CN118221945A - Preparation method and application of hyperbranched polysiloxazane - Google Patents
Preparation method and application of hyperbranched polysiloxazane Download PDFInfo
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- CN118221945A CN118221945A CN202410436603.XA CN202410436603A CN118221945A CN 118221945 A CN118221945 A CN 118221945A CN 202410436603 A CN202410436603 A CN 202410436603A CN 118221945 A CN118221945 A CN 118221945A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
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- 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
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- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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Abstract
The invention discloses a preparation method and application of hyperbranched polysiloxazane, wherein cyclosilazane and hydrogen-containing silicone oil are subjected to condensation reaction under the action of a catalyst to obtain hyperbranched polysiloxazane; the heat-resistant auxiliary agent for the silicone rubber is prepared by kneading and uniformly mixing hyperbranched polysiloxazane, polysiloxane and metal compound, and the heat-resistant auxiliary agent for the silicone rubber has mild and efficient synthesis reaction conditions, and can greatly improve the thermal oxidative aging performance of the silicone rubber.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to siloxane silazane, and in particular relates to a preparation method and application of hyperbranched polysiloxazane.
Background
The silicone rubber can be used for a long time within the temperature range of-50 to 220 ℃ and keeps elasticity, and is widely applied to the industrial fields of aerospace, electronics, buildings and the like. At higher temperatures, the siloxane chains undergo thermal cleavage reactions to cyclic siloxanes and the pendant groups undergo oxidation reactions to produce crosslinked structures. Polysilazane is an inorganic polymer with Si-N bonds as repeating units of the main chain, and the inorganic Si-N main chain has higher temperature resistance. The polar character of Si-N gives it the possibility to react with other compounds, while the designability of the side groups gives it different physicochemical properties. Chinese patent application number CN93117929.7 discloses a silazane polymer which can prevent and delay the degradation of the main chain of silicone rubber, so that the temperature resistance of room temperature vulcanized silicone rubber is improved from about 200 ℃ to about 350 ℃.
The polysiloxane and polysilazane have large polarity difference and insufficient compatibility, and the polysiloxazane with Si-O bond introduced into the polysilazane can obtain polysiloxazane with a main chain containing Si-O and Si-N bonds at the same time, so that the polysiloxazane has more excellent thermal stability. Chinese patent application No. CN 98103244.3 uses lithium cyclotrisilazane salt to initiate ring-opening polymerization of cyclosiloxane to prepare polysiloxane with main chain containing cyclosilazane. Chinese patent application No. CN 201811308395.6 is prepared by co-ammonolysis of methylhydrochlorosilane and other chlorosilanes to prepare silazane containing Si-H bond, and then condensation reaction is carried out with Si-OH OR Si-OR group under the catalysis of tris (pentafluorophenyl) borane to prepare polysilosilazane. However, the process disclosed in the above patent is severe in conditions, and the reaction process is complex and difficult to control.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a preparation method and application of hyperbranched polysiloxazane; the heat-resistant auxiliary agent for the silicone rubber is prepared by kneading and uniformly mixing hyperbranched polysiloxazane, polysiloxane and metal compound, and the heat-resistant auxiliary agent for the silicone rubber has mild and efficient synthesis reaction conditions, and can greatly improve the thermal oxidative aging performance of the silicone rubber.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention firstly provides a preparation method of hyperbranched polysiloxazane, which comprises the steps of carrying out condensation reaction on cyclosilazane and hydrogen-containing silicone oil under the action of a catalyst to obtain hyperbranched polysiloxazane;
the hyperbranched polysiloxazanes comprise A2+B4 hyperbranched polysiloxazanes or A2+B3 hyperbranched polysiloxazanes;
The structural formula of the A2+B4 type hyperbranched polysiloxazane is shown as formula 1, and the structural formula of the A2+B3 type hyperbranched polysiloxazane is shown as formula 2:
Wherein: r 1、R2、R4、R5 is the same or different, and is any one or the combination of methyl and phenyl, R 3 -is any one of H-, (methylphenyl vinyl) silicon base, (dimethylphenyl) silicon base and (triethyl) silicon base, and a1, a2, a3, a4 and a5 are any integers of 2-50, and the values are the same or different.
As a preferable scheme of the invention, the A2+B4 hyperbranched polysiloxazane comprises a cyclosilazane end-capped A2+B4 hyperbranched polysiloxazane or a modified cyclosilazane end-capped A2+B4 hyperbranched polysiloxazane, and the A2+B3 hyperbranched polysiloxazane comprises a cyclosilazane end-capped A2+B3 hyperbranched polysiloxazane or a modified cyclosilazane end-capped A2+B3 hyperbranched polysiloxazane.
As a preferable scheme of the invention, the cyclosilazane end-capped A2+B4 hyperbranched polysiloxazane and the cyclosilazane end-capped A2+B3 hyperbranched polysiloxazane comprise the following synthesis steps:
adding cyclosilazane, a solvent and a catalyst into a reaction container, controlling the reaction temperature to be 10-100 ℃ under the condition of mechanical stirring and nitrogen protection, slowly dropwise adding hydrogen-containing silicone oil to react for 0.5-3h, adding a catalyst terminator, continuously reacting for 1-2h at the temperature, filtering and distilling to remove the solvent to obtain the cyclosilazane-terminated hyperbranched polysiloxazane.
As a preferable scheme of the invention, the modified cyclosilazane end-capped A2+B4 hyperbranched polysiloxazane and the modified cyclosilazane end-capped A2+B3 hyperbranched polysiloxazane comprise the following synthesis steps:
Adding cyclosilazane, a solvent and a catalyst into a reaction container, controlling the reaction temperature to be 10-100 ℃ under the condition of mechanical stirring and nitrogen protection, slowly dropwise adding hydrogen-containing silicone oil to react for 0.5-3h, adding a terminal modifier to react for 0.5-3h, continuously adding a catalyst terminator to react for 1-2h at the temperature, filtering and distilling to remove the solvent to obtain the modified cyclosilazane-terminated hyperbranched polysiloxazane.
As a preferred embodiment of the present invention, the cyclosilazane is
Any one of the following.
As a preferable scheme of the invention, the solvent is any one of ethyl acetate, butyl acetate, toluene, xylene, tetrahydrofuran and cyclohexane, and the addition amount of the solvent is 0-50wt%; the catalyst is any one of potassium fluoride, sodium fluoride, tetramethyl ammonium fluoride and tetrabutyl ammonium fluoride, and the adding amount of the catalyst is 200-10000ppm; the hydrogen-containing silicone oil is as follows:
Wherein R 4、R5 is any one or a combination of methyl and phenyl, and a1 represents any integer of 2-50;
the catalyst terminator is any one of calcium chloride, calcium oxide, calcium carbonate, calcium borohydride, cerium chloride, cerium oxide, cerium hydroxide and cerium acetate, and the adding mass of the catalyst terminator is 10-100 times of the adding mass of the catalyst.
As a preferable scheme of the invention, the molar ratio of the cyclosilazane to the hydrogen-containing silicone oil is 1:0.9-1.
As a preferable mode of the present invention, the terminal modifier is any one of methyl phenyl vinyl silane, dimethyl phenyl silane and triethyl silane; the molar ratio of the cyclosilazane to the hydrogen-containing silicone oil to the terminal modifier is 1:0.9-1:1-2.
The invention also provides application of the hyperbranched polysiloxazane prepared by the preparation method in preparing heat-resistant auxiliary agents for silicone rubber, wherein the hyperbranched polysiloxazane, methyl vinyl polysiloxane and metal compound are kneaded for 2-3 hours at the temperature of 100-150 ℃ to prepare the heat-resistant auxiliary agents for silicone rubber.
As a preferred embodiment of the present invention, the methyl vinyl polysiloxane has a molecular weight of 10000-600000g/mol and a vinyl content of 0.01-0.30%; the metal compound is any one of cerium oxide, ferric hydroxide, cerium hydroxide, titanium dioxide, ferric stearate, cerium stearate, iron isooctanoate and cerium isooctanoate; the mass ratio of the hyperbranched polysiloxazane to the methyl vinyl polysiloxane to the metal compound is 5-40:100:5-40.
Compared with the prior art, the invention has the following beneficial effects:
1) The reaction condition of the invention is mild and efficient, and the polysilosilazane prepared by the invention and other metal compounds have synergistic effect in the aspect of heat resistance of the silicone rubber.
2) According to the invention, hyperbranched polysiloxazane, polysiloxane and metal compounds are kneaded and uniformly mixed to prepare the heat-resistant auxiliary agent for the silicone rubber, so that the thermal oxidative aging performance of the silicone rubber can be greatly improved.
Drawings
FIG. 1 is a 29 Si NMR spectrum of a cyclosilazane-terminated hyperbranched polysiloxazane prepared in example 1 of the present invention.
FIG. 2 is an infrared spectrum of cyclosilazane-terminated hyperbranched polysiloxazane and cyclosilazane, hydrogen terminated silicone oil prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of cyclosilazane-terminated hyperbranched polysiloxazane, which comprises the following steps:
Will be (1 Mol,219 g), ethyl acetate (214 g) and tetrabutylammonium fluoride (200 ppm,0.09 g) as catalysts were charged into a reaction vessel, and the reaction temperature was controlled to 10℃under mechanical stirring and nitrogen protection, and a hydrogen-containing silicone oil was added(A1=2, 1mol,208 g) was slowly added dropwise to the reaction vessel, and after reacting at this temperature for 0.5h, the reaction was continued for 1h with the addition of a catalyst terminator calcium chloride (9 g), and the solvent was filtered and distilled off to obtain a cyclosilazane-terminated hyperbranched polysiloxazane.
FIG. 1 is a 29 Si NMR spectrum of a cyclosilazane-terminated hyperbranched polysiloxazane prepared in example 1 of the present invention; at δ= -3.95ppm and δ= -3.96ppm correspond to silicon on the terminal ring trisilazane, respectively, at δ= -18.62ppm to silicon on the silazane-linked siloxane chain, at δ= -21.03 ppm-22.09 ppm to silicon on the siloxane chain, no Si peak in Si-H was seen around-7 ppm.
FIG. 2 is an infrared spectrum of cyclosilazane-terminated hyperbranched polysiloxazane, cyclosilazane and hydrogen terminated silicone oil prepared in example 1 of the present invention. The asymmetric stretching vibration absorption peaks and symmetric stretching vibration corresponding to methyl at 2963cm -1 and 2905cm -1, respectively, the asymmetric bending vibration and symmetric bending vibration corresponding to methyl at 1447cm -1 and 1412cm -1, respectively, the stretching vibration corresponding to Si-C bond at 1261cm -1, the bending vibration corresponding to Si-N-Si at 1170cm -1, the bending vibration corresponding to Si-O-Si at 1093cm -1 and 1023cm -1, respectively, the stretching vibration corresponding to S-N-Si at 939cm -1, the rocking vibration corresponding to Si-C bond at 864cm -1 and 800cm -1, respectively, and the disappearance of the Si-H bond absorption peak at 2128cm -1 indicates that the Si-H bond has reacted completely.
Example 2
The embodiment provides a preparation method of a heat-resistant auxiliary agent for silicone rubber, which comprises the following steps:
The cyclic silazane-terminated hyperbranched polysiloxazane (5 g) prepared in example 1, methyl phenyl vinyl polysiloxane (m=10000 g/mol, vinyl content 0.01%,100 g) and cerium stearate (5 g) were kneaded at a temperature of 100 ℃ for 2 hours to obtain a heat-resistant aid H-a for silicone rubber.
After mixing H-A (2 parts) and rubber compound XJ-3155 (Xin' an chemical industry, 100 parts) uniformly, adding vulcanizing agent C-6A 1 part, vulcanizing for 5 minutes at 175 ℃ by a flat vulcanizing machine, vulcanizing for 2 hours at 200 ℃ in a second stage in an oven, and aging for 72 hours under the hot air condition at 280 ℃ to obtain the mechanical property. As a control, cerium stearate was added to the rubber compound XJ-3155 in the same amount as the heat-resistant additive H-A, and the results are shown in Table 1.
TABLE 1 influence of Heat-resistant auxiliaries H-A and cerium stearate on the thermal oxidative ageing behavior in Silicone rubber
From Table 1, the influence of XJ3155+H-A on the thermal oxidative aging performance of the silicone rubber is obviously better than that of cerium stearate, and therefore, the heat-resistant auxiliary agent for the silicone rubber prepared from the cyclosilazane-terminated hyperbranched polysiloxazane can greatly improve the thermal oxidative aging performance of the silicone rubber.
Example 3
The embodiment provides a preparation method of modified cyclosilazane-terminated hyperbranched polysiloxazane, which comprises the following steps:
Will be (1 Mol,405 g), butyl acetate (1895 g) and tetrabutylammonium fluoride (10000 ppm,37.89 g) as catalysts were charged into a reaction vessel, and the reaction temperature was controlled to 10℃under mechanical stirring and nitrogen protection, and hydrogen-containing silicone oil/>(A1=50, 0.9mol,3384 g) was slowly added dropwise into the reaction vessel, reacted at this temperature for 3 hours, then the end modifier dimethylphenylsilane (1 mol,136 g) was added for 3 hours, then the reaction was continued for 2 hours with the catalyst terminator calcium chloride (378.9 g), filtered and distilled to remove the solvent to obtain the modified cyclosilazane-terminated hyperbranched polysiloxazane.
Example 4
The embodiment provides a preparation method of a heat-resistant auxiliary agent for silicone rubber, which comprises the following steps:
The modified cyclosilazane-terminated hyperbranched polysiloxazane (40 g) prepared in example 3, methyl phenyl vinyl polysiloxane (m=600000 g/mol, vinyl content 0.30%,100 g) and cerium oxide (40 g) were kneaded at a temperature of 150 ℃ for 2 hours to obtain a heat-resistant aid H-B for silicone rubber.
After mixing H-B (2 parts) and rubber compound XJ-3155 (Xin' an chemical industry, 100 parts) uniformly, adding 1 part of vulcanizing agent C-6A, vulcanizing for 5 minutes at 175 ℃ by a flat vulcanizing machine, vulcanizing for 2 hours at 200 ℃ in a second stage in an oven, and testing hardness and mechanical properties after ageing for 72 hours by hot air. As a control, cerium oxide and rubber compound XJ-3155 were added in the same amounts as the heat-resistant auxiliary agent H-B, and the results are shown in Table 2.
TABLE 2 influence of polysilosilazane and cerium oxide on the heat resistance of rubber compounds
From Table 2, the influence of XJ3155+H-B on the thermal oxidative aging performance in the silicone rubber is obviously better than that of cerium oxide on the thermal oxidative aging performance in the silicone rubber, and the heat-resistant auxiliary agent for the silicone rubber prepared from the modified cyclosilazane-terminated hyperbranched polysiloxazane can greatly improve the thermal oxidative aging performance of the silicone rubber.
Example 5
The embodiment provides a preparation method of cyclosilazane-terminated hyperbranched polysiloxazane, which comprises the following steps:
The cyclic silazane is prepared (1 Mol,405 g), solvent (0 g) and sodium fluoride (10000 ppm,41.65 g) are added into a reaction vessel, the reaction temperature is controlled to 10 ℃ under the protection of nitrogen and mechanical stirring, and hydrogen-containing silicone oil/>(A1=50, n=1 mol,3760 g) was slowly added dropwise to the reaction vessel, and after 3 hours of reaction at this temperature, a catalyst terminator calcium oxide (416.5 g) was added to continue the reaction for 2 hours, and the cyclosilazane-terminated hyperbranched polysiloxazane was obtained by filtration.
Example 6
The embodiment provides a preparation method of cyclosilazane-terminated hyperbranched polysiloxazane, which comprises the following steps:
The cyclic silazane is prepared (1 Mol,591 g), solvent xylene (3757 g) and catalyst tetramethyl ammonium fluoride (200 ppm,1.50 g) were added to a reaction vessel and the reaction temperature was controlled to 100℃under mechanical stirring and nitrogen protection, and hydrogen-containing silicone oil/>(A1=50, 1mol,6922 g) was slowly added dropwise to the reaction vessel, and after reacting at this temperature for 3 hours, a catalyst terminator calcium carbonate (2000 ppm,15 g) was added to continue the reaction for 2 hours, and the solvent was filtered and distilled off to obtain a cyclosilazane-terminated hyperbranched polysiloxazane.
Example 7
The embodiment provides a preparation method of modified cyclosilazane-terminated hyperbranched polysiloxazane, which comprises the following steps:
The cyclic silazane is prepared (1 Mol,292 g), cyclohexane (3261 g) as a solvent and tetrabutylammonium fluoride (200 ppm) as a catalyst were charged into a reaction vessel, and the reaction temperature was controlled to 10℃under mechanical stirring and nitrogen protection, and hydrogen-containing silicone oil/>(A1=50, 0.9mol,6230 g) is slowly added into a reaction vessel until the mixture is dripped into the reaction vessel, after the reaction for 0.5 to 3 hours at the temperature, a terminal modifier methyl phenyl vinyl silane (2 mol, 256 g) is added into the reaction vessel for 3 hours, a catalyst terminator cerium chloride (2000 ppm,13 g) is continuously added into the reaction vessel for 2 hours, and the reaction vessel is filtered and distilled to remove the solvent to obtain the modified cyclosilazane-terminated hyperbranched polysiloxazane.
Example 8
The embodiment provides a preparation method of modified cyclosilazane-terminated hyperbranched polysiloxazane, which comprises the following steps:
The cyclic silazane is prepared (1 Mol,540 g), tetrahydrofuran (3435 g) and tetrabutylammonium fluoride (200 ppm,1.37 g) as a catalyst were added to a reaction vessel, and the reaction temperature was controlled to 10℃under mechanical stirring and nitrogen protection, and hydrogen-containing silicone oil/>(A1=50, 0.9mol,6330 g) is slowly added into a reaction vessel until the mixture is dripped into the reaction vessel, after 3 hours of reaction at the temperature, a terminal modifier dimethyl phenyl silane (2 mol,272 g) is added into the reaction vessel for 3 hours, a catalyst terminator cerium oxide (2000 ppm,13.7 g) is continuously added into the reaction vessel for 2 hours, and the reaction vessel is filtered and distilled to remove the solvent to obtain the modified cyclosilazane-terminated hyperbranched polysiloxazane.
Example 9
The embodiment provides a preparation method of modified cyclosilazane-terminated hyperbranched polysiloxazane, which comprises the following steps:
The cyclic silazane is prepared (1 Mol,788 g), solvent and catalyst were added to a reaction vessel, and the reaction temperature was controlled to 10℃under mechanical stirring and nitrogen protection, and hydrogen-containing silicone oil/>(A1=2, 0.9mol,187 g) is slowly added into the reaction vessel until the mixture is dripped into the reaction vessel, the triethylsilane (2 mol,232 g) serving as a terminal modifier is added into the reaction vessel for reaction for 3 hours, the cerium acetate serving as a catalyst terminator is continuously added into the reaction vessel for reaction for 2 hours, and the solvent is filtered and distilled off to obtain the modified cyclosilazane-terminated hyperbranched polysiloxazane.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method is characterized in that cyclosilazane and hydrogen-containing silicone oil are subjected to condensation reaction under the action of a catalyst to obtain hyperbranched polysiloxazane;
the hyperbranched polysiloxazanes comprise A2+B4 hyperbranched polysiloxazanes or A2+B3 hyperbranched polysiloxazanes;
The structural formula of the A2+B4 type hyperbranched polysiloxazane is shown as formula 1, and the structural formula of the A2+B3 type hyperbranched polysiloxazane is shown as formula 2:
Wherein: r 1、R2、R4、R5 is the same or different, and is any one or the combination of methyl and phenyl, R 3 -is any one of H-, (methylphenyl vinyl) silicon base, (dimethylphenyl) silicon base and (triethyl) silicon base, and a1, a2, a3, a4 and a5 are any integers of 2-50, and the values are the same or different.
2. The method for preparing hyperbranched polysiloxazane according to claim 1, wherein the A2+B4 hyperbranched polysiloxazane comprises a cyclosilazane end-capped A2+B4 hyperbranched polysiloxazane or a modified cyclosilazane end-capped A2+B4 hyperbranched polysiloxazane, and the A2+B3 hyperbranched polysiloxazane comprises a cyclosilazane end-capped A2+B3 hyperbranched polysiloxazane or a modified cyclosilazane end-capped A2+B3 hyperbranched polysiloxazane.
3. The method for preparing hyperbranched polysiloxazane according to claim 2, wherein the cyclosilazane end-capping a2+b4 type hyperbranched polysiloxazane and the cyclosilazane end-capping a2+b3 type hyperbranched polysiloxazane comprise the following synthesis steps:
under the stirring and protecting atmosphere, the reaction temperature is controlled, hydrogen-containing silicone oil is dropwise added to react for a period of time, a catalyst terminator is added to continue the reaction, and the solvent is filtered and distilled to obtain the cyclosilazane-terminated hyperbranched polysiloxazane.
4. The method for preparing hyperbranched polysiloxazane according to claim 2, wherein the modified cyclic silazane end-capping a2+b4 type hyperbranched polysiloxazane and the modified cyclic silazane end-capping a2+b3 type hyperbranched polysiloxazane are synthesized by the steps of:
under the stirring and protecting atmosphere, the reaction temperature is controlled, hydrogen-containing silicone oil is added dropwise for reaction, a terminal modifier is added for reaction, a catalyst terminator is added for continuous reaction, and the solvent is removed by filtration and distillation to obtain the modified cyclosilazane-terminated hyperbranched polysiloxazane.
5. The method for preparing hyperbranched polysiloxazane according to claim 3 or 4, wherein the cyclosilazane is Any one of the following.
6. The preparation method of hyperbranched polysiloxazane according to claim 3 or 4, wherein the solvent is any one of ethyl acetate, butyl acetate, toluene, xylene, tetrahydrofuran and cyclohexane, and the addition amount of the solvent is 0-50wt%; the catalyst is any one of potassium fluoride, sodium fluoride, tetramethyl ammonium fluoride and tetrabutyl ammonium fluoride, and the adding amount of the catalyst is 200-10000ppm; the hydrogen-containing silicone oil is as follows:
Wherein R 4、R5 is any one or a combination of methyl and phenyl, and a1 represents any integer of 2-50;
the catalyst terminator is any one of calcium chloride, calcium oxide, calcium carbonate, calcium borohydride, cerium chloride, cerium oxide, cerium hydroxide and cerium acetate, and the adding mass of the catalyst terminator is 10-100 times of the adding mass of the catalyst.
7. A method of preparing hyperbranched polysiloxazane according to claim 3 characterised in that the molar ratio of cyclosilazane to hydrogen containing silicone oil is 1:0.9-1.
8. The method for preparing hyperbranched polysilosilazane according to claim 4, wherein the end modifier is any one of methyl phenyl vinyl silane, dimethyl phenyl silane and triethyl silane; the molar ratio of the cyclosilazane to the hydrogen-containing silicone oil to the terminal modifier is 1:0.9-1:1-2.
9. The use of hyperbranched polysiloxazane prepared by the preparation method of any one of claims 1-8 in the preparation of heat-resistant auxiliaries for silicone rubber, wherein the hyperbranched polysiloxazane, methyl vinyl polysiloxane and metal compound are kneaded at 100-150 ℃ for 2-3 hours to prepare the heat-resistant auxiliaries for silicone rubber.
10. The use according to claim 9, wherein the methyl vinyl polysiloxane has a molecular weight of 10000-600000g/mol and a vinyl content of 0.01-0.30%; the metal compound is any one of cerium oxide, ferric hydroxide, cerium hydroxide, titanium dioxide, ferric stearate, cerium stearate, iron isooctanoate and cerium isooctanoate; the mass ratio of the hyperbranched polysiloxazane to the methyl vinyl polysiloxane to the metal compound is 5-40:100:5-40.
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