CN110922599B - Bisphenol S hybrid silicon resin and synthetic method thereof - Google Patents
Bisphenol S hybrid silicon resin and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses bisphenol S hybrid silicon resin and a synthesis method thereof, belonging to the technical field of novel resin materials. The specific scheme is as follows: a method for synthesizing bisphenol S hybrid silicone resin comprises the following steps: step one, stirring 50-100 parts of silane monomer, 0.5-25 parts of bisphenol S and 10-200 parts of solvent until the bisphenol S is completely dissolved to obtain a mixed solution A; step two, mixing 10-40 parts of distilled water and 0.05-10 parts of catalyst to obtain a mixed solution B; step three, dropwise adding the mixed solution B into the mixed solution A, and then heating to 65-70 ℃ to react for 2-8h to obtain a mixed solution C; and step four, distilling the mixed solution C at the temperature of 120-150 ℃ under reduced pressure to remove the solvent to obtain the bisphenol S hybrid silicon resin. The bisphenol S hybrid silicone resin is convenient to transport and store and easy to process; the heat resistance of the resin is adjusted by changing the content of the bisphenol S, so that the resin has a great application prospect.
Description
Technical Field
The invention belongs to the technical field of novel resin materials, and particularly relates to bisphenol S hybrid high-temperature-resistant silicon resin and a synthesis method thereof.
Background
The silicon resin is a typical organic-inorganic hybrid polymer and consists of an inorganic part Si-O-Si structure and an organic part Si-C structure, and the silicon-oxygen bond energy in the Si-O-Si inorganic structure is up to 460 kJ/mol, so the silicon resin has good high temperature resistance; the Si-C organic structure of the silicon resin enables the silicon resin to have the characteristics of easy processing and forming and the like, and the silicon resin is widely applied to the industries of aerospace, mechanical manufacturing, electronic device packaging, chemical engineering and the like. In the field of aerospace, the silicone resin has the advantages of high and low temperature resistance, weather resistance, aging resistance, electrical insulation, corrosion resistance, ozone resistance, flame resistance and the like compared with other thermosetting resins, and is not only one of the most widely used high polymer materials in aerospace, but also one of the most potential high polymer materials in the future aerospace development. The improvement of the high temperature resistance of the silicone resin not only promotes the improvement of aerospace technology, but also greatly improves the competitiveness of industries such as mechanical manufacturing, electronic device packaging, chemical engineering and the like, and has great promotion effect on improving the scientific and technological competitiveness of China, so the improvement of the heat resistance of the silicone resin is very important.
The improvement of the heat resistance of the silicone resin in the prior art is mainly realized by adding heat-resistant fillers such as ferric oxide, cerium oxide, aluminum oxide, graphite powder, copper powder, aluminum powder, mica powder and the like, for example, patent publication No. CN 106047159B discloses a high temperature resistant material based on silicone resin, the high temperature resistance of the silicone resin is improved by adding the inorganic heat-resistant filler and the metal powder with excellent conductivity such as nickel powder, silver powder, zinc powder, copper powder and the like, although the metal fillers can improve the heat resistance of the silicone resin, the addition of the metal fillers also changes the electrical insulation performance, increases the electrical conductivity of the silicone resin, is not beneficial to being used in the environment with high requirement on the insulation performance, therefore, it is very important to improve the heat resistance of silicone resin and maintain excellent properties of weather resistance, aging resistance, electrical insulation, corrosion resistance, ozone resistance, flame retardancy and the like of silicone resin.
Disclosure of Invention
The invention provides a bisphenol S hybrid silicone resin in order to make up the defects of the prior art and further improve the heat resistance of the silicone resin.
The second purpose of the invention is to provide a method for synthesizing the bisphenol S hybrid silicone resin.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a bisphenol S hybrid silicone resin having the following structural formula:
wherein R is one or more of H, methyl, phenyl, vinyl, ethyl, propyl and propenyl;
0＜n≤50，0＜m≤50。
the silicone resin comprises condensed silicone resin, vinyl silicone resin, hydrogen-containing silicone resin, methyl silicone resin, phenyl silicone resin and the like; the silicone resin prepared is in the state of a solid, a low viscosity fluid or a high viscosity fluid.
A method for synthesizing bisphenol S hybrid silicone resin comprises the following steps:
step one, stirring 50-100 parts of silane monomer, 0.5-25 parts of bisphenol S and 10-200 parts of solvent until the bisphenol S is completely dissolved to obtain a mixed solution A;
step two, uniformly mixing 10-40 parts of distilled water and 0.05-10 parts of catalyst to obtain a mixed solution B;
step three, dropwise adding the mixed solution B into the mixed solution A at 0-40 ℃, stirring at the speed of 200-1000 r/min, heating to 65-70 ℃ after dropwise adding, and reacting for 2-8h to obtain a mixed solution C;
and step four, distilling the mixed solution C at the temperature of 120-150 ℃ under reduced pressure to remove the solvent to obtain the bisphenol S hybrid silicon resin.
In the first step, the silane monomer is tetraethyl orthosilicate, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, dimethyldiethoxymethane silane, vinyltrimethoxysilane, methylphenyldimethoxysilane, trimethoxysilane, vinyltriethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, tetramethyldivinyldisiloxane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and methyltrichlorosilane, or a combination of more thereof.
Further, in the first step, the solvent is one or more of methanol, n-propanol, ethanol, butanol, isopropanol, tetrahydrofuran and acetone.
Further, in the second step, the catalyst is one or a combination of more of hydrochloric acid, glacial acetic acid, sulfuric acid, nitric acid and sulfonic acid.
Compared with the prior art, the invention has the following advantages:
1. the bisphenol S hybrid silicone resin prepared by the invention not only further improves the heat resistance of the silicone resin, but also enables the silicone resin to have excellent performances such as weather resistance, aging resistance, electrical insulation, corrosion resistance, ozone resistance, flame retardancy and the like;
2. the bisphenol S hybrid silicone resin is solid at normal temperature, is very favorable for transportation and storage, is heated and melted into liquid with excellent fluidity, and is easy to process;
3. the preparation of the bisphenol S hybrid silicone resin adopts a non-toxic or low-toxic reagent as a solvent, and is more environment-friendly than the traditional silicone resin which adopts benzene toxic organic matters as the solvent;
4. the heat resistance of the bisphenol S hybrid silicon resin can be adjusted by adjusting the content of bisphenol S, and when the content of bisphenol S is less than 7%, the heat resistance of the bisphenol S hybrid silicon resin is increased along with the increase of the content of bisphenol S.
5. The invention adopts the in-situ polymerization method to synthesize the bisphenol S hybrid silicon resin, and the method is simple, efficient, safe and economical.
Drawings
FIG. 1 is a structural formula of bisphenol S hybrid silicone resin;
FIG. 2 is a weight loss analysis test chart of bisphenol S hybrid silicone resin;
FIG. 3 is a weight loss analysis test chart of bisphenol S hybrid silicone resin with different bisphenol S contents.
Detailed Description
The technical solutions of the present invention are further described below with reference to the embodiments shown in fig. 1-3, but not limited thereto, and all modifications or equivalent substitutions that do not depart from the spirit and scope of the technical solutions of the present invention should be covered by the protection scope of the present invention.
Example 1:
adding 53.49g of methyltriethoxysilane, 19.83g of phenyltrimethoxysilane, 6.01g of dimethyldiethoxysilane, 12.2g of diphenyldimethoxysilane, 5.21g of tetraethyl orthosilicate, 6.26g of bisphenol S and 25g of ethanol into a 250ml clean three-neck flask, mixing, stirring until the bisphenol S is completely dissolved to obtain a mixed solution A, diluting 1mol/L of 1.52g of hydrochloric acid with 25.8g of distilled water and uniformly mixing to obtain a mixed solution B, slowly dripping the mixed solution B into the mixed solution A at 0 ℃, stirring at the speed of 800 revolutions per minute, heating the reaction system to 70 ℃ after dripping is finished, stirring for 6 hours to obtain a mixed solution C, stopping stirring after the reaction is finished, adding 100g of distilled water into the three-neck flask, standing for more than 4 hours to obtain a transparent liquid with an upper layer and a lower layer, distilling the transparent liquid mixed solution C at 135 ℃ under reduced pressure to remove the solvent, and cooling to obtain the solid bisphenol S hybrid silicon resin.
Example 2:
adding 89.15g of methyltriethoxysilane, 8.5g of vinyltriethoxysilane, 99.15g of phenyltrimethoxysilane, 6.01g of dimethyldiethoxysilane, 4.05g of hexamethyldisiloxane, 16.32g of diphenyldimethoxysilane, 6.19g of tetraethyl orthosilicate, 8.34g of bisphenol S and 40g of ethanol into a 500ml clean three-neck flask, mixing until the bisphenol S is completely dissolved to obtain a mixed solution A, diluting 1mol/L of 2.87g of hydrochloric acid with 36.3g of distilled water and uniformly mixing to obtain a mixed solution B, slowly dripping the mixed solution B into the mixed solution A at 25 ℃, stirring at the speed of 500 revolutions per minute, heating the reaction system to 70 ℃ after dripping, stirring for 6 hours to obtain a mixed solution C, stopping stirring after the reaction is finished, then adding 100g of distilled water into the three-neck flask, standing for more than 4 hours to obtain transparent liquid of the upper layer and the lower layer, and (3) distilling the lower layer transparent liquid mixed solution C at 150 ℃ under reduced pressure to remove the solvent, reacting for 1h, and cooling to obtain the solid bisphenol S hybrid silicon resin.
Example 3:
adding 67.25g of methyltriethoxysilane, 16.89g of phenyltrimethoxysilane, 9.31g of dimethyldiethoxysilane, 12.35g of tetramethyldisiloxane, 6.1g of diphenyldimethoxysilane, 10.42g of tetraethyl orthosilicate, 12.52g of bisphenol S and 25g of ethanol into a 250ml clean three-neck flask, mixing, stirring until the bisphenol S is completely dissolved to obtain a mixed solution A, diluting and uniformly mixing 1mol/L of 1.65g of hydrochloric acid with 26.8g of distilled water to obtain a mixed solution B, slowly dripping the mixed solution B into the mixed solution A at 40 ℃, stirring at the speed of 1000 r/min, heating a reaction system to 70 ℃ after dripping, stirring for 6h to obtain a mixed solution C, stopping stirring after the reaction is finished, adding 100g of distilled water into the three-neck flask, standing for more than 4h to obtain a transparent liquid with two layers at the top and the bottom, distilling the transparent liquid mixed solution C at 135 ℃ under reduced pressure to remove the solvent and condensing for 1h, and cooling to obtain the solid bisphenol S hybrid silicon resin.
Example 4:
adding 72.35g of methyltriethoxysilane, 26.38g of phenyltrimethoxysilane, 8.34g of dimethyldiethoxysilane and 13.6g of hexamethyldisilazane into a 250ml clean three-neck flask, mixing the materials, stirring until the bisphenol S is completely dissolved to obtain a mixed solution A, diluting and uniformly mixing 1mol/L of 1.82g of hydrochloric acid with 27.5g of distilled water to obtain a mixed solution B, slowly dripping the mixed solution B into the mixed solution A at 20 ℃, stirring at the speed of 200 revolutions per minute, heating the reaction system to 70 ℃ after dripping is finished, stirring for 6 hours to obtain a mixed solution C, stopping stirring after the reaction is finished, adding 100g of distilled water into the three-neck flask, standing for more than 4 hours to obtain upper and lower transparent liquid layers, taking the lower transparent liquid mixed solution C, distilling at 150 ℃ under reduced pressure to remove the solvent, and reacting for 1 hour, and cooling to obtain the solid bisphenol S hybrid silicon resin.
FIG. 2 is a weight loss analysis and test chart of bisphenol S hybrid silicone resin, wherein the bisphenol S hybrid silicone resin begins to lose mass at about 320 ℃ and the temperature (T) at which the mass loss is 5%5%) The residual mass was 82.41% at 548 ℃ and 1000 ℃.
FIG. 3 is a weight loss analysis test chart of bisphenol S hybrid silicone resin with different bisphenol S contents, wherein the bisphenol S content is 3%, the mass loss begins to occur about 246 ℃, 290 ℃ and 320 ℃ when the bisphenol S content is 5% and the temperature (T) is 5% when the mass loss begins to occur at about5%) 527 ℃, 537 ℃ and 548 ℃ respectively, and the residual mass at 1000 ℃ is 80.01%, 81.24% and 82.41% respectively.
Claims (5)
1. A method for synthesizing bisphenol S hybrid silicone resin is characterized by comprising the following steps:
step one, stirring 50-100 parts of silane monomer, 0.5-25 parts of bisphenol S and 10-200 parts of solvent until the bisphenol S is completely dissolved to obtain a mixed solution A;
step two, uniformly mixing 10-40 parts of distilled water and 0.05-10 parts of catalyst to obtain a mixed solution B;
step three, dropwise adding the mixed solution B into the mixed solution A, uniformly stirring, heating to 65-70 ℃ after dropwise adding, and reacting for 2-8 hours to obtain a mixed solution C;
step four, distilling the mixed solution C under reduced pressure at the temperature of 120-150 ℃ to remove the solvent to obtain the bisphenol S hybrid silicon resin;
the silane monomer is a combination of methyltriethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane and tetraethyl orthosilicate, or a combination of methyltriethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, hexamethyldisiloxane, diphenyldimethoxysilane and tetraethyl orthosilicate, or a combination of methyltriethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, tetramethyldisiloxane, diphenyldimethoxysilane and tetraethyl orthosilicate, or a combination of methyltriethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, hexamethyldisiloxane, diphenyldimethoxysilane and tetraethyl orthosilicate.
2. The method for synthesizing bisphenol S hybrid silicone resin according to claim 1, wherein the method comprises the following steps: in the first step, the solvent is one or more of methanol, n-propanol, ethanol, butanol, isopropanol, tetrahydrofuran and acetone.
3. The method for synthesizing bisphenol S hybrid silicone resin according to claim 1, wherein the method comprises the following steps: in the second step, the catalyst is one or a combination of more of hydrochloric acid, glacial acetic acid, sulfuric acid, nitric acid and sulfonic acid.
4. The method for synthesizing bisphenol S hybrid silicone resin according to claim 1, wherein the method comprises the following steps: in the third step, the process of dripping the mixed solution B into the mixed solution A is carried out in the environment of 0-40 ℃.
5. The method for synthesizing bisphenol S hybrid silicone resin according to claim 1, wherein the method comprises the following steps: in the third step, the stirring speed is 200 and 1000 revolutions per minute.
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| JPH01132631A (en) * | 1987-11-19 | 1989-05-25 | Tonen Sekiyukagaku Kk | Siloxane-modified polysulfone-imide and its production |
| US7138108B2 (en) * | 2002-06-13 | 2006-11-21 | L'oreal | Photoprotective UV-screening compositions comprising (phenylsulfonyl) acrylonitrile-substituted silanes/siloxanes |
| FR2912410B1 (en) * | 2007-02-12 | 2009-04-17 | Specific Polymers Sarl | SILICONES SULFONES FORMING ELASTOMERS BY SELF - ASSEMBLING, METHODS FOR PREPARING SUCH SILICONES AND USES THEREOF. |
| GB201119824D0 (en) * | 2011-11-17 | 2011-12-28 | Dow Corning | Silicone resins comprising metallosiloxane |
| CN105254896B (en) * | 2015-11-13 | 2017-11-21 | 苏州太湖电工新材料股份有限公司 | A kind of high temperature resistant vinyl ester resin and its synthetic method |
| CN108484917A (en) * | 2018-04-28 | 2018-09-04 | 哈尔滨玻璃钢研究院有限公司 | A kind of preparation method of the bi-phthalonitrile polymer of the structures of POSS containing silsesquioxane |
| CN109096490B (en) * | 2018-08-21 | 2021-02-02 | 合肥工业大学 | Boron-containing silicone oil with main chain belt sulfoxide structure and preparation method thereof |
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