CN115819774B - Air-drying type organic silicon resin with high phenyl content and preparation method thereof - Google Patents
Air-drying type organic silicon resin with high phenyl content and preparation method thereof Download PDFInfo
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Abstract
The application relates to an air-dried organic silicon resin with high phenyl content and a preparation method thereof, wherein a structural precursor with high crosslinking density is synthesized firstly, a difunctional structure is added when the molecular weight grows gradually to increase toughness, then the structure of the organic silicon resin is completed by heating under the condition of a specific catalyst, the organic silicon resin structure with high crosslinking density has a molecular chain segment matched with an elastic molecular chain segment to form an organic silicon resin structure with excellent heat stability, a plurality of alkoxy structures such as methoxy, ethoxy and the like are maintained, alkoxy groups on the organic silicon resin are easy to catalyze and remove alcohols and water with water molecules in the air to generate Si-OH on the organic silicon resin, the Si-OH is easy to condense and dehydrate with each other to form the Si-O-Si structure, and the water removed by the reaction can be continuously matched with the reaction, so that the organic silicon resin can be solidified on the surface in a short time, and the solidification can be completed in a heating mode.
Description
Technical Field
The application belongs to the technical field of organic silicon resin, and particularly relates to an air-dried organic silicon resin with high phenyl content and a preparation method thereof.
Background
The organic silicon resin is a polymer taking Si-O-Si as a main chain, and side chains are mostly organic groups with different proportions such as monophenyl, diphenyl, methylphenyl and the like, and the organic silicon resin is generally used as a film forming material of a coating to improve the heat resistance of the coating, in particular to a cooker coating which is used at the contact part of a stove, an oven, an electromagnetic oven and the like with open fire or high temperature parts and is subjected to long-time alternating circulation of high temperature and cold and heat in the use process because the organic silicon resin has better heat stability. The existing organosilicon paint can basically meet the use requirement in a short-time high-temperature environment, but is easy to oxidize and decompose at a long-time high temperature, the coating is seriously discolored after the high temperature is continued, and the cold-hot alternating circulating coating is easy to paint off after the high temperature is continued, so that the service life of the product is seriously influenced. Therefore, higher requirements are put on the performances of the organic silicon resin, such as thermal stability, and the like, and generally, the phenyl structure is introduced to improve the thermal stability of the organic silicon resin, and the methyl structure is introduced to improve the curing hardness, but the monofunctional structure is introduced to effectively improve the crosslinking density of the resin, so that the organic silicon resin with high phenyl content and high toughness is difficult to synthesize due to lack of toughness. Therefore, it is necessary to introduce a proper difunctional structure to reduce the crosslinking density and improve the elasticity.
Disclosure of Invention
The application aims to solve the technical problem of providing the air-drying type organic silicon resin with high phenyl content and the preparation method thereof, wherein the organic silicon resin has the effects of high temperature resistance, cold and hot shock resistance and air drying under normal temperature environment without baking.
In order to solve the technical problems, the application adopts a technical scheme that: the high-phenyl-content air-drying type organic silicon resin comprises M M monomers and N N monomers, and the structural formula is as follows:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein m and n are positive integers in the range of 5-30; r is R 1 Methoxy, ethoxy, isopropyl or n-butyl, preferably methoxy or ethoxy; r is R 2 Methoxy, ethoxy, isopropyl, n-butyl or phenyl, preferably methoxy, ethoxy or phenyl; r is R 3 Methoxy, ethoxy, isopropyl, n-butyl, phenyl or methyl, preferably methoxy, ethoxy, phenyl or methyl; r is R 4 Methoxy, ethoxy, isopropyl, n-butyl; preferably methoxy and ethoxy; r is R 5 Methoxy, ethoxy, isopropyl, n-butyl, phenyl or methyl, preferably methoxy, ethoxy, phenyl or methyl;
the high phenyl content means that the phenyl content is more than 55%.
Further, the M monomer is phenyl trimethoxysilane, phenyl triethoxysilane, diphenyl dimethoxy silane or diphenyl diethoxy silane; the N monomer is dimethyl dimethoxy silane, methyl phenyl diethoxy silane, methyl orthosilicate or ethyl orthosilicate.
The application also provides a preparation method of the air-dried organic silicon resin with high phenyl content, which comprises the following steps:
(1) Placing 200-250 parts by weight of M monomer into a reaction kettle under the protection of nitrogen, adding 0.1-0.3 part by weight of hydrolysis catalyst, slowly dropwise adding 20-30 parts by weight of deionized water at 15-30 ℃ for 1-4 hours; after the dripping is completed, the temperature of the reaction kettle is raised to 55-60 ℃ for 16-18 hours, then the temperature in the kettle is raised to 140-150 ℃ and kept constant for 4-6 hours, and then vacuum is pumped at the temperature, so that the vacuum keeping degree is less than 800pa and is kept for 1-1.5 hours, and the organosilicon resin prepolymer is obtained;
(2) Taking out 150-180 parts by weight of the organosilicon resin prepolymer prepared in the step (1) and mixing with 30-40 parts by weight of N monomer; after uniformly mixing, dropwise adding 30-50 parts by weight of deionized water at 15-30 ℃ for 1-2 hours, and after the dropwise adding is finished, raising the temperature in the kettle to 55-60 ℃ and maintaining for 16-18 hours;
(3) Slowly adding 30-40 parts by weight of N monomer, fully mixing for 2-3 hours, heating to 140-150 ℃, adding 60-80 parts by weight of PMA and 0.75-1 part by weight of reaction catalyst when the water removal amount reaches 4-6 parts by weight, maintaining at the temperature for 3-4 hours, slowly dropwise adding 8.4-10 parts by weight of KOH solution with the mass percentage concentration of 1% -2% at 140-150 ℃ for 2-4 hours; maintaining the temperature at 140-150 ℃ after the dripping is completed, and preserving the temperature for 4-5 hours; then vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 1-2 hours, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin;
the M monomer is phenyl trimethoxy silane, phenyl triethoxy silane, diphenyl dimethoxy silane or diphenyl diethoxy silane; the N monomer is dimethyl dimethoxy silane, methyl phenyl diethoxy silane, methyl orthosilicate or ethyl orthosilicate.
Further, the hydrolysis catalyst adopts concentrated sulfuric acid, hydrochloric acid, nitric acid, citric acid or acetic acid.
Further, the reaction catalyst adopts Pb, zn, sn, co, fe, ce naphthenate or carboxylate or isoacid salt, perfluorinated sulfonic acid amine or titanate.
Further, the high phenyl content means that the phenyl content is more than 55%.
The application has the following advantages:
(1) The application synthesizes the structure precursor with high crosslinking density, adds the difunctional structure to increase the toughness when the molecular weight grows gradually, then heats the structure of the organic silicon resin under the condition of specific catalyst, the organic silicon resin structure with high crosslinking density has the molecular chain segment matched with the elastic molecular chain segment to form the organic silicon resin structure with excellent heat stability, and simultaneously maintains a plurality of alkoxy structures such as methoxy, ethoxy and the like, the alkoxy on the organic silicon resin is easy to catalyze with water molecules in the air to remove alcohols and water and generate Si-OH on the organic silicon resin, the Si-OH is easy to condense and dehydrate each other to form Si-O-Si structure, and the water removed by the reaction can continuously participate in the reaction, so the organic silicon resin structure can be solidified on the surface in a short time, and can be matched with proper catalyst to finish the solidification in a heating mode;
(2) The application can promote the solidification of the organic silicon resin by utilizing trace moisture in the air without a catalyst in the air, can dry the surface of the resin within 5 minutes, can be heated and solidified more if a specific catalyst is used, and can form the organic silicon resin with excellent thermal stability, thus being widely applied to heat-resistant paint;
(3) The air-dried organic silicon resin with high phenyl content can be used for preparing the coating of the cooker outer layer, and the prepared coating can resist open fire, resist high temperature at 260 ℃ for 100 hours, not change color and not fall off after 100 cycles of cold and hot impact.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be embodied in other ways than those described herein, and persons skilled in the art will be able to make similar generalizations without departing from the spirit of the application and therefore the application is not limited to the specific embodiments disclosed below.
The high phenyl content of the high phenyl content air-dried organic silicon resin disclosed by the application means that the phenyl content is more than 55%, and the structural formula is shown as follows, and the high phenyl content air-dried organic silicon resin comprises M M monomers and N N monomers:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein m and n are positive integers in the range of 5-30; r is R 1 May be methoxy, ethoxy, isopropyl or n-butyl, preferably methoxy or ethoxy; r is R 2 May be methoxy, ethoxy, isopropyl, n-butyl or phenyl, preferably methoxy, ethoxy or phenyl; r is R 3 May be methoxy, ethoxy, isopropyl, n-butyl, phenyl or methyl, preferably methoxy, ethoxy, phenyl or methyl; r is R 5 May be methoxy, ethoxy, isopropyl, n-butyl, phenyl or methyl, preferably methoxy, ethoxy, phenyl or methyl; r is R 4 Can be methoxy, ethoxy, isopropyl, n-butyl; preferably methoxy and ethoxy;
wherein, the M monomer is preferably phenyl trimethoxy silane, phenyl triethoxy silane, diphenyl dimethoxy silane or diphenyl diethoxy silane; the N monomer is preferably dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methyl orthosilicate or ethyl orthosilicate.
The hydrolysis catalyst in the embodiment of the application adopts concentrated sulfuric acid, hydrochloric acid, nitric acid, citric acid or acetic acid and the like.
The reaction catalyst of the embodiment of the application adopts naphthenate, carboxylate, isoacid salt, perfluorinated sulfonic acid amine, titanate, and the like of Pb, zn, sn, co, fe, ce and the like.
Example 1: a preparation method of an air-dried organic silicon resin with high phenyl content comprises the following steps:
(1) Firstly, taking 200 parts by weight of M monomer (phenyl trimethoxy silane is adopted in the embodiment) as a starting material, placing the starting material into a reaction kettle under the protection of nitrogen, adding 0.1 part by weight of hydrolysis catalyst (concentrated sulfuric acid), and slowly dropwise adding 20 parts by weight of deionized water at 15 ℃ for 1 hour; after the dripping is completed, the temperature of the reaction kettle is increased to 55 ℃ for 18 hours to ensure the integrity of the hydrolysis reaction, then the temperature in the kettle is increased to 140 ℃ and kept constant for 6 hours, and then vacuum is pumped at the temperature, so that the vacuum retention degree is kept to be less than 800pa for 1 hour to complete the polycondensation reaction, and the organosilicon resin prepolymer with medium molecular weight is generated;
(2) Then 150 parts by weight of the silicone resin prepolymer prepared in step (1) was taken out and mixed with 30 parts by weight of N monomer (dimethyl dimethoxy silane was used in this example); after uniform mixing, dropwise adding 30 parts by weight of deionized water at 15 ℃ for 1 hour, and after the dropwise adding is completed, raising the temperature in the kettle to 55 ℃ and maintaining for 18 hours;
(3) Then, 30 parts by weight of N monomer (dimethyl dimethoxy silane is adopted in the embodiment) is slowly added, fully mixed for 2 hours, heated to 140 ℃, 60 parts by weight of PMA and 0.75 part by weight of reaction catalyst (zinc isooctanoate is adopted in the embodiment) are added when the water removal amount reaches 4 parts by weight, the mixture is maintained at the temperature for 3 hours, then 8.4 parts by weight of KOH solution with the mass percentage concentration of 1% is slowly added dropwise at 140 ℃ for 2 hours, and water is removed in the dropwise adding process; maintaining the temperature at 140 ℃ after the dripping is completed, and preserving the temperature for 4 hours; and vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 1 hour, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin.
Example 2: a preparation method of an air-dried organic silicon resin with high phenyl content comprises the following steps:
(1) Firstly, 250 parts by weight of M monomer (phenyl trimethoxy silane is adopted in the embodiment) is taken as a starting material, 0.3 part by weight of hydrolysis catalyst (concentrated sulfuric acid) is added into a reaction kettle under the protection of nitrogen, 30 parts by weight of deionized water is slowly added dropwise at 30 ℃ for 4 hours; after the dripping is completed, the temperature of the reaction kettle is increased to 60 ℃ for 18 hours to ensure the integrity of the hydrolysis reaction, then the temperature in the kettle is increased to 150 ℃ and kept constant for 6 hours, and then vacuum is pumped at the temperature, so that the vacuum retention degree is kept to be less than 800pa for 1.5 hours to complete the polycondensation reaction, and the organosilicon resin prepolymer with medium molecular weight is generated;
(2) Then 180 parts by weight of the silicone resin prepolymer prepared in step (1) was taken out and mixed with 35 parts by weight of N monomer (dimethyldimethoxysilane was used in this example); after uniform mixing, 50 parts by weight of deionized water is dripped at 30 ℃ for 2 hours, and the temperature in the kettle is raised to 60 ℃ for 18 hours after dripping is completed;
(3) Then, 35 parts by weight of N monomer (dimethyl dimethoxy silane is adopted in the embodiment) is slowly added, fully mixed for 3 hours, heated to 150 ℃, 80 parts by weight of PMA and 1 part by weight of reaction catalyst (zinc isooctanoate is adopted in the embodiment) are added when the water removal amount reaches 6 parts by weight, the temperature is maintained for 4 hours, then 10 parts by weight of KOH solution with the mass percentage concentration of 2% is slowly added dropwise at 150 ℃ for 4 hours, and water is removed in the dropwise adding process; maintaining the temperature at 150 ℃ after the dripping is completed, and preserving the temperature for 5 hours; and vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 2 hours, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin.
Example 3: a preparation method of an air-dried organic silicon resin with high phenyl content comprises the following steps:
(1) Firstly, taking 220 parts by weight of M monomer (phenyl trimethoxy silane is adopted in the embodiment) as a starting material, placing the starting material in a reaction kettle under the protection of nitrogen, adding 0.15 part by weight of hydrolysis catalyst (concentrated sulfuric acid), and slowly dropwise adding 22 parts by weight of deionized water at 20 ℃ for 2 hours; after the dripping is completed, the temperature of the reaction kettle is increased to 56 ℃ for 17 hours to ensure the integrity of the hydrolysis reaction, then the temperature in the kettle is increased to 145 ℃ and kept constant for 4.5 hours, and then vacuum is pumped at the temperature to ensure that the vacuum retention degree is less than 800pa and is maintained for 1.2 hours to complete the polycondensation reaction, so as to generate the organosilicon resin prepolymer with medium molecular weight;
(2) Then 160 parts by weight of the silicone resin prepolymer prepared in step (1) was taken out and mixed with 40 parts by weight of N monomer (methyl phenyl dimethoxy silane was used in this example); after uniform mixing, 35 parts by weight of deionized water is dripped at 20 ℃ for 1.2 hours, and the temperature in the kettle is raised to 56 ℃ for 17 hours after dripping is completed;
(3) Then, 40 parts by weight of N monomer (methyl phenyl dimethoxy silane is adopted in the embodiment) is slowly added, fully mixed for 2.5 hours, heated to 145 ℃, 65 parts by weight of PMA and 0.8 part by weight of reaction catalyst (zinc isooctanoate is adopted in the embodiment) are added when the water removal amount reaches 4.5 parts by weight, the temperature is maintained for 3.5 hours, then 9 parts by weight of KOH solution with the mass percentage concentration of 1.5% is slowly added at 145 ℃ for 2.5 hours, and water is removed in the dropping process; maintaining 145 ℃ after the dripping is completed, and preserving the heat for 4.5 hours; and vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 1.2 hours, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin.
Example 4: a preparation method of an air-dried organic silicon resin with high phenyl content comprises the following steps:
(1) Firstly, taking 220 parts by weight of M monomer (diphenyl triethoxysilane is adopted in the embodiment) as a starting material, placing the starting material in a reaction kettle under the protection of nitrogen, adding 0.12 part by weight of hydrolysis catalyst (concentrated sulfuric acid), and slowly dropwise adding 25 parts by weight of deionized water at 25 ℃ for 3 hours; after the dripping is completed, the temperature of the reaction kettle is increased to 58 ℃ for 16.5 hours to ensure the integrity of the hydrolysis reaction, then the temperature in the kettle is increased to 145 ℃ and kept constant for 5 hours, and then vacuum is pumped at the temperature to ensure that the vacuum retention degree is less than 800pa for 1.2 hours to complete the polycondensation reaction, so as to generate the organosilicon resin prepolymer with medium molecular weight;
(2) Then, 170 parts by weight of the silicone resin prepolymer prepared in step (1) was taken out and mixed with 35 parts by weight of N monomer (dimethyl dimethoxy silane was used in this example); after uniform mixing, dropwise adding 40 parts by weight of deionized water at 20 ℃ for 1.2 hours, and after the dropwise adding is completed, raising the temperature in the kettle to 55 ℃ and maintaining for 17 hours;
(3) Then, 35 parts by weight of N monomer (dimethyl dimethoxy silane is adopted in the embodiment) is slowly added, fully mixed for 2.5 hours, heated to 145 ℃, 70 parts by weight of PMA and 0.9 part by weight of reaction catalyst (zinc isooctanoate is adopted in the embodiment) are added when the water removal amount reaches 6 parts by weight, the temperature is maintained for 3.5 hours, then 9 parts by weight of KOH solution with the mass percentage concentration of 1.5% is slowly added dropwise at 145 ℃ for 4 hours, and water is removed in the dropwise adding process; maintaining 145 ℃ after the dripping is completed, and preserving the heat for 4.5 hours; and vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 1.5 hours, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin.
Example 5: a preparation method of an air-dried organic silicon resin with high phenyl content comprises the following steps:
(1) Firstly, 250 parts by weight of M monomer (diphenyl triethoxysilane is adopted in the embodiment) is taken as a starting material, 0.2 part by weight of hydrolysis catalyst (concentrated sulfuric acid) is added into a reaction kettle under the protection of nitrogen, 30 parts by weight of deionized water is slowly added dropwise at 30 ℃ for 4 hours; after the dripping is completed, the temperature of the reaction kettle is increased to 60 ℃ for 18 hours to ensure the integrity of the hydrolysis reaction, then the temperature in the kettle is increased to 150 ℃ and kept constant for 6 hours, and then vacuum is pumped at the temperature, so that the vacuum retention degree is kept to be less than 800pa for 1.5 hours to complete the polycondensation reaction, and the organosilicon resin prepolymer with medium molecular weight is generated;
(2) Then 180 parts by weight of the silicone resin prepolymer prepared in step (1) was taken out and mixed with 35 parts by weight of N monomer (methyl phenyl dimethoxy silane was used in this example); after uniform mixing, 50 parts by weight of deionized water is dripped at 30 ℃ for 2 hours, and the temperature in the kettle is raised to 60 ℃ for 18 hours after dripping is completed;
(3) Then, 35 parts by weight of N monomer (methyl phenyl dimethoxy silane is adopted in the embodiment) is slowly added, fully mixed for 3 hours, heated to 150 ℃, 80 parts by weight of PMA and 1 part by weight of reaction catalyst (zinc isooctanoate is adopted in the embodiment) are added when the water removal amount reaches 6 parts by weight, the temperature is maintained for 4 hours, then 10 parts by weight of KOH solution with the mass percentage concentration of 2% is slowly added dropwise at 150 ℃ for 4 hours, and water is removed in the dropwise adding process; maintaining the temperature at 150 ℃ after the dripping is completed, and preserving the temperature for 5 hours; and vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 2 hours, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin.
Comparative example 1:
other than in example 1, methyltrimethoxysilane was used as the M monomer and dimethyldimethoxysilane was used as the N monomer.
Comparative example 2:
other than in example 1, methyl phenyl dimethoxy silane was used as the M monomer, and dimethyl dimethoxy silane was used as the N monomer.
The silicone resins obtained in examples 1 to 5 and comparative examples 1 to 2 were mixed with a solvent to adjust the solid content to 80%, sprayed onto the substrate surface, left at room temperature, and the test coating surface was dried for the times shown in Table 1.
The silicone resins obtained in examples 1 to 5 and comparative example 1 were mixed with a solvent and necessary auxiliaries to prepare a coating, and sprayed onto the surface of a substrate, air-dried or baked to obtain a coating, the relevant parameters of which are shown in Table 1.
TABLE 1
The cold and hot impact testing method comprises the following steps: after heating at 260℃for 30 minutes, the coating was impacted with cold water and the damage to the coating was observed.
As can be seen from Table 1, the high phenyl content air-dried organic silicon resin obtained in the examples 1-5 of the application can realize surface drying in air within 5 minutes at normal temperature, and can be used for preparing cooker outer layer coating, and the prepared coating can resist open fire, resist high temperature of 260 ℃ for 100 hours, does not change color and does not fall off after 100 cycles of cold and hot impact.
The above describes in detail a high phenyl content air-dried silicone resin provided by the present application, and specific examples are applied herein to illustrate the principles and embodiments of the present application, and the above examples are only for aiding in understanding the method and core idea of the present application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Claims (2)
1. An air-drying type organic silicon resin with high phenyl content, which is characterized in that: the high-phenyl-content air-drying type organic silicon resin is prepared by the following steps:
(1) Placing 200-250 parts by weight of M monomer into a reaction kettle under the protection of nitrogen, adding 0.1-0.3 part by weight of hydrolysis catalyst, slowly dropwise adding 20-30 parts by weight of deionized water at 15-30 ℃ for 1-4 hours; after the dripping is completed, the temperature of the reaction kettle is raised to 55-60 ℃ for 16-18 hours, then the temperature in the kettle is raised to 140-150 ℃ and kept constant for 4-6 hours, and then vacuum is pumped at the temperature, so that the vacuum keeping degree is less than 800pa and is maintained for 1-1.5 hours, and the organosilicon resin prepolymer is obtained; the hydrolysis catalyst adopts concentrated sulfuric acid, hydrochloric acid, nitric acid, citric acid or acetic acid;
(2) Taking out 150-180 parts by weight of the organosilicon resin prepolymer prepared in the step (1) and mixing with 30-40 parts by weight of N monomer; after uniformly mixing, dropwise adding 30-50 parts by weight of deionized water at 15-30 ℃ for 1-2 hours, and after the dropwise adding is finished, raising the temperature in the kettle to 55-60 ℃ and maintaining for 16-18 hours;
(3) Slowly adding 30-40 parts by weight of N monomer, fully mixing for 2-3 hours, heating to 140-150 ℃, adding 60-80 parts by weight of PMA and 0.75-1 part by weight of reaction catalyst when the water removal amount reaches 4-6 parts by weight, maintaining at the temperature for 3-4 hours, slowly dropwise adding 8.4-10 parts by weight of KOH solution with the mass percentage concentration of 1% -2% at 140-150 ℃ for 2-4 hours; maintaining the temperature at 140-150 ℃ after the dripping is completed, and preserving the temperature for 4-5 hours; then vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 1-2 hours, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin; the reaction catalyst adopts Pb, zn, sn, co, fe, ce naphthenate or carboxylate or isoacid salt, perfluorinated sulfonic acid amine or titanate;
the M monomer is phenyl trimethoxy silane or phenyl triethoxy silane; the N monomer is dimethyl dimethoxy silane or methyl phenyl dimethoxy silane;
the high phenyl content means that the phenyl content is more than 55%.
2. The preparation method of the air-dried organic silicon resin with high phenyl content is characterized by comprising the following steps of:
(1) Placing 200-250 parts by weight of M monomer into a reaction kettle under the protection of nitrogen, adding 0.1-0.3 part by weight of hydrolysis catalyst, slowly dropwise adding 20-30 parts by weight of deionized water at 15-30 ℃ for 1-4 hours; after the dripping is completed, the temperature of the reaction kettle is raised to 55-60 ℃ for 16-18 hours, then the temperature in the kettle is raised to 140-150 ℃ and kept constant for 4-6 hours, and then vacuum is pumped at the temperature, so that the vacuum keeping degree is less than 800pa and is maintained for 1-1.5 hours, and the organosilicon resin prepolymer is obtained; the hydrolysis catalyst adopts concentrated sulfuric acid, hydrochloric acid, nitric acid, citric acid or acetic acid;
(2) Taking out 150-180 parts by weight of the organosilicon resin prepolymer prepared in the step (1) and mixing with 30-40 parts by weight of N monomer; after uniformly mixing, dropwise adding 30-50 parts by weight of deionized water at 15-30 ℃ for 1-2 hours, and after the dropwise adding is finished, raising the temperature in the kettle to 55-60 ℃ and maintaining for 16-18 hours;
(3) Slowly adding 30-40 parts by weight of N monomer, fully mixing for 2-3 hours, heating to 140-150 ℃, adding 60-80 parts by weight of PMA and 0.75-1 part by weight of reaction catalyst when the water removal amount reaches 4-6 parts by weight, maintaining at the temperature for 3-4 hours, slowly dropwise adding 8.4-10 parts by weight of KOH solution with the mass percentage concentration of 1% -2% at 140-150 ℃ for 2-4 hours; maintaining the temperature at 140-150 ℃ after the dripping is completed, and preserving the temperature for 4-5 hours; then vacuumizing at the temperature to ensure that the vacuum retention degree is less than 800pa for 1-2 hours, and filtering with 400-mesh filter cloth when the temperature is reduced to 100 ℃ to obtain the high-phenyl-content air-dried organic silicon resin; the reaction catalyst adopts Pb, zn, sn, co, fe, ce naphthenate or carboxylate or isoacid salt, perfluorinated sulfonic acid amine or titanate;
the M monomer is phenyl trimethoxy silane or phenyl triethoxy silane; the N monomer is dimethyl dimethoxy silane or methyl phenyl dimethoxy silane;
the high phenyl content means that the phenyl content is more than 55%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB858065A (en) * | 1956-06-21 | 1961-01-04 | Wacker Chemie Gmbh | Cold-hardenable organosilicon coating compositions |
| CN103030358A (en) * | 2012-12-13 | 2013-04-10 | 慧智科技（中国）有限公司 | Ceramic paint and coating having stereoscopic effect |
| CN107641466A (en) * | 2017-11-15 | 2018-01-30 | 株洲时代新材料科技股份有限公司 | A kind of organosilicon solvent-free dip varnish and preparation method thereof |
| CN107892748A (en) * | 2017-12-14 | 2018-04-10 | 成都硅宝科技股份有限公司 | A kind of preparation method of room-temperature moisture cured silicones |
| CN111518505A (en) * | 2020-05-15 | 2020-08-11 | 浙江新安化工集团股份有限公司 | Moisture-hardening resin composition, preparation method thereof and application thereof as sealant |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9156981B2 (en) * | 2013-07-24 | 2015-10-13 | Momentive Performance Materials Inc. | Moisture curable compositions with enhanced elongation and tear strength properties |
-
2022
- 2022-12-26 CN CN202211672871.9A patent/CN115819774B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB858065A (en) * | 1956-06-21 | 1961-01-04 | Wacker Chemie Gmbh | Cold-hardenable organosilicon coating compositions |
| CN103030358A (en) * | 2012-12-13 | 2013-04-10 | 慧智科技（中国）有限公司 | Ceramic paint and coating having stereoscopic effect |
| CN107641466A (en) * | 2017-11-15 | 2018-01-30 | 株洲时代新材料科技股份有限公司 | A kind of organosilicon solvent-free dip varnish and preparation method thereof |
| CN107892748A (en) * | 2017-12-14 | 2018-04-10 | 成都硅宝科技股份有限公司 | A kind of preparation method of room-temperature moisture cured silicones |
| CN111518505A (en) * | 2020-05-15 | 2020-08-11 | 浙江新安化工集团股份有限公司 | Moisture-hardening resin composition, preparation method thereof and application thereof as sealant |
Non-Patent Citations (1)
| Title |
|---|
| 室温湿气固化硅树脂的制备;陈良兵;有机硅材料;第33卷(第1期);39-43 * |
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