play a flame retardant role, and the low smoke and flame retardant property of a system are further enhanced;
(3) The combination of the white carbon black composite aluminum hydroxide modified flame retardant and the flame retardant microcapsule in the low-smoke flame-retardant rubber compound synergistically improves the flame retardant property of the rubber compound formed by ethylene propylene diene monomer, fluororubber and chloroprene rubber. The oxygen index can reach more than 30% according to GB/T10707 test.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific embodiments, structures, features and effects according to the present invention in conjunction with examples.
Example 1
The low-smoke flame-retardant rubber compound consists of 50 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 29 parts by weight of neoprene, 43 parts by weight of filler (14 parts by weight of talcum powder, 14 parts by weight of silica powder and 15 parts by weight of calcium carbonate), 5 parts by weight of white carbon black composite aluminum hydroxide modified flame retardant, 4 parts by weight of flame retardant microcapsule, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto-s-triazine and 2 parts by weight of lubricant ethylene bis-stearamide.
The white carbon black composite aluminum hydroxide modified flame retardant is prepared by the following method: mixing 25 parts by weight of fumed silica and 30 parts by weight of aluminum hydroxide, grinding the mixture to the particle size of 10-20nm to obtain a mixture, adding 11 parts by weight of titanate coupling agent and 38 parts by weight of surfactant sodium stearyl sulfate, adding water, stirring and heating to 55 ℃ to obtain the white carbon black composite aluminum hydroxide modified flame retardant.
The preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 12 parts by weight of ferric oxide, 10 parts by weight of zinc oxide and 44 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 16 parts by weight of styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding the styrene solution and 0.03 weight part of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating to 85 ℃ in a water bath, and carrying out copolymerization reaction on styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin which is deposited on the surfaces of ferric oxide and zinc oxide and wraps the surface of the ferric oxide and the zinc oxide to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Example 2
The low-smoke flame-retardant rubber compound consists of 58 parts by weight of ethylene propylene diene monomer rubber, 32 parts by weight of fluororubber, 28 parts by weight of chloroprene rubber, 40 parts by weight of filler (14 parts by weight of talcum powder, 12 parts by weight of silica powder and 14 parts by weight of calcium carbonate), 6 parts by weight of white carbon black composite aluminum hydroxide modified flame retardant, 3 parts by weight of flame retardant microcapsule, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 4 parts by weight of vulcanizing agent 4,4' -dimorpholine disulfide and 2 parts by weight of lubricant ethylene distearamide.
The white carbon black composite aluminum hydroxide modified flame retardant is prepared by the following method: mixing 22 parts by weight of fumed silica and 39 parts by weight of aluminum hydroxide, grinding the mixture to the particle size of 10-20nm to obtain a mixture, adding 15 parts by weight of titanate coupling agent and 35 parts by weight of surfactant sodium stearyl sulfate, adding water, stirring and heating to 50 ℃ to obtain the white carbon black composite aluminum hydroxide modified flame retardant.
The preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 18 parts by weight of ferric oxide, 12 parts by weight of zinc oxide and 46 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 14 parts by weight of styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding the styrene solution and 0.05 part by weight of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating to 90 ℃ in a water bath, and carrying out copolymerization reaction on styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin which is deposited on the surfaces of ferric oxide and zinc oxide and wraps the surface of the ferric oxide and the zinc oxide to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Example 3
The low-smoke flame-retardant rubber compound consists of 60 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 25 parts by weight of chloroprene rubber, 46 parts by weight of filler (13 parts by weight of talcum powder, 16 parts by weight of silica powder and 17 parts by weight of calcium carbonate), 8 parts by weight of white carbon black composite aluminum hydroxide modified flame retardant, 5 parts by weight of flame retardant microcapsule, 3 parts by weight of accelerator zinc dimethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto-s-triazine and 1 part by weight of lubricant ethylene bis-stearamide.
The white carbon black composite aluminum hydroxide modified flame retardant is prepared by the following method: mixing 30 parts by weight of fumed silica and 30 parts by weight of aluminum hydroxide, grinding the mixture to the particle size of 10-20nm to obtain a mixture, adding 13 parts by weight of titanate coupling agent and 40 parts by weight of surfactant sodium stearyl sulfate, adding water, stirring and heating to 60 ℃ to obtain the white carbon black composite aluminum hydroxide modified flame retardant.
The preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 19 parts by weight of ferric oxide, 12 parts by weight of zinc oxide and 40 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 15 parts by weight of styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding the styrene solution and 0.02 weight part of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating to 80 ℃ in a water bath, and carrying out copolymerization reaction on styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin which is deposited on the surfaces of ferric oxide and zinc oxide and wraps the surface of the ferric oxide and the zinc oxide to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Comparative example 1
The low-smoke flame-retardant rubber compound consists of 50 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 29 parts by weight of chloroprene rubber, 43 parts by weight of filler (14 parts by weight of talcum powder, 14 parts by weight of silica powder and 15 parts by weight of calcium carbonate), 9 parts by weight of white carbon black composite aluminum hydroxide modified flame retardant, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto-s-triazine and 2 parts by weight of lubricant ethylene bis-stearamide.
The white carbon black composite aluminum hydroxide modified flame retardant is prepared by the following method: mixing 25 parts by weight of weather white carbon black and 30 parts by weight of aluminum hydroxide, grinding the mixture to the particle size of 10-20nm to obtain a mixture, adding 11 parts by weight of titanate coupling agent and 38 parts by weight of surfactant sodium stearyl sulfate, adding water, stirring and heating to 55 ℃ to obtain the white carbon black composite aluminum hydroxide modified flame retardant.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Comparative example 2
The low-smoke flame-retardant rubber compound consists of 50 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 29 parts by weight of chloroprene rubber, 43 parts by weight of filler (14 parts by weight of talcum powder, 14 parts by weight of silica micropowder and 15 parts by weight of calcium carbonate), 9 parts by weight of flame retardant microcapsule, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto-s-triazine and 2 parts by weight of lubricant ethylene bis-stearamide.
The preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 12 parts by weight of ferric oxide, 10 parts by weight of zinc oxide and 44 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 16 parts by weight of styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding the styrene solution and 0.03 weight part of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating to 85 ℃ in a water bath, and carrying out copolymerization reaction on styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin which is deposited on the surfaces of ferric oxide and zinc oxide and wraps the surface of the ferric oxide and the zinc oxide to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Comparative example 3
The low-smoke flame-retardant rubber compound consists of 50 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 29 parts by weight of neoprene, 43 parts by weight of filler (14 parts by weight of talcum powder, 14 parts by weight of silica powder and 15 parts by weight of calcium carbonate), 2.3 parts by weight of fumed silica, 2.7 parts by weight of aluminum hydroxide, 4 parts by weight of flame retardant microcapsules, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto-s-triazine and 2 parts by weight of lubricant ethylene bis-stearamide.
The preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 12 parts by weight of ferric oxide, 10 parts by weight of zinc oxide and 44 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 16 parts by weight of styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding the styrene solution and 0.03 weight part of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating to 85 ℃ in a water bath, and carrying out copolymerization reaction on styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin which is deposited on the surfaces of ferric oxide and zinc oxide and wraps the surface of the ferric oxide and the zinc oxide to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, fumed silica, aluminum hydroxide, flame retardant microcapsules, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Comparative example 4
The low-smoke flame-retardant rubber compound consists of 50 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 29 parts by weight of neoprene, 43 parts by weight of filler (14 parts by weight of talcum powder, 14 parts by weight of silica powder and 15 parts by weight of calcium carbonate), 5 parts by weight of white carbon black composite aluminum hydroxide modified flame retardant, 2.2 parts by weight of ferric oxide, 1.8 parts by weight of zinc oxide, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto s-triazine and 2 parts by weight of lubricant ethylene bis-stearamide.
The white carbon black composite aluminum hydroxide modified flame retardant is prepared by the following method: mixing 25 parts by weight of fumed silica and 30 parts by weight of aluminum hydroxide, grinding the mixture to the particle size of 10-20nm to obtain a mixture, adding 11 parts by weight of titanate coupling agent and 38 parts by weight of surfactant sodium stearyl sulfate, adding water, stirring and heating to 55 ℃ to obtain the white carbon black composite aluminum hydroxide modified flame retardant.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, ferric oxide, zinc oxide, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Comparative example 5
The low-smoke flame-retardant rubber compound consists of 50 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 29 parts by weight of neoprene, 43 parts by weight of filler (14 parts by weight of talcum powder, 14 parts by weight of silica micropowder and 15 parts by weight of calcium carbonate), 5 parts by weight of white carbon black modified flame retardant, 4 parts by weight of flame retardant microcapsule, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto-s-triazine and 2 parts by weight of lubricant ethylene bis-stearamide.
The white carbon black modified flame retardant is prepared by the following method: grinding 55 parts by weight of fumed silica to a particle size of 10-20nm to obtain a mixture, adding 11 parts by weight of titanate coupling agent and 38 parts by weight of surfactant sodium stearyl sulfate, adding water, stirring and heating to 55 ℃ to obtain the white carbon black modified flame retardant.
The preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 12 parts by weight of ferric oxide, 10 parts by weight of zinc oxide and 44 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 16 parts by weight of styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding the styrene solution and 0.03 weight part of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating to 85 ℃ in a water bath, and carrying out copolymerization reaction on styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin which is deposited on the surfaces of ferric oxide and zinc oxide and wraps the surface of the ferric oxide and the zinc oxide to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
Comparative example 6
The low-smoke flame-retardant rubber compound consists of 50 parts by weight of ethylene propylene diene monomer rubber, 35 parts by weight of fluororubber, 29 parts by weight of chloroprene rubber, 43 parts by weight of filler (14 parts by weight of talcum powder, 14 parts by weight of silica micropowder and 15 parts by weight of calcium carbonate), 5 parts by weight of aluminum hydroxide modified flame retardant, 4 parts by weight of flame retardant microcapsule, 3 parts by weight of accelerator zinc diethyl dithiocarbamate, 2 parts by weight of vulcanizing agent 2,4, 6-trimercapto-s-triazine and 2 parts by weight of lubricant ethylene bis-stearamide.
The aluminum hydroxide modified flame retardant is prepared by the following method: 55 parts by weight of aluminum hydroxide is ground to have the particle size of 10-20nm to obtain a mixture, 11 parts by weight of titanate coupling agent and 38 parts by weight of surfactant sodium stearyl sulfate are added, and then water is added, stirring and heating are carried out to 55 ℃ to obtain the aluminum hydroxide modified flame retardant.
The preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 12 parts by weight of ferric oxide, 10 parts by weight of zinc oxide and 44 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 16 parts by weight of styrene in n-hexane to form a styrene solution;
(3) Under the protection of inert gas, adding the styrene solution and 0.03 weight part of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), heating to 85 ℃ in a water bath, and carrying out copolymerization reaction on styrene and methyl methacrylate to generate methyl methacrylate-styrene copolymer resin which is deposited on the surfaces of ferric oxide and zinc oxide and wraps the surface of the ferric oxide and the zinc oxide to form a microcapsule structure taking the resin as a shell and taking the ferric oxide and the zinc oxide as cores;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
The preparation method of the low-smoke flame-retardant rubber compound comprises the following steps: mixing the ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
The low smoke flame retardant rubber compounds of examples 1 to 3 and comparative examples 1 to 6 were measured for self-extinguishing time of the materials according to UL-94, oxygen index of the materials according to GB/T10107-89, and the final test results are shown in Table 1 below, and it can be seen from the test results:
TABLE 1 flame retardant Property test results of Low Smoke flame retardant rubber Compound
The low-smoke flame-retardant rubber compound of comparative example 1 replaces the same quality white carbon black composite aluminum hydroxide modified flame retardant and flame retardant microcapsule with the white carbon black composite aluminum hydroxide modified flame retardant on the basis of the low-smoke flame-retardant rubber compound of example 1, the self-extinguishing time is 1.6s longer than that of example 1, and the oxygen index is 11.8% lower than that of example 1; the low-smoke flame-retardant rubber compound of comparative example 2 replaces the white carbon black composite aluminum hydroxide modified flame retardant and flame retardant microcapsule with the same quality with microcapsule on the basis of the low-smoke flame-retardant rubber compound of example 1, the self-extinguishing time is 2.1s longer than that of example 1, and the oxygen index is 13.2% lower than that of example 1; the carbon black composite aluminum hydroxide modified flame retardant and the flame retardant microcapsule are shown to synergistically improve the flame retardant property of the rubber material.
The low-smoke flame-retardant rubber compound of the comparative example 3 is prepared by mixing and modifying the white carbon black and the aluminum hydroxide by the gas phase method on the basis of the low-smoke flame-retardant rubber compound of the example 1, the self-extinguishing time is 2.7s longer than that of the example 1, and the oxygen index is 14.1 percent lower than that of the example 1; the low smoke flame retardant rubber compound of comparative example 4 was not coated with iron oxide and zinc oxide on the basis of the low smoke flame retardant rubber compound of example 1, and had a self-extinguishing time 2.5s longer than that of example 1 and an oxygen index 13.8% lower than that of example 1; the method has the advantages that the mixing modification of the white carbon black and the aluminum hydroxide by the gas phase method and the wrapping modification of the ferric oxide and the zinc oxide can enhance the low smoke and flame retardant performance of the system;
the low smoke flame retardant rubber compound of comparative example 5 replaces the white carbon black composite aluminum hydroxide modified flame retardant with equal quality with the white carbon black modified flame retardant based on the low smoke flame retardant rubber compound of example 1, the self-extinguishing time is 1.0s longer than that of example 1, and the oxygen index is 5.3% lower than that of example 1; comparative example 6 the same mass of white carbon black composite aluminum hydroxide modified flame retardant was replaced with the aluminum hydroxide modified flame retardant on the basis of example 1, which had a self-extinguishing time 1.0s longer than that of example 1 and an oxygen index 5.3% lower than that of example 1; the white carbon black and the aluminum hydroxide can also synergistically play a role in flame retardance, so that the low smoke and flame retardance of the system are further enhanced.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. The low-smoke flame-retardant rubber compound is characterized by comprising 50-60 parts by weight of ethylene propylene diene monomer rubber, 30-45 parts by weight of fluororubber, 25-35 parts by weight of chloroprene rubber, 40-50 parts by weight of filler, 5-9 parts by weight of white carbon black composite aluminum hydroxide modified flame retardant, 3-8 parts by weight of flame retardant microcapsule, 3-8 parts by weight of accelerator, 2-5 parts by weight of vulcanizing agent and 1-3 parts by weight of lubricant;
the white carbon black composite aluminum hydroxide modified flame retardant is prepared by the following method: mixing 20-35 parts by weight of fumed silica and 30-40 parts by weight of aluminum hydroxide, grinding to a particle size of 10-20nm to obtain a mixture, adding 10-15 parts by weight of titanate coupling agent and 35-45 parts by weight of surfactant sodium stearyl sulfate, adding water, stirring and heating to 50-60 ℃ to obtain the white carbon black composite aluminum hydroxide modified flame retardant;
the preparation method of the flame retardant microcapsule comprises the following steps:
(1) Adding 12-20 parts by weight of ferric oxide, 8-15 parts by weight of zinc oxide and 40-50 parts by weight of methyl methacrylate into water, and stirring to form a mixed solution;
(2) Dissolving 10-20 parts by weight of styrene in normal hexane to form a styrene solution;
(3) Under the protection of inert gas, adding a styrene solution and 0.01-0.05 part by weight of initiator tert-butyl peroxyacetate into the mixed solution in the step (1), and heating in a water bath to 80-90 ℃ to obtain a microcapsule structural substance;
(4) Filtering, washing and drying to obtain the flame retardant microcapsule.
2. The low smoke, flame retardant rubber compound of claim 1 wherein said accelerator is one of zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate and zinc dimethyldithiocarbamate.
3. The low smoke flame retardant rubber compound according to claim 1, wherein said vulcanizing agent is one of sulfur, 4' -dimorpholine disulfide and 2,4, 6-trimercapto-s-triazine.
4. The low-smoke flame-retardant rubber compound according to claim 1, wherein the filler consists of talcum powder, silicon micropowder and calcium carbonate, and the mass ratio is 1-3:1-5:2-6.
5. The low smoke, flame retardant rubber compound of claim 1 wherein said lubricant is one of ethylene bis stearamide and pentaerythritol stearate.
6. A method of preparing a low smoke flame retardant rubber compound according to any one of claims 1 to 5, comprising the steps of: and mixing ethylene propylene diene monomer rubber, fluororubber, chloroprene rubber, filler, white carbon black composite aluminum hydroxide modified flame retardant, flame retardant microcapsule, accelerator, vulcanizing agent and lubricant, and then mixing to obtain the low-smoke flame retardant rubber compound.
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