CN108841005B - Hydrosilylation type silicone resin high-temperature catalysis inhibition system and preparation method and application thereof - Google Patents
Hydrosilylation type silicone resin high-temperature catalysis inhibition system and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hydrosilylation type silicone resin high-temperature catalysis inhibition system and a preparation method and application thereof, the system comprises a silicone resin coated platinum catalyst and an alkynol modified silane inhibitor, wherein the silicone resin coated platinum catalyst is a core-shell microsphere which is formed by taking a platinum complex formed by taking vinyl alkoxy silane as a ligand as a core and an active component and taking crosslinking type silicone resin as a coating layer and has platinum catalysis hydrosilylation activity; the alkynol modified silane inhibitor is phenyl silane modified by alkynol containing terminal alkynyl. The system can not only keep the long-term storage stability of the single-component hydrosilylation type silicon resin under the normal temperature condition, but also gradually catalyze the silicon resin to carry out crosslinking reaction under the high temperature condition.
Description
Technical Field
The invention relates to a high-temperature catalytic inhibition system, and belongs to the technical field of hydrosilylation silicone resin preparation.
Background
The traditional addition type silicone resin usually needs to adopt a two-component form due to the high-efficiency catalytic effect of a catalyst system per se so as to avoid the rapid and violent crosslinking reaction generated when the vinyl-containing silicone resin and the hydrogen-containing component are fully mixed. With the continuous expansion of a hydrosilylation silicone resin system in the practical application field, the two-component system is limited by practical conditions due to the metering accuracy and the glue mixing manufacturability, and the market urgently needs the single-component hydrosilylation system so as to facilitate the application of the silicone resin. For example, in the field of high temperature insulating impregnating resins, it is desirable that the resin system be capable of long term storage at low temperatures, but polymerize slowly and efficiently at high temperatures to avoid stress concentrations in the system caused by severe addition reactions. In addition, the high insulation requirement of an insulation system is limited, and the material is not allowed to carry any air bubbles and the like in the glue mixing process to cause insulation failure of the material, so that the glue mixing process of the two-component hydrosilylation silicone resin becomes particularly critical, and the requirements of the glue mixing and defoaming process are extremely strict. In view of the above disadvantages of the two-component hydrosilylation-type silicone resin, it is imperative to develop a one-component silicone resin system that can be stored for a long period of time.
In order to solve the problem of rapid curing of the hydrosilylation-type silicone resin system, an inhibitor and a catalyst are often used. However, the currently used inhibitor system generally uses alkynol with a lower boiling point, and such inhibitors can maintain the stability of the silicone resin system at normal temperature, but under high temperature conditions, for example, the temperature exceeds 150 ℃, with the gradual volatilization of the alkynol, the silicone resin generates a violent crosslinking reaction, which results in inhibition failure. In addition, a coated catalyst may also be used to inhibit low temperature reactions of hydrosilylation silicones. The preparation and application of the coated catalyst are reported in various ways, and patent CN 104998694B proposes that a porous inert ceramic ball is used for coating the composite metal oxide catalyst and is used for catalyzing the strong exothermic reaction of unsaturated olefin oxidation to generate unsaturated aldehyde (acid), so that the problem of temperature runaway in the reaction process is effectively solved, and the reaction conversion rate and selectivity are improved; patent US4481341(a) prepares a silicone resin coated platinum catalyst by mixing a silicone resin solution and a platinum catalyst solution, evaporating, and pulverizing. The coated catalyst takes soluble silicone resin as a coating material, is applied to a silica gel system, the coating of the catalyst is easy to be dissolved by a base gel system, the stability of the silica gel system is reduced, and on the other hand, the coated catalyst prepared by a solution method has the defects of difficult crushing, uneven catalyst particle size, exposed catalyst active ingredients and the like, so that the application of the catalyst system in an addition type silica gel system is limited.
Disclosure of Invention
The invention aims to overcome the defects and provide a high-temperature catalysis inhibiting system for silicon hydride addition type silicon resin as well as a preparation method and application thereof, wherein the system can keep the long-term storage stability of the single-component silicon hydride addition type silicon resin under the normal temperature condition and can gradually catalyze the silicon resin to carry out crosslinking reaction under the high temperature condition, so that the problems of the two-component system in the storage and glue mixing processes can be avoided, and the mechanical defects of stress cracking and the like generated after the resin is cured can be avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hydrosilylation-type silicone resin high-temperature catalysis inhibition system comprises a silicone resin coated platinum catalyst and an alkynol modified silane inhibitor, wherein the silicone resin coated platinum catalyst is a core-shell microsphere which is formed by taking a platinum complex formed by taking vinyl alkoxy silane as a ligand as a core and an active component and taking crosslinking silicone resin as a coating and has platinum catalysis hydrosilylation activity; the alkynol modified silane inhibitor is phenyl silane modified by alkynol containing terminal alkynyl. The mass ratio of the silicone resin coated platinum catalyst to the alkynol modified silane inhibitor is 1-2: 1.
The alkynol containing the terminal alkynyl is preferably selected from one or more of 2-methyl-3-butyne-2-ol, 2-phenyl-3-butyne-2-ol and 3-methyl-4-pentyne-3-ol.
The alkynyloxy functionality of the alkynol-modified silane inhibitor may be monofunctional, difunctional or trifunctional, preferably difunctional or higher.
The silane for synthesizing the phenyl silane is preferably phenyl trichlorosilane.
The platinum complex can be prepared by adopting a conventional preparation method of the platinum complex. The vinyl alkoxy silane can be one or more selected from diethyl tetramethyl disiloxane, tetravinyl tetramethyl cyclotetrasiloxane, vinyl trimethoxy silane, vinyl triethoxy silane, allyl trimethoxy silane and allyl triethoxy silane, preferably vinyl trimethoxy silane and vinyl triethoxy silane. The coating layer can be selected according to different application systems, the coating layer material is a cross-linked structure silicon resin system, the components of the coating layer comprise M structure, D structure, T structure, Q structure and the like, the distribution ratio of different components can be selected according to the activity release speed of the catalyst, and the basic structure of the used organic silicon resin is (SiO)2)m(SiO3/ 2R1)n(SiO2/2R2R3)O(SiO1/2R4 3) p, wherein R1、R2、R3、R4At least one of which is selected from methyl, phenyl and vinyl, and is vinyl, the value of m/(m + n + o + p) is more than 0 and less than or equal to 0.2, the value of n/(m + n + o + p) is more than or equal to 0.8 and less than or equal to 1, the value of o/(m + n + o + p) is more than 0 and less than or equal to 0.1, and the value of p/(m + n + o + p) is more than 0 and less than or equal to 0.05; the basic structure is preferably (Visio)3/2)n1(MeSiO3/2)n2(PhSiO3/2)n3(MePhSiO2/2)o1(Me2SiO2/2)o2(Ph2SiO2/2)o3Wherein the value of n1/(n1+ n2+ n3+ o1+ o2+ o3) ranges from 0.05 to 0.15, and the value of (n1+ n2+ n3)/(n1+ n2+ n3+ o1+ o2+ o3) is greater than or equal to 0.8 and smaller than 1.
The shape of the silicon resin coated platinum catalyst microsphere is a sphere with uniform size, the average particle diameter of the silicon resin coated platinum catalyst microsphere is between 0.1 and 50 micrometers, and the average diameter of the silicon resin coated platinum catalyst microsphere is preferably between 1 and 20 micrometers. The interior of the microsphere is of a porous structure, and the platinum catalyst is adsorbed in the microsphere to play a role of a storage chamber of the catalyst.
The preparation method of the hydrosilylation type silicone resin high-temperature catalysis inhibition system comprises the following steps of preparing alkynol modified silane inhibitor and preparing silicone resin coated platinum catalyst:
(1) the preparation method of the alkynol modified silane inhibitor comprises the following steps:
a. adding alkynol and pyridine into toluene, and stirring uniformly;
b. slowly dripping phenyl silane into the solution, heating to 120 ℃ after dripping, and continuously stirring for reaction for 3-5 hours under a reflux state;
c. cooling the reactants to room temperature, and filtering out a solid generated by the reaction by using filter paper;
d. and distilling the filtrate under reduced pressure to remove toluene, thereby obtaining the alkynol modified silane inhibitor.
(2) And (3) preparing a silicone resin coated platinum catalyst.
In the preparation process, the mass ratio of the alkynol, the pyridine and the phenyl silane is 1 (0.5-2) to 0.5-2. The dosage of the toluene is 1.5 to 2 times of the sum of the mass of the alkynol and the pyridine.
The preparation method of the silicone resin coated platinum catalyst comprises the following steps:
(1) slowly adding sodium bicarbonate into a mixed solution of chloroplatinic acid, ligand silane monomer and isopropanol, stirring and reacting for 20-30 minutes at 70-80 ℃, and filtering solid components to obtain a platinum vinyl siloxane complex isopropanol solution; the mass ratio of the chloroplatinic acid to the ligand silane monomer to the isopropanol to the sodium bicarbonate is 1: 2-10: 20-60: 0.5-2;
(2) dripping the mixture of isopropanol solution of platinum vinyl siloxane complex and primary coating silane monomer into water-in-oil emulsion formed by water, organic solvent and emulsifier with HLB value between 2 and 8, and stirring and reacting for 0.5 to 5 hours at the temperature of between 15 and 80 ℃;
(3) slowly dripping the secondary coating silane monomer into the system obtained in the step (2) for secondary polymerization, and continuously reacting for 0.5-5 hours at the temperature of 15-80 ℃;
(4) and filtering, washing and drying the prepared solid microspheres to obtain the catalyst.
In the preparation method of the silicone resin coated platinum catalyst, the ligand silane monomer in the step (1) is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, divinyl tetramethyl disiloxane and tetravinyl tetramethyl cyclic monomer.
The primary coating silane monomer in the step (2) is one or more of phenyl trimethoxy silane, vinyl triethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, ethyl orthosilicate and methyl orthosilicate. The organic solvent in the step (2) is alkane or aromatic hydrocarbon, wherein toluene, n-hexane, n-heptane and n-octane are preferred, and n-octane is most preferred. The HLB value is between 2 and 8, and sorbitan fatty acid ester is preferred. In order to ensure the stability of the water-in-oil system, the mass ratio of the organic solvent to the emulsifier with the HLB value of 2-8 in the step (2) can be controlled within the range of 50-95: 5-50, the used amount of water can be controlled to be 10-100% of the total mass of the organic solvent and the emulsifier, and the used amount of the primary coating silane monomer can be controlled to be 10-100% of the total mass of the organic solvent and the emulsifier. The dosage of the isopropanol solution of the platinum vinyl siloxane complex is controlled to be 0.1-30% of the mass of the silane monomer coated once.
The secondary coating silane monomer in the step (3) is one or more of phenyl trimethoxy silane, vinyl trimethoxy silane, methyl trimethoxy silane and methyl phenyl alkoxy silane. The mass ratio of the used amount of the secondary coating silane monomer to the used amount of the primary coating silane monomer in the step (2) can be controlled to be 0.01-1: 1.
the application of the hydrosilylation type silicone resin high-temperature catalysis inhibition system in addition curing of the hydrosilylation type single-component liquid silicone resin is provided.
The application method comprises the following steps: adding the hydrosilylation type silicone resin high-temperature catalysis suppression system into silicone resin consisting of vinyl silicone resin, hydrogen-containing silicone oil and vinyl silicone oil, wherein the mass ratio of the hydrosilylation type silicone resin high-temperature catalysis suppression system to the silicone resin is 1:50-100, stirring and mixing uniformly, and curing at the temperature of 80-200 ℃.
The invention adopts alkynol modified phenyl silane as an inhibitor of a high-temperature catalysis inhibition system of silicon-hydrogen addition type silicon resin, and the high-temperature catalysis inhibition system is formed by matching with a platinum catalyst coated by the silicon resin, compared with the existing catalyst and catalysis inhibition system, the problem that addition type silicon resin is easy to polymerize quickly after being mixed by the catalyst is solved, and the service time of the resin under the high-temperature condition, especially above 150 ℃, can be fully and effectively prolonged. The possibility of internal stress generation of the silicone resin can be sufficiently reduced due to the slow progress of high-temperature curing. In addition, the catalytic inhibition system is beneficial to normal-temperature and low-temperature storage of the hydrosilylation silicone resin, so that the catalytic inhibition system can be applied to a single-component hydrosilylation silicone resin system on a large scale.
Drawings
FIG. 1 is a scanning electron microscope image of a silicone resin coated platinum catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph showing the viscosity of different systems of catalyzed addition silicone resins as a function of cure time.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The preparation method of the hydrosilylation type silicone resin high-temperature catalysis inhibition system comprises the preparation of alkynol modified silane inhibitor and the preparation of silicone resin coated platinum catalyst. The mass ratio of the silicone resin coated platinum catalyst to the alkynol modified silane inhibitor is 1: 1.
(1) The preparation method of the alkynol modified silane inhibitor comprises the following steps:
a. adding 25g of 2-methyl-3-butyn-2-ol and 20g of pyridine into 80g of toluene, and starting stirring;
b. to the solution was slowly dropped 15g of phenyltrichlorosilane, and the dropping was completed within 3 hours. After the dropwise addition, the temperature is raised to 120 ℃, and the stirring reaction is continued for 4 hours under the reflux state;
c. cooling the reactants to room temperature, and filtering out a solid generated by the reaction by using filter paper;
d. and distilling the filtrate under reduced pressure, and removing the toluene to obtain the product.
(2) Preparation of silicone resin coated platinum catalyst:
a. slowly adding 1g of sodium bicarbonate into a mixed solution of 1g of chloroplatinic acid, 5g of vinyl trimethoxy silane and 30g of isopropanol, stirring and reacting for 30 minutes at 75 ℃, and filtering solid components to obtain a platinum vinyl siloxane complex isopropanol solution;
b. b, quickly dripping 10g of the mixture of the platinum vinyl siloxane complex isopropanol solution prepared in the step a, 40 g of phenyltrimethoxysilane, 4g of vinyltrimethoxysilane, 8 g of methyltrimethoxysilane and 4g of methylphenyldimethoxyalkoxysilane into a W/O emulsion formed by mixing 50 g of water, 90 g of n-octane and 10g of sorbitan trioleate, and reacting for 3 hours at the temperature of 50 ℃;
c. 5g of phenyl trimethoxy silane, 1g of vinyl trimethoxy silane and 1g of methyl trimethoxy silane are mixed and added into a constant-pressure dropping funnel, and are added into the system dropwise, and after the dropwise addition is finished, the reaction time is 2 hours at the temperature of 60 ℃;
d. after the reaction is finished, stopping stirring, standing, removing supernatant liquor, filtering microspheres, washing and drying to obtain the catalyst.
Example 2
The preparation method of the hydrosilylation type silicone resin high-temperature catalysis inhibition system comprises the preparation of alkynol modified silane inhibitor and the preparation of silicone resin coated platinum catalyst. The mass ratio of the silicone resin coated platinum catalyst to the alkynol modified silane inhibitor is 1: 1.
(1) The preparation method of the alkynol modified silane inhibitor comprises the following steps:
a. adding 5g of 2-methyl-3-butyn-2-ol, 15g of 2-phenyl-3-butyn-2-ol and 30g of pyridine into 80g of toluene, and stirring;
b. to the solution was slowly dropped 27g of phenyltrichlorosilane, and the dropping was completed within 3 hours. After the dropwise addition, the temperature is raised to 120 ℃, and the stirring reaction is continued for 4 hours under the reflux state;
c. cooling the reactants to room temperature, and filtering out a solid generated by the reaction by using filter paper;
d. and distilling the filtrate under reduced pressure, and removing the toluene to obtain the product.
(2) Preparation of silicone resin coated platinum catalyst:
a. slowly adding 1.07 g of sodium bicarbonate into a mixed solution of 1g of chloroplatinic acid, 2.8 g of divinyl tetramethyl disiloxane and 40 g of isopropanol, stirring and reacting for 30 minutes at 70 ℃, and filtering solid components to obtain an isopropanol solution of a platinum vinyl siloxane complex;
b. b, quickly dripping a mixture of 6g of the isopropanol solution of the platinum vinyl siloxane complex prepared in the step a, 10g of phenyltrimethoxysilane, 10g of vinyltrimethoxysilane, 40 g of methyltrimethoxysilane and 4g of methylphenyldimethoxyalkoxysilane into a W/O emulsion formed by mixing 30g of water, 70 g of n-octane and 30g of sorbitan trioleate, and reacting for 3 hours at the temperature of 50 ℃;
c. 8 g of phenyltrimethoxysilane and 2 g of methyltrimethoxysilane are mixed and added into a constant pressure dropping funnel, and are added into the system dropwise, and after the dropwise addition is finished, the reaction time is 2 hours at the temperature of 60 ℃;
d. after the reaction is finished, stopping stirring, standing, removing supernatant liquor, filtering microspheres, washing and drying to obtain the catalyst.
Example 3
The preparation method of the hydrosilylation type silicone resin high-temperature catalysis inhibition system comprises the preparation of alkynol modified silane inhibitor and the preparation of silicone resin coated platinum catalyst. The mass ratio of the silicone resin coated platinum catalyst to the alkynol modified silane inhibitor is 1: 1.
(1) The preparation method of the alkynol modified silane inhibitor comprises the following steps:
a. adding 20g of 2-methyl-3-butyn-2-ol, 5g of 2-phenyl-3-butyn-2-ol, 10g of 3-methyl-4-pentyn-3-ol and 30g of pyridine into 100g of toluene, and stirring;
b. 31g of phenyltrichlorosilane was slowly dropped into the solution, and the dropping was completed within 3 hours. After the dropwise addition, the temperature is raised to 120 ℃, and the stirring reaction is continued for 4 hours under the reflux state;
c. cooling the reactants to room temperature, and filtering out a solid generated by the reaction by using filter paper;
d. and distilling the filtrate under reduced pressure, and removing the toluene to obtain the product.
(2) The preparation of the silicone resin-coated platinum catalyst was the same as in example 1.
Example 4
The preparation method of the hydrosilylation type silicone resin high-temperature catalysis inhibition system comprises the preparation of alkynol modified silane inhibitor and the preparation of silicone resin coated platinum catalyst. The mass ratio of the silicone resin coated platinum catalyst to the alkynol modified silane inhibitor is 2: 1.
(1) The preparation method of the alkynol modified silane inhibitor comprises the following steps:
a. adding 46g of 2-methyl-3-butyn-2-ol, 1g of 2-phenyl-3-butyn-2-ol and 30g of pyridine into 100g of toluene, and stirring;
b. 24g of phenyltrichlorosilane was slowly dropped into the solution, and the dropping was completed within 3 hours. After the dropwise addition, the temperature is raised to 120 ℃, and the stirring reaction is continued for 4 hours under the reflux state;
c. cooling the reactants to room temperature, and filtering out a solid generated by the reaction by using filter paper;
d. and distilling the filtrate under reduced pressure, and removing the toluene to obtain the product.
(2) The preparation of the silicone resin-coated platinum catalyst was the same as in example 1.
An application test of a hydrosilylation silicone resin high-temperature catalysis inhibition system in addition curing of single-component liquid silicone resin is as follows:
(one) the hydrosilylation silicone high temperature catalyst inhibition system prepared in example 1 was applied to an addition silicone system, wherein the addition silicone system was used in an amount of 20g and consisted of three parts, wherein methylphenyl vinyl silicone oil contained 1.3 wt% vinyl as a diluent, phenyl vinyl silicone resin contained 5.7 wt% vinyl, and methylphenyl hydrogen silicone oil contained 0.6 wt% terminal hydrogen, and the molar ratio of hydrogen to vinyl was 1.1: 1. And (3) stirring and mixing the hydrosilylation high-temperature catalysis inhibition system and the silicon resin uniformly by using a vacuum defoaming stirrer, carrying out curing experiments at different temperatures after stirring uniformly, and determining the curing speed of the single-component silicon resin system by using the gel time. Table 1 lists the gel times for three cases using uncoated plain catalyst, silicone coated platinum catalyst (prepared as described in example 1) and a hydrosilylation silicone high temperature catalyst inhibition system of the present invention. Schemes 1 to 4 adopt a silicone resin coated platinum catalyst, schemes 5 and 6 adopt an uncoated common pure catalyst, and schemes 7 to 10 adopt a hydrosilylation-type silicone resin high-temperature catalysis inhibition system. It can be seen that the gel time of the addition type silicone resin adopting the hydrosilylation type silicone resin high-temperature catalysis inhibition system is obviously prolonged compared with the gel time of the silicone resin adopting the common pure catalyst and the silicone resin coated platinum catalyst, particularly the gel time of the silicone resin adopting the hydrosilylation type silicone resin high-temperature catalysis inhibition system is up to 147 minutes at 160 ℃, and even up to 20 days at 80 ℃. In the scheme of only adopting the silicone resin coated platinum catalyst, although the gel time is greatly improved compared with the common pure catalyst under the high-temperature condition, compared with the scheme of adopting the catalytic inhibition system of the invention, the gel time is only about half of the gel time of the latter.
TABLE 1
Table 2 shows the gel times at different temperatures for silicones employing a silicone-coated platinum catalyst and 2-methyl-3-butyn-2-ol as the catalytic inhibition system. Compared with the hydrosilylation-type silicone resin high-temperature catalytic inhibition system in the table 1, the gelling time is obviously shortened. The high-temperature catalysis inhibition system for the hydrosilylation silicone resin has a good inhibition effect on the hydrosilylation silicone resin under a high-temperature condition.
TABLE 2
(II) the hydrosilylation silicone high temperature catalyst inhibition system prepared in example 1 was applied to an addition silicone system, wherein the addition silicone system was used in an amount of 20g and consisted of three parts, wherein methylphenyl vinyl silicone oil contained 1.3 wt% vinyl as a diluent, phenyl vinyl silicone resin contained 5.7 wt% vinyl, and methylphenyl hydrogen silicone oil contained 0.6 wt% terminal hydrogen, and the molar ratio of hydrogen to vinyl was 1.1: 1. And (3) stirring and mixing the hydrosilylation type silicone high-temperature catalysis inhibition system and the silicone uniformly by using a vacuum defoaming stirrer, carrying out curing experiments at 120 ℃,150 ℃ and 160 ℃ after stirring uniformly, and determining the curing speed of the single-component silicone system by adopting viscosity change. Fig. 2 shows the viscosity change of the silicon resin coated with the unhindered normal pure catalyst, the silicon resin coated platinum catalyst and the hydrosilylation high-temperature catalysis inhibition system of the present invention, wherein the sample a is the silicon resin coated with the unhindered normal pure catalyst, the sample B is the silicon resin coated with the silicon resin coated platinum catalyst, and the sample C is the silicon resin coated with the hydrosilylation high-temperature catalysis inhibition system of the present invention. 1. 2, 3 refer to temperature conditions at 120 ℃,150 ℃ and 160 ℃, respectively. It can be seen that the viscosity change of the silicone resin adopting the hydrosilylation-type silicone resin high-temperature catalysis inhibition system is obviously delayed compared with the silicone resin adopting an uncoated common pure catalyst and a silicone resin coated platinum catalyst. The viscosity of the silicone resin adopting the silicone resin coated platinum catalyst is obviously delayed compared with the silicone resin adopting a common pure catalyst which is not coated, but compared with the silicone resin adopting the hydrosilylation type silicone resin high-temperature catalysis inhibition system, the viscosity inhibition effect is relatively poorer.
Therefore, the hydrosilylation type silicone resin high-temperature catalysis inhibition system can meet the application process requirements in a single-component silicone resin system, can realize the storage stability and the appropriate catalytic activity in a high-temperature stage of the single-component system, and can be applied to systems such as impregnating varnish for insulating coils of motors and the like.
Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. The hydrosilylation-type silicone resin high-temperature catalysis inhibition system is characterized by comprising a silicone resin coated platinum catalyst and an alkynol modified silane inhibitor, wherein the silicone resin coated platinum catalyst is a core-shell microsphere with platinum catalysis hydrosilylation activity, which is formed by taking a platinum complex formed by taking vinyl siloxane as a ligand as a core and an active component and taking cross-linked silicone resin as a coating layer; the alkynol modified silane inhibitor is phenyl silane modified by alkynol containing terminal alkynyl; the coating material is a cross-linked structure silicone resin system, and the basic structure of the used silicone resin is (SiO)2)m(SiO3/ 2R1)n(SiO2/2R2R3)O(SiO1/2R4 3) p, wherein R1、R2、R3、R4At least one of which is selected from methyl, phenyl and vinyl, and is vinyl, the value of m/(m + n + o + p) is more than 0 and less than or equal to 0.2, the value of n/(m + n + o + p) is more than or equal to 0.8 and less than or equal to 1, the value of o/(m + n + o + p) is more than 0 and less than or equal to 0.1, and the value of p/(m + n + o + p) is more than 0 and less than or equal to 0.05; the vinyl siloxane is selected from one or more of diethyl tetramethyl disiloxane and tetravinyl tetramethyl cyclotetrasiloxane.
2. The hydrosilylation-type silicone resin high-temperature catalysis inhibition system as claimed in claim 1, wherein the mass ratio of the silicone resin-coated platinum catalyst to the alkynol-modified silane inhibitor is 1-2: 1.
3. The hydrosilylation type silicone resin high temperature catalyst inhibition system as set forth in claim 1 wherein said alkynol containing terminal alkynyls is selected from one or more of 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 3-methyl-4-pentyn-3-ol.
4. The system of claim 1, wherein the alkynol-modified silane inhibitor has an alkynyloxy functionality greater than or equal to a single functionality.
5. The method for preparing the hydrosilylation catalyst inhibition system as defined in any one of claims 1 to 4, comprising the steps of preparing the alkynol-modified silane inhibitor and preparing the silicone resin-coated platinum catalyst,
(1) the preparation method of the alkynol modified silane inhibitor comprises the following steps:
a. adding alkynol and pyridine into toluene, and stirring uniformly;
b. slowly dripping phenyl silane into the solution, heating to 120 ℃ after dripping, and continuously stirring for reaction for 3-5 hours under a reflux state; the mass ratio of the alkynol to the pyridine to the phenyl silane is 1: 0.5-2;
c. cooling the reactants to room temperature, and filtering out a solid generated by the reaction by using filter paper;
d. carrying out reduced pressure distillation on the filtrate to remove toluene, thus obtaining the alkynol modified silane inhibitor;
(2) preparation of silicone resin coated platinum catalyst:
(a) slowly adding sodium bicarbonate into a mixed solution of chloroplatinic acid, ligand silane monomer and isopropanol, stirring and reacting for 20-30 minutes at 70-80 ℃, and filtering solid components to obtain a platinum vinyl siloxane complex isopropanol solution; the mass ratio of the chloroplatinic acid to the ligand silane monomer to the isopropanol to the sodium bicarbonate is 1: 2-10: 20-60: 0.5-2;
(b) dripping the mixture of isopropanol solution of platinum vinyl siloxane complex and primary coating silane monomer into water-in-oil emulsion formed by water, organic solvent and emulsifier with HLB value between 2 and 8, and stirring and reacting for 0.5 to 5 hours at the temperature of between 15 and 80 ℃;
(c) slowly dripping the secondary coating silane monomer into the system obtained in the step (b) for secondary polymerization, and continuously reacting for 0.5-5 hours at the temperature of 15-80 ℃;
(d) and filtering, washing and drying the prepared solid microspheres to obtain the catalyst.
6. Use of the high temperature catalysis inhibition system of hydrosilylation as defined in claim 1 in addition cure of addition single component liquid silicone.
7. The application of the silicone resin composition as claimed in claim 6, wherein the application method comprises adding the hydrosilylation-type silicone resin high-temperature catalysis suppression system into the silicone resin consisting of vinyl silicone resin, hydrogen-containing silicone oil and vinyl silicone oil, wherein the mass ratio of the hydrosilylation-type silicone resin high-temperature catalysis suppression system to the silicone resin is 1:50-100, stirring and mixing uniformly, and curing at the temperature of 80-200 ℃.
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| CN111450883A (en) * | 2020-05-09 | 2020-07-28 | 九江学院 | Polyvinyl siloxane resin microsphere Pt-loaded catalyst and preparation method thereof |
| CN111592764B (en) * | 2020-05-29 | 2021-08-31 | 浙江新安化工集团股份有限公司 | Silicone resin reinforced organosilicon elastomer aqueous dispersion liquid and preparation method and application thereof |
| CN114377727B (en) * | 2021-12-30 | 2023-08-01 | 安徽壹石通材料科学研究院有限公司 | Embedding type metal catalyst |
| CN114789066A (en) * | 2022-03-04 | 2022-07-26 | 九江学院 | Method for preparing nano magnetic silicon dioxide immobilized platinum catalyst by one-pot method |
| CN115216269B (en) * | 2022-08-25 | 2023-10-13 | 厦门捌斗新材料科技有限公司 | Single-component organic silicon pouring sealant and preparation method thereof |
| CN115672401A (en) * | 2022-11-01 | 2023-02-03 | 安徽壹石通材料科学研究院有限公司 | Supported noble metal catalyst and preparation method and application thereof |
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