CN114958001A - High-strength ablation-resistant silicone rubber and preparation method thereof - Google Patents
High-strength ablation-resistant silicone rubber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to high-strength ablation-resistant silicone rubber and a preparation method thereof, belonging to the technical field of silicone rubber. The invention discloses a high-strength ablation-resistant silicone rubber which comprises the following raw materials: 50 parts of component A, 50 parts of component B, 10-15 parts of a mixture of decabromodiphenyl ether and antimony trioxide, 2-5 parts of a mixed filler, 0.5-1 part of hollow phenolic microspheres, 1-3 parts of iron oxide red, 3-5 parts of fumed silica and 2-3 parts of azodicarbonamide. The liquid T7-POSS organic silicon polymer is used as the filler, so that the liquid T7-POSS organic silicon polymer can be uniformly dispersed when being mixed with the raw silicon rubber, the shrinkage rate of the silicon rubber after heating and curing is effectively reduced, and the ablation resistance of the silicon rubber is improved.
Description
Technical Field
The invention belongs to the technical field of silicone rubber, and particularly relates to high-strength ablation-resistant silicone rubber and a preparation method thereof.
Background
The silicone rubber is an elastomer material which is formed by linear polysiloxane after cross-linking reaction and has a three-dimensional network structure, and has a unique organic-inorganic hybrid molecular chain structure. According to different vulcanization mechanisms, silicone rubber can be divided into three types: room temperature vulcanization type, heat vulcanization type, and addition reaction type. The addition reaction type silicon rubber can be used for a long time in the temperature range of-65-200 ℃, can keep the soft elastic performance, has excellent electrical performance and chemical stability, simultaneously has weather resistance, water resistance and ozone resistance, has the remarkable characteristics of no toxicity, no odor, no corrosion, physiological inertia, low linear shrinkage rate, easy operation and the like, and is widely applied to the fields of military affairs, buildings, medical treatment, automobiles, aerospace, daily chemicals, articles for daily use and the like.
The fireproof silicone rubber is used as a sealing material which is applied more at present, and has good flame retardant property and higher requirement on ablation resistance of the silicone rubber. The material is required not to be burnt through under the impact of flame at extremely high temperature, and a carbonized heat insulation layer can be formed to protect the back component from being damaged due to the impact of strong heat, and meanwhile, higher strength is required to ensure that the back component is not damaged in the using process.
In order to improve the ablation resistance, most of the prior art adopts a method of adding inorganic particles with heat insulation and reinforcement properties into silicone rubber, such as Khristorpher of Dow Corning company, adding 7-20% of wollastonite and 10-60% of reinforcement filler into liquid silicone rubber, and firing a test piece with the thickness of 0.635cm in flame of a Bunsen burner at 1093 ℃ for 15min, wherein the back surface of the test piece is not burnt through or burnt. However, the existing silicone rubber matrix resin still has the following technical problems: (1) because inorganic particles are agglomerated when the content of the inorganic particles in the silicone rubber exceeds a certain content, the addition amount is limited, and the strength and the ablation resistance of the material cannot be greatly improved; (2) under the flame ignition at 1050-1100 ℃, the formed carbonized ceramic layer is stable in a static state, but is easy to fall off under the vibration condition, so that the back part cannot be well protected; (3) the density and toxicity are high; (4) the strength is obviously reduced after being heated, and the heat resistance and the rupture resistance are not good.
Disclosure of Invention
In view of the above, the present invention provides a high-strength ablation-resistant silicone rubber and a preparation method thereof to solve the above technical problems.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The invention also provides high-strength ablation-resistant silicone rubber which comprises the following raw materials: 50 parts of component A, 50 parts of component B, 10-15 parts of a mixture of decabromodiphenyl ether and antimony trioxide, 2-5 parts of a mixed filler, 0.5-1 part of hollow phenolic microspheres, 1-3 parts of iron oxide red, 3-5 parts of fumed silica and 2-3 parts of azodicarbonamide.
The mixed filler is a mixture of zirconia, rare earth doped oxide and hollow ceramic microspheres;
the component A is formed by uniformly mixing 30-80 parts by weight of T7-POSS organic silicon polymer and 20-30 parts by weight of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing organic silicone oil;
the structural formula of the T7-POSS organic silicon polymer is as follows:
wherein R is isobutyl or cyclohexyl;
the average molecular weight of the T7-POSS organic silicon polymer is 1100-120000.
Preferably, in the mixture of decabromodiphenyl ether and antimony trioxide, the decabromodiphenyl ether accounts for 70-75 wt%, and the antimony trioxide accounts for 25-30 wt%.
Preferably, the mixed filler is a mixture of zirconia, rare earth doped oxide and hollow ceramic microspheres in a mass ratio of 1:1: 1.
Preferably, the rare earth doped oxide is light yellow granular and has the specific gravity less than or equal to 1.15g/cm 3 The particle size is 120-180 mu m, and the softening point is more than or equal to 120 ℃.
Preferably, the particle size of the hollow ceramic microspheres is 80-120 meshes.
Preferably, the preparation method of the T7-POSS organic silicon polymer comprises the following steps:
1) preparation method of vinyl methyl organosilicon
Dissolving methyl phenyl dimethoxysilane, methyl vinyl silicone oil and dimethyl dimethoxysilane in an organic solvent, stirring uniformly, adding potassium hydroxide, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering to remove unreacted potassium hydroxide, distilling under reduced pressure to remove the organic solvent, and drying under vacuum to obtain vinyl methyl organosilicon;
2) process for preparing incompletely condensed cyclohexyltrisilanols
Under the protection of inert atmosphere, dropwise adding reactants into a device containing lithium hydroxide monohydrate, deionized water and an organic solvent, heating and refluxing to react after dropwise adding is finished, cooling to room temperature, adding concentrated hydrochloric acid to acidify, performing suction filtration, washing a product to be neutral by water, washing the product by acetonitrile to obtain a white solid, and performing vacuum drying to obtain incompletely condensed cyclohexyl trisilanol;
3) preparation method of T7-POSS organic silicon polymer
Dissolving the incompletely condensed cyclohexyl trisilanol prepared in the step 2) and the vinyl methyl organosilicon prepared in the step 1) in an organic solvent, heating and refluxing for reaction, cooling to room temperature after the reaction is finished, removing the organic solvent by reduced pressure distillation, and drying in vacuum to obtain the T7-POSS organosilicon polymer.
It is more preferable that the content of the organic compound,
in the step 1), the mass ratio of the methyl phenyl dimethoxysilane to the methyl vinyl silicone oil to the dimethyl dimethoxysilane to the potassium hydroxide is 2:1:2: 0.4;
in the step 2), the reactant is isobutyl trimethoxy silane or cyclohexyl trimethoxy silane, and the mass ratio of the lithium hydroxide monohydrate to the reactant is 3.3: 20;
in the step 3), the mass ratio of the incompletely condensed cyclohexyl trisilanol to the vinyl methyl organosilicon polymer is 1: 3.
It is more preferable that the content of the organic compound,
in the step 1), the heating reflux reaction is carried out at 85 ℃ for 10 hours;
in the step 2), the heating reflux reaction is carried out for 14 hours at 65 ℃ and the acidification time is 2 hours;
in the step 3), the heating reflux reaction is carried out for 6 hours at 90 ℃.
Preferably, the component A is formed by uniformly mixing 30-80 parts by weight of T7-POSS organic silicon polymer and 25-30 parts by weight of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing organic silicone oil.
The invention also provides a preparation method of the high-strength ablation-resistant silicone rubber, which comprises the following steps:
weighing the components according to the proportion, uniformly mixing, placing in a mold, pressurizing, heating and vulcanizing to obtain the high-strength ablation-resistant silicone rubber.
Preferably, before weighing the components, the decabromodiphenyl ether, the antimony trioxide, the zirconium oxide, the rare earth doped oxide, the hollow ceramic microspheres, the hollow phenolic microspheres, the iron oxide red, the gas-phase silicon dioxide and the azodicarbonamide are dried.
Preferably, a three-roll mill is used to mix the components uniformly.
Preferably, the vulcanization temperature is 160 +/-10 ℃, the vulcanization pressure is 5-10 MPa, and the vulcanization time is 20-30 min.
Compared with the prior art, the invention has the beneficial effects that:
the T7-POSS organic silicon polymer is in a liquid state at room temperature, can be uniformly mixed with raw silicon rubber, can participate in a silicon rubber cross-linking network, is not limited, greatly reduces the shrinkage rate of the silicon rubber during curing, can improve the ablation resistance of the cured silicon rubber, and plays a role of the T7-POSS organic silicon polymer in reducing the curing shrinkage rate of the silicon rubber and improving the ablation resistance of the silicon rubber to the maximum extent.
The liquid T7-POSS organic silicon polymer is used as the filler, so that the T7-POSS organic silicon polymer can be uniformly dispersed when the liquid T7-POSS organic silicon polymer is mixed with raw silicone rubber, the shrinkage rate of the silicone rubber after being heated and cured can be effectively reduced, and the ablation resistance of the silicone rubber can be improved. Through test detection, the high-strength ablation-resistant silicone rubber has the following tensile strength at room temperature: not less than 6.5 MPa; volatile content (%): not less than 99; the working life is as follows: the time is more than or equal to 3 hours; specific gravity: 0.83 to 1.4g/cm 3 (ii) a Shore a hardness after 14 days: not less than 70; shear strength: not less than 1.75 MPa; the cohesive failure area rate is more than or equal to 85 percent; peel strength: not less than 1.875 kN/m; the cohesive failure area rate is more than or equal to 85 percent; fireproof and heat-insulating properties: after 1093 ℃ for 15min, the film is not burnt through, and the cold surface temperature is lower than 350 ℃.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention, but it is to be understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the claims.
The invention discloses high-strength ablation-resistant silicon rubber which comprises the following raw materials: 50 parts of component A, 50 parts of component B, 10-15 parts of a mixture of decabromodiphenyl ether and antimony trioxide, 2-5 parts of a mixed filler, 0.5-1 part of hollow phenolic microspheres, 1-3 parts of iron oxide red, 3-5 parts of fumed silica and 2-3 parts of azodicarbonamide;
the component A is formed by uniformly mixing 30-80 parts by weight of T7-POSS organic silicon polymer and 20-30 parts by weight of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing organic silicone oil;
wherein the structural formula of the T7-POSS organic silicon polymer is as follows:
wherein R is isobutyl or cyclohexyl;
the average molecular weight of the T7-POSS organic silicon polymer is 1100-120000.
In the technical scheme, in the mixture of the decabromodiphenyl ether and the antimony trioxide, the decabromodiphenyl ether accounts for 70-75 wt%, and the antimony trioxide accounts for 25-30 wt%.
In the technical scheme, the mixed filler is a mixture of zirconia, rare earth doped oxide and hollow ceramic microspheres in a mass ratio of 1:1: 1; the grain size of the hollow ceramic microspheres is 80-120 meshes. The rare earth doped oxide is light yellow granular with specific gravity less than or equal to 1.15g/cm 3 The particle size is 120-180 mu m, and the softening point is more than or equal to 120 ℃.
In the technical scheme, the T7-POSS organic silicon polymer is in a liquid state at room temperature, can be uniformly mixed with raw silicone rubber, can participate in a silicone rubber cross-linking network, is not limited, greatly reduces the shrinkage rate of the cured silicone rubber, can improve the ablation resistance of the cured silicone rubber, and plays a role in reducing the curing shrinkage rate of the silicone rubber and improving the ablation resistance of the silicone rubber to the maximum extent. The invention provides a preparation method of a T7-POSS organic silicon polymer, which is not limited in the preparation method and comprises the following steps:
1) preparation method of vinyl methyl organosilicon
Dissolving 100g of methyl phenyl dimethoxysilane, 50g of methyl vinyl silicone oil and 100g of dimethyl dimethoxysilane in toluene, stirring for 15min, adding 20g of potassium hydroxide, heating the system to 85 ℃, stirring and refluxing for 10h, cooling to room temperature, filtering to remove unreacted potassium hydroxide, distilling under reduced pressure to remove toluene, and drying in vacuum at 40 ℃ for 24h to obtain a transparent semisolid substance, namely vinyl methyl silicone, wherein the yield is about 85%.
2) Process for the preparation of incompletely condensed cyclohexyltrisilanols
Weighing 3.3g of lithium hydroxide monohydrate catalyst and 1.27g of deionized water (total water amount is 2.67g), placing the mixture in a 500mL three-neck flask, adding 165mL of acetone + methanol (88 vol.% +12 vol.%) mixed solvent, slowly adding 20g of cyclohexyltrimethoxysilane or isobutyltrimethoxysilane under the protection of nitrogen, heating to 65 ℃, stirring for reacting for 14h, stopping heating, cooling to room temperature, adding 150mL of concentrated hydrochloric acid (1mol/L), acidifying, stirring for reacting for 2h, stopping reaction, performing suction filtration, washing a product with water to be neutral, washing the product with acetonitrile for three times to obtain a white solid, and performing vacuum drying at 35 ℃ for 48h to obtain incompletely condensed cyclohexyltrisilanol (T7-POSS), wherein the yield is about 60%.
3) Preparation method of T7-POSS organic silicon polymer
50g of incompletely condensed cyclohexyl trisilanol (T7-POSS) prepared in the step 2) and 150g of vinyl methyl organosilicon polymer prepared in the step 1) are dissolved in 500mL of toluene, the temperature is raised to 90 ℃, the mixture is stirred and refluxed for 6h, after the mixture is cooled to room temperature, the toluene is removed through reduced pressure distillation, and vacuum drying is carried out for 4h at the temperature of 40 ℃, so that the T7-POSS organosilicon polymer is obtained, wherein the yield is about 91%.
The synthetic route of the T7-POSS organic silicon polymer is as follows:
in the technical scheme, the component A is preferably formed by uniformly mixing 30-80 parts by weight of T7-POSS organic silicon polymer and 25-30 parts by weight of methyl vinyl silicone oil, and the component B is preferably formed by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing organic silicone oil. More preferably, the component A is formed by uniformly mixing 80 parts of T7-POSS organic silicon polymer and 20 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 80 parts of palladium catalyst and 5 parts of hydrogen-containing silicone oil; or the component A is formed by uniformly mixing 30 parts of T7-POSS organic silicon polymer and 30 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20 parts of palladium catalyst and 20 parts of hydrogen-containing organic silicone oil; or the component A is formed by uniformly mixing 70 parts of T7-POSS organic silicon polymer and 30 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 70 parts of palladium catalyst and 15 parts of hydrogen-containing organic silicone oil; or the component A is formed by uniformly mixing 70 parts of T7-POSS organic silicon polymer and 25 parts of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 80 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicone oil.
The invention also provides a preparation method of the high-strength ablation-resistant silicone rubber, which comprises the following steps:
weighing the components according to the proportion, uniformly mixing, placing in a mold, pressurizing, heating and vulcanizing to obtain the high-strength ablation-resistant silicone rubber.
In the above technical scheme, a three-roll grinder is preferably used for uniformly mixing the component A and the component B.
In the technical scheme, the vulcanization temperature is preferably 160 +/-10 ℃, the vulcanization pressure is preferably 5-10 MPa, and the vulcanization time is preferably 20-30 min.
In the technical scheme, before weighing the components, preferably, decabromodiphenyl oxide, antimony trioxide, zirconium oxide, rare earth doped oxide, hollow ceramic microspheres, hollow phenolic microspheres, iron oxide red, fumed silica and azodicarbonamide are dried. Preferably, the drying equipment is a blast box, the drying temperature is 110 ℃, and the drying time is 6 h.
The liquid T7-POSS organic silicon polymer is used as the filler, so that the T7-POSS organic silicon polymer can be uniformly dispersed when the liquid T7-POSS organic silicon polymer is mixed with raw silicone rubber, the shrinkage rate of the silicone rubber after heating and curing can be effectively reduced, and the ablation resistance of the silicone rubber can be improved. Through test detection, the high-strength ablation-resistant silicone rubber has the following tensile strength at room temperature: not less than 6.5 MPa; volatile matter content (%): not less than 99; the working life is as follows: the time is more than or equal to 3 hours; specific gravity: 0.83 to 1.4g/cm 3 (ii) a Shore a hardness after 14 days: not less than 70; shear strength: not less than 1.75 MPa; the cohesive failure area rate is more than or equal to 85 percent; peel strength: not less than 1.875 kN/m; the cohesive failure area rate is more than or equal to 85 percent; fireproof and heat-insulating properties: after 1093 ℃ for 15min, the film is not burnt through, and the cold surface temperature is lower than 350 ℃.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified. In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified.
The present invention is further illustrated by the following examples.
Example 1
1) Placing decabromodiphenyl ether, antimony trioxide, zirconia, rare earth doped oxide, hollow ceramic microspheres, hollow phenolic microspheres, iron oxide red, fumed silica and azodicarbonamide into a blast drying oven, and drying at 110 ℃ for 6 h;
2) weighing 50 parts of component A, 50 parts of component B, 7 parts of decabromodiphenyl ether, 3 parts of antimony trioxide, 5 parts of mixed filler (zirconium oxide, rare earth doped oxide and hollow ceramic microspheres in a mass ratio of 1:1: 1), 0.5 part of hollow phenolic microspheres, 3 parts of iron oxide red, 5 parts of fumed silica and 3 parts of azodicarbonamide, adding into a three-roll grinder, grinding and mixing for 10-15 min until the powder filler has no caking particles, completely and uniformly mixing with the component A and the component B, putting the obtained rubber material into a mold, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain high-strength anti-burning silicone rubber (rubber sheet) with the thickness of 3.2 mm;
by weight: the component A is prepared by uniformly mixing 80 parts of T7-POSS organic silicon polymer (prepared according to the method in the specific embodiment) and 20 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 80 parts of palladium catalyst and 5 parts of hydrogen-containing organic silicone oil (202 organic silicone oil).
Example 2
1) Placing decabromodiphenyl ether, antimony trioxide, zirconia, rare earth doped oxide, hollow ceramic microspheres, hollow phenolic microspheres, iron oxide red, fumed silica and azodicarbonamide into a blast drying oven, and drying at 110 ℃ for 6 h;
2) weighing 50 parts by weight of a component A, 50 parts by weight of a component B, 10.5 parts by weight of decabromodiphenyl oxide, 4.5 parts by weight of antimony trioxide, 2 parts by weight of mixed filler (zirconium oxide, rare earth doped oxide and hollow ceramic microspheres in a mass ratio of 1:1: 1), 1 part by weight of hollow phenolic microspheres, 1 part by weight of iron oxide red, 3 parts by weight of fumed silica and 2 parts by weight of azodicarbonamide, adding the mixture into a three-roll grinder, grinding and mixing for 10-15 min until the powder filler has no caking particles, completely and uniformly mixing the powder filler with the component A and the component B, putting the obtained rubber material into a mold, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain high-strength anti-burning silicone rubber (rubber sheet) with the thickness of 3.2 mm;
by weight: the component A is formed by uniformly mixing 30 parts of T7-POSS organic silicon polymer (prepared according to the method in the specific embodiment) and 30 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 20 parts of palladium catalyst and 20 parts of hydrogen-containing organic silicone oil (202 organic silicone oil).
Example 3
1) Placing decabromodiphenyl ether, antimony trioxide, zirconia, rare earth doped oxide, hollow ceramic microspheres, hollow phenolic microspheres, iron oxide red, fumed silica and azodicarbonamide into a blast drying oven, and drying at 110 ℃ for 6 h;
2) weighing 50 parts of component A, 50 parts of component B, 9 parts of decabromodiphenyl oxide, 3 parts of antimony trioxide, 3 parts of mixed filler (zirconium oxide, rare earth doped oxide and hollow ceramic microspheres in a mass ratio of 1:1: 1), 1 part of hollow phenolic microspheres, 2 parts of iron oxide red, 4 parts of fumed silica and 3 parts of azodicarbonamide, adding into a three-roll grinder, grinding and mixing for 10-15 min until the powder filler has no caking particles, completely and uniformly mixing with the component A and the component B, putting the obtained rubber material into a mould, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain a high-strength ablation-resistant silicone rubber sheet (film) with the thickness of 3.2 mm;
by weight: the component A is prepared by uniformly mixing 70 parts of T7-POSS organic silicon polymer (prepared according to the method in the specific embodiment) and 30 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 70 parts of palladium catalyst and 15 parts of hydrogen-containing organic silicone oil (202 organic silicone oil).
Example 4
1) Placing decabromodiphenyl ether, antimony trioxide, zirconia, rare earth doped oxide, hollow ceramic microspheres, hollow phenolic microspheres, iron oxide red, fumed silica and azodicarbonamide into a blast drying oven, and drying at 110 ℃ for 6 h;
2) weighing 50 parts of component A, 50 parts of component B, 7 parts of decabromodiphenyl ether, 3 parts of antimony trioxide, 3 parts of mixed filler (zirconium oxide, rare earth doped oxide and hollow ceramic microspheres in a mass ratio of 1:1: 1), 0.5 part of hollow phenolic microspheres, 1 part of iron oxide red, 4 parts of fumed silica and 3 parts of azodicarbonamide, adding into a three-roll grinder, grinding and mixing for 10-15 min until the powder filler has no caking particles, completely and uniformly mixing with the component A and the component B, putting the obtained rubber material into a mold, pressurizing at 160 +/-10 ℃ for 5-10 MPa, and vulcanizing for 20-30 min to obtain high-strength anti-burning silicone rubber (rubber sheet) with the thickness of 3.2 mm;
by weight: the component A is prepared by uniformly mixing 70 parts of T7-POSS organic silicon polymer (prepared according to the method in the specific embodiment) and 25 parts of methyl vinyl silicone oil; the component B is formed by uniformly mixing 80 parts of palladium catalyst and 10 parts of hydrogen-containing organic silicone oil (202 organic silicone oil).
The properties of the high-strength ablation-resistant silicone rubbers (films) of examples 1 to 6 were examined. The test results are shown in table 1.
Table 1 properties of high strength ablation resistant silicone rubber (film) of examples 1 to 6
As can be seen from Table 1, the liquid T7-POSS organic silicon polymer is used as the filler, so that the T7-POSS organic silicon polymer can be uniformly dispersed when being mixed with raw silicone rubber, the shrinkage rate of the silicone rubber after being heated and cured can be effectively reduced, and the ablation resistance of the silicone rubber can be improved. Through test detection, the high-strength ablation-resistant silicone rubber has the following tensile strength at room temperature: not less than 6.5 MPa; volatile matter content (%): not less than 99; the working life is as follows: the time is more than or equal to 3 hours; specific gravity: 0.83 to 1.4g/cm 3 (ii) a Shore a hardness after 14 days: not less than 70; shear strength: not less than 1.75 MPa; the cohesive failure area rate is more than or equal to 85 percent; peel strength: not less than 1.875 kN/m; the cohesive failure area rate is more than or equal to 85 percent; fireproof and heat-insulating properties: after 1093 ℃ for 15min, the film is not burnt through, and the cold surface temperature is lower than 350 ℃.
The upper and lower limits and interval values of the raw materials and the upper and lower limits and interval values of the process parameters (time, temperature and the like) can all realize the invention, and the examples are not necessarily given here.
It should be understood that the above-described embodiments are merely examples for clarity of description and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither necessary nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The high-strength ablation-resistant silicone rubber is characterized by comprising the following raw materials: 50 parts of component A, 50 parts of component B, 10-15 parts of a mixture of decabromodiphenyl ether and antimony trioxide, 2-5 parts of a mixed filler, 0.5-1 part of hollow phenolic microspheres, 1-3 parts of iron oxide red, 3-5 parts of fumed silica and 2-3 parts of azodicarbonamide;
the mixed filler is a mixture of zirconia, rare earth doped oxide and hollow ceramic microspheres;
the component A is formed by uniformly mixing 30-80 parts by weight of T7-POSS organic silicon polymer and 20-30 parts by weight of methyl vinyl silicone oil, and the component B is formed by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing organic silicone oil;
the structural formula of the T7-POSS organic silicon polymer is as follows:
wherein R is isobutyl or cyclohexyl;
the average molecular weight of the T7-POSS organic silicon polymer is 1100-120000.
2. The high-strength ablation-resistant silicone rubber according to claim 1, wherein the mixture of decabromodiphenyl oxide and antimony trioxide comprises 70-75 wt% of decabromodiphenyl oxide and 25-30 wt% of antimony trioxide.
3. The high-strength ablation-resistant silicone rubber according to claim 1, wherein the mixed filler is a mixture of zirconia, rare earth doped oxide and hollow ceramic microspheres in a mass ratio of 1:1: 1;
the rare earth doped oxide is light yellow granular and has a specific gravity of less than or equal to 1.15g/cm 3 The particle size is 120-180 mu m, and the softening point is more than or equal to 120 ℃;
the particle size of the hollow ceramic microspheres is 80-120 meshes.
4. The high-strength ablation-resistant silicone rubber according to claim 1, wherein the component A is prepared by uniformly mixing 30-80 parts by weight of T7-POSS silicone polymer and 25-30 parts by weight of methyl vinyl silicone oil, and the component B is prepared by uniformly mixing 20-80 parts by weight of palladium catalyst and 5-20 parts by weight of hydrogen-containing silicone oil.
5. The high-strength ablation-resistant silicone rubber according to claim 1, wherein the preparation method of the T7-POSS silicone polymer comprises the following steps:
1) preparation method of vinyl methyl organosilicon
Dissolving methyl phenyl dimethoxysilane, methyl vinyl silicone oil and dimethyl dimethoxysilane in an organic solvent, stirring uniformly, adding potassium hydroxide, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering to remove unreacted potassium hydroxide, distilling under reduced pressure to remove the organic solvent, and drying under vacuum to obtain vinyl methyl organosilicon;
2) process for preparing incompletely condensed cyclohexyltrisilanols
Under the protection of inert atmosphere, dropwise adding reactants into a device containing lithium hydroxide monohydrate, deionized water and an organic solvent, heating and refluxing to react after dropwise adding is finished, cooling to room temperature, adding concentrated hydrochloric acid to acidify, performing suction filtration, washing a product to be neutral by water, washing the product by acetonitrile to obtain a white solid, and performing vacuum drying to obtain incompletely condensed cyclohexyl trisilanol;
3) preparation method of T7-POSS organic silicon polymer
Dissolving the incompletely condensed cyclohexyl trisilanol prepared in the step 2) and the vinyl methyl organosilicon prepared in the step 1) in an organic solvent, heating and refluxing for reaction, cooling to room temperature after the reaction is finished, removing the organic solvent by reduced pressure distillation, and drying in vacuum to obtain the T7-POSS organosilicon polymer.
6. The high-strength ablation-resistant silicone rubber according to claim 5,
in the step 1), the mass ratio of the methyl phenyl dimethoxysilane to the methyl vinyl silicone oil to the dimethyl dimethoxysilane to the potassium hydroxide is 2:1:2: 0.4;
in the step 2), the reactant is isobutyl trimethoxy silane or cyclohexyl trimethoxy silane, and the mass ratio of the lithium hydroxide monohydrate to the reactant is 3.3: 20;
in the step 3), the mass ratio of the incompletely condensed cyclohexyl trisilanol to the vinyl methyl organosilicon polymer is 1: 3.
7. The high-strength ablation-resistant silicone rubber according to claim 5,
in the step 1), the heating reflux reaction is carried out at 85 ℃ for 10 hours;
in the step 2), the heating reflux reaction is carried out for 14 hours at 65 ℃ and the acidification time is 2 hours;
in the step 3), the heating reflux reaction is carried out for 6 hours at 90 ℃.
8. The method for preparing the high-strength ablation-resistant silicone rubber according to any one of claims 1 to 7, characterized by comprising the steps of:
weighing the components according to the proportion, uniformly mixing, placing in a mold, pressurizing, heating and vulcanizing to obtain the high-strength ablation-resistant silicone rubber.
9. The high-strength ablation-resistant silicone rubber according to claim 1, wherein decabromodiphenyl oxide, antimony trioxide, zirconia, rare earth doped oxides, hollow ceramic microspheres, hollow phenolic microspheres, iron oxide red, fumed silica, and azodicarbonamide are dried before weighing the components.
10. The high-strength ablation-resistant silicone rubber according to claim 8,
uniformly mixing all the components by a three-roller grinding machine;
the vulcanization temperature is 160 +/-10 ℃, the vulcanization pressure is 5-10 MPa, and the vulcanization time is 20-30 min.
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| CN103602070A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院长春应用化学研究所 | Silicone rubber composite material and preparation method thereof |
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| CN103602070A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院长春应用化学研究所 | Silicone rubber composite material and preparation method thereof |
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