CN114181536A - Flame-retardant silicone rubber material and preparation method and application thereof - Google Patents
Flame-retardant silicone rubber material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant silicon rubber material and a preparation method and application thereof, wherein the flame-retardant silicon rubber material comprises the following components in parts by weight: 100 parts of silicon rubber, 30-60 parts of white carbon black, 6-12 parts of a structure regulator, 20-55 parts of a phosphorus-nitrogen-silicon flame retardant, 0.3-5 parts of a plasticizer, 25-50 parts of a filler and 2-7 parts of a vulcanizing agent. The flame-retardant silicon rubber material has good physical and mechanical properties and excellent flame-retardant property, the components in the flame-retardant silicon rubber material have good compatibility and dispersibility, and the components have synergistic action, so that the mechanical properties such as tensile strength and tearing strength, the thermal aging property, the flame-retardant property and the like of the material are improved together.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a flame-retardant silicone rubber material, and a preparation method and application thereof.
Background
With the development of social economy, the flame retardant requirement of human beings on rubber materials is higher and higher, and compared with natural rubber and other synthetic rubbers, the main chain of the silicone rubber mainly comprises a Si-O inorganic structure, and the side group is methyl or vinyl and other structural elements. Along with the characteristics of saturated, semi-inorganic, amorphous and nonpolar main chains, the silicon rubber is determined to mainly have two reactions of side chain organic group oxidative decomposition and main chain tripping degradation after being heated, and the generated micromolecule cyclic siloxane further accelerates the degradation of the silicon rubber.
The flame retardancy of silicone rubber is still mainly achieved by adding flame retardant. In terms of flame retardant technology, the synergistic flame retardant effect is widely utilized, flame retardants with different flame retardant mechanisms are matched together, and the flame retardant efficiency of a flame retardant system can be rapidly improved through lower component addition, so that the silicone rubber material can meet the use requirements in some special fields. The typical synergistic flame retardant systems at present mainly include: halogen-antimony synergy, halogen-boron synergy, bromine-ammonium synergy, halogen-phosphorus synergy, halogen-nitrogen synergy, chlorine-bromine synergy, phosphorus-nitrogen synergy, phosphorus-phosphorus synergy, phosphorus-antimony synergy, and the like. The traditional halogen flame retardant has the smoke density and smoke toxicity problems in the combustion process, so that the related synergistic flame retardant system is gradually exiting the flame retardant market. In a phosphorus-nitrogen synergistic flame-retardant system, the matched components with higher use frequency are as follows: ammonium polyphosphate, melamine cyanurate, and melamine polyphosphate. When the four flame retardants are compounded and synergically flame-retardant, the theoretical optimal proportioning relationship of each component is uncertain, so that the system formula cannot reach the optimal proportioning, and moreover, the compatibility of each component and the silicon rubber is poor, so that the components are easy to agglomerate in the mixing process, and the physical and mechanical properties of the silicon rubber material such as strength, resilience and the like at normal temperature are damaged.
Disclosure of Invention
In order to overcome the problems of the prior art, an object of the present invention is to provide a flame retardant silicone rubber material.
The second purpose of the invention is to provide a preparation method of the flame-retardant silicone rubber material.
The invention also aims to provide the application of the flame-retardant silicone rubber material in the flame-retardant material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a flame-retardant silicon rubber material in a first aspect, which comprises the following components in parts by weight: 100 parts of silicon rubber, 30-60 parts of white carbon black, 6-12 parts of a structure regulator, 20-55 parts of a phosphorus-nitrogen-silicon flame retardant, 0.3-5 parts of a plasticizer, 25-50 parts of a filler and 2-7 parts of a vulcanizing agent. According to the invention, through organically combining three different flame retardant elements of nitrogen, phosphorus and silicon on the same molecule, the phosphorus-nitrogen-silicon flame retardant and the silicon rubber have good compatibility, and the physical and mechanical properties of the material and the synergistic effect of a flame retardant system are improved to the maximum extent.
Preferably, the silicone rubber comprises methyl vinyl silicone rubber.
Preferably, the methyl vinyl silicone rubber meets the condition of at least one of the following:
(1) the molecular weight is 45-80 ten thousand;
(2) the content of vinyl is 0.08% -0.4%;
(3) the volatile content is less than or equal to 2.0 percent;
(4) the terminal group is at least one of methyl and vinyl.
By adopting the methyl vinyl silicone rubber with the molecular weight of 45-80 ten thousand, the silicone rubber can be ensured to have good processing fluidity, a small amount of vinyl side chains can improve the vulcanization activity of the silicone rubber, improve the internal crosslinking density of the material, and indirectly improve the heat resistance stability and the flame retardance of the material.
Preferably, the molecular weight of the methyl vinyl silicone rubber is 45 to 50 ten thousand; further preferably, the molecular weight of the methyl vinyl silicone rubber is 48 to 50 ten thousand.
Preferably, the phosphorus-nitrogen-silicon flame retardant comprises DPPA-Si, and the formula of DPPA-Si is as follows:
preferably, the initial decomposition temperature of the DPPA-Si is 210-240 ℃.
DPPA-Si is a ternary flame retardant for organically combining three elements of P/N/Si, the molecule contains an Si-O, Si-C structure, the initial decomposition temperature is between 210 ℃ and 240 ℃, the heat stability and the char formation are good, and a Si-O or Si-C inorganic oxygen-insulating protective layer peculiar to siloxane can be formed on the surface of silicon rubber at a high temperature, so that the substrate is further protected. The DPPA-Si ternary flame retardant can fully solve the problems of single flame-retardant element and low flame-retardant efficiency. The structure of silicon hydroxyl generated by hydrolysis of the DPPA-Si flame retardant in the mixing process is similar to that of silicon rubber, and the silicon hydroxyl and the silicon rubber have strong interaction according to the similar compatibility principle, so that the overall physical and mechanical properties of the flame-retardant silicon rubber are improved.
Preferably, the preparation method of the DPPA-Si flame retardant comprises the following steps: mixing and reacting gamma-aminopropyltriethoxysilane, triethylamine, toluene and diphenyl phosphorus chloride, and purifying to obtain the DPPA-Si flame retardant.
Preferably, the mixing reaction is carried out under the protection of protective gas; further preferably, the protective gas comprises at least one of nitrogen and argon.
Preferably, the temperature of the mixing reaction is-35 ℃ to-45 ℃; further preferably, the temperature of the mixing reaction is-40 ℃ to-45 ℃.
Preferably, the purification step comprises a step of removing triethylamine hydrochloride and a silica gel column chromatography purification step.
Preferably, the step of removing triethylamine hydrochloride is specifically to remove triethylamine hydrochloride by suction filtration.
Preferably, the white carbon black accounts for 35-45 parts by weight based on the total weight of the flame-retardant silicone rubber material; further preferably, the white carbon black accounts for 40-45 parts by weight based on the total weight of the flame-retardant silicone rubber material.
Preferably, the weight part of the structure regulator is 7-9 parts based on the total weight part of the flame-retardant silicone rubber material; further preferably, the weight part of the structure regulator is 8-9 parts based on the total weight part of the flame-retardant silicone rubber material.
Preferably, the weight part of the phosphorus-nitrogen-silicon flame retardant is 30-50 parts based on the total weight part of the flame-retardant silicon rubber material; further preferably, the weight part of the phosphorus-nitrogen-silicon flame retardant is 35-45 parts based on the total weight part of the flame-retardant silicon rubber material.
Preferably, the weight part of the plasticizer is 0.5-2.5 parts based on the total weight part of the flame-retardant silicone rubber material; further preferably, the weight part of the plasticizer is 1-2 parts based on the total weight part of the flame-retardant silicone rubber material.
Preferably, the weight part of the filler is 25-45 parts based on the total weight part of the flame-retardant silicone rubber material; more preferably, the weight part of the filler is 25-30 parts based on the total weight part of the flame-retardant silicone rubber material.
Preferably, the vulcanizing agent is 3-5 parts by weight based on the total weight of the flame-retardant silicone rubber material; further preferably, the vulcanizing agent is 3-4.5 parts by weight based on the total weight of the flame-retardant silicone rubber material.
Preferably, the structure regulator is at least one of dihydroxy polydimethylsiloxane, dimethyl dimethoxysilane, methyl phenyl diethoxysilane and polydimethyl diphenylsiloxane.
Preferably, the white carbon black meets at least one of the following conditions:
(1) the CTAB specific surface area is 160-190 m2/g；
(2) The DBP oil absorption value is 2.3-2.7 cm3/g；
(3) The heating decrement is less than or equal to 8 percent;
(4) the mass percent of the silicon dioxide is more than or equal to 97 percent;
(5) the white carbon black is at least one of precipitated white carbon black and gas-phase white carbon black.
The white carbon black can obviously improve the hardness, tensile strength and tear strength of the silicon rubber, and can indirectly improve the carbon layer strength of the silicon rubber in a combustion state.
Preferably, the CTAB specific surface area of the white carbon black is 170-180 m2(ii)/g; more preferably, the CTAB specific surface area of the white carbon black is 170-175 m2(ii)/g; still further preferably, the whiteThe carbon black has a CTAB specific surface area of 175m2/g。
Preferably, the DBP oil absorption value of the white carbon black is 2.5-2.7 cm3(ii)/g; further preferably, the DBP oil absorption value of the white carbon black is 2.6cm3/g。
Preferably, the filler is at least one of kaolin, calcium carbonate and magnesium silicate.
Preferably, the plasticizer is at least one of coumarone, rosin, disproportionated rosin and microcrystalline wax.
Preferably, the vulcanizing agent is a peroxide vulcanizing agent; further preferably, the vulcanizing agent is at least one of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and di-tert-butylperoxy diisopropylbenzene.
The second aspect of the invention provides a method for preparing the flame-retardant silicone rubber material provided by the first aspect of the invention,
s1: mixing silicon rubber and a phosphorus-nitrogen-silicon flame retardant;
s2: mixing the mixed product obtained in the step S1 with white carbon black, a structure regulator, a filler and a plasticizer to obtain mixed rubber;
s3: and mixing the rubber compound with a vulcanizing agent, and then vulcanizing to obtain the flame-retardant silicone rubber material.
Preferably, the step S1 is specifically: adding the phosphorus-nitrogen-silicon flame retardant into the silicon rubber in batches for mixing; further preferably, the step S1 specifically includes: adding the phosphorus-nitrogen-silicon flame retardant into silicon rubber in 2-5 batches for mixing; still further preferably, the step S1 is specifically: adding the phosphorus-nitrogen-silicon flame retardant into silicon rubber in 2-5 batches for mixing, wherein the adding time of each batch is 5-12 min.
Preferably, the step S2 is specifically: adding the white carbon black, the structure regulator, the filler and the plasticizer into the mixing product obtained in the step S1 in batches for mixing; further preferably, the step S2 specifically includes: adding the white carbon black, the structure regulator, the filler and the plasticizer into the mixing product obtained in the step S1 in batches of 2-5 for mixing; still further preferably, the step S2 is specifically: and adding the white carbon black, the structure regulator, the filler and the plasticizer into the mixing product obtained in the step S1 in 2-5 batches for mixing, wherein the adding time of each batch is 5-12 min.
Preferably, the step S3 is performed by kneading in a triangular bag manner.
Preferably, in the step S3, the vulcanization temperature is 165-180 ℃, the vulcanization pressure is 9-11 MPa, and the vulcanization time is 5-20 min.
Preferably, in the step S3, the vulcanization temperature is 170-180 ℃; further preferably, in the step S3, the vulcanization temperature is 170-175 ℃; still further preferably, in the step S3, the vulcanization temperature is 170 ℃ or 175 ℃.
Preferably, in the step S3, the vulcanization pressure is 9.5-10.5 MPa; further preferably, in the step S3, the vulcanization pressure is 10 MPa.
Preferably, in the step S3, the vulcanization time is 5-10 min; further preferably, in the step S3, the vulcanization time is 6-8 min; still more preferably, in the step S3, the vulcanizing time is 6min, 7min or 8 min.
Preferably, the step S1 is mixing by using an open mill.
Preferably, the temperature of the roller of the open mill is 30-45 ℃, and the roller spacing is 2-5 mm.
Preferably, the temperature of the roller of the open mill is 30-40 ℃, and the roller spacing is 2-3 mm.
The third aspect of the invention is to provide an application of the flame-retardant silicone rubber material in a flame-retardant material.
The invention has the beneficial effects that: the flame-retardant silicon rubber material has good physical and mechanical properties and excellent flame-retardant property, the components in the flame-retardant silicon rubber material have good compatibility and dispersibility, and the components have synergistic action, so that the mechanical properties such as tensile strength and tearing strength, the thermal aging property, the flame-retardant property and the like of the material are improved together.
Specifically, the method comprises the following steps:
(1) compared with the conventional aluminum-boron and phosphorus-nitrogen flame-retardant synergistic system, the DPPA-Si flame retardant used in the invention organically combines three flame-retardant elements of phosphorus, nitrogen and silicon, fundamentally solves the problems of single flame-retardant element and low flame-retardant efficiency, and can remarkably improve the flame-retardant and environment-friendly characteristics of silicone rubber.
(2) Due to the existence of the silicon ethoxy structure, the DPPA-Si flame retardant is easy to hydrolyze in the mixing process to generate silicon hydroxyl, the Si-O bond and the silicon hydroxyl of the DPPA-Si flame retardant are similar to the main structure of the silicon rubber, and according to the similar compatibility principle, the DPPA-Si flame retardant has good compatibility and dispersibility in the silicon rubber and can enhance the physical and mechanical properties of the material, such as tensile strength, tearing strength and the like.
(3) In the invention, the surface of the flame-retardant silicon rubber material can form a Si-O or Si-C carbon protective layer peculiar to more siloxane under the high-temperature state, and the substrate is further prevented from being ignited through the condensed phase flame-retardant effect.
(4) The addition of a proper amount of fillers such as kaolin, calcium carbonate and the like can help improve the flame retardant property of the silicone rubber material and reduce the overall production cost to the maximum extent.
Detailed Description
Specific embodiments of the present invention are described in further detail below with reference to examples, but the practice and protection of the present invention are not limited thereto. It is noted that the following processes, if not described in particular detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of precipitated white carbon black, 7 parts of dihydroxy polydimethylsiloxane, 30 parts of DPPA-Si ternary flame retardant, 1.0 part of rosin, 25 parts of kaolin and 2.0 parts of dipenta vulcanizing agent. The DPPA-Si ternary flame retardant comprises the following preparation raw materials in parts by weight: 4.0g gamma-aminopropyltriethoxysilane, 4.2g triethylamine, 62.4g toluene, 8.4g diphenylphosphinochloride.
In the formulation of the flame retardant silicone rubber material in this example, the methyl vinyl silicone rubber has a molecular weight of 48 ten thousand and is vinylThe content of the mole fraction is 0.16 percent, and the volatile content is less than or equal to 2.0 percent; precipitation method of SiO in white carbon black2The mass content of the CTAB is more than or equal to 97 percent, and the specific surface area of CTAB is 170m2(g), DBP oil absorption 2.6cm3The heating decrement is less than or equal to 8 percent; the dihydroxy polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 pas, and the hydroxyl content is 8%.
The DPPA-Si ternary flame retardant is prepared by the following preparation method, and the preparation method comprises the following specific steps:
adopting an anhydrous oxygen-free operation technology, performing closed nitrogen exchange on a Schlenk bottle for 3 times, sequentially injecting 4.0g of gamma-aminopropyltriethoxysilane, 4.2g of triethylamine and 62.4g of toluene into the Schlenk bottle under the conditions of nitrogen protection and low temperature of-40 ℃, stirring for 15min, slowly dropwise adding 8.4g of diphenyl phosphorus chloride, finishing the delivery within 30min, stirring at-40 deg.C for 15min, removing, stirring at room temperature for 2.5h, filling a sand core funnel with diatomite, carrying out suction filtration to remove generated triethylamine hydrochloride, washing a Schlenk bottle and the triethylamine hydrochloride with toluene and n-hexane in sequence, combining filtrates, carrying out rotary evaporation to remove a solvent to obtain a light yellow viscous liquid crude product, purifying by silica gel column chromatography, carrying out rotary evaporation to remove the solvent, and then placing in a vacuum drying oven at 50 ℃ for drying treatment for 12 hours to obtain a white powdery product.
The synthetic route of the DPPA-Si ternary flame retardant is as follows:
the flame-retardant silicone rubber material in the embodiment is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after the methyl vinyl silicone rubber fully wraps the roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time of each time is 6 min;
(3) slowly adding accurately weighed precipitated white carbon black, dihydroxy polydimethylsiloxane, kaolin and rosin for 5 times, and fully mixing after the methyl vinyl silicone rubber coats the powder;
(4) keeping the roll spacing unchanged, adding a dipentavulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting with the roll spacing of 3.0mm to prepare a rubber sheet;
(5) and (3) putting the rubber sheet into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material in the embodiment.
Example 2
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 80 parts of methyl vinyl silicone rubber with the molecular weight of 50 ten thousand, 20 parts of methyl vinyl silicone rubber with the molecular weight of 65 ten thousand, 45 parts of precipitated white carbon black, 9.0 parts of dimethyl dimethoxy silane, 45 parts of DPPA-Si ternary flame retardant, 0.5 part of solid coumarone, 1.0 part of microcrystalline wax, 30 parts of magnesium silicate and 5.0 parts of BIPB-40B vulcanizing agent. The DPPA-Si ternary flame retardant comprises the following preparation raw materials: 6.0g of gamma-aminopropyltriethoxysilane, 6.3g of triethylamine, 94g of toluene, 13g of diphenylphosphorochloride.
In the formula of the flame-retardant silicon rubber material, the vinyl mole fraction content of the methyl vinyl silicone rubber with the molecular weight of 50 ten thousand is 0.24 percent, the vinyl mole fraction content of the methyl vinyl silicone rubber with the molecular weight of 65 ten thousand is 0.10 percent, and the volatile components are less than or equal to 2.0 percent; SiO in white carbon black by precipitation method2The mass content is more than or equal to 97 percent, and the CTAB specific surface area is 170m2(g), DBP oil absorption 2.6cm3The heating decrement is less than or equal to 8 percent; the dimethyl dimethoxy silane is colorless transparent liquid, the purity is 99 percent, the molecular weight is 120, and the density is 0.8g/cm3。
The DPPA-Si ternary flame retardant is prepared by the following preparation method, and the preparation method comprises the following specific steps:
by adopting an anhydrous oxygen-free operation technology, after a Schlenk bottle is closed to exchange nitrogen for 3 times, under the conditions of nitrogen protection and low temperature of minus 40 ℃, 6.0g of gamma-aminopropyltriethoxysilane, 6.3g of triethylamine and 94g of toluene are sequentially injected into the Schlenk bottle, after stirring for 15min, 13g of diphenyl phosphorus chloride is slowly dripped, then a sand core funnel is filled with diatomite, generated triethylamine hydrochloride is removed by suction filtration, the Schlenk bottle and the triethylamine hydrochloride are sequentially washed by the toluene and the n-hexane, filtrate is combined, a solvent is removed by rotary evaporation to obtain a light yellow viscous liquid crude product, the product is purified by silica gel column chromatography, after the solvent is removed by rotary evaporation, the product is placed in a vacuum drying oven at 50 ℃ and dried for 12h, and a white powdery product is obtained.
The flame-retardant silicone rubber material in the embodiment is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after the methyl vinyl silicone rubber fully wraps the roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time of each time is 6 min;
(3) slowly adding accurately weighed precipitated white carbon black, dimethyl dimethoxysilane, microcrystalline wax, solid coumarone and magnesium silicate for 5 times, and fully mixing after the powder is coated by the methyl vinyl silicone rubber;
(4) keeping the roll spacing unchanged, adding a BIPB-40B vulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting at the roll spacing of 3.0mm to prepare a rubber sheet;
(5) and (3) putting the rubber sheet into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 8min, so as to obtain the flame-retardant silicone rubber material in the embodiment.
Example 3
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 40 parts of fumed silica, 4.0 parts of dihydroxy polydimethylsiloxane, 5.0 parts of methyl phenyl diethoxy silane, 35 parts of DPPA-Si ternary flame retardant, 2.0 parts of microcrystalline wax, 25 parts of kaolin, 20 parts of calcium carbonate, 1.5 parts of bis-penta vulcanizing agent and 3.0 parts of BIPB-40B vulcanizing agent. The DPPA-Si ternary flame retardant comprises the following preparation raw materials: 4.7g gamma-aminopropyl triethoxysilane, 5.0g triethylamine, 73g toluene, 10g diphenyl phosphorus chloride.
Flame-retardant silicone rubberIn the formula of the rubber material, the molecular weight of the methyl vinyl silicone rubber is 48 ten thousand, the vinyl mole fraction content is 0.16 percent, and the volatile component is less than or equal to 2.0 percent; SiO in white carbon black by gas phase method2Mass content is more than or equal to 97 percent, and CTAB specific surface area is 190m2(g), DBP oil absorption 2.7cm3The heating decrement is less than or equal to 8 percent; the dihydroxy polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 pas, and the hydroxyl content is 8%; the methyl phenyl diethoxy silane is colorless transparent liquid, the molecular weight is 210.3, and the content is more than or equal to 99.0 percent.
The DPPA-Si ternary flame retardant is prepared by the following preparation method, and the preparation method comprises the following specific steps:
by adopting an anhydrous oxygen-free operation technology, after a Schlenk bottle is closed to exchange nitrogen for 3 times, under the conditions of nitrogen protection and low temperature of-40 ℃, 4.7g of gamma-aminopropyltriethoxysilane, 5.0g of triethylamine and 73g of toluene are sequentially injected into the Schlenk bottle, 10g of diphenyl phosphorus chloride is slowly dripped after stirring for 15min, then a sand core funnel is filled with diatomite, generated triethylamine hydrochloride is removed by suction filtration, the Schlenk bottle and the triethylamine hydrochloride are sequentially washed by the toluene and n-hexane, filtrate is combined, a solvent is removed by rotary evaporation to obtain a light yellow viscous liquid crude product, the product is purified by silica gel column chromatography, the solvent is removed by rotary evaporation, and the product is dried in a vacuum drying oven at 50 ℃ for 12h to obtain a white powdery product.
The flame-retardant silicone rubber material in the embodiment is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after the methyl vinyl silicone rubber fully wraps the roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time of each time is 6 min;
(3) slowly adding accurately weighed fumed silica, dihydroxy polydimethylsiloxane, methyl phenyl diethoxysilane, microcrystalline wax, kaolin and calcium carbonate for 5 times, and fully mixing after the powder is coated by the methyl vinyl silicone rubber;
(4) keeping the roll spacing unchanged, adding a dipentavulcanizing agent and a BIPB-40B vulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting with the roll spacing of 3.0mm to prepare a rubber sheet;
(5) and (3) putting the film into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 175 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 6min, so as to obtain the flame-retardant silicone rubber material in the example.
Example 4
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 40 parts of methyl vinyl silicone rubber with the molecular weight of 50 ten thousand, 60 parts of methyl vinyl silicone rubber with the molecular weight of 65 ten thousand, 15 parts of fumed silica, 35 parts of precipitated silica, 8.0 parts of polydimethylsiloxane, 50 parts of DPPA-Si ternary flame retardant, 2.5 parts of microcrystalline wax, 20 parts of magnesium silicate and 3.0 parts of dipenta vulcanizing agent. The DPPA-Si ternary flame retardant comprises the following preparation raw materials: 6.6g of gamma-aminopropyltriethoxysilane, 7.0g of triethylamine, 102g of toluene, 14g of diphenylphosphorochloride.
In the formula of the flame-retardant silicon rubber material, the vinyl mole fraction content of the methyl vinyl silicone rubber with the molecular weight of 50 ten thousand is 0.24 percent, the vinyl mole fraction content of the methyl vinyl silicone rubber with the molecular weight of 65 ten thousand is 0.10 percent, and the volatile components are less than or equal to 2.0 percent; SiO in white carbon black by precipitation method2The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; SiO in white carbon black by gas phase method2The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; the polydimethylsiloxane is colorless transparent liquid with the density of 1.05g/cm3The content of effective substances is more than or equal to 99.5 percent.
The DPPA-Si ternary flame retardant is prepared by the following preparation method, and the preparation method comprises the following specific steps:
by adopting an anhydrous and anaerobic operation technology, after a Schlenk bottle is closed to exchange nitrogen for 3 times, under the conditions of nitrogen protection and low temperature of-40 ℃, 6.6g of gamma-aminopropyltriethoxysilane, 7.0g of triethylamine and 102g of toluene are sequentially injected into the Schlenk bottle, after stirring for 15min, 14g of diphenyl phosphorus chloride is slowly dripped, then a sand core funnel is filled with diatomite, the generated triethylamine hydrochloride is removed by suction filtration, the Schlenk bottle and the triethylamine hydrochloride are sequentially washed by the toluene and n-hexane, the filtrate is combined, the solvent is removed by rotary evaporation to obtain a light yellow viscous liquid crude product, the light yellow viscous liquid crude product is purified by silica gel column chromatography, after the solvent is removed by rotary evaporation, the light yellow viscous liquid crude product is placed in a vacuum drying oven at 50 ℃ and is dried for 12 hours to obtain a white powdery product.
The flame-retardant silicone rubber material in the embodiment is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after the methyl vinyl silicone rubber fully wraps the roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time of each time is 6 min;
(3) slowly adding accurately weighed fumed silica, precipitated silica, polydimethyl diphenyl siloxane, microcrystalline wax and magnesium silicate for 5 times, and fully mixing after the powder is coated by the methyl vinyl silicone rubber;
(4) keeping the roll spacing unchanged, adding a dipentavulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting with the roll spacing of 3.0mm to prepare a rubber sheet;
(5) and (3) putting the rubber sheet into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material in the embodiment.
Comparative example 1
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 35 parts of fumed silica, 7.0 parts of dimethyl dimethoxy silane, 1.0 part of rosin, 25 parts of kaolin and 2.0 parts of bis-dipenta vulcanizing agent.
In the formula of the flame-retardant silicon rubber material, the molecular weight of the methyl vinyl silicon rubber is 48 ten thousand, the vinyl mole fraction content is 0.16 percent, and the volatile component is less than or equal to 2.0 percent; SiO in white carbon black by gas phase method2Mass content is more than or equal to 97 percent, and CTAB specific surface area is 190m2(g), DBP oil absorption 2.7cm3The heating decrement is less than or equal to 8 percent; the dimethyl dimethoxy silane is colorless transparent liquid with the purity of 99 percent and the molecular weight of 120,density 0.8g/cm3。
The flame-retardant silicone rubber material is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after fully wrapping the roll with the methyl vinyl silicone rubber, slowly adding accurately weighed fumed silica, dimethyl dimethoxysilane, rosin and kaolin 5 times, and fully mixing after the powder is coated with the methyl vinyl silicone rubber;
(3) keeping the roll spacing unchanged, adding a dipentavulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting with the roll spacing of 3.0mm to prepare a rubber sheet;
(4) and (3) putting the rubber sheet into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 7min, so as to obtain the flame-retardant silicone rubber material in the embodiment.
Comparative example 2
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 15 parts of precipitated silica, 25 parts of fumed silica, 8.5 parts of methyl phenyl diethoxy silane, 2.0 parts of microcrystalline wax and 3.0 parts of dipenta-vulcanizing agent.
In the formula of the flame-retardant silicon rubber material, the molecular weight of the methyl vinyl silicon rubber is 48 ten thousand, the vinyl mole fraction content is 0.16 percent, and the volatile component is less than or equal to 2.0 percent; SiO in white carbon black by precipitation method2The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; SiO in white carbon black by gas phase method2The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; the methyl phenyl diethoxy silane is colorless transparent liquid, the molecular weight is 210.3, and the content is more than or equal to 99.0 percent.
The flame-retardant silicone rubber material in the embodiment is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after fully wrapping the roll with the methyl vinyl silicone rubber, slowly adding accurately weighed precipitated white carbon black, gas-phase white carbon black, methyl phenyl diethoxy silane and microcrystalline wax for 5 times, and fully mixing after the methyl vinyl silicone rubber coats the powder;
(3) keeping the roll spacing unchanged, adding a dipentavulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting with the roll spacing of 3.0mm to prepare a rubber sheet;
(4) and (3) putting the rubber sheet into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 5min, so as to obtain the flame-retardant silicone rubber material in the embodiment.
Comparative example 3
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 30 parts of fumed silica, 3.5 parts of dihydroxy polydimethylsiloxane, 4.0 parts of methyl phenyl diethoxysilane, 35 parts of chlorinated paraffin-70, 10 parts of antimony trioxide, 3.5 parts of rosin, 30 parts of calcium carbonate and 5.5 parts of BIPB-40B vulcanizing agent.
In the formula of the flame-retardant silicon rubber material, the molecular weight of the methyl vinyl silicon rubber is 48 ten thousand, the vinyl mole fraction content is 0.16 percent, and the volatile component is less than or equal to 2.0 percent; SiO of white carbon black by gas phase method2Mass content is more than or equal to 97 percent, and CTAB specific surface area is 190m2(g), DBP oil absorption 2.7cm3The heating decrement is less than or equal to 8 percent; the dihydroxy polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 pas, and the hydroxyl content is 8%; the methyl phenyl diethoxy silane is colorless transparent liquid, the molecular weight is 210.3, and the content is more than or equal to 99.0 percent;
the flame-retardant silicone rubber material in the embodiment is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after the methyl vinyl silicone rubber fully wraps the roller, adding chlorinated paraffin-70 and antimony trioxide for 3 times, wherein the interval time is 6min each time;
(3) after the rubber is fully wrapped by the roller, accurately weighed fumed silica, dihydroxy polydimethylsiloxane, methyl phenyl diethoxy silane, rosin and calcium carbonate are slowly added in 5 times, and the silicon rubber is fully mixed after the powder is coated by the silicon rubber;
(4) keeping the roll spacing unchanged, adding a BIPB-40B vulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting at the roll spacing of 3.0mm to prepare a rubber sheet;
(5) and (3) putting the film into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 175 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 8min, so as to obtain the flame-retardant silicone rubber material in the example.
Comparative example 4
The flame-retardant silicone rubber material in the embodiment comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 15 parts of fumed silica, 30 parts of precipitated silica, 8.0 parts of dihydroxy polydimethylsiloxane, 40 parts of aluminum hydroxide, 20 parts of magnesium hydroxide, 10 parts of zinc borate, 2.5 parts of microcrystalline wax, 35 parts of magnesium silicate and 3.5 parts of dipenta-vulcanizing agent.
In the formula of the flame-retardant silicon rubber material, the molecular weight of the methyl vinyl silicon rubber is 48 ten thousand, the vinyl mole fraction content is 0.16 percent, and the volatile component is less than or equal to 2.0 percent; SiO in white carbon black by precipitation method2The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; SiO in white carbon black by gas phase method2The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; the dihydroxy polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 pas, and the hydroxyl content is 8%; the average particle sizes of the aluminum hydroxide and the magnesium hydroxide are both 2 mu m, and the average particle size of the zinc borate is 6 mu m.
The flame-retardant silicone rubber material in the embodiment is prepared by the following preparation method, which comprises the following specific steps:
(1) placing the methyl vinyl silicone rubber with the formula amount on an open mill with a roller temperature of 40 ℃, adjusting the roller distance to 3.0mm, and plasticating;
(2) after the methyl vinyl silicone rubber fully wraps the roller, adding aluminum hydroxide, magnesium hydroxide and zinc borate for 3 times, wherein the interval time of each time is 6 min;
(3) after the rubber is fully wrapped by the roller, accurately weighed fumed silica, precipitated silica, dihydroxy polydimethylsiloxane, microcrystalline wax and magnesium silicate are slowly added for 5 times, and the silicon rubber is fully mixed after being coated with the powder;
(4) keeping the roll spacing unchanged, adding a dipentavulcanizing agent into the rubber compound, adjusting the roll spacing to 1.0mm after 3min, fully mixing the silicon rubber again in a triangular bag mode, and finally tabletting with the roll spacing of 3.0mm to prepare a rubber sheet;
(5) and (3) putting the rubber sheet into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 10min, so as to obtain the flame-retardant silicone rubber material in the embodiment.
Performance testing
(1) Physical mechanical Property test
The physical and mechanical properties of the flame retardant silicone rubber material samples prepared in examples 1-4 and comparative examples 1-4 were respectively tested according to the test methods described in the standards in table 1 below, and the test results are recorded in table 1 below.
TABLE 1 test results of physical and mechanical Properties of flame retardant Silicone rubber materials in examples 1-4 and comparative examples 1-4
As can be seen from the test results in Table 1, the overall physical and mechanical properties of the flame retardant silicone rubber materials in examples 1-4 of the present invention are better than those of the flame retardant silicone rubber materials in comparative examples 1-4. The flame-retardant silicon rubber material in the embodiments 1 to 4 has a silicon ethoxy structure, so that the DPPA-Si ternary flame retardant is easy to hydrolyze in a mixing process to generate silicon hydroxyl, the Si-O bond and the silicon hydroxyl of the flame-retardant silicon rubber material are similar to the main structure of the silicon rubber, the DPPA-Si ternary flame retardant is well compatible and dispersed in the silicon rubber according to a similar compatibility principle, and the mechanical properties such as tensile strength and tearing strength are naturally and effectively improved. According to the provisions of GB/T3512-: the retention of properties, i.e., after-aging properties/before-aging properties × 100%, still showed high retention in terms of tensile strength, elongation at break, and tear strength.
The compatibility of flame retardants such as chlorinated paraffin-70, antimony trioxide and aluminum hydroxide with the silicone rubber is poor, so that after the silicone rubber is subjected to long-time high-temperature treatment, self thermal oxidation decomposition products seriously damage a cross-linked network structure in the silicone rubber, and the silicone rubber shows lower physical and mechanical properties and aging resistance, and the phenomena are increasingly obvious along with the increase of the addition of the components.
(2) Test for flame retardancy
The flame retardant properties of the flame retardant silicone rubber material samples prepared in examples 1-4 and comparative examples 1-4 were tested, respectively, according to the test methods described in the standards in table 2 below, and the test results are reported in tables 2 and 3.
Table 2 results of testing flame retardancy of flame retardant silicone rubber materials in examples 1 to 4 and comparative examples 1 to 4
TABLE 3 self-extinguishing property test results of the flame retardant silicone rubber materials in examples 1-4 and comparative examples 1-4
The results of various flame retardant property tests in tables 2 and 3 show that the flame retardant silicone rubber materials in embodiments 1-4 of the present invention do not drip during two delayed combustions, the bottom cotton is not ignited, the sample strips are not completely combusted, and the two combustions can reach a state of extinguishing after leaving fire, which indicates that the organic combination of three flame retardant elements of phosphorus, nitrogen and silicon enables the materials to generate substances such as phosphoric acid, metaphosphoric acid and the like during the secondary combustion, the substances converge into a high aggregation state at a high temperature, so as to promote dehydration and carbonization of the flame retardant, and simultaneously due to the existence of the siloxane structure, a large number of Si-O or Si-C carbon protective layers cover the surface of the combustible substance, and the Si-O or Si-C carbon protective layers are unified as the protective layer of the rubber to isolate air and combustible substances, thereby further reducing the heat feedback strength of the flame to the substrate while reducing the generation of smoke, the nitrogen, moisture and other incombustible gases continuously released in the combustion process effectively reduce the temperature and oxygen concentration of a combustion system, further prevent the combustion of the flame-retardant silicone rubber material and improve the flame-retardant efficiency of the flame-retardant silicone rubber material. In addition, the filler such as calcium carbonate, kaolin and the like can be used as a weak reinforcing agent to enhance the mechanical property of the flame-retardant silicone rubber material, and can also be used as an isolation layer to prevent oxygen from permeating into a silicone rubber substrate in the combustion process, so that the overall cost of the material can be reduced to a certain extent while flame extinguishment is promoted.
Similar to the synergistic combination of aluminum hydroxide, magnesium hydroxide and zinc borate, the chlorinated paraffin-70 and antimony trioxide are matched and act on the silicone rubber together, and in the process of adding a large amount of the chlorinated paraffin-70 and antimony trioxide, the negative phenomena of uneven particle dispersion, reduced mechanical property, increased smoke density in the combustion process and the like are inevitably caused due to the self environmental protection property, compatibility and the like.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A flame-retardant silicone rubber material is characterized in that: the flame-retardant silicone rubber material comprises the following components in parts by weight: 100 parts of silicon rubber, 30-60 parts of white carbon black, 6-12 parts of a structure regulator, 20-55 parts of a phosphorus-nitrogen-silicon flame retardant, 0.3-5 parts of a plasticizer, 25-50 parts of a filler and 2-7 parts of a vulcanizing agent.
2. The flame retardant silicone rubber material of claim 1, wherein: the silicone rubber comprises methyl vinyl silicone rubber.
3. The flame retardant silicone rubber material of claim 2, wherein: the methyl vinyl silicone rubber meets at least one of the following conditions:
(1) the number average molecular weight is 45-80 ten thousand;
(2) the content of vinyl is 0.08% -0.4%;
(3) the volatile content is less than or equal to 2.0 percent;
(4) the terminal group is at least one of methyl and vinyl.
4. The flame retardant silicone rubber material according to any one of claims 1 to 3, wherein: the phosphorus nitrogen silicon flame retardant comprises DPPA-Si.
5. The flame retardant silicone rubber material of claim 4, wherein: the initial decomposition temperature of the DPPA-Si is 210-240 ℃.
6. The flame retardant silicone rubber material of claim 1, wherein: the structure regulator is at least one of dihydroxy polydimethylsiloxane, dimethyl dimethoxysilane, methyl phenyl diethoxysilane and polydimethyl diphenyl siloxane.
7. The flame retardant silicone rubber material of claim 1, wherein: the plasticizer is at least one of coumarone, rosin, disproportionated rosin and microcrystalline wax.
8. The method for preparing the flame-retardant silicone rubber material according to any one of claims 1 to 7, characterized in that:
s1: mixing silicon rubber and a phosphorus-nitrogen-silicon flame retardant;
s2: mixing the mixed product obtained in the step S1 with white carbon black, a structure regulator, a filler and a plasticizer to obtain mixed rubber;
s3: and mixing the rubber compound with a vulcanizing agent, and then vulcanizing to obtain the flame-retardant silicon rubber material.
9. The method for preparing a flame retardant silicone rubber material according to claim 8, wherein: in the step S3, the vulcanization temperature is 165-180 ℃, the vulcanization pressure is 9-11 MPa, and the vulcanization time is 5-20 min.
10. Use of the flame retardant silicone rubber material according to any one of claims 1 to 7 in flame retardant materials.
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