CN114181536B - 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
- Publication number
- CN114181536B CN114181536B CN202111603786.2A CN202111603786A CN114181536B CN 114181536 B CN114181536 B CN 114181536B CN 202111603786 A CN202111603786 A CN 202111603786A CN 114181536 B CN114181536 B CN 114181536B
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- flame
- parts
- flame retardant
- rubber material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant silicone rubber material, a preparation method and application thereof, wherein 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. The flame-retardant silicone rubber material has good physical and mechanical properties and excellent flame retardant properties, and has good compatibility and dispersibility among the components, and the components have synergistic effect, so that the mechanical properties such as tensile strength and tear strength, thermal aging property and flame retardant property 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 requirement of human on flame retardance of rubber materials is higher and higher, and compared with natural rubber and other synthetic rubber, the main chain of the silicone rubber mainly consists of an Si-O inorganic structure, and side groups are other structural elements such as methyl or vinyl. With the characteristics of saturated main chain, semi-inorganic, amorphous and nonpolar, it can be determined that the silicon rubber is subjected to heat, and the main chain unbuckled degradation and the side chain organic group oxidative decomposition mainly occur, so that the generated micromolecular cyclic siloxane further accelerates the degradation of the silicon rubber.
Flame retardance of silicone rubber is still currently achieved mainly by the addition of flame retardants. For the flame retardant technology, the synergistic flame retardant effect is widely utilized, and the flame retardant with different flame retardant mechanisms is matched together, so that the flame retardant efficiency of a flame retardant system can be rapidly improved through lower component addition, and the silicone rubber material can meet the use requirements in some special fields. Typical synergistic flame retardant systems at present mainly comprise: halogen-antimony synergism, halogen-boron synergism, bromine-ammonium synergism, halogen-phosphorus synergism, halogen-nitrogen synergism, chlorine-bromine synergism, phosphorus-nitrogen synergism, phosphorus-phosphorus synergism, phosphorus-antimony synergism, and the like. Traditional halogen flame retardants are also gradually exiting the flame retardant market due to the problems of smoke density and smoke toxicity during combustion, which results in a synergistic flame retardant system associated therewith. In the 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 used for synergistic flame retardance, the theoretical optimal ratio relation of all the components is not clear, so that the system formula cannot reach the optimal ratio, and moreover, the compatibility of all the components and the silicone rubber is poor, so that the components are easy to agglomerate in the mixing process, and the physical and mechanical properties such as strength, rebound and the like of the silicone rubber material at normal temperature are damaged.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes 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 further aims to provide an application of the flame-retardant silicone rubber material in flame-retardant materials.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a flame-retardant silicone rubber material, 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, three different flame retardant elements of nitrogen, phosphorus and silicon are organically combined on the same molecule, so that the phosphorus-nitrogen-silicon flame retardant has good compatibility with silicon rubber, and the physical and mechanical properties of the material and the synergistic effect of a flame retardant system are improved to the greatest extent.
Preferably, the silicone rubber comprises methyl vinyl silicone rubber.
Preferably, the methyl vinyl silicone rubber meets at least one of the following conditions:
(1) The molecular weight is 45-80 ten thousand;
(2) Vinyl content is 0.08% -0.4%;
(3) Volatile components are 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 intrinsic crosslinking density of the material, and indirectly improve the heat resistance stability and the flame retardance of the material.
Preferably, the methyl vinyl silicone rubber has a molecular weight of 45-50 ten thousand; further preferably, the methyl vinyl silicone rubber has a molecular weight of 48 to 50 ten thousand.
Preferably, the phosphorus nitrogen silicon flame retardant comprises DPPA-Si, and the structural formula of the DPPA-Si is as follows:
preferably, the DPPA-Si has an initial decomposition temperature of 210-240 ℃.
DPPA-Si is a ternary flame retardant which organically combines three elements P/N/Si, has an Si-O, si-C structure in the molecule, has an initial decomposition temperature of 210-240 ℃, has good thermal stability and char formation, can form a Si-O or Si-C inorganic oxygen insulation heat insulation protective layer special for siloxane on the surface of silicone rubber at a high temperature, and further plays a role in protecting a matrix. The DPPA-Si ternary flame retardant can fully solve the problems of single flame retardant element and low flame retardant efficiency. The silicon hydroxyl generated by hydrolysis of the DPPA-Si flame retardant in the mixing process is similar to the silicon rubber in structure, and the two have strong interaction according to a similar compatibility principle, so that the integral 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 gamma-aminopropyl triethoxysilane, triethylamine, toluene and diphenyl phosphorus chloride for reaction, and purifying to obtain the DPPA-Si flame retardant.
Preferably, the mixing reaction is carried out under the protection of a protective gas; further preferably, the shielding gas includes 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 includes a step of removing triethylamine hydrochloride and a silica gel column chromatography purification step.
Preferably, the step of removing triethylamine hydrochloride is specifically removing triethylamine hydrochloride by suction filtration.
Preferably, the weight part of the white carbon black is 35-45 parts based on the total weight part of the flame-retardant silicone rubber material; further preferably, the weight portion of the white carbon black is 40-45 portions based on the total weight portion 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 to 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 portion of the phosphorus nitrogen silicon flame retardant is 35 to 45 portions based on the total weight portion of the flame retardant silicon rubber material.
Preferably, the plasticizer is 0.5-2.5 parts by weight based on the total weight of the flame-retardant silicone rubber material; further preferably, the plasticizer is 1 to 2 parts by weight based on the total weight 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; further preferably, the filler is 25 to 30 parts by weight based on the total weight 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 to 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 dihydroxypolydimethylsiloxane, dimethyldimethoxysilane, methylphenyl diethoxysilane and polydimethyldiphenylsiloxane.
Preferably, the white carbon black meets at least one of the following conditions:
(1) CTAB specific surface area of 160-190 m 2 /g；
(2) DBP oil absorption value is 2.3-2.7 cm 3 /g；
(3) The heating decrement is less than or equal to 8 percent;
(4) The mass percentage of the silicon dioxide is more than or equal to 97 percent;
(5) The white carbon black is at least one of precipitation white carbon black and gas phase white carbon black.
The hardness, tensile strength and tear resistance of the silicon rubber can be obviously improved by adopting the white carbon black, and the carbon layer strength of the silicon rubber can be indirectly improved when the silicon rubber is in a burning state.
Preferably, the CTAB specific surface area of the white carbon black is 170-180 m 2 /g; further preferably, the CTAB specific surface area of the white carbon black is 170 to 175m 2 /g; still more preferably, the silica has a CTAB specific surface area of 175m 2 /g。
Preferably, the DBP oil absorption value of the white carbon black is 2.5-2.7 cm 3 /g; further preferably, the white carbon black has a DBP oil absorption value of 2.6cm 3 /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 preparation method of the flame retardant silicone rubber material provided by the first aspect of the invention,
s1: mixing silicon rubber with phosphorus nitrogen silicon flame retardant;
s2: mixing the mixed product in the step S1 with white carbon black, a structure regulator, a filler and a plasticizer to prepare a mixed rubber;
s3: and mixing the mixed rubber with a vulcanizing agent, and vulcanizing to obtain the flame-retardant silicone rubber material.
Preferably, the step S1 specifically includes: adding the phosphorus-nitrogen-silicon flame retardant into the silicon rubber in batches for mixing; further preferably, the step S1 specifically includes: adding 2-5 batches of phosphorus-nitrogen-silicon flame retardant into silicon rubber for mixing; still further preferably, the step S1 specifically includes: adding the phosphorus-nitrogen-silicon flame retardant into the silicon rubber in 2-5 batches for mixing, wherein the adding time of each batch is 5-12 min.
Preferably, the step S2 specifically includes: adding white carbon black, a structure regulator, a filler and a plasticizer into the mixed product in the step S1 in batches for mixing; further preferably, the step S2 specifically includes: adding white carbon black, a structure regulator, a filler and a plasticizer into the mixed product in the step S1 in 2-5 batches for mixing; still further preferably, the step S2 specifically includes: adding white carbon black, a structure regulator, a filler and a plasticizer into the mixed product obtained in the step S1 in 2-5 batches for mixing, wherein the adding time of each batch is 5-12 min apart.
Preferably, the step S3 is performed by triangle kneading.
Preferably, in the step S3, the vulcanization temperature is 165-180 ℃, the vulcanization pressure is 9-11MPa, and the vulcanization time is 5-20min.
Preferably, in the step S3, the vulcanization temperature is 170-180 ℃; further preferably, in the step S3, the vulcanization temperature is 170 to 175 ℃; still further preferably, in the step S3, the vulcanizing temperature is 170 ℃ or 175 ℃.
Preferably, in the step S3, the vulcanization pressure is 9.5 to 10.5MPa; further preferably, in the step S3, the vulcanization pressure is 10MPa.
Preferably, in the step S3, the vulcanizing time is 5-10min; further preferably, in the step S3, the vulcanizing time is 6 to 8 minutes; still more preferably, in the step S3, the vulcanizing time is 6min, 7min or 8min.
Preferably, the step S1 is mixing by an open mill.
Preferably, the roller temperature of the open mill is 30-45 ℃, and the roller spacing is 2-5mm.
Preferably, the roller temperature of the open mill is 30-40 ℃, and the roller spacing is 2-3mm.
The third aspect of the invention is to provide an application of the flame-retardant silicone rubber material in the flame-retardant material.
The beneficial effects of the invention are as follows: the flame-retardant silicone rubber material has good physical and mechanical properties and excellent flame retardant properties, and has good compatibility and dispersibility among the components, and the components have synergistic effect, so that the mechanical properties such as tensile strength and tear strength, thermal aging property and flame retardant property of the material are improved together.
Specifically:
(1) Compared with the conventional aluminum-boron, phosphorus-nitrogen flame-retardant synergistic system, the DPPA-Si flame retardant disclosed by the invention organically combines three flame-retardant elements of phosphorus, nitrogen and silicon, so that the problems of single flame-retardant element and low flame-retardant efficiency are fundamentally solved, and the flame retardance and environmental protection characteristics of the silicone rubber can be obviously improved.
(2) Because of the existence of the silicon ethoxy structure, the DPPA-Si flame retardant is easy to hydrolyze in the mixing process to generate silicon hydroxyl, si-O bonds of the DPPA-Si flame retardant and the silicon hydroxyl are similar to the main body structure of the silicon rubber, and the DPPA-Si flame retardant has good compatibility and dispersibility in the silicon rubber according to a similar compatibility principle, and can enhance the physical and mechanical properties of materials such as tensile strength, tearing strength and the like.
(3) The surface of the flame-retardant silicone rubber material can form a Si-O or Si-C carbon protective layer special for more siloxane under the high-temperature state, and the ignition of a matrix is further prevented 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 to improve the flame retardant property of the silicone rubber material and simultaneously reduce the overall production cost to the greatest extent.
Detailed Description
Specific implementations of the invention are described in further detail below with reference to examples, but the practice and protection of the invention is not limited thereto. It should be noted that the following processes, unless otherwise specified, are all realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1
The flame-retardant silicone rubber material in the example 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 dihydroxypolydimethylsiloxane, 30 parts of DPPA-Si ternary flame retardant, 1.0 part of rosin, 25 parts of kaolin and 2.0 parts of bis-dipentaerythritol vulcanizing agent. Wherein, the DPPA-Si ternary flame retardant comprises the following raw materials in parts by weight: 4.0g of gamma-aminopropyl triethoxysilane, 4.2g of triethylamine, 62.4g of toluene and 8.4g of diphenyl phosphorus chloride.
In the formula of the flame-retardant silicone rubber material in the example, the molecular weight of methyl vinyl silicone rubber is 48 ten thousand, the mol fraction content of vinyl is 0.16%, and the volatile is less than or equal to 2.0%; siO in white carbon black by precipitation method 2 The mass content of (C) is more than or equal to 97%, and the CTAB specific surface area is 170m 2 Per g, DBP oil absorption value 2.6cm 3 Per gram, heating decrement is less than or equal to 8%; the dihydroxyl polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 Pa.s, and the hydroxyl content is 8%.
The DPPA-Si ternary flame retardant is prepared by adopting the following preparation method, and comprises the following specific steps:
adopting anhydrous anaerobic operation technology, after the frank bottle is closed and exchanged with nitrogen for 3 times, under the condition of nitrogen protection and low temperature of minus 40 ℃, sequentially injecting 4.0g of gamma-aminopropyl triethoxysilane, 4.2g of triethylamine and 62.4g of toluene into the frank bottle, stirring for 15min, slowly dropwise adding 8.4g of diphenyl phosphorus chloride, finishing the delivery within 30min, stirring for 15min at the low temperature of minus 40 ℃, then removing, stirring for 2.5h at room temperature, filling a sand core funnel with diatomite, filtering to remove generated triethylamine hydrochloride, washing the frank bottle and triethylamine hydrochloride with toluene and normal hexane in sequence, merging filtrate, removing solvent by rotary evaporation to obtain a light yellow viscous liquid crude product, purifying by adopting silica gel column chromatography, drying in a vacuum drying box at 50 ℃ for 12h 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 example is prepared by adopting the following preparation method, and the specific steps are as follows:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) After the methyl vinyl silicone rubber is fully divided into a roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time is 6 minutes each time;
(3) Slowly adding accurately weighed precipitated white carbon black, dihydroxypolydimethylsiloxane, kaolin and rosin for 5 times, and fully mixing after the methyl vinyl silicone rubber coats the powder;
(4) Keeping the roll gap unchanged, adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a rubber sheet;
(5) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 170 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 7min, so that the flame-retardant silicone rubber material in the example is obtained.
Example 2
The flame-retardant silicone rubber material in the example 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. Wherein the DPPA-Si ternary flame retardant comprises the following raw materials: 6.0g of gamma-aminopropyl triethoxysilane, 6.3g of triethylamine, 94g of toluene and 13g of diphenyl phosphorus chloride.
In the formula of the flame-retardant silicone rubber material, the vinyl molar fraction content of methyl vinyl silicone rubber with the molecular weight of 50 ten thousand is 0.24 percent, the vinyl molar fraction content of methyl vinyl silicone rubber with the molecular weight of 65 ten thousand is 0.10 percent, and volatile matters are less than or equal to 2.0 percent; siO in white carbon black by precipitation method 2 The mass content is more than or equal to 97 percent, the CTAB specific surface area is 170m 2 Per g, DBP oil absorption value 2.6cm 3 Per gram, heating decrement is less than or equal to 8%; the dimethyl dimethoxy silane is colorless transparent liquid with purity of 99%, molecular weight of 120 and density of 0.8g/cm 3 。
The DPPA-Si ternary flame retardant is prepared by adopting the following preparation method, and comprises the following specific steps:
adopting anhydrous and anaerobic operation technology, after the frank bottle is closed and exchanged with nitrogen for 3 times, under the condition of nitrogen protection and low temperature of minus 40 ℃, 6.0g of gamma-aminopropyl triethoxysilane, 6.3g of triethylamine and 94g of toluene are sequentially injected into the frank bottle, after stirring for 15min, 13g of diphenyl phosphorus chloride is slowly added dropwise, then a sand core funnel is filled with diatomite, the generated triethylamine hydrochloride is removed by suction filtration, the frank bottle and the triethylamine hydrochloride are sequentially washed by toluene and n-hexane, the filtrate is combined, the solvent is removed by rotary evaporation, a light yellow viscous liquid crude product is obtained, the silica gel column chromatography purification is adopted, the solvent is removed by rotary evaporation, and the mixture is placed in a vacuum drying oven at 50 ℃ for drying treatment for 12h, so that a white powdery product is obtained.
The flame-retardant silicone rubber material in the example is prepared by adopting the following preparation method, and the specific steps are as follows:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) After the methyl vinyl silicone rubber is fully divided into a roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time is 6 minutes each time;
(3) Slowly adding accurately weighed precipitation white carbon black, dimethyl dimethoxy silane, microcrystalline wax, solid coumarone and magnesium silicate for 5 times, and fully mixing after the methyl vinyl silicone rubber coats the powder;
(4) Keeping the roll gap unchanged, adding BIPB-40B vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a film;
(5) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 170 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 8min, so that the flame-retardant silicone rubber material in the example is obtained.
Example 3
The flame-retardant silicone rubber material in the example 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 dihydroxypolydimethylsiloxane, 5.0 parts of methyl phenyl diethoxysilane, 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-dipentaerythritol vulcanizing agent and 3.0 parts of BIPB-40B vulcanizing agent. Wherein the DPPA-Si ternary flame retardant comprises the following raw materials: 4.7g of gamma-aminopropyl triethoxysilane, 5.0g of triethylamine, 73g of toluene and 10g of diphenyl phosphorus chloride.
In the formula of the flame-retardant silicone rubber material, the molecular weight of methyl vinyl silicone rubber is 48 ten thousand, the mol fraction content of vinyl is 0.16%, and the volatile component is less than or equal to 2.0%; siO in white carbon black by gas phase method 2 The mass content is more than or equal to 97 percent, the CTAB specific surface area is 190m 2 Per g, DBP oil absorption value 2.7cm 3 Per gram, heating decrement is less than or equal to 8%; the dihydroxyl polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 Pa.s, 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 adopting the following preparation method, and comprises the following specific steps:
adopting anhydrous and anaerobic operation technology, after the frank bottle is closed and exchanged with nitrogen for 3 times, under the condition of nitrogen protection and low temperature of minus 40 ℃, sequentially injecting 4.7g of gamma-aminopropyl triethoxysilane, 5.0g of triethylamine and 73g of toluene into the frank bottle, stirring for 15min, slowly dropwise adding 10g of diphenyl phosphorus chloride, filling a sand core funnel with diatomite, removing generated triethylamine hydrochloride by suction filtration, sequentially washing the frank bottle and the triethylamine hydrochloride with toluene and n-hexane, merging filtrate, removing solvent by rotary evaporation to obtain a light yellow viscous liquid crude product, purifying by adopting a silica gel column chromatography, removing the solvent by rotary evaporation, and then drying in a vacuum drying oven at 50 ℃ for 12h to obtain a white powdery product.
The flame-retardant silicone rubber material in the example is prepared by adopting the following preparation method, and the specific steps are as follows:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) After the methyl vinyl silicone rubber is fully divided into a roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time is 6 minutes each time;
(3) Slowly adding the accurately weighed fumed silica, dihydroxypolydimethylsiloxane, 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 gap unchanged, adding a double-penta vulcanizing agent and a BIPB-40B vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a film;
(5) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 175 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 6min, so that the flame-retardant silicone rubber material in the example is obtained.
Example 4
The flame-retardant silicone rubber material in the example 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 polydimethyl diphenyl siloxane, 50 parts of DPPA-Si ternary flame retardant, 2.5 parts of microcrystalline wax, 20 parts of magnesium silicate and 3.0 parts of bis-penta-vulcanizing agent. Wherein the DPPA-Si ternary flame retardant comprises the following raw materials: 6.6g of gamma-aminopropyl triethoxysilane, 7.0g of triethylamine, 102g of toluene and 14g of diphenyl phosphorus chloride.
Flame-retardant silicon rubberIn the formula of the 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 method 2 The 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 method 2 The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; the polydimethyl diphenyl siloxane is colorless transparent liquid with the density of 1.05g/cm 3 The content of the effective substances is more than or equal to 99.5 percent.
The DPPA-Si ternary flame retardant is prepared by adopting the following preparation method, and comprises the following specific steps:
adopting anhydrous and anaerobic operation technology, after the frank bottle is closed and exchanged with nitrogen for 3 times, under the condition of nitrogen protection and low temperature of minus 40 ℃, 6.6g of gamma-aminopropyl triethoxysilane, 7.0g of triethylamine and 102g of toluene are sequentially injected into the frank bottle, after stirring for 15min, 14g of diphenyl phosphorus chloride is slowly added dropwise, then a sand core funnel is filled with diatomite, the generated triethylamine hydrochloride is removed by suction filtration, the frank bottle and the triethylamine hydrochloride are sequentially washed by toluene and n-hexane, the filtrate is combined, the solvent is removed by rotary evaporation, a light yellow viscous liquid crude product is obtained, the silica gel column chromatography purification is adopted, the solvent is removed by rotary evaporation, and the mixture is placed in a vacuum drying oven at 50 ℃ for drying treatment for 12h, so that a white powdery product is obtained.
The flame-retardant silicone rubber material in the example is prepared by adopting the following preparation method, and the specific steps are as follows:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) After the methyl vinyl silicone rubber is fully divided into a roller, adding the DPPA-Si ternary flame retardant for 3 times, wherein the interval time is 6 minutes each time;
(3) Slowly adding the accurately weighed fumed silica, precipitation white carbon, 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 gap unchanged, adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a rubber sheet;
(5) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 170 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 7min, so that the flame-retardant silicone rubber material in the example is obtained.
Comparative example 1
The flame-retardant silicone rubber material in the example 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-penta-vulcanizing agent.
In the formula of the flame-retardant silicone rubber material, the molecular weight of methyl vinyl silicone rubber is 48 ten thousand, the mol fraction content of vinyl is 0.16%, and the volatile component is less than or equal to 2.0%; siO in white carbon black by gas phase method 2 The mass content is more than or equal to 97 percent, the CTAB specific surface area is 190m 2 Per g, DBP oil absorption value 2.7cm 3 Per gram, heating decrement is less than or equal to 8%; the dimethyl dimethoxy silane is colorless transparent liquid with purity of 99%, molecular weight of 120 and density of 0.8g/cm 3 。
The flame-retardant silicone rubber material is prepared by adopting the following preparation method, and comprises the following specific steps:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) After the methyl vinyl silicone rubber is fully divided into rolls, adding the accurately weighed fumed silica, dimethyl dimethoxy silane, rosin and kaolin slowly for 5 times, and fully mixing after the powder is coated by the methyl vinyl silicone rubber;
(3) Keeping the roll gap unchanged, adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a rubber sheet;
(4) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 170 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 7min, so that the flame-retardant silicone rubber material in the example is obtained.
Comparative example 2
The flame-retardant silicone rubber material in the example comprises the following raw materials in parts by weight: 100 parts of methyl vinyl silicone rubber, 15 parts of precipitated white carbon black, 25 parts of gas phase white carbon black, 8.5 parts of methyl phenyl diethoxy silane, 2.0 parts of microcrystalline wax and 3.0 parts of bis-dipentaerythritol vulcanizing agent.
In the formula of the flame-retardant silicone rubber material, the molecular weight of methyl vinyl silicone rubber is 48 ten thousand, the mol fraction content of vinyl is 0.16%, and the volatile component is less than or equal to 2.0%; siO in white carbon black by precipitation method 2 The 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 method 2 The 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 example is prepared by adopting the following preparation method, and the specific steps are as follows:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) Slowly adding accurately weighed precipitated white carbon black, gas-phase white carbon black, methyl phenyl diethoxysilane and microcrystalline wax for 5 times after the methyl vinyl silicone rubber is fully divided into rolls, and fully mixing after the powder is coated by the methyl vinyl silicone rubber;
(3) Keeping the roll gap unchanged, adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a rubber sheet;
(4) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 170 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 5min, so that the flame-retardant silicone rubber material in the example is obtained.
Comparative example 3
The flame-retardant silicone rubber material in the example 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 methylphenyl diethoxysilane, 35 parts of chlorinated paraffin-70, 10 parts of antimonous oxide, 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 silicone rubber material, the molecular weight of methyl vinyl silicone rubber is 48 ten thousand, the mol fraction content of vinyl is 0.16%, and the volatile component is less than or equal to 2.0%; siO of white carbon black by gas phase method 2 The mass content is more than or equal to 97 percent, the CTAB specific surface area is 190m 2 Per g, DBP oil absorption value 2.7cm 3 Per gram, heating decrement is less than or equal to 8%; the dihydroxyl polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 Pa.s, 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 example is prepared by adopting the following preparation method, and the specific steps are as follows:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) After the methyl vinyl silicone rubber is fully divided into a 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 divided into rolls, adding the accurately weighed fumed silica, dihydroxy polydimethylsiloxane, methyl phenyl diethoxysilane, rosin and calcium carbonate into the rolls for 5 times slowly, and fully mixing the materials after the silicone rubber coats the powder;
(4) Keeping the roll gap unchanged, adding BIPB-40B vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a film;
(5) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 175 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 8min, so that the flame-retardant silicone rubber material in the example is obtained.
Comparative example 4
The flame-retardant silicone rubber material in the example 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 dihydroxypolydimethylsiloxane, 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 bis-penta-vulcanizing agent.
In the formula of the flame-retardant silicone rubber material, the molecular weight of methyl vinyl silicone rubber is 48 ten thousand, the mol fraction content of vinyl is 0.16%, and the volatile component is less than or equal to 2.0%; siO in white carbon black by precipitation method 2 The 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 method 2 The mass content is more than or equal to 97 percent, and the heating decrement is less than or equal to 8 percent; the dihydroxyl polydimethylsiloxane is colorless transparent oily liquid, the viscosity at 25 ℃ is 15-25 Pa.s, and the hydroxyl content is 8%; the average particle diameters of the aluminum hydroxide and the magnesium hydroxide were 2. Mu.m, and the average particle diameter of the zinc borate was 6. Mu.m.
The flame-retardant silicone rubber material in the example is prepared by adopting the following preparation method, and the specific steps are as follows:
(1) Placing the methyl vinyl silicone rubber with the formula amount on an open mill with the roller temperature of 40 ℃, adjusting the roller spacing to 3.0mm, and beginning plasticating;
(2) After the methyl vinyl silicone rubber is fully divided into a roller, adding aluminum hydroxide, magnesium hydroxide and zinc borate for 3 times, wherein the interval time is 6min each time;
(3) After the rubber is fully divided into rolls, adding the accurately weighed fumed silica, precipitated silica, dihydroxypolydimethylsiloxane, microcrystalline wax and magnesium silicate into the rolls for 5 times slowly, and fully mixing the materials after the silicone rubber is coated with the powder;
(4) Keeping the roll gap unchanged, adding a double-penta vulcanizing agent into the rubber compound, adjusting the roll gap to 1.0mm after 3min, fully mixing the silicone rubber again in a triangle bag mode, and finally tabletting with the roll gap of 3.0mm to prepare a rubber sheet;
(5) And (3) putting the rubber sheet into a flat vulcanizing machine for vulcanizing, wherein the vulcanizing temperature is 170 ℃, the vulcanizing pressure is 10MPa, and the vulcanizing time is 10min, so that the flame-retardant silicone rubber material in the example is obtained.
Performance testing
(1) Physical and mechanical property test
The samples of the flame retardant silicone rubber materials prepared in examples 1 to 4 and comparative examples 1 to 4 were respectively tested for their physical and mechanical properties according to the test methods described in the standards in the following table 1, and the test results are recorded in the following table 1.
Table 1 results of physical mechanical property test of flame retardant silicone rubber materials in examples 1 to 4 and comparative examples 1 to 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 to 4 of the present invention were better than those of the flame retardant silicone rubber materials in comparative examples 1 to 4. The flame-retardant silicone rubber materials in examples 1 to 4 have a silicon ethoxy structure, so that the DPPA-Si ternary flame retardant is easy to hydrolyze in the mixing process to generate silicon hydroxyl, the Si-O bond and the silicon hydroxyl of the flame-retardant silicone rubber material are similar to the main structure of the silicone rubber, and according to the similar compatibility principle, the DPPA-Si ternary flame retardant is well compatible and dispersed in the silicone rubber, and the mechanical properties such as tensile strength, tear strength and the like are naturally and effectively improved. According to GB/T3512-2014, after the flame retardant silicone rubber materials in examples 1-4 are placed in a 200 ℃ oven for 24 hours of continuous and uninterrupted baking, the following characterization method is adopted: performance retention = post aging performance/pre aging performance x 100%, which still shows higher retention in terms of tensile strength, elongation at break, tear strength.
The compatibility of flame retardants such as chlorinated paraffin-70, antimonous oxide, aluminum hydroxide and the like with silicone rubber is poor, so that after the flame retardants are subjected to long-time high-temperature treatment, the self thermal oxidation decomposition products seriously damage the crosslinked network structure in the silicone rubber, so that the flame retardants show lower physical and mechanical properties and ageing resistance, and the phenomena are more obvious along with the increase of the added parts.
(2) Flame retardant Performance test
The flame retardant properties of the flame retardant silicone rubber material samples prepared in examples 1 to 4 and comparative examples 1 to 4 were respectively tested according to the test methods described in the standards in table 2 below, and the test results are recorded in tables 2 and 3.
Table 2 flame retardant property test results of flame retardant silicone rubber materials in examples 1 to 4 and comparative examples 1 to 4
TABLE 3 self-extinguishing test results of flame retardant Silicone rubber materials in examples 1 to 4 and comparative examples 1 to 4
As can be seen from the test results of various flame retardant properties in tables 2 and 3, the flame retardant silicone rubber materials in examples 1 to 4 of the present invention do not have dripping phenomenon in the two flame retardant processes, the cotton at the bottom is not ignited, the sample bar is not burnt, the two flame retardant elements can reach the state of extinguishing after being separated from fire, which indicates that the three flame retardant elements of phosphorus, nitrogen and silicon are organically combined, so that the materials generate substances such as phosphoric acid, metaphosphoric acid and the like in the secondary combustion process, the substances are converged into a high polymer state in the high temperature state, the dehydration and the char formation of the flame retardant materials are promoted, meanwhile, due to the existence of the siloxane structure, a large amount of Si-O or Si-C carbon protective layers are covered on the surfaces of the combustible materials, and the Si-O or Si-C carbon protective layers are uniformly used as the protective layers of the rubber, so that air and the combustible materials are isolated, the heat feedback strength of the flame to the base body is further reduced while the heat feedback strength of the flame is reduced, the temperature and the oxygen concentration of the flame system are effectively reduced in the combustion process, the combustion of the flame is further prevented, and the flame retardant efficiency of the flame is further improved. In addition, the filler such as calcium carbonate and kaolin can be added to not only serve as a weak reinforcing agent to enhance the mechanical property of the flame-retardant silicone rubber material, but also serve as an isolating layer to prevent oxygen from penetrating into a silicone rubber matrix in the combustion process, so that flame extinction is promoted, and meanwhile, the overall cost of the material is reduced to a certain extent.
Similar to the synergistic combination of aluminum hydroxide/magnesium hydroxide/zinc borate, chlorinated paraffin-70 and antimony trioxide are matched to act on silicon rubber together, and in the process of adding a large amount of the silicon rubber, the negative phenomena of uneven particle dispersion, reduced mechanical property, increased smoke density in the combustion process and the like are necessarily caused due to the reasons of self environmental protection, compatibility and the like.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (9)
1. The 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; the phosphorus nitrogen silicon flame retardant is DPPA-Si, and the preparation method of the DPPA-Si flame retardant comprises the following steps: mixing gamma-aminopropyl triethoxysilane, triethylamine, toluene and diphenyl phosphorus chloride for reaction, and purifying to obtain the DPPA-Si flame retardant; the filler is at least one of kaolin, calcium carbonate and magnesium silicate;
the preparation method of the flame-retardant silicone rubber material comprises the following steps:
s1: mixing silicon rubber with phosphorus nitrogen silicon flame retardant;
s2: mixing the mixed product in the step S1 with white carbon black, a structure regulator, a filler and a plasticizer to prepare a mixed rubber;
s3: and mixing the mixed rubber with a vulcanizing agent, and vulcanizing to obtain the flame-retardant silicone rubber material.
2. The flame retardant silicone rubber material according to claim 1, wherein: the silicone rubber comprises methyl vinyl silicone rubber.
3. The flame retardant silicone rubber material according to 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) Vinyl content is 0.08% -0.4%;
(3) Volatile components are less than or equal to 2.0 percent;
(4) The terminal group is at least one of methyl and vinyl.
4. A flame retardant silicone rubber material according to claim 3, characterized in that: the DPPA-Si has an initial decomposition temperature of 210-240 ℃.
5. The flame retardant silicone rubber material according to claim 1, wherein: the structure regulator is at least one of dihydroxypolydimethylsiloxane, dimethyldimethoxy silane, methylphenyl diethoxy silane and polydimethyl diphenyl siloxane.
6. The flame retardant silicone rubber material according to claim 1, wherein: the plasticizer is at least one of coumarone, rosin, disproportionated rosin and microcrystalline wax.
7. The method for preparing a flame retardant silicone rubber material according to any one of claims 1 to 6, characterized in that:
s1: mixing silicon rubber with phosphorus nitrogen silicon flame retardant;
s2: mixing the mixed product in the step S1 with white carbon black, a structure regulator, a filler and a plasticizer to prepare a mixed rubber;
s3: and mixing the mixed rubber with a vulcanizing agent, and vulcanizing to obtain the flame-retardant silicone rubber material.
8. The method for preparing a flame retardant silicone rubber material according to claim 7, wherein: in the step S3, the vulcanization temperature is 165-180 ℃, the vulcanization pressure is 9-11MPa, and the vulcanization time is 5-20min.
9. Use of the flame retardant silicone rubber material according to any one of claims 1 to 6 in flame retardant materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111603786.2A CN114181536B (en) | 2021-12-24 | 2021-12-24 | Flame-retardant silicone rubber material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111603786.2A CN114181536B (en) | 2021-12-24 | 2021-12-24 | Flame-retardant silicone rubber material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114181536A CN114181536A (en) | 2022-03-15 |
| CN114181536B true CN114181536B (en) | 2023-05-09 |
Family
ID=80544946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111603786.2A Active CN114181536B (en) | 2021-12-24 | 2021-12-24 | Flame-retardant silicone rubber material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114181536B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260767B (en) * | 2022-08-05 | 2023-09-15 | 深圳市捷超行模具有限公司 | Flame-retardant high-temperature vulcanized silicone rubber and preparation method thereof |
| CN115785676B (en) * | 2022-11-30 | 2024-02-06 | 清远市普塞呋磷化学有限公司 | Flame-retardant silicone rubber material and preparation method and application thereof |
| CN117866443A (en) * | 2023-12-29 | 2024-04-12 | 池州聚石化学有限公司 | Flame-retardant silicone rubber material and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633917B (en) * | 2016-12-28 | 2019-08-20 | 华南理工大学 | A kind of nano-meter flame retardants and nitrogen phosphorus system expanding fire retardant cooperative flame retardant silastic material and preparation method thereof |
| KR102010146B1 (en) * | 2017-07-19 | 2019-08-12 | 최기면 | Silicone composition having expandable graphite and method for manufacturing gasket using the composition |
| CN107698765A (en) * | 2017-10-09 | 2018-02-16 | 常州大学 | A kind of Nitrogen-and Phosphorus-containing silicon fire retardant and preparation method thereof |
| CN109867963A (en) * | 2019-01-14 | 2019-06-11 | 东莞市南炬高分子材料有限公司 | A kind of High-temperature-resandant andant flame-retardant silicone rubber and preparation method thereof |
| CN110105767A (en) * | 2019-05-31 | 2019-08-09 | 昆山兆科电子材料有限公司 | A kind of heat conductive flame-retarding insulating materials |
| CN112662184B (en) * | 2020-12-08 | 2022-10-28 | 清远市普塞呋磷化学有限公司 | Flame-retardant silicone rubber material and preparation method thereof |
| CN112812572B (en) * | 2021-01-26 | 2022-10-04 | 国光电器股份有限公司 | Silicone rubber and preparation method and application thereof |
-
2021
- 2021-12-24 CN CN202111603786.2A patent/CN114181536B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114181536A (en) | 2022-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114181536B (en) | Flame-retardant silicone rubber material and preparation method and application thereof | |
| CN110746706B (en) | Low-smoke halogen-free ethylene propylene diene monomer composition and preparation method thereof | |
| CN108299633B (en) | ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant and preparation method thereof and application of ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant in flame-retardant polymer | |
| CN103483707A (en) | Process for preparing rubber cable sheath material | |
| CN107057346B (en) | Flame-retardant nylon composition | |
| JPS60179436A (en) | Flame-retarding polyolefin rubber composition | |
| CN109369958B (en) | Preparation method and application of organically modified zirconium phosphate | |
| CN107434878A (en) | A kind of high glow-wire, water boiling resistance flame-retardant polypropylene composite material and preparation method | |
| CN110776635B (en) | Single-component intumescent flame retardant with free radical quenching function and preparation method and application thereof | |
| CN103483708A (en) | Low-temperature-resistance flame-retardant rubber cable sheath material | |
| Xiang et al. | A novel halogen‐free intumescent flame retardant containing phosphorus and nitrogen and its application in polypropylene systems | |
| CN105153467A (en) | Intumescent flame retardant functionalized hydrotalcite flame retardant and preparation method thereof | |
| CN108623844A (en) | DOPO-LDH composite fire retardants and preparation method thereof and halogen-free flame retardant ethylene propylene diene monomer (EPDM) material and its application | |
| CN111704687A (en) | Application of polymer as anti-dripping flame retardant | |
| CN114656702B (en) | Flame-retardant rubber for building safety net and preparation method thereof | |
| CN111501374A (en) | Modified asphalt waterproof coiled material with excellent flame retardant property and preparation method thereof | |
| CN109054395B (en) | High-temperature-resistant halogen-free flame-retardant silicone rubber and preparation method thereof | |
| CN102757652A (en) | Environment-friendly flame-retardant silicone rubber and preparation method thereof | |
| CN105462087B (en) | A kind of rubber antioxidant and preparation method thereof | |
| FI76821B (en) | OEVERDRAGNA FINFOERDELADE FYLLNADSAEMNEN, FOERFARANDE FOER DERAS FRAMSTAELLNING OCH POLYMERKOMPOSITION INNEHAOLLANDE DEM. | |
| CN115246927B (en) | Graphene oxide-based phosphorus-nitrogen-silicon composite flame-retardant copolyester and preparation method thereof | |
| CN112646245A (en) | Flame-retardant all-steel engineering radial tire tread rubber material and preparation method thereof | |
| CN115785676B (en) | Flame-retardant silicone rubber material and preparation method and application thereof | |
| CN118359917B (en) | TPE material and preparation method thereof | |
| CN117866443A (en) | Flame-retardant silicone rubber material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |