CN110734548A - fluorine-silicon resin and preparation method thereof - Google Patents
fluorine-silicon resin and preparation method thereof Download PDFInfo
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- CN110734548A CN110734548A CN201911035502.7A CN201911035502A CN110734548A CN 110734548 A CN110734548 A CN 110734548A CN 201911035502 A CN201911035502 A CN 201911035502A CN 110734548 A CN110734548 A CN 110734548A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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Abstract
The invention provides kinds of fluorosilicone resins, which are prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to kinds of fluorosilicone resin and a preparation method of kinds of fluorosilicone resin.
Background
The silicon resin is generally hydrolyzed by various mixtures of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane or methylphenyldichlorosilane in the presence of an organic solvent such as toluene at a lower temperature to obtain an acidic hydrolysate, the acidic hydrolysate is washed with water to remove acid and neutral primary condensation polymers, and is thermally oxidized in air or subjected to -step condensation polymerization in the presence of a catalyst to finally form a highly crosslinked three-dimensional network structure.
MQ resin is of most -generic silicon resin, other groups are introduced into the MQ silicon resin to expand the application, but after other structures are introduced into the MQ silicon resin, the structures are not favorable for the heat-resistant performance of the silicon resin due to the reactivity of the structures under conditions, and even if the silicon resin with a phenyl M structure is introduced, the silicon resin can be heated at 250 ℃ for 24 hours to generate mass loss of 8 percent, so that the application of the silicon resin as a composite material component under the temperature condition of higher than 250 ℃ is limited.
Disclosure of Invention
The invention aims to provide kinds of fluorosilicone resin, which solves the problem that the heat resistance of the silicone resin is insufficient in the prior art.
Another objective of the present invention is to provide a preparation method of fluorosilicone resins, which solves the problem of poor heat resistance of fluorosilicone resins prepared by the prior art.
The technical scheme adopted by the invention is that,
kinds of fluorosilicone resin is prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organochlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.
Yet another feature of the present invention is that,
the organic alcohol is dodecyl mercaptan.
preparation method of fluorosilicone resin, comprising the following steps:
, weighing 100-200 parts of butyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane according to mass fractions.
Secondly, adding 100-200 parts of ethyl butyl perfluoroether and 200-600 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 20-30 ℃ for 1-2 hours to obtain a prepolymer 1;
adding 80-200 parts of organic chlorosilane into the prepolymer 1 obtained in the second step, uniformly stirring at the temperature of 20-30 ℃, adding 10-30 parts of catalyst, continuously stirring and heating to 70-90 ℃, and reacting for 15-18 hours to obtain a prepolymer 2;
fourthly, at the temperature of 70-80 ℃, 100-300 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step, and after the dripping is finished, the temperature is preserved for polycondensation for 40-60 minutes to obtain a prepolymer 3;
and fifthly, dripping 30-100 parts of trihydrocarbyl chlorosilane into the prepolymer 3 obtained in the fourth step, and after finishing dripping, keeping the temperature to perform polycondensation reaction for 90-120 minutes to obtain the target product, namely the fluorosilicone resin.
The stirring speed in the third step is 200-500 r/min.
And in the fourth step, the time for dripping the tetraethoxysilane is 30-40 minutes.
And in the fifth step, the time for dripping the alkyl chlorosilane is 40-50 minutes.
The invention has the beneficial effects that the phenyl conjugated plane structure and the fluorocarbon bond energy of the fluorosilicone resin disclosed by the invention are large, so organic silicon materials with excellent heat resistance are provided, the commercially available ethyl butyl perfluoroether, ethyl orthosilicate, trialkyl chlorosilane and the like are utilized to prepare series fluorosilicone resins, and the synthetic method is scientific and reasonable, so that general methods for synthesizing series fluorosilicone resins are provided.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention provides kinds of fluorosilicone resin, which is prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.
The invention also provides a preparation method of fluorosilicone resins, which is characterized by comprising the following steps:
, weighing 100-200 parts of butyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane according to mass fractions.
Secondly, adding 100-200 parts of ethyl butyl perfluoroether and 200-600 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 20-30 ℃ for 1-2 hours to obtain a prepolymer 1;
adding 80-200 parts of organic chlorosilane into the prepolymer 1 obtained in the second step, uniformly stirring at the temperature of 20-30 ℃ at the speed of 200-500 r/min, adding 10-30 parts of catalyst, continuously stirring and heating to 70-90 ℃, and reacting for 15-18 hours to obtain a prepolymer 2;
fourthly, at the temperature of 70-80 ℃, 100-300 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step, the dropwise addition is carried out for 30-40 minutes, and the temperature is kept for polycondensation for 40-60 minutes after the dropwise addition is finished, so that a prepolymer 3 is obtained;
and fifthly, dripping 30-100 parts of trihydrocarbyl chlorosilane into the prepolymer 3 obtained in the fourth step for 40-50 minutes, and preserving heat after finishing dripping to perform polycondensation reaction for 90-120 minutes to obtain the target product, namely the fluorosilicone resin.
Example 1
And , weighing 100 parts of butyl perfluoroether, 200 parts of organic alcohol, 80 parts of organic chlorosilane, 10 parts of catalyst, 10 parts of ethyl orthosilicate and 30 parts of trihydrocarbyl chlorosilane according to mass fractions.
Secondly, adding 100 parts of ethyl butyl perfluoroether and 200 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 20 ℃ for 1 hour to obtain a prepolymer 1;
step three, adding 80 parts of organic chlorosilane into the prepolymer 1 obtained in the step two, stirring uniformly at the temperature of 20 ℃ at the speed of 200r/min, adding 10 parts of catalyst, continuously stirring and heating to 70 ℃, and reacting for 15 hours to obtain a prepolymer 2;
fourthly, at the temperature of 70 ℃, 100 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step for 30 minutes, and after the dripping is finished, the temperature is preserved for polycondensation for 40 minutes to obtain a prepolymer 3;
and fifthly, dripping 30 parts of trihydrocarbon chlorosilane into the prepolymer 3 obtained in the fourth step for 40 minutes, and preserving heat after finishing dripping to perform polycondensation reaction for 90 minutes to obtain the target product, namely the fluorosilicone resin.
Example 2
And , weighing 200 parts of butyl perfluoroether, 600 parts of organic alcohol, 200 parts of organochlorosilane, 30 parts of catalyst, 300 parts of ethyl orthosilicate and 100 parts of trihydrocarbyl chlorosilane in parts by mass.
Secondly, adding 200 parts of ethyl butyl perfluoroether and 600 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 30 ℃ for 1-2 hours to obtain a prepolymer 1;
thirdly, adding 200 parts of organic chlorosilane into the prepolymer 1 obtained in the second step, uniformly stirring at the temperature of 30 ℃ at the speed of 500r/min, adding 30 parts of catalyst, continuously stirring and heating to 90 ℃, and reacting for 18 hours to obtain a prepolymer 2;
fourthly, at 80 ℃, 300 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step for 40 minutes, and after the dripping is finished, the temperature is kept for polycondensation for 60 minutes to obtain a prepolymer 3;
and fifthly, dripping 100 parts of trihydrocarbyl chlorosilane into the prepolymer 3 obtained in the fourth step for 50 minutes, and preserving heat after finishing dripping to perform polycondensation reaction for 120 minutes to obtain the target product, namely the fluorosilicone resin.
Example 3
And , weighing 150 parts of butyl perfluoroether, 400 parts of organic alcohol, 140 parts of organochlorosilane, 20 parts of catalyst, 200 parts of ethyl orthosilicate and 65 parts of trihydrocarbyl chlorosilane in parts by mass.
Secondly, adding 150 parts of ethyl butyl perfluoroether and 400 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 25 ℃ for 1.5 hours to obtain a prepolymer 1;
thirdly, adding 140 parts of organic chlorosilane into the prepolymer 1 obtained in the second step, uniformly stirring at the temperature of 25 ℃ at the speed of 350r/min, adding 20 parts of catalyst, continuously stirring and heating to 80 ℃, and reacting for 16.5 hours to obtain a prepolymer 2;
fourthly, at the temperature of 70-80 ℃, dropwise adding 200 parts of tetraethoxysilane into the prepolymer 2 obtained in the third step for 35 minutes, and after dropwise adding, carrying out thermal insulation for polycondensation for 50 minutes to obtain a prepolymer 3;
and fifthly, dripping 65 parts of trialkyl chlorosilane into the prepolymer 3 obtained in the fourth step for 45 minutes, and preserving heat after finishing dripping to perform polycondensation reaction for 100 minutes to obtain the target product, namely the fluorosilicone resin.
Claims (6)
- kinds of fluorosilicone resin is characterized by being prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.
- 2. The fluorosilicone resin of claim 1, wherein the organic alcohol is dodecyl mercaptan.
- 3, preparation method of fluorosilicone resin, characterized by comprising the following steps:, weighing 100-200 parts of butyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane according to mass fractions.Secondly, adding 100-200 parts of ethyl butyl perfluoroether and 200-600 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 20-30 ℃ for 1-2 hours to obtain a prepolymer 1;step three, adding 80-200 parts of organic chlorosilane into the prepolymer 1 obtained in the step two, uniformly stirring at the temperature of 20-30 ℃, adding 10-30 parts of catalyst, continuously stirring and heating to 70-90 ℃, and reacting for 15-18 hours to obtain a prepolymer 2;fourthly, at the temperature of 70-80 ℃, 100-300 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step, and after the dripping is finished, the temperature is preserved for polycondensation for 40-60 minutes to obtain a prepolymer 3;and fifthly, dripping 30-100 parts of trihydrocarbyl chlorosilane into the prepolymer 3 obtained in the fourth step, and after finishing dripping, keeping the temperature to perform polycondensation reaction for 90-120 minutes to obtain the target product, namely the fluorosilicone resin.
- 4. The method for preparing kinds of fluorosilicone resins, according to claim 3, wherein the stirring speed in the third step is 200-500 r/min.
- 5. The method for preparing kinds of fluorosilicone resins, as claimed in claim 3, wherein the time for dropping tetraethoxysilane in the fourth step is 30-40 minutes.
- 6. The method for preparing kinds of fluorosilicone resins, as claimed in claim 3, wherein the time for dropping chlorosilane in the fifth step is 40-50 minutes.
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| CN201911035502.7A CN110734548A (en) | 2019-10-29 | 2019-10-29 | fluorine-silicon resin and preparation method thereof |
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| CN201911035502.7A CN110734548A (en) | 2019-10-29 | 2019-10-29 | fluorine-silicon resin and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440758A (en) * | 2018-03-23 | 2018-08-24 | 哈尔滨工业大学 | A kind of preparation method of hydrophobic fluorine silicon resin |
| CN108484914A (en) * | 2018-03-13 | 2018-09-04 | 苏州大学 | Fluorine silicon resin and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484914A (en) * | 2018-03-13 | 2018-09-04 | 苏州大学 | Fluorine silicon resin and preparation method thereof |
| CN108440758A (en) * | 2018-03-23 | 2018-08-24 | 哈尔滨工业大学 | A kind of preparation method of hydrophobic fluorine silicon resin |
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Application publication date: 20200131 |