CN111471178A - High-temperature-resistant hybrid organic silicon resin with framework doped with hafnium and preparation method thereof - Google Patents
High-temperature-resistant hybrid organic silicon resin with framework doped with hafnium and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant hybrid organic silicon resin with a hafnium-doped framework and a preparation method thereof, belongs to the technical field of L ED packaging material research, and aims to further improve the heat resistance and the refractive index of a L ED packaging resin material, wherein the structural formula of the organic silicon resin is as follows (R)2SiO2/2)m(RSiO3/2)n(SiO4/2)p(HfO4/2)l(A)kIn the formula, R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2Respectively represent a difunctional-unit siloxane, a trifunctional-unit siloxane, a tetrafunctional-unit siloxane and an organohafnium source; m, n, p, l and k represent R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2And the number of building blocks of A. The operation steps adopted by the invention are suitable for the hafnium-containing organic silicon resin prepared by industrial large-scale production, and the hafnium-containing organic silicon resin has excellent heat resistance (500 ℃) and high refractive index (n)>1.55)。
Description
Technical Field
The invention belongs to the technical field of L ED packaging material research, and particularly relates to a high-temperature-resistant hybrid organic silicon resin with a hafnium-doped framework and a preparation method thereof.
Background
With the development of science and technology, lighting equipment is widely applied, the consumption of electric energy is increasing day by day, and in order to effectively alleviate the problem, a Light Emitting Diode (LED) is produced, in the past decades, the LED can be widely used for producing high-quality lighting, however, when the LED is applied, the fact that the internal quantum efficiency needs to be improved is found, research on L ED packaging materials is developed, materials with high refractive index are needed to relieve the mismatching of interface indexes, the improvement of light extraction and the good thermal conductivity of the materials are beneficial to heat dissipation, and the junction temperature of L ED chips is reduced, so that the quantum yield is improved.
Epoxy resin is a mainstream packaging material of current L ED due to good moisture resistance, adhesion to metal and mechanical robustness, but the service life of the epoxy resin is too low and the refractive index is low (n is approximately equal to 1.53). The organic silicon resin is a substance with a three-dimensional structure, the structure of the organic silicon resin contains an organic group and an inorganic structure, and the special composition and the molecular structure enable the organic silicon resin to integrate the characteristics of organic matters and the functions of inorganic matters, show excellent performances in weather resistance, high temperature resistance, insulation, low surface tension and the like compared with common organic resin, are superior to epoxy resin in heat and humidity stability, and are lower than epoxy resin in the refractive index (n is approximately equal to 1.41), but the refractive index can be improved by adding inorganic nanoparticles or introducing transition metal elements into the silicon resin structure.
At present, researches show that more oxides of transition metal elements have better refractive index, wherein Ti and Zr are hot spots for research. Ti and Zr elements are introduced into organic silicon resin due to TiO2、ZrO2The Hf serving as the element Hf of the same family is superior to Ti and Zr in high temperature resistance and refractive index according to the periodic property of the elements, so that Hf is introduced into an organic silicon resin main chain to prepare a novel resin, the novel resin has better moist heat stability and refractive index, and can be used in the field of L ED packaging materials.
Disclosure of Invention
The invention aims to further improve the heat resistance and the refractive index of an L ED packaging resin material, and provides a high-temperature resistant hybrid organic silicon resin with a hafnium-doped framework and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-temperature resistant hybrid organic silicon resin with a hafnium-doped framework has the following structural formula:
(R2SiO2/2)m(RSiO3/2)n(SiO4/2)p(HfO4/2)l(A)k
in the formula, R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2Respectively represent a difunctional-unit siloxane, a trifunctional-unit siloxane, a tetrafunctional-unit siloxane and an organohafnium source; m, n, p, l and k represent R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2And the number of structural units of A; wherein m and p are natural numbers; n, l and k are positive integers;
r is one of methyl, phenyl, acrylate group or epoxypropyl;
a is-Si (OH)3、-RSi(OH)2、-R2Si(OH)、-R2SiOR、-RSiOR2or-SiOR3One of (1);
HfO4/2is one of alkoxide hafnium, hafnocene hafnium or acetylacetone hafnium salt.
The preparation method of the high-temperature-resistant hybrid organic silicon resin with the hafnium-doped framework is characterized by comprising the following steps of: the method comprises the following steps:
the method comprises the following steps: according to the mass ratio of 1: 1: 1-1: 4: 20, taking an organic hafnium source, a chelating agent and a chelating agent dispersing agent, uniformly mixing the chelating agent and the chelating agent dispersing agent, adding the organic hafnium source into the mixture, uniformly stirring the mixture, and recording the mixture as a solution A;
step two: according to the siloxane: 1-8 parts of an organohafnium source: 1 quantitative ratio of substances siloxane R is weighed out2SiO2/2、RSiO3/2、SiO4/2According to the siloxane: absolute ethyl alcohol ═ 1-4: 1, dissolving siloxane in absolute ethyl alcohol, adding deionized water according to the amount of the substance which is 1.1-1.5 times of the alkoxy ratio at a speed of one drop per 2-3 s for hydrolysis, and recording the solution as solution B;
step three: adding the solution B into the solution A at a speed of 20-30 drops/min, adding 1M catalyst solution at a speed of 2-3 s drop per drop according to the amount of substances 0.001 times of the alkoxy ratio, and performing hydrolytic polycondensation to obtain a hafnium-containing organic silicon resin prepolymer;
step four: centrifuging the hafnium-containing organic silicon resin prepolymer, and then drying in vacuum to obtain a hybrid organic silicon resin prepolymer with a framework of removed small molecules doped with hafnium;
step five: putting the framework hafnium-doped hybrid organic silicon resin prepolymer into an oven to be cured for 3 to 15 hours at the temperature of between 100 and 300 ℃ to prepare the high-temperature-resistant hafnium-doped hybrid organic silicon resin.
Compared with the prior art, the invention has the beneficial effects that: the element hafnium is a metal with high melting point, corrosion resistance and capability of continuously changing the transistor efficiency, the melting point of the element hafnium is as high as 2227 ℃, the melting points of oxides and carbides of the element hafnium are higher than that of silicon element compounds, and therefore, the heat resistance of the resin is improved and the refractive index of the resin is enhanced by doping the hafnium element into the main chain of the organic silicon resin. The operation steps adopted by the invention are suitable for industrial large-scale production of the prepared hafnium-containing organic silicon resin, and the hafnium-containing organic silicon resin has excellent heat resistance (500 ℃ resistance) and high refractive index (n is more than 1.55).
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
The invention contains R2SiO2/2、RSiO3/2、SiO4/2The silane of (2) is introduced with an organohafnium source, and the hydrolysis and self-polymerization rate of the organohafnium source are controlled by a chelating agent and a dispersing agent thereof (the dispersing agent of the chelating agent can further reduce the hydrolysis rate of the hafnium source)Hafnium element is introduced into the three-dimensional structure of the traditional organic silicon resin to form a Si-O-Hf structure, so that the heat resistance stability of the organic silicon resin is improved.
The preparation method of the hafnium-containing organic silicon resin provided by the invention considers that the hydrolysis rate and the self-polymerization rate of the hafnium-containing organic source are too fast and faster under the acidic or alkaline condition of the catalyst, and the hafnium-containing organic silicon resin is difficult to be introduced into the main chain of the organic silicon resin. The chelating agent is selected to be firstly coordinated with the organohafnium source, then the mixed solution is dropwise added into the siloxane for hydrolytic polymerization to form a Si-O-Hf structure, and the condensation polymerization is carried out at a certain temperature to prepare the hafnium-containing organic silicon resin.
The first embodiment is as follows: the embodiment describes a high-temperature resistant hybrid organic silicon resin with a hafnium-doped framework, and the structural formula of the organic silicon resin is as follows:
(R2SiO2/2)m(RSiO3/2)n(SiO4/2)p(HfO4/2)l(A)k
in the formula, R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2Respectively represent a difunctional-unit siloxane, a trifunctional-unit siloxane, a tetrafunctional-unit siloxane and an organohafnium source; m, n, p, l and k represent R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2And the number of structural units of A; wherein m and p are natural numbers; n, l and k are positive integers;
r is one of methyl, phenyl, acrylate group or epoxypropyl;
a is-Si (OH)3、-RSi(OH)2、-R2Si(OH)、-R2SiOR、-RSiOR2or-SiOR3One of (1);
HfO4/2is one of alkoxide hafnium, hafnocene hafnium or acetylacetone hafnium salt.
The second embodiment is as follows: in the second step, the difunctional siloxane unit is one or more of diphenyldiethoxysilane, dimethyldiethoxysilane or methylphenyldiethoxysilane; the trifunctional siloxane is one or more of 3-propyl methacrylate trimethoxy silane, 3-glycidoxypropyltrimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane or methyl trimethoxy silane; the tetrafunctional siloxane unit is one or more of ethyl orthosilicate, methyl orthosilicate or silicate.
The third concrete implementation mode: in the second embodiment, the high-temperature resistant hybrid silicone resin with the hafnium-doped framework is prepared by mixing a bifunctional siloxane unit and a silane unit, wherein the bifunctional siloxane unit is methyl phenyl diethoxysilane; the trifunctional siloxane is 3-propyl methacrylate trimethoxy silane, methyl triethoxy silane and phenyl trimethoxy silane; the tetrafunctional siloxane unit is tetraethoxysilane. The selected siloxane takes the difference of the hydrolysis rates of all the siloxanes into consideration, and the copolymerization rate can be ensured to be close.
The fourth concrete implementation mode: in the first specific embodiment, the skeleton doped with hafnium is a high-temperature resistant hybrid organic silicon resin, and the molar ratio of silicon atoms to hafnium atoms in the structural formula is 1-8: 1.
the fifth concrete implementation mode: in the first specific embodiment, the skeleton doped with hafnium is a high-temperature resistant hybrid organic silicon resin, and in the structural formula, the molar ratio of R to silicon atoms is 1-1.5: 1.
the sixth specific implementation mode: in the high-temperature resistant hybrid organic silicon resin with a hafnium-doped framework, the hafnium alkoxide is hafnium isopropoxide or hafnium n-butoxide; the hafnocene is hafnocene dichloride; the acetylacetone hafnium salt is hafnium acetylacetonate or hafnium trifluoroacetylacetonate.
The seventh embodiment: a method for preparing a high temperature resistant hybrid silicone resin with a hafnium-doped framework according to any one of the first to sixth embodiments, the method comprising the following steps:
the method comprises the following steps: according to the mass ratio of 1: 1: 1-1: 4: 20, taking an organic hafnium source, a chelating agent and a chelating agent dispersing agent, uniformly mixing the chelating agent and the chelating agent dispersing agent, adding the organic hafnium source into the mixture, uniformly stirring the mixture, and recording the mixture as a solution A;
step two: according to the siloxane: 1-8 parts of an organohafnium source: 1 quantitative ratio of substances siloxane R is weighed out2SiO2/2、RSiO3/2、SiO4/2According to the siloxane: and (3) anhydrous ethanol is 1-4: 1, dissolving siloxane in absolute ethyl alcohol, adding deionized water according to the amount of the substance which is 1.1-1.5 times of the alkoxy ratio at a speed of one drop per 2-3 s for hydrolysis, and recording the solution as solution B;
step three: adding the solution B into the solution A at a speed of 20-30 drops/min, adding 1M catalyst solution at a speed of 2-3 s drop per drop according to the amount of substances 0.001 times of the alkoxy ratio, and performing hydrolytic polycondensation to obtain a hafnium-containing organic silicon resin prepolymer;
step four: loading the hafnium-containing organic silicon resin prepolymer into a centrifugal tube for centrifugation, and then carrying out vacuum drying to obtain the hybrid organic silicon resin prepolymer with the framework of small molecules removed and doped with hafnium;
step five: putting the framework hafnium-doped hybrid organic silicon resin prepolymer into an oven to be cured for 3 to 15 hours at the temperature of between 100 and 300 ℃ to prepare the high-temperature-resistant hafnium-doped hybrid organic silicon resin.
The specific implementation mode is eight: in the preparation method of the high-temperature resistant hybrid silicone resin with a hafnium-doped skeleton, in the first step, the amount ratio of the organic hafnium source, the chelating agent and the chelating agent dispersant is 1: 1: 1-1: 3: 12.
the specific implementation method nine: in the preparation method of the high-temperature resistant hybrid silicone resin with the hafnium-doped framework, in the first step, the chelating agent is an organic unsaturated oxygen-containing acidic substance.
The organic unsaturated oxygen-containing acidic substance is one of β -diketone, a halogenated derivative of β -diketone, acrylic acid, a homolog of acrylic acid and a diphenol compound with a benzene ring.
The specific embodiment eleventh is the preparation method of the high temperature resistant hybrid silicone resin with the hafnium-doped skeleton, in the specific embodiment tenth, the β -diketone is acetylacetone or benzoylacetone, the halogenated derivative of the β -diketone is trifluoroacetylacetone or hexafluoroacetylacetone, the acrylic acid homologue is one of methacrylic acid or 1, 1-dimethylacrylic acid, and the diphenol compound with a benzene ring is resorcinol or catechol.
The specific implementation mode twelve: in the first step, the chelating agent dispersant is one of polyethylene glycol methyl ether acetate, polyethylene glycol methyl ether propionate, pentasodium diethylenetriamine penta-carboxylate, cetyltrimethylammonium bromide or sodium dodecylbenzenesulfonate.
The specific implementation mode is thirteen: in the third step, the catalyst is one of hydrochloric acid, boric acid, acetic acid, ethylenediamine, tetramethylammonium hydroxide, triethylamine, sodium hydroxide or barium hydroxide.
The specific implementation mode is fourteen: in the third step, the hydrolysis and polycondensation reaction conditions are as follows: the temperature is 30-75 ℃, the rotating speed is 300-900 rpm/min, and the time is 2-9 h.
The concrete implementation mode is fifteen: the preparation method of the high temperature resistant hybrid silicone resin with hafnium-doped backbone comprises the following hydrolysis and polycondensation reaction conditions: the temperature is 50-75 ℃, the rotating speed is 400-800 rpm/min, and the time is 3-8 h.
The specific implementation mode is sixteen: the preparation method of the framework hafnium-doped high-temperature-resistant hybrid organic silicon resin comprises the following fourth step, wherein the centrifugal rotation speed is 4000-6000 rpm/min, and the time is 5-30 min; the temperature of the vacuum drying is 30-70 ℃, and the time is 20 min-2 h.
Seventeenth embodiment: in the fifth step, the curing temperature is 150-280 ℃ and the curing time is 6-12 hours.
The rotation speed, time or temperature can make the prepared hafnium-containing silicone resin more uniform, have better polymerization degree, and have stable thermal property and refractive index in later use.
Example 1:
the siloxane adopts methyltriethoxysilane as trifunctional unit siloxane, the methylphenyldiethoxysilane as difunctional unit siloxane, the tetraethoxysilane as tetrafunctional unit siloxane, the hafnium isopropoxide as an organic hafnium source and the acetylacetone as a chelating agent, and the organosilicon resin containing the Si-O-Hf structure is formed by hydrolysis and polycondensation reaction.
The preparation method comprises the following steps:
(1) according to the mass ratio of 1: 2: 6, measuring 0.42mol of organic hafnium source isopropanol hafnium, 0.84mol of chelating agent acetylacetone and 2.52mol of chelating agent dispersant polyethylene glycol methyl ether propionate, firstly uniformly mixing acetylacetone and polyethylene glycol methyl ether propionate, then adding the isopropanol hafnium, uniformly stirring, and recording as a solution A;
(2) according to the siloxane: organohafnium source 7: 2, weighing 0.28mol of siloxane methyl phenyl diethoxysilane, 0.56mol of methyl triethoxysilane and 0.14mol of tetraethoxysilane according to the weight ratio of siloxane: anhydrous ethanol ═ 1: 1, weighing absolute ethyl alcohol to dissolve siloxane, weighing 1.078mol of deionized water according to the amount of the substance 1.1 times of the alkoxy ratio, adding the deionized water at the speed of one drop per 2-3 s to hydrolyze, and recording the solution as solution B;
(3) gradually adding the mixed solution B into the mixed solution A at a rate of 30 drops/min, wherein the temperature is not more than 75 ℃ in the whole process, and then adding 2.80 × 10-3M L1M hydrochloric acid, after the dropwise addition, keeping the temperature at 75 ℃ for reaction for 6h to obtain a hafnium-containing organic silicon resin prepolymer;
(4) transferring the hafnium-containing organic silicon resin prepolymer obtained in the step (3) into a centrifugal tube of 50m L, centrifuging for 10min at the rotating speed of 5000rpm/min, and then vacuum drying for 1h at the temperature of 45 ℃ to obtain the solvent-free hafnium-containing organic silicon resin prepolymer;
(5) and (3) putting the prepolymer into a high-temperature oven, and curing for 2 hours at 150 ℃, 200 ℃ and 250 ℃ respectively to prepare the hafnium-containing organic silicon resin.
For the prepared hafnium-containing organic silicon resin, the refractive index is 1.5673 by an Abbe refractometer, and the index of the heat resistance is as follows by thermogravimetric analysis test:
| T0％/℃ | T5％/℃ | residual weight/% at 800 ℃ |
| 369.22 | 568.49 | 82.67 |
Example 2:
the siloxane adopts methyltriethoxysilane as trifunctional siloxane unit, the diphenyldiethoxysilane as difunctional siloxane unit, the tetrafunctional siloxane unit is not adopted, the hafnocene dichloride is selected as an organic hafnium source, the resorcinol is selected as a chelating agent, and the hydrolysis polycondensation reaction is carried out to form the organic silicon resin containing the Si-O-Hf structure.
The preparation method comprises the following steps:
(1) according to the mass ratio of 1: 1: 3, measuring 0.32mol of hafnocene dichloride serving as an organic hafnium source, 0.32mol of resorcinol serving as a chelating agent and 0.96mol of polyethylene glycol methyl ether propionate serving as a chelating agent dispersant, uniformly mixing the resorcinol and the polyethylene glycol methyl ether propionate, adding the hafnocene dichloride into the mixture, uniformly stirring the mixture, and recording the mixture as a solution A;
(2) according to the siloxane: organohafnium source 15: 4, 0.48mol of siloxane diphenyl diethoxysilane and 0.72mol of methyl triethoxysilane are weighed according to the weight ratio of siloxane: anhydrous ethanol ═ 1: weighing absolute ethyl alcohol according to the weight proportion of the substances of 1.1 to dissolve siloxane, weighing 1.44mol of deionized water according to the weight proportion of the substances of 1.2 times of the alkoxy proportion, adding the deionized water at the speed of one drop per 2-3 s to hydrolyze, and recording the deionized water as solution B;
(3) gradually adding the mixed solution B into the mixed solution A at 25 drops/min, wherein the temperature is not more than 70 ℃ in the whole process, and then adding 3.12 × 10-3M L1M hydrochloric acid, after the dropwise addition, keeping the temperature at 70 ℃ for reaction for 8h to obtain the hafnium-containing organic silicon resin prepolymer.
(4) And (3) transferring the hafnium-containing organic silicon resin prepolymer obtained in the step (3) into a centrifugal tube of 50m L, centrifuging for 10min at the rotating speed of 6000rpm/min, and then vacuum drying for 45min at 50 ℃ to obtain the solvent-free hafnium-containing organic silicon resin prepolymer.
(5) And (3) putting the prepolymer into a high-temperature oven, and curing at 180 ℃ for 2h, 240 ℃ for 3h and 280 ℃ for 3h to prepare the hafnium-containing organic silicon resin.
For the prepared zirconium-containing organic silicon resin, the refractive index is 1.5726 by using an Abbe refractometer, and the heat resistance indexes are as follows through thermogravimetric analysis and test:
| T0％/℃ | T5％/℃ | residual weight/% at 800 ℃ |
| 360.55 | 565.28 | 82.52 |
Example 3:
phenyl triethoxysilane is selected as trifunctional siloxane, dimethyl diethoxysilane is selected as difunctional siloxane, tetrafunctional siloxane is not adopted, hafnium isopropoxide is selected as an organic hafnium source, resorcinol is selected as a chelating agent, and hydrolysis and polycondensation are carried out to form the organic silicon resin containing the Si-O-Hf structure.
The preparation method comprises the following steps:
(1) according to the mass ratio of 1: 2: 4, measuring 0.15mol of organic hafnium source isopropanol hafnium, 0.30mol of chelating agent resorcinol and 0.60mol of chelating agent dispersant polyethylene glycol methyl ether propionate, firstly, uniformly mixing resorcinol and polyethylene glycol methyl ether propionate, then adding isopropanol hafnium, uniformly stirring, and recording as a solution A;
(2) according to the siloxane: organohafnium source 4: 1, 0.16mol of siloxane dimethyldiethoxysilane and 0.48mol of phenyltriethoxysilane are weighed out in the following weight ratio of siloxane: anhydrous ethanol ═ 1: 1, weighing absolute ethyl alcohol to dissolve siloxane, weighing 0.704mol of deionized water according to the amount of the substance 1.1 times of the alkoxy proportion, adding the deionized water at the speed of one drop per 2-3 s to hydrolyze, and recording the solution as solution B;
(3) gradually adding the mixed solution B into the mixed solution A at 20 drops/min, wherein the temperature is not more than 70 ℃ in the whole process, and adding 1.76 × 10-3M L1M hydrochloric acid, after the dropwise addition, keeping the temperature at 70 ℃ for reaction for 8h to obtain the hafnium-containing organic silicon resin prepolymer.
(4) And (3) transferring the hafnium-containing organic silicon resin prepolymer obtained in the step (3) into a centrifugal tube of 50m L, centrifuging for 15min at the rotating speed of 4000rpm/min, and then drying in vacuum for 1h at the temperature of 50 ℃ to obtain the solvent-free hafnium-containing organic silicon resin prepolymer.
(5) The prepolymer is put into a high-temperature oven to be cured for 2 hours at 150 ℃, 2 hours at 180 ℃, 3 hours at 210 ℃ and 2 hours at 250 ℃ to prepare the hafnium-containing organic silicon resin,
for the prepared zirconium-containing organic silicon resin, the refractive index is 1.5917 by using an Abbe refractometer, and the heat resistance indexes are as follows through thermogravimetric analysis and test:
| T0％/℃ | T5％/℃ | residual weight/% at 800 ℃ |
| 351.88 | 560.84 | 79.31 |
Claims (17)
1. A high-temperature resistant hybrid organic silicon resin with a hafnium-doped framework is characterized in that: the structural formula of the organic silicon resin is as follows:
(R2SiO2/2)m(RSiO3/2)n(SiO4/2)p(HfO4/2)l(A)k
in the formula, R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2Respectively represent a difunctional-unit siloxane, a trifunctional-unit siloxane, a tetrafunctional-unit siloxane and an organohafnium source; m, n, p, l and k represent R2SiO2/2、RSiO3/2、SiO4/2、HfO4/2And the number of structural units of A; wherein m and p are natural numbers; n, l and k are positive integers;
r is one of methyl, phenyl, acrylate group or epoxypropyl;
a is-Si (OH)3、-RSi(OH)2、-R2Si(OH)、-R2SiOR、-RSiOR2or-SiOR3One of (1);
HfO4/2is one of alkoxide hafnium, hafnocene hafnium or acetylacetone hafnium salt.
2. The high-temperature-resistant hybrid silicone resin with the hafnium-doped framework as claimed in claim 1, wherein: in the second step, the difunctional unit siloxane is one or more of diphenyl diethoxysilane, dimethyl diethoxysilane or methylphenyl diethoxysilane; the trifunctional siloxane is one or more of 3-propyl methacrylate trimethoxy silane, 3-glycidoxypropyltrimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane or methyl trimethoxy silane; the tetrafunctional siloxane unit is one or more of ethyl orthosilicate, methyl orthosilicate or silicate.
3. The high-temperature-resistant hybrid silicone resin with the hafnium-doped framework as claimed in claim 2, wherein: the difunctional siloxane unit is methyl phenyl diethoxysilane; the trifunctional siloxane is 3-propyl methacrylate trimethoxy silane, methyl triethoxy silane and phenyl trimethoxy silane; the tetrafunctional siloxane unit is tetraethoxysilane.
4. The high-temperature-resistant hybrid silicone resin with the hafnium-doped framework as claimed in claim 1, wherein: the molar ratio of silicon atoms to hafnium atoms in the structural formula is 1-8: 1.
5. the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework as claimed in claim 1, wherein: in the structural formula, the molar ratio of R to silicon atoms is 1-1.5: 1.
6. the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework as claimed in claim 1, wherein: the hafnium alkoxide is hafnium isopropoxide or hafnium n-butyl alcohol; the hafnocene is hafnocene dichloride; the acetylacetone hafnium salt is hafnium acetylacetonate or hafnium trifluoroacetylacetonate.
7. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: according to the mass ratio of 1: 1: 1-1: 4: 20, taking an organic hafnium source, a chelating agent and a chelating agent dispersing agent, uniformly mixing the chelating agent and the chelating agent dispersing agent, adding the organic hafnium source into the mixture, uniformly stirring the mixture, and recording the mixture as a solution A;
step two: according to the siloxane: 1-8 parts of an organohafnium source: 1 quantitative ratio of substances siloxane R is weighed out2SiO2/2、RSiO3/2、SiO4/2According to the siloxane: and (3) anhydrous ethanol is 1-4: 1, dissolving siloxane in absolute ethyl alcohol, adding deionized water according to the amount of the substance which is 1.1-1.5 times of the alkoxy ratio at a speed of one drop per 2-3 s for hydrolysis, and recording the solution as solution B;
step three: adding the solution B into the solution A at a speed of 20-30 drops/min, adding 1M catalyst solution at a speed of 2-3 s drop per drop according to the amount of substances 0.001 times of the alkoxy ratio, and performing hydrolytic polycondensation to obtain a hafnium-containing organic silicon resin prepolymer;
step four: centrifuging the hafnium-containing organic silicon resin prepolymer, and then drying in vacuum to obtain a hybrid organic silicon resin prepolymer with a framework of removed small molecules doped with hafnium;
step five: putting the framework hafnium-doped hybrid organic silicon resin prepolymer into an oven to be cured for 3 to 15 hours at the temperature of between 100 and 300 ℃ to prepare the high-temperature-resistant hafnium-doped hybrid organic silicon resin.
8. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 7, characterized in that: in the first step, the mass ratio of the organohafnium source, the chelating agent and the chelating agent dispersant is 1: 1: 1-1: 3: 12.
9. the preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 7, characterized in that: in the first step, the chelating agent is an organic unsaturated oxygen-containing acidic substance.
10. The method for preparing the high-temperature resistant hybrid organic silicon resin with the hafnium-doped framework is characterized in that the organic unsaturated oxygen-containing acidic substance is one of β -diketone, a halogenated derivative of β -diketone, acrylic acid homologue and diphenol with benzene ring series compound.
11. The preparation method of the high-temperature-resistant hybrid organic silicon resin with the hafnium-doped framework is characterized in that β -diketone is acetylacetone or benzoylacetone, the halogenated derivative of β -diketone is trifluoroacetylacetone or hexafluoroacetylacetone, the acrylic acid homologue is one of methacrylic acid or 1, 1-dimethylacrylic acid, and the diphenol compound with a benzene ring is resorcinol or catechol.
12. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 7, characterized in that: in the first step, the chelating agent dispersant is one of polyethylene glycol methyl ether acetate, polyethylene glycol methyl ether propionate, pentasodium diethylenetriamine penta-carboxylate, hexadecyl trimethyl ammonium bromide or sodium dodecyl benzene sulfonate.
13. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 7, characterized in that: in the third step, the catalyst is one of hydrochloric acid, boric acid, acetic acid, ethylenediamine, tetramethylammonium hydroxide, triethylamine, sodium hydroxide or barium hydroxide.
14. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 7, characterized in that: in the third step, the conditions of the hydrolytic polycondensation reaction are as follows: the temperature is 30-75 ℃, the rotating speed is 300-900 rpm/min, and the time is 2-9 h.
15. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 14, wherein the preparation method comprises the following steps: the conditions of the hydrolytic polycondensation reaction are as follows: the temperature is 50-75 ℃, the rotating speed is 400-800 rpm/min, and the time is 3-8 h.
16. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 7, characterized in that: in the fourth step, the rotating speed of the centrifugation is 4000-6000 rpm/min, and the time of the centrifugation is 5-30 min; the temperature of the vacuum drying is 30-70 ℃, and the time is 20 min-2 h.
17. The preparation method of the high-temperature-resistant hybrid silicone resin with the hafnium-doped framework according to claim 7, characterized in that: in the fifth step, the curing temperature is 150-280 ℃ and the curing time is 6-12 h.
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