CN115678013A - Phenyl vinyl siloxane resin and preparation method thereof - Google Patents
Phenyl vinyl siloxane resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of phenyl vinyl siloxane resin, which comprises the following steps: s1) mixing phenyltrimethoxysilane and tetramethyldivinyl disiloxane, adding a hydrolysis catalyst, and carrying out hydrolysis reaction to obtain a reaction mixture; s2) adding toluene or xylene into the reaction mixture obtained in the step S1), distilling, and stopping distilling when the temperature of the material rises to 75-150 ℃ to obtain a distilled product; s3) adding an alkali catalyst into the distilled product obtained in the step S2) to adjust the pH value to 8-14, concentrating, carrying out condensation reaction, washing with water, and carrying out reduced pressure distillation to obtain the phenyl vinyl siloxane resin. Compared with the prior art, the preparation method adopts specific process steps, realizes better integral interaction, and the obtained phenyl vinyl siloxane resin has high refractive index, excellent flexibility and excellent storage stability; the further prepared LED packaging silicone resin has high refractive index, excellent tensile strength, hardness and aging resistance.
Description
Technical Field
The invention relates to the technical field of organic silicon packaging materials, in particular to phenyl vinyl siloxane resin and a preparation method thereof.
Background
A Light Emitting Diode (LED) is a semiconductor device that can directly convert electrical energy into optical energy. Compared with the illumination mode of an incandescent lamp or a fluorescent lamp, the LED lamp has the advantages of energy conservation, low consumption, long service life, environmental protection, controllable color, small volume and the like, and is expected to be used as a new generation of illumination light source to replace the traditional light source. The packaging materials used by the LED lighting equipment are mainly epoxy resin and phenyl vinyl silicone resin. Compared with epoxy resin, phenyl vinyl silicone resin has numerous advantages: such as excellent ultraviolet aging resistance, weather resistance, thermal stability, high light transmittance, high refractive index, insulativity and the like, and is an ideal choice for LED packaging materials.
With the continuous improvement of LED manufacturing technology, the requirements for p-phenyl vinyl silicone resin are also higher and higher. At present, high-performance organic silicon resin for LED packaging basically depends on import, the main core technology is monopolized by a few foreign companies such as Dow Corning, xinyue and the like, and the high cost limits the popularization of high-power LED devices. Therefore, the need for high performance transparent silicon material for LED package is more and more urgent. At present, domestic research still belongs to a starting stage, a lot of blanks exist, and the domestic produced organic silicon packaging material can only be used for middle and low-end products with low performance requirements. The high-performance LED packaging silicone resin has the performances of high refractive index, high hardness, thermal aging resistance and the like. Therefore, the development of the organic silicon packaging material with high performance has important research significance and application value.
Disclosure of Invention
In view of the above, the present invention provides a phenyl vinyl siloxane resin and a preparation method thereof, and the phenyl vinyl siloxane resin obtained by the preparation method provided by the present invention has high refractive index, high hardness and excellent thermal aging resistance.
The invention provides a preparation method of phenyl vinyl siloxane resin, which comprises the following steps:
s1) mixing phenyltrimethoxysilane and tetramethyldivinyl disiloxane, adding a hydrolysis catalyst, and carrying out hydrolysis reaction to obtain a reaction mixture;
s2) adding toluene or xylene into the reaction mixture obtained in the step S1), distilling, and stopping distilling when the temperature of the material rises to 75-150 ℃ to obtain a distilled product;
s3) adding an alkali catalyst into the distilled product obtained in the step S2) to adjust the pH value to 8-14, concentrating, carrying out condensation reaction, washing with water, and carrying out reduced pressure distillation to obtain the phenyl vinyl siloxane resin.
Preferably, the mass ratio of the phenyltrimethoxysilane to the tetramethyldivinyldisiloxane in the step S1) is 100: (10-60).
Preferably, the hydrolysis catalyst in step S1) is trifluoromethanesulfonic acid; the mass ratio of the hydrolysis catalyst to the phenyl trimethoxy silane is (0.1-0.5): 100.
preferably, the hydrolysis reaction in step S1) is specifically performed by:
after adding a hydrolysis catalyst, slowly dripping pure water for 1-5 h at 20-30 ℃ for hydrolysis reaction, and after dripping, heating to reflux temperature for reflux.
Preferably, the mass ratio of the pure water to the phenyltrimethoxysilane is (10-50): 100.
preferably, the reflux temperature is 65-75 ℃; the refluxing time is 2-6 h.
Preferably, the ratio of the mass of the added toluene or xylene to the mass of the phenyltrimethoxysilane in the step S2) is (5-25): 100.
preferably, the distillation temperature in step S2) is 110 ℃ to 130 ℃.
Preferably, the alkali catalyst in step S3) is 5wt% to 15wt% of potassium hydroxide/sodium water solution;
the process of concentrating and carrying out condensation reaction is specifically as follows:
concentrating to 55-65% of solid content and carrying out condensation reaction for 1-8 h at 110-170 ℃.
The invention also provides phenyl vinyl siloxane resin which is prepared by the preparation method of the technical scheme.
The invention provides a preparation method of phenyl vinyl siloxane resin, which comprises the following steps: s1) mixing phenyltrimethoxysilane and tetramethyldivinyl disiloxane, adding a hydrolysis catalyst, and carrying out hydrolysis reaction to obtain a reaction mixture; s2) adding toluene or xylene into the reaction mixture obtained in the step S1), distilling, and stopping distilling when the temperature of the material rises to 75-150 ℃ to obtain a distilled product; s3) adding an alkali catalyst into the distilled product obtained in the step S2) to adjust the pH value to 8-14, concentrating, carrying out condensation reaction, washing with water, and carrying out reduced pressure distillation to obtain the phenyl vinyl siloxane resin. Compared with the prior art, the preparation method provided by the invention adopts specific process steps, so that the overall good interaction is realized, the content of alkoxy in the prepared phenyl vinyl siloxane resin is greatly reduced, the performances such as aging resistance, hardness and the like are improved, meanwhile, the storage stability of the phenyl vinyl siloxane resin is favorably improved due to the reduction of the content of alkoxy, and the finally obtained phenyl vinyl siloxane resin has high refractive index and excellent flexibility and storage stability; when the high-refractive-index silicone resin is further used for preparing LED packaging silicone resin, the high-refractive-index silicone resin has high refractive index, excellent tensile strength, excellent hardness and excellent aging resistance; compared with the traditional method, the method has the characteristics of large polymerization degree and good reinforcing effect, part of the performance reaches or is higher than the level of similar imported products abroad, the basic requirements of LED packaging can be met, and the packaged surface-mounted LED device has excellent air tightness.
In addition, the preparation method provided by the invention can reduce the washing after the hydrolysis reaction through the normal pressure distillation after the hydrolysis reaction, and the generated wastewater is obviously reduced along with the reduction of the washing steps; meanwhile, the preparation method has the advantages of simple process, easy post-treatment, no corrosive substances and wide application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of phenyl vinyl siloxane resin, which comprises the following steps:
s1) mixing phenyltrimethoxysilane and tetramethyldivinyl disiloxane, adding a hydrolysis catalyst, and carrying out hydrolysis reaction to obtain a reaction mixture;
s2) adding toluene or xylene into the reaction mixture obtained in the step S1), distilling, and stopping distilling when the temperature of the material rises to 75-150 ℃ to obtain a distilled product;
s3) adding an alkali catalyst into the distilled product obtained in the step S2) to adjust the pH value to 8-14, concentrating, carrying out condensation reaction, washing with water, and carrying out reduced pressure distillation to obtain the phenyl vinyl siloxane resin.
According to the invention, phenyltrimethoxysilane and tetramethyldivinyldisiloxane are mixed, and a hydrolysis catalyst is added to carry out hydrolysis reaction, so as to obtain a reaction mixture. The sources of the phenyltrimethoxysilane and tetramethyldivinyldisiloxane are not particularly limited in the present invention, and commercially available products or self-prepared products known to those skilled in the art can be used.
In the present invention, the mass ratio of phenyltrimethoxysilane to tetramethyldivinyldisiloxane is preferably 100: (10 to 60), more preferably 100: (12-50); under the preferable mass ratio, the prepared phenyl vinyl siloxane resin has more excellent refraction, hardness and light transmittance.
In the present invention, the hydrolysis catalyst is preferably trifluoromethanesulfonic acid; furthermore, the reaction system can be made acidic, which is beneficial to the hydrolysis reaction. The present invention is not particularly limited with respect to the source of the hydrolysis catalyst, and commercially available products well known to those skilled in the art may be used.
In the present invention, the mass ratio of the hydrolysis catalyst to the phenyltrimethoxysilane is preferably (0.1 to 0.5): 100, more preferably (0.2 to 0.25): 100.
in the present invention, the hydrolysis reaction is preferably performed specifically by:
after adding a hydrolysis catalyst, slowly dripping pure water for 1-5 h at 20-30 ℃ for hydrolysis reaction, and heating to reflux temperature for reflux after dripping;
more preferably:
after adding the hydrolysis catalyst, slowly dropwise adding pure water at 25 ℃ within 3h for hydrolysis reaction, and after dropwise adding, heating to reflux temperature for reflux.
In the present invention, the mass ratio of the pure water to the phenyltrimethoxysilane is preferably (10 to 50): 100, more preferably (25 to 30): 100; the invention adopts the pure water with the specific proportion for hydrolysis reaction, and can realize better hydrolysis reaction effect.
In the present invention, the reflux temperature is preferably 65 to 75 ℃, more preferably 70 ℃.
In the present invention, the time for the reflux is preferably 2 to 6 hours, and more preferably 3 to 5 hours.
After the reaction mixture is obtained, adding toluene or xylene into the obtained reaction mixture for distillation, and stopping distillation until the temperature of the material is raised to 75-150 ℃ to obtain a distilled product.
The source of the toluene or xylene in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used. In a preferred embodiment of the invention, xylene is added to the resulting reaction mixture because the difference in boiling points of xylene with methanol and water is greater than toluene, resulting in a decrease in the amount of solvent evaporated as the feed temperature is increased.
In the present invention, the ratio of the mass of the added toluene or xylene to the mass of the phenyltrimethoxysilane is preferably (5 to 25): 100, more preferably (8 to 15): 100.
in the present invention, the temperature of the distillation is preferably 110 to 130 ℃, more preferably 120 ℃; the aim is to distill off methanol and water.
In the distillation process, the distillation is stopped when the material temperature is increased from the previous reflux temperature of 70 ℃ to 75-150 ℃, preferably 80-100 ℃; the distillation is stopped when the temperature is preferably raised to 80 ℃ to 100 ℃ because a temperature higher than 100 ℃ may cause resin gelation, and a temperature too low may cause excessive alkoxy residue to result in poor aging resistance; in addition, the material temperature is not higher than 100 ℃ in order to keep the water in the reactants from yellowing, but the residual methanol is distilled as much as possible so that the hydrolysis reaction is as full as possible.
After the distilled product is obtained, adding an alkali catalyst into the obtained distilled product to adjust the pH value to 8-14, concentrating, carrying out condensation reaction, washing with water, and carrying out reduced pressure distillation to obtain the phenyl vinyl siloxane resin.
In the present invention, the alkali catalyst is preferably a 5wt% to 15wt% aqueous potassium hydroxide/sodium hydroxide solution, more preferably a 10wt% aqueous potassium hydroxide solution; the present invention is not particularly limited in its origin.
The pH value is adjusted to 8-14, preferably 10 by adding an alkali catalyst.
In the present invention, the concentration and condensation reaction are preferably carried out by the following specific steps:
concentrating to 55-65% of solid content and carrying out condensation reaction for 1-8 h at 110-170 ℃;
more preferably:
concentrating to 58-62% of solid content and carrying out condensation reaction for 2-6 h at 150-160 ℃.
In the present invention, the above concentration process evaporates a part of toluene or xylene, during which condensation reaction is carried out at the same temperature; the condensation reaction temperature is the temperature during the concentration process, and increasing the condensation reaction temperature allows lower reactive hydroxyl groups to react.
The process of the water washing is not particularly limited in the invention, and the technical scheme of washing to be neutral, which is well known to those skilled in the art, can be adopted.
In the present invention, the vacuum distillation process is preferably embodied as follows:
the solvent and water are pumped out in vacuum at 140-160 ℃.
The preparation method provided by the invention can reduce the washing after the hydrolysis reaction through the normal pressure distillation after the hydrolysis reaction, and the generated wastewater is obviously reduced along with the reduction of the washing steps; meanwhile, the preparation method has the advantages of simple process, easy post-treatment, no corrosive substances and wide application prospect.
The invention also provides phenyl vinyl siloxane resin which is prepared by the preparation method of the technical scheme. The preparation method provided by the invention adopts specific process steps, so that the integral better interaction is realized, the content of alkoxy and hydroxyl in the prepared phenyl vinyl siloxane resin is greatly reduced, the performances such as aging resistance, hardness and the like are improved, meanwhile, the storage stability of the phenyl vinyl siloxane resin is favorably improved due to the reduction of the content of alkoxy and hydroxyl, and the finally obtained phenyl vinyl siloxane resin has high refractive index and excellent flexibility and storage stability; when the epoxy resin is further used for preparing LED packaging silicone resin, the epoxy resin has high refractive index, excellent tensile strength, hardness and aging resistance; compared with the traditional method, the method has the characteristics of large polymerization degree and good reinforcing effect, part of the performances of the method reach or are higher than the level of similar imported products abroad, the basic requirements of LED packaging can be met, and the packaged surface-mounted LED device has excellent air tightness.
The invention provides a preparation method of phenyl vinyl siloxane resin, which comprises the following steps: s1) mixing phenyltrimethoxysilane and tetramethyldivinyl disiloxane, adding a hydrolysis catalyst, and carrying out hydrolysis reaction to obtain a reaction mixture; s2) adding toluene or xylene into the reaction mixture obtained in the step S1), distilling, and stopping distilling when the temperature of the material rises to 75-150 ℃ to obtain a distilled product; s3) adding an alkali catalyst into the distilled product obtained in the step S2) to adjust the pH value to 8-14, concentrating, carrying out condensation reaction, washing with water, and carrying out reduced pressure distillation to obtain the phenyl vinyl siloxane resin. Compared with the prior art, the preparation method provided by the invention adopts specific process steps, so that the overall good interaction is realized, the content of alkoxy and hydroxyl in the prepared phenyl vinyl siloxane resin is greatly reduced, the performances such as aging resistance, hardness and the like are improved, meanwhile, the storage stability of the phenyl vinyl siloxane resin is favorably improved due to the reduction of the content of alkoxy and hydroxyl, and the finally obtained phenyl vinyl siloxane resin has high refractive index and excellent flexibility and storage stability; when the epoxy resin is further used for preparing LED packaging silicone resin, the epoxy resin has high refractive index, excellent tensile strength, hardness and aging resistance; compared with the traditional method, the method has the characteristics of large polymerization degree and good reinforcing effect, part of the performances of the method reach or are higher than the level of similar imported products abroad, the basic requirements of LED packaging can be met, and the packaged surface-mounted LED device has excellent air tightness.
In addition, the preparation method provided by the invention can reduce the washing after the hydrolysis reaction through the normal pressure distillation after the hydrolysis reaction, and the generated wastewater is obviously reduced along with the reduction of the washing steps; meanwhile, the preparation method has the advantages of simple process, easy post-treatment, no corrosive substances and wide application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials, reagents and the like used in the following examples of the present invention are all commercially available materials and reagents from the general market and the like, unless otherwise specified.
Example 1
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 95 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Example 2
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 90 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction at 160 ℃ for 4h, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin.
Example 3
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 80 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Example 4
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 85 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction at 160 ℃ for 4h, transferring to a separating funnel, washing to be neutral, and vacuumizing at 150 ℃ to remove the solvent and water to obtain the phenyl vinyl siloxane resin.
Example 5
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 100 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Example 6
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 95 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 2h at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Example 7
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 5 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 95 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Comparative example 1
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 1 hour after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 95 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Comparative example 2
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. Adding 200g of dimethylbenzene, washing to be neutral, adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Comparative example 3
1983g of phenyltrimethoxysilane and 363g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 90 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Example 8
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 90 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 6h at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Comparative example 4
1983g of phenyltrimethoxysilane and 121g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 200g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 90 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
Comparative example 5
1983g of phenyltrimethoxysilane and 242g of tetramethyldivinyldisiloxane were mixed and placed in a round-bottomed flask, and 4.5g of trifluoromethanesulfonic acid were added to make the solution acidic. 540g of pure water is slowly dripped into the mixture within 3 hours at the temperature of 25 ℃ for hydrolysis reaction, and the mixture is heated to the reflux temperature of 70 ℃ for reflux for 3 hours after the dripping is finished. 600g of xylene are added, the temperature is raised to 120 ℃, methanol and water are distilled off, and the distillation is stopped until the temperature of the material is raised to 90 ℃. Adding 10wt% of potassium hydroxide aqueous solution to adjust the pH value to 10, concentrating to about 60% of solid content, carrying out condensation reaction for 4 hours at 160 ℃, transferring to a separating funnel, washing to be neutral, and removing the solvent and water at 150 ℃ in vacuum to obtain the phenyl vinyl siloxane resin.
And (3) performance test and characterization:
the phenyl vinyl siloxane resins obtained in the above examples and comparative examples were subjected to various performance tests, respectively:
50g of phenyl vinyl siloxane resin and 22.5g of 3770 hydrogen-containing silicone oil (produced by Beteli New Material Co., ltd., dongguan) are mixed, then 2ppm of Karstedt catalyst is added, the mixture is stirred uniformly, vacuum defoamed until no bubbles appear, the mixture is placed in an oven to be cured at 100 ℃ for 1h, cured at 130 ℃ for 2h and cured at 150 ℃ for 3h, and a transparent silicone resin precured product is obtained.
Test refractive index, hardness, appearance and aging data:
the viscosity of liquid silicone resin (25 ℃) was tested using a DV-i Prime type viscometer from Bohler Miller, USA, and a karstedt catalyst was not added for curing before the viscosity test;
testing the hardness of the cured product by using a Shore A type durometer, and testing at least 3 parallel samples to obtain an average value;
the aging performance is represented by testing the weight loss of the cured product by using an oven to bake for 8 hours at 150 ℃; less than 1% is preferable, 1% to 1.5% is preferable, 1.5% to 2% is worse, and more than 2% is worse.
The results are shown in Table 1.
TABLE 1 examples and comparative examples various performance data of phenyl vinyl siloxane resins were obtained
The experimental results show that:
as can be seen from examples 1 to 5, as the distillation termination temperature in the step S2 is increased, the viscosity and hardness of the silicone resin are increased and increased, but the refractive index is almost unchanged, it is known that the hydrolysis reaction degree is increased more and more severely by the increase of the distillation termination temperature, but the performances of the resin are not improved too much when the distillation termination temperature is 90 ℃, 95 ℃ or 100 ℃; compared with the example 2, in the example 6, the condensation time is reduced from 4h to 2h, and the viscosity, the hardness and the aging resistance are slightly reduced; in addition, in the example 8, the condensation time is increased to 6h, and the differences of the viscosity, the hardness, the appearance and the aging resistance are not large; compared with example 2, the hydrolysis time is increased from 3h to 5h in example 7, and the viscosity, hardness and appearance are not greatly different from the aging resistance.
Compared with example 2, the hydrolysis time in comparative example 1 was reduced from 3h to 1h, and the viscosity, hardness, appearance and aging resistance were all significantly reduced because the degree of hydrolysis reaction was insufficient, resulting in excessive alkoxy residue and an excessively small resin structure.
In the comparative example 2, the method is a traditional methyl vinyl silicone resin synthesis method, only toluene is added in the step S2, distillation is not carried out, and concentration is not carried out in the step S3, so that the viscosity, the hardness and the aging resistance of the resin are greatly reduced; the absence of distillation results in the absence of hydrolysis of some of the less reactive alkoxy groups, and the absence of condensation in the condensation reaction results in the absence of condensation of the less reactive hydroxyl groups; the main effects of distillation and concentration are to make the residual alkoxy react completely during hydrolysis and to make the residual hydroxyl react completely during condensation; therefore, compared with the traditional method, the preparation method provided by the invention has the characteristics of large polymerization degree and good reinforcing effect. In addition, the step S1 in the comparative example 2 is washed with water after the hydrolysis reaction is finished, so that the waste water generated in the production process is doubled because the washing is needed twice; the invention only needs to wash once, which can effectively reduce the generation of waste water.
Compared with the embodiment 2, in the comparative example 3, the proportion of the main components of the synthetic resin is changed, and the amount of the tetramethyl divinyl disiloxane is increased, so that the overall structure of the resin is changed from big to small, and the refractive index and the viscosity are reduced; therefore we can adjust the ratio of phenyltrimethoxysilane to tetramethyldivinyldisiloxane to achieve the desired refractive index and viscosity; however, as can be seen from comparative example 4, excessively lowering the amount of tetramethyldivinyldisiloxane results in an excessively large resin structure leading to cloudiness of the final product; in comparison with example 2, comparative example 5 has a solid content of 60% reduced to 30% upon condensation, and also has a reduced aging property.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of phenyl vinyl siloxane resin comprises the following steps:
s1) mixing phenyltrimethoxysilane and tetramethyldivinyl disiloxane, adding a hydrolysis catalyst, and carrying out hydrolysis reaction to obtain a reaction mixture;
s2) adding toluene or xylene into the reaction mixture obtained in the step S1), distilling, and stopping distilling when the temperature of the material rises to 75-150 ℃ to obtain a distilled product;
s3) adding an alkali catalyst into the distilled product obtained in the step S2) to adjust the pH value to 8-14, concentrating, carrying out condensation reaction, washing with water, and carrying out reduced pressure distillation to obtain the phenyl vinyl siloxane resin.
2. The method according to claim 1, wherein the mass ratio of phenyltrimethoxysilane to tetramethyldivinyldisiloxane in step S1) is 100: (10-60).
3. The method according to claim 1, wherein the hydrolysis catalyst in step S1) is trifluoromethanesulfonic acid; the mass ratio of the hydrolysis catalyst to the phenyl trimethoxy silane is (0.1-0.5): 100.
4. the preparation method according to claim 1, wherein the hydrolysis reaction in step S1) is specifically performed by:
after adding a hydrolysis catalyst, slowly dropwise adding pure water at the temperature of 20-30 ℃ within 1-5 h for hydrolysis reaction, and after dropwise adding, heating to reflux temperature for reflux.
5. The preparation method according to claim 4, wherein the mass ratio of pure water to phenyltrimethoxysilane is (10-50): 100.
6. the method of claim 4, wherein the reflux temperature is 65 ℃ to 75 ℃; the refluxing time is 2-6 h.
7. The process according to claim 1, wherein the ratio of the mass of toluene or xylene added to the mass of phenyltrimethoxysilane added in step S2) is (5 to 25): 100.
8. the method according to claim 1, wherein the temperature of the distillation in the step S2) is 110 to 130 ℃.
9. The method according to claim 1, wherein the base catalyst in step S3) is a 5wt% to 15wt% aqueous solution of potassium hydroxide/sodium hydroxide;
the process of concentrating and carrying out condensation reaction is specifically as follows:
concentrating to 55-65% of solid content and carrying out condensation reaction for 1-8 h at 110-170 ℃.
10. A phenyl vinyl siloxane resin, characterized by being produced by the production method according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB755198A (en) * | 1954-01-11 | 1956-08-15 | Midland Silicones Ltd | Organosiloxane co-polymers |
| CN103848990A (en) * | 2012-12-04 | 2014-06-11 | 中化蓝天集团有限公司 | High-refractive index vinyl phenyl silicon resin for light-emitting diode (LED) package |
| CN104974349A (en) * | 2014-04-07 | 2015-10-14 | 马凤国 | Preparation method of silicone resin |
| 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 |
| CN110229339A (en) * | 2019-05-24 | 2019-09-13 | 中山大学 | A kind of phenylethylene based siloxane resins, high refractive index LED encapsulation silicon resin composition and preparation method thereof |
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2022
- 2022-11-18 CN CN202211446122.4A patent/CN115678013A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB755198A (en) * | 1954-01-11 | 1956-08-15 | Midland Silicones Ltd | Organosiloxane co-polymers |
| CN103848990A (en) * | 2012-12-04 | 2014-06-11 | 中化蓝天集团有限公司 | High-refractive index vinyl phenyl silicon resin for light-emitting diode (LED) package |
| CN104974349A (en) * | 2014-04-07 | 2015-10-14 | 马凤国 | Preparation method of silicone resin |
| 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 |
| CN110229339A (en) * | 2019-05-24 | 2019-09-13 | 中山大学 | A kind of phenylethylene based siloxane resins, high refractive index LED encapsulation silicon resin composition and preparation method thereof |
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