CN113278289A - Flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof - Google Patents
Flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof. The flame-retardant room-temperature vulcanized silicone rubber comprises alpha, omega-dihydroxy polydimethylsiloxane, hollow glass microspheres with the average particle size of 45-60 mu m, hollow glass microspheres with the average particle size of 60-85 mu m, methyl silicone oil, methyltrimethoxysilane, diisopropyl bis (ethyl acetoacetate) titanate, a silane coupling agent, fumed silica, methyl MQ resin, melamine cyanurate and polytetrafluoroethylene powder. The preparation method of the flame-retardant room-temperature vulcanized silicone rubber is very simple, and the flame-retardant room-temperature vulcanized silicone rubber is prepared by mixing the raw materials in batches and then mixing and vulcanizing. The room temperature vulcanized silicone rubber has the advantages of low density, excellent flame retardant property, good mechanical property and the like, and is easy to obtain raw materials, simple in preparation process and beneficial to realizing industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of silicon rubber, in particular to flame-retardant room-temperature vulcanized silicon rubber and a preparation method thereof.
Background
The room temperature vulcanized silicone rubber can be vulcanized at room temperature, is simple to construct, has excellent electrical insulation, ozone aging resistance, weather resistance, radiation resistance, high and low temperature resistance and other performances, and is widely applied to the insulation field of the power industry. However, the common room temperature vulcanized silicone rubber mainly adopts white carbon black, calcium carbonate and the like as reinforcing fillers, has the defects of high density, lack of flame retardant property and the like, and is difficult to completely meet the requirements of practical application, such as: the silicone rubber for insulating and coating the high-voltage overhead bare conductor and parts thereof close to residential areas, tree vegetation and cross-over (rivers, ponds, viaducts and the like) has low density and good flame retardant property due to the need of using under high-voltage and discharge environments.
At present, room temperature vulcanized silicone rubber with low density and flame retardant function mainly comprises a silicone rubber matrix, reinforcing fillers (white carbon black, calcium carbonate, montmorillonite and the like), weight-reducing fillers, flame retardants (magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate and the like), and the like, the density of the room temperature vulcanized silicone rubber is still large, and because the flame retardant efficiency of the flame retardants such as the aluminum hydroxide and the magnesium hydroxide is low, the good flame retardant property can be achieved by using a high addition amount, so that the mechanical property of the silicone rubber is damaged, and the density of the silicone rubber is obviously increased. For example: CN 108003628A discloses a flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof, wherein melamine and one or two of lipophilic magnesium hydroxide and lipophilic aluminum hydroxide are compounded to serve as a flame retardant, the addition amount of the flame retardant is high and needs to reach 60-100 parts by mass, and the prepared silicone rubber can pass UL 94V-0 level test, which can cause poor mechanical property and high density of the silicone rubber.
Therefore, it is highly desirable to develop a room temperature vulcanized silicone rubber having a low density, good mechanical properties and excellent flame retardancy.
Disclosure of Invention
The invention aims to provide flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the flame-retardant room-temperature vulcanized silicone rubber comprises the following components in parts by mass:
α, ω -dihydroxy polydimethylsiloxane: 100 parts of (A);
hollow glass beads: 10-20 parts;
methyl silicone oil: 10-30 parts;
methyltrimethoxysilane: 3-8 parts;
diisopropyl bis (acetoacetate) titanate: 2-4 parts;
silane coupling agent: 1-3 parts;
gas-phase white carbon black: 15-25 parts;
methyl MQ resin: 5-15 parts;
melamine cyanurate: 25-35 parts;
polytetrafluoroethylene powder: 1-5 parts;
the hollow glass beads are compounded by hollow glass beads with the average particle size of 45-60 mu m and hollow glass beads with the average particle size of 60-85 mu m.
Preferably, the hollow glass beads are prepared by compounding hollow glass beads with the average particle size of 45-60 microns and hollow glass beads with the average particle size of 60-85 microns according to the mass ratio of 1: 1-1: 4.
Preferably, the alpha, omega-dihydroxy polydimethylsiloxane is compounded by alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 1000mPa & s-2000 mPa & s and alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 15000mPa & s-25000 mPa & s.
More preferably, the alpha, omega-dihydroxy polydimethylsiloxane is prepared by compounding alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 1000 mPas-2000 mPas and alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 15000 mPas-25000 mPas according to the mass ratio of 3: 7-1: 9.
Preferably, the viscosity of the methyl silicone oil is 30 to 100 mPas.
Preferably, the silane coupling agent is at least one of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, gamma-aminopropyltriethoxysilane and gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
Preferably, the specific surface area of the fumed silica is 200m2/g～300m2/g。
Preferably, the M/Q ratio of the methyl MQ resin is 0.8-1.2.
Preferably, the particle size of the polytetrafluoroethylene powder is 2 to 20 μm.
The preparation method of the flame-retardant room-temperature vulcanized silicone rubber comprises the following steps:
1) mixing alpha, omega-dihydroxy polydimethylsiloxane and fumed silica, and mixing to obtain a silicone rubber base material;
2) dispersing methyl MQ resin in methyl silicone oil to obtain MQ resin solution;
3) mixing the silicon rubber base material and the MQ resin solution, mixing, adding hollow glass microspheres, a silane coupling agent, melamine cyanurate and polytetrafluoroethylene powder, continuously mixing, adding methyltrimethoxysilane and diisopropyl bis (ethyl acetoacetate) titanate, continuously mixing, and vulcanizing to obtain the flame-retardant room-temperature vulcanized silicon rubber.
Preferably, the preparation method of the flame-retardant room-temperature vulcanized silicone rubber comprises the following steps:
1) mixing alpha, omega-dihydroxy polydimethylsiloxane and fumed silica, and vacuumizing and mixing for 3-5 h at 110-150 ℃ to obtain a silicone rubber base material;
2) dispersing methyl MQ resin in methyl silicone oil to obtain MQ resin solution;
3) mixing the silicon rubber base material and the MQ resin solution, mixing for 2 min-5 min, adding hollow glass beads, a silane coupling agent, melamine cyanurate and polytetrafluoroethylene powder, mixing for 10 min-20 min, adding methyltrimethoxysilane and diisopropyl bis (ethyl acetoacetate) titanate, mixing for 2 min-5 min, and vulcanizing at 20-35 ℃ for 3-10 days to obtain the flame-retardant room temperature vulcanized silicon rubber.
The invention has the beneficial effects that: the room temperature vulcanized silicone rubber has the advantages of low density, excellent flame retardant property, good mechanical property and the like, and is easy to obtain raw materials, simple in preparation process and beneficial to realizing industrial large-scale production.
Specifically, the method comprises the following steps:
1) according to the invention, the hollow glass microspheres with different particle sizes are compounded, the hollow glass microspheres with small particle sizes have stronger binding force with the room temperature vulcanized silicone rubber and good dispersibility, and the hollow glass microspheres with large particle sizes have smaller density, so that the compounding of the hollow glass microspheres and the large particle sizes can effectively reduce the density of the room temperature vulcanized silicone rubber while the mechanical property and the processing property of the room temperature vulcanized silicone rubber are not obviously damaged;
2) according to the invention, the melamine cyanurate and the polytetrafluoroethylene are compounded to be used as a flame retardant, the melamine cyanurate can absorb a large amount of heat after being heated and decomposed, and simultaneously release gases such as flame-retardant ammonia gas and carbon dioxide to dilute oxygen and combustible gas, so that the flame retardant effect is exerted in a gas phase, fluorine free radicals can be generated when polytetrafluoroethylene powder is heated and combusted to capture HO & free radicals generated in the combustion process of silicone rubber, and the silicone rubber is promoted to generate compact residues, so that the flame retardant effect is exerted in a condensed phase, the melamine cyanurate and the polytetrafluoroethylene have good synergistic flame retardant effect, so that the excellent flame retardant property can be given to the room temperature vulcanized silicone rubber with lower consumption, and the mechanical property of the room temperature vulcanized silicone;
3) the room temperature vulcanized silicone rubber has the advantages of easily available raw materials, simple preparation process, contribution to realizing industrial production and good application prospect.
Drawings
FIG. 1 is a digital photograph of the vertical burning process of the RTV silicone rubber of example 1.
FIG. 2 is an SEM image of the combustion residue of the room temperature vulcanized silicone rubber of example 1.
FIG. 3 is a digital photograph of the vertical burning process of the RTV silicone rubber of comparative example 2.
Fig. 4 is an SEM image of a tensile section of the room-temperature vulcanized silicone rubber of comparative example 2.
Fig. 5 is an SEM image of the combustion residue of the room-temperature vulcanized silicone rubber of comparative example 4.
FIG. 6 is an infrared spectrum of a gas-phase product of the RTV-IR combination of comparative example 4.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof comprise the following steps:
1) 200g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1500 mPas, 800g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 20000 mPas and 200g of a specific surface area of 250m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 4 hours at 120 ℃ to obtain a silicon rubber base material;
2) fully dissolving 10g of methyl MQ resin with the M/Q value of 0.8 in 20g of methyl silicone oil with the viscosity of 50mPa & s at 25 ℃ to obtain MQ resin solution;
3) adding 120g of silicon rubber base material and 30g of MQ resin solution into a planetary mixer, mixing for 3min, adding 5g of hollow glass microspheres with the average particle size of 60 mu m, 10g of hollow glass microspheres with the average particle size of 85 mu m, 1g of N- (beta-aminoethyl) -gamma-aminopropyltriethoxy silicon, 1g of gamma-aminopropyltriethoxy silane, 30g of melamine cyanurate and 3g of polytetrafluoroethylene powder with the average particle size of 5 mu m, mixing for 15min, adding 6g of methyltrimethoxy silane and 3g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 3min, discharging, casting in a polytetrafluoroethylene mould, and vulcanizing for 7 days at 25 ℃ to obtain the flame retardant room temperature silicon sulfide rubber.
Example 2:
a flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof comprise the following steps:
1) 300g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1000 mPas, 700g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas and 250g of a specific surface area of 200m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 3 hours at 150 ℃ to obtain a silicon rubber base material;
2) fully dissolving 5g of methyl MQ resin with the M/Q value of 1.2 in 10g of methyl silicone oil with the viscosity of 30mPa & s at the temperature of 20 ℃ to obtain MQ resin solution;
3) adding 125g of silicon rubber base material and 15g of MQ resin solution into a planetary mixer, mixing for 5min, adding 10g of hollow glass microspheres with the average particle size of 45 mu m, 10g of hollow glass microspheres with the average particle size of 60 mu m, 0.5g of N- (beta-aminoethyl) -gamma-aminopropyl triethoxy silicon, 0.5g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 25g of melamine cyanurate and 5g of polytetrafluoroethylene powder with the average particle size of 20 mu m, mixing for 10min, adding 8g of methyl trimethoxy silane and 4g of bis (ethyl acetoacetate) diisopropyl titanate, mixing for 2min, discharging, casting in a polytetrafluoroethylene mould, and vulcanizing for 3 days at 35 ℃ to obtain the flame retardant room temperature silicon sulfide rubber.
Example 3:
a flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof comprise the following steps:
1) 100g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 2000 mPas, 900g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 15000 mPas and 150g of a specific surface area of 300m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 5 hours at 110 ℃ to obtain a silicon rubber base material;
2) fully dissolving 15g of methyl MQ resin with the M/Q value of 1 in 30g of methyl silicone oil with the viscosity of 100mPa & s at 35 ℃ to obtain MQ resin solution;
3) adding 115g of silicon rubber base material and 45g of MQ resin solution into a planetary mixer, mixing for 2min, adding 10g of hollow glass microspheres with the average particle size of 45 mu m, 10g of hollow glass microspheres with the average particle size of 85 mu m, 1g of N- (beta-aminoethyl) -gamma-aminopropyltriethoxy silicon, 2g of gamma-aminopropyltriethoxy silane, 35g of melamine cyanurate and 1g of polytetrafluoroethylene powder with the average particle size of 2 mu m, mixing for 20min, adding 3g of methyltrimethoxy silane and 2g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 5min, discharging, casting in a polytetrafluoroethylene mould, and vulcanizing for 10 days at 20 ℃ to obtain the flame retardant room temperature silicon sulfide rubber.
Example 4:
a flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof comprise the following steps:
1) 200g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1500 mPas, 800g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 20000 mPas and 200g of a specific surface area of 250m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 4 hours at 120 ℃ to obtain a silicon rubber base material;
2) fully dissolving 10g of methyl MQ resin with the M/Q value of 0.8 in 20g of methyl silicone oil with the viscosity of 50mPa & s at 25 ℃ to obtain MQ resin solution;
3) adding 120g of silicon rubber base material and 30g of MQ resin solution into a planetary mixer, mixing for 3min, adding 10g of hollow glass microspheres with the average particle size of 45 mu m, 10g of hollow glass microspheres with the average particle size of 80 mu m, 2g of N- (beta-aminoethyl) -gamma-aminopropyl triethoxy silicon, 30g of melamine cyanurate and 2g of polytetrafluoroethylene powder with the average particle size of 10 mu m, mixing for 10min, adding 6g of methyltrimethoxysilane and 2g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 3min, discharging, casting in a polytetrafluoroethylene mould, and vulcanizing for 7 days at 25 ℃ to obtain the flame retardant room temperature silicon sulfide rubber.
Example 5:
a flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof comprise the following steps:
1) 200g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1500 mPas, 800g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 20000 mPas and 200g of a specific surface area of 250m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 4 hours at 120 ℃ to obtain a silicon rubber base material;
2) fully dissolving 10g of methyl MQ resin with the M/Q value of 0.8 in 20g of methyl silicone oil with the viscosity of 50mPa & s at 25 ℃ to obtain MQ resin solution;
3) adding 120g of silicon rubber base material and 30g of MQ resin solution into a planetary mixer, mixing for 3min, adding 2g of hollow glass microspheres with the average particle size of 60 mu m, 8g of hollow glass microspheres with the average particle size of 85 mu m, 3g of gamma-aminopropyltriethoxysilane, 25g of melamine cyanurate and 4g of polytetrafluoroethylene powder with the average particle size of 20 mu m, mixing for 15min, adding 6g of methyltrimethoxysilane and 3g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 3min, discharging, casting into a polytetrafluoroethylene mould, and vulcanizing for 7 days at 25 ℃ to obtain the flame-retardant room-temperature silicon sulfide rubber.
Comparative example 1:
the preparation method of the room temperature vulcanized silicone rubber comprises the following steps:
1) 200g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1500 mPas, 800g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 20000 mPas and 200g of a specific surface area of 250m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 4 hours at 120 ℃ to obtain a silicon rubber base material;
2) fully dissolving 10g of methyl MQ resin with the M/Q value of 0.8 in 20g of methyl silicone oil with the viscosity of 50mPa & s at 25 ℃ to obtain MQ resin solution;
3) adding 120g of silicon rubber base material and 30g of MQ resin solution into a planetary mixer, mixing for 3min, adding 6g of methyltrimethoxysilane and 3g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 2min, discharging, casting in a polytetrafluoroethylene mold, and vulcanizing at 25 ℃ for 7 days to obtain the room-temperature vulcanized silicon rubber.
Comparative example 2:
the preparation method of the room temperature vulcanized silicone rubber comprises the following steps:
1) 200g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1500 mPas, 800g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 20000 mPas and 200g of a specific surface area of 250m2Per g fumed silica is added into power and mixedVacuumizing and mixing for 4h at 120 ℃ in a machine to obtain a silicon rubber base material;
2) fully dissolving 10g of methyl MQ resin with the M/Q value of 0.8 in 20g of methyl silicone oil with the viscosity of 50mPa & s at 25 ℃ to obtain MQ resin solution;
3) adding 120g of silicon rubber base material and 30g of MQ resin solution into a planetary mixer, mixing for 3min, adding 5g of hollow glass microspheres with the average particle size of 60 mu m, 10g of hollow glass microspheres with the average particle size of 85 mu m, 1g of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 1g of gamma-aminopropyltriethoxysilane, mixing for 15min, adding 6g of methyltrimethoxysilane and 3g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 3min, discharging, casting in a polytetrafluoroethylene mould, and vulcanizing for 7 days at 25 ℃ to obtain the room-temperature vulcanized silicon rubber.
Comparative example 3:
the preparation method of the room temperature vulcanized silicone rubber comprises the following steps:
1) 200g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1500 mPas, 800g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 20000 mPas and 200g of a specific surface area of 250m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 4 hours at 120 ℃ to obtain a silicon rubber base material;
2) fully dissolving 10g of methyl MQ resin with the M/Q value of 0.8 in 20g of methyl silicone oil with the viscosity of 50mPa & s at 25 ℃ to obtain MQ resin solution;
3) adding 120g of silicon rubber base material and 30g of MQ resin solution into a planetary mixer, mixing for 3min, adding 5g of hollow glass microspheres with the average particle size of 60 mu m, 10g of hollow glass microspheres with the average particle size of 85 mu m, 1g of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, 1g of gamma-aminopropyltriethoxysilane and 3g of polytetrafluoroethylene powder with the average particle size of 5 mu m, mixing for 15min, adding 6g of methyltrimethoxysilane and 3g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 3min, discharging, casting in a polytetrafluoroethylene mould, and vulcanizing for 7 days at 25 ℃ to obtain the room-temperature silicon sulfide rubber.
Comparative example 4:
the preparation method of the room temperature vulcanized silicone rubber comprises the following steps:
1) 200g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 1500 mPas, 800g of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 20000 mPas and 200g of a specific surface area of 250m2Adding/g fumed silica into a power mixer, and vacuumizing and mixing for 4 hours at 120 ℃ to obtain a silicon rubber base material;
2) fully dissolving 10g of methyl MQ resin with the M/Q value of 0.8 in 20g of methyl silicone oil with the viscosity of 50mPa & s at 25 ℃ to obtain MQ resin solution;
3) adding 120g of silicon rubber base material and 30g of MQ resin solution into a planetary mixer, mixing for 3min, adding 5g of hollow glass microspheres with the average particle size of 60 mu m, 10g of hollow glass microspheres with the average particle size of 85 mu m, 1g of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, 1g of gamma-aminopropyltriethoxysilane and 30g of melamine cyanurate, mixing for 15min, adding 6g of methyltrimethoxysilane and 3g of diisopropyl bis (ethyl acetoacetate) titanate, mixing for 3min, discharging, casting in a polytetrafluoroethylene mold, and vulcanizing for 7 days at 25 ℃ to obtain the room-temperature vulcanized silicon rubber.
And (3) performance testing:
1) the flame retardancy of the rtps of examples 1 to 5 and comparative examples 1 to 4 was tested, and the test results are shown in table 1, the digital photograph of the vertical burning process of the rtps of example 1 is shown in fig. 1, the Scanning Electron Microscope (SEM) image of the burning residue of the rtps of example 1 is shown in fig. 2, the digital photograph of the vertical burning process of the rtps of comparative example 2 is shown in fig. 3, the SEM image of the tensile cross section of the rtps of comparative example 2 is shown in fig. 4, the SEM image of the burning residue of the rtps of comparative example 4 is shown in fig. 5, and the infrared spectrum of the gas phase product of the rtps of comparative example 4 is shown in fig. 6:
TABLE 1 flame retardancy test results of RTV silicone rubber
Note:
oxygen Index (LOI): the test is carried out according to the GB/T10707-2008 rubber combustion performance measurement;
vertical burning Performance (UL-94): the test was conducted with reference to "ASTM 635-2003", where t1 of the vertical burning rating test is the flaming burning time after the first application of the flame to the specimen, and t2+ t3 is the sum of the flaming burning time and the flameless burning time after the second application of the flame to the specimen.
As can be seen from Table 1: the room temperature vulcanized silicone rubber (comparative example 3) with a small amount of polytetrafluoroethylene powder added alone has an unobvious flame retardant effect, and the Limiting Oxygen Index (LOI) of the room temperature vulcanized silicone rubber is only 23 percent and fails a vertical combustion test; the flame retardant property of room temperature vulcanized silicone rubber (comparative example 4) can be improved by adding melamine cyanurate alone, the LOI thereof is increased to 27%, and the vertical burning rate reaches UL 94V-1 level, because melamine cyanurate decomposes under heat, absorbs a large amount of heat and generates a large amount of CO2、NH3The flame-retardant gases (see figure 6) dilute the concentration of the combustible volatile gases and oxygen and play a role in flame retardance in a gas phase; meanwhile, the flame retardant performance of the room temperature vulcanized silicone rubber (examples 1-5) added with the melamine cyanurate and the polytetrafluoroethylene powder is remarkably improved, the LOI reaches more than 27%, the vertical burning grades reach UL 94V-0 grade, and the density is lower (the ratio is lower)<1.0g/cm3) The room temperature vulcanized silicone rubber of example 1 self-extinguished within 7s after the first flame application, and exhibited more excellent flame retardant performance (see fig. 1 and 3), because the polytetrafluoroethylene powder generated fluorine radicals when heated by combustion captured HO-radicals generated during the silicone rubber combustion process, and formed relatively dense residues (see fig. 2 and 5), and acted as a flame retardant in the condensed phase, and it was found that the polytetrafluoroethylene powder and melamine cyanurate produced good synergistic flame retardant effect on the room temperature vulcanized silicone rubber.
2) The density and mechanical properties of the room temperature vulcanized silicone rubbers of examples 1 to 5 and comparative examples 1 to 4 were tested, and the test results are shown in table 2:
TABLE 2 Density and mechanical Properties test results of Room temperature vulcanized Silicone rubber
Note:
tensile strength and elongation at break: the test is carried out according to the determination of the tensile stress strain performance of GB/T528-2009 vulcanized rubber or thermoplastic rubber, and the tensile rate is 500 mm/min;
shore A hardness: referring to "GB/T531.1-2008 vulcanized rubber or thermoplastic rubber indentation hardness test method part 1: shore durometer (shore hardness) "was performed.
As can be seen from Table 2: by compounding the hollow glass microspheres with different particle sizes, the density of the room temperature vulcanized silicone rubber can be effectively reduced, and the mechanical property of the room temperature vulcanized silicone rubber is not greatly damaged, because the hollow glass microspheres with proper particle sizes have good dispersibility in the silicone rubber and strong binding force with the silicone rubber (see figure 4).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The flame-retardant room-temperature vulcanized silicone rubber is characterized by comprising the following components in parts by mass:
α, ω -dihydroxy polydimethylsiloxane: 100 parts of (A);
hollow glass beads: 10-20 parts;
methyl silicone oil: 10-30 parts;
methyltrimethoxysilane: 3-8 parts;
diisopropyl bis (acetoacetate) titanate: 2-4 parts;
silane coupling agent: 1-3 parts;
gas-phase white carbon black: 15-25 parts;
methyl MQ resin: 5-15 parts;
melamine cyanurate: 25-35 parts;
polytetrafluoroethylene powder: 1-5 parts;
the hollow glass beads are compounded by hollow glass beads with the average particle size of 45-60 mu m and hollow glass beads with the average particle size of 60-85 mu m.
2. The flame retardant room temperature vulcanized silicone rubber according to claim 1, wherein: the hollow glass beads are prepared by compounding hollow glass beads with the average particle size of 45-60 mu m and hollow glass beads with the average particle size of 60-85 mu m according to the mass ratio of 1: 1-1: 4.
3. The flame retardant room temperature vulcanized silicone rubber according to claim 1 or 2, wherein: the alpha, omega-dihydroxy polydimethylsiloxane is prepared by compounding alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 1000-2000 mPas and alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 15000-25000 mPas.
4. The flame retardant room temperature vulcanized silicone rubber according to claim 1 or 2, wherein: the viscosity of the methyl silicone oil is 30mPa & s-100 mPa & s.
5. The flame retardant room temperature vulcanized silicone rubber according to claim 1 or 2, wherein: the silane coupling agent is at least one of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, gamma-aminopropyltriethoxysilane and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane.
6. The flame retardant room temperature vulcanized silicone rubber according to claim 1 or 2, wherein: the specific surface area of the fumed silica is 200m2/g～300m2/g。
7. The flame retardant room temperature vulcanized silicone rubber according to claim 1 or 2, wherein: the M/Q ratio of the methyl MQ resin is 0.8-1.2.
8. The flame retardant room temperature vulcanized silicone rubber according to claim 1 or 2, wherein: the particle size of the polytetrafluoroethylene powder is 2-20 microns.
9. The method for preparing the flame-retardant room temperature vulcanized silicone rubber according to any one of claims 1 to 8, characterized by comprising the steps of:
1) mixing alpha, omega-dihydroxy polydimethylsiloxane and fumed silica, and mixing to obtain a silicone rubber base material;
2) dispersing methyl MQ resin in methyl silicone oil to obtain MQ resin solution;
3) mixing the silicon rubber base material and the MQ resin solution, mixing, adding hollow glass microspheres, a silane coupling agent, melamine cyanurate and polytetrafluoroethylene powder, continuously mixing, adding methyltrimethoxysilane and diisopropyl bis (ethyl acetoacetate) titanate, continuously mixing, and vulcanizing to obtain the flame-retardant room-temperature vulcanized silicon rubber.
10. The method of claim 9, comprising the steps of:
1) mixing alpha, omega-dihydroxy polydimethylsiloxane and fumed silica, and vacuumizing and mixing for 3-5 h at 110-150 ℃ to obtain a silicone rubber base material;
2) dispersing methyl MQ resin in methyl silicone oil to obtain MQ resin solution;
3) mixing the silicon rubber base material and the MQ resin solution, mixing for 2 min-5 min, adding hollow glass beads, a silane coupling agent, melamine cyanurate and polytetrafluoroethylene powder, mixing for 10 min-20 min, adding methyltrimethoxysilane and diisopropyl bis (ethyl acetoacetate) titanate, mixing for 2 min-5 min, and vulcanizing at 20-35 ℃ for 3-10 days to obtain the flame-retardant room temperature vulcanized silicon rubber.
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