CN112358618A - Preparation method of methyl fluorosilicone oil - Google Patents
Preparation method of methyl fluorosilicone oil Download PDFInfo
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- CN112358618A CN112358618A CN202011314331.4A CN202011314331A CN112358618A CN 112358618 A CN112358618 A CN 112358618A CN 202011314331 A CN202011314331 A CN 202011314331A CN 112358618 A CN112358618 A CN 112358618A
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- fluorosilicone oil
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- siloxane ring
- methyl fluorosilicone
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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 discloses methyl fluorosilicone oil and a preparation method thereof, and the preparation method of the methyl fluorosilicone oil comprises the following steps: (1) respectively drum-drying siloxane ring bodies and trifluoropropylmethylcyclotrisiloxane (D3F) at 70-90 ℃ for negative pressure dehydration for 1-2 hours by using nitrogen, and uniformly mixing the siloxane ring bodies and D3F according to a certain proportion after dehydration; (2) adding a sealing agent under a stirring state; (3) adding a catalyst under a stirring state, stirring and reacting for 1-1.5 h at the temperature of 60-80 ℃, and then heating to the temperature of 100-110 ℃ to react for 2-4 h; (4) heating to 150-160 ℃ for 0.5-1 h; (5) and (3) reducing the vacuum degree of the mixture for 3-5 hours at the temperature of 160-180 ℃ and under the vacuum degree of less than 0.095 MPa.
Description
Technical Field
The invention relates to methyl fluorosilicone oil and a preparation method thereof, belonging to the technical field of polysiloxane synthesis.
Background
Methyl fluorosilicone oil is methyl terminated linear polysiloxane with side chain introduced with fluorine-containing group, and belongs to modified silicone oil. Due to the fact that trifluoropropyl is introduced on silicon atoms, methyl fluorosilicone oil has the common characteristics of siloxane and fluorocarbon, and has excellent performances such as low surface tension, weather resistance, oil resistance, solvent resistance, high and low temperature resistance (-60-200 ℃), lubricity, chemical stability and the like. The methyl fluorosilicone oil can be used as a defoaming agent, a lubricating agent, a release agent and a fabric finishing agent and is widely applied to the fields of cosmetics, leather, aerospace, automobiles, textiles and the like.
The hydrosilylation method is a common method for preparing fluorosilicone oil, and is carried out by utilizing Si-H bonds and C = C bonds of hydrogen-containing silicone oil to carry out addition reaction in the presence of a catalyst, but in order to make the hydrogen-containing silicone oil and fluorine-containing compounds fully contact, a large amount of toxic and harmful organic solution such as tetrahydrofuran, toluene, dioxane or isooctane is needed to be used as a solvent, solution separation is needed after the reaction is finished, the reaction process is complex and energy is consumed, and part of toxic and harmful solvent can be remained in the product.
In order to solve the technical problem, the invention provides a preparation method of methyl fluorosilicone oil.
Disclosure of Invention
Aiming at the technical difficulties of using a large amount of toxic and harmful organic solvents, having complex reaction process and the like in the prior art, the invention provides the methyl fluorosilicone oil and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
methyl fluorosilicone oil and a preparation method thereof comprise the following steps:
(1) respectively drum-drying siloxane ring bodies and trifluoropropylmethylcyclotrisiloxane (D3F) at 70-90 ℃ for negative pressure dehydration for 1-2 hours by using nitrogen, and uniformly mixing the siloxane ring bodies and D3F according to a certain proportion after dehydration;
(2) adding a sealing agent under a stirring state;
(3) adding a catalyst under a stirring state, stirring and reacting for 1-1.5 h at the temperature of 60-80 ℃, and then heating to the temperature of 100-110 ℃ to react for 2-4 h;
(4) heating to 150-160 ℃ for 0.5-1 h;
(5) and (3) reducing the vacuum degree of the mixture for 3 to 5 hours at the temperature of between 160 and 180 ℃ and under the pressure of less than-0.095 MPa.
The siloxane ring body is one or a mixture of more of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) … D12. The dehydration pressure is-0.095 MPa to-0.01 MPa; the purity of the nitrogen is more than or equal to 99.999 percent.
The mass ratio of the dried siloxane ring body to the trifluoropropylmethylcyclotrisiloxane is 0.2-5: 1.
The end capping agent is hexamethyldisiloxane (MM) and low-viscosity methyl silicone oil (MDM). The using amount of the end sealing agent is 0.1-5% of the total amount of the siloxane ring body and the D3F. The temperature of the two-stage reaction is 60-80 ℃ in the first stage and 100-110 ℃ in the second stage, the obtained catalyst is tetramethyl ammonium hydroxide alkali glue, and the dosage of the catalyst is 100-150 ppm.
Compared with the prior art, the invention has the following beneficial effects:
(1) the siloxane ring body and the D3F are respectively dehydrated, so that the reuse of the dehydrated products is facilitated, and the situation that the content of the siloxane ring body and the content of the D3F in the dehydrated products after mixing and dehydration are not constant is effectively avoided;
(2) in the whole process, any organic solution is not used as a solvent, so that the environmental protection performance is greatly improved, and meanwhile, storage and separation equipment of toxic and harmful solvents are saved, and the process advantage is more obvious;
(3) the low molecules obtained by the low-molecular removal are continuously recycled, so that the utilization rate of raw materials is improved;
(4) the process route is simple, efficient and continuous, and is convenient for continuous and industrial production.
Detailed Description
Example 1:
500g D3F and 500g DMC were added to a 1000ml three-necked flask, respectively; heating to 80 deg.C in oil bath, and dehydrating with nitrogen under-0.095 MPa for 1 hr to obtain 6.0% water; adding 300g of dehydrated D3F 300 and 300g of DMC into a 1000ml three-neck flask, adding 9.7g of end sealing agent MDM, uniformly stirring, heating to 80 ℃, then adding 4g of tetramethylammonium hydroxide alkali gel with the alkali content of 2%, stirring and reacting for 1h at 80 ℃, heating to 110 ℃, and reacting for 3h for further polymerization; after polymerization is finished, the temperature is raised to 160 ℃ for 30min, and the catalyst is removed for 3h under the pressure of-0.099 MPa at 180 ℃ to obtain the methyl fluorosilicone oil product. Viscosity 12868cp, volatile component 0.43%, conversion rate 82.5%, and colorless and transparent appearance.
Example 2:
adding 3F 200g of D3 dehydrated in example 1 and 400g of DMC into a 1000ml three-neck flask, adding 5.6g of end sealing agent MDM, stirring uniformly, heating to 80 ℃, then adding 4g of tetramethylammonium hydroxide alkali gel with 2% of alkali content, stirring and reacting for 1h at 80 ℃, heating to 110 ℃, reacting for 3h, and further polymerizing; after polymerization is finished, the temperature is raised to 160 ℃ for 30min, and the catalyst is removed for 3h under the pressure of-0.098 MPa at 180 ℃ to obtain the methyl fluorosilicone oil product. The viscosity was 64756cp, the volatile matter was 0.47%, the conversion was 83.4%, and the appearance was colorless and transparent.
Example 3:
adding 200g of DMC and 3F 400g of D3 dehydrated in example 1 into a 1000ml three-neck flask, adding 25.5g of end sealing agent MDM, stirring uniformly, heating to 80 ℃, adding 4g of tetramethylammonium hydroxide alkali gel with 2% of alkali content, stirring and reacting for 1h at 80 ℃, heating to 110 ℃, reacting for 3h, and further polymerizing; after polymerization is finished, the temperature is raised to 160 ℃ for 30min, and the catalyst is broken, and the methyl fluorosilicone oil product is obtained after the catalyst is removed for 3h under the pressure of 180 ℃ to 0.098 MPa. Viscosity 1021cp, volatile 0.39%, conversion 82.7%, colorless and transparent appearance.
Example 4:
adding 3F 600g of dehydrated D3 obtained in the embodiment 1 into a 1000ml three-neck flask, adding an end sealing agent MDM5.1, uniformly stirring, adding 3g of tetramethylammonium hydroxide alkali gel with the alkali content of 2%, stirring and reacting for 2h at 80 ℃, heating to 160 ℃ after polymerization is finished, breaking the medium for 30min, and removing the alkali content for 3h at 180 ℃ to 0.098MPa to obtain a methyl fluorosilicone oil product with the conversion rate of 23.4%.
Example 5:
adding 3F 600g of dehydrated D3 obtained in the embodiment 1 into a 1000ml three-neck flask, adding 7.5 g of sealing agent MDM, uniformly stirring, adding 3g of tetramethylammonium hydroxide alkali gel with the alkali content of 2%, stirring and reacting for 2h at 110 ℃, heating to 160 ℃ after polymerization, breaking the medium for 30min, and removing the solvent for 3h at 180-0.098 MPa to obtain a methyl fluorosilicone oil product with the conversion rate of 25.7%.
Example 6:
adding 300g of dehydrated D3F 300 and 300g of DMC in example 1 into a 1000ml three-neck flask, adding 38.5g of end sealing agent MDM, uniformly stirring, adding 4g of tetramethylammonium hydroxide alkali gum with the alkali content of 2%, stirring and reacting for 2h at 70 ℃, heating to 160 ℃ after polymerization is finished, breaking the medium for 30min, and removing the solvent for 3h at 180 ℃ to 0.098MPa to obtain the methyl fluorosilicone oil product. The conversion rate is 68.7%, and the appearance is turbid and transparent.
Example 7:
600g of the dehydrated DMC obtained in the embodiment 1 is added into a 1000ml three-neck flask, 26.9g of an end sealing agent MDM is added, the mixture is uniformly stirred, 2g of tetramethylammonium hydroxide alkali gel with the alkali content of 2% is added, the mixture is stirred and reacted for 2 hours at the temperature of 110 ℃, the temperature is increased to 160 ℃ after polymerization is finished, the catalyst is broken for 30 minutes, the temperature is raised to 180 ℃ and the pressure is reduced for 3 hours at the pressure of 0.098MPa to obtain a methyl fluorosilicone oil product, the viscosity is 1121cp, the volatile component is 0.32%, the conversion rate is 83.4%, and the appearance is colorless and transparent.
Example 8:
adding 600g of the DMC dehydrated in the embodiment 1 into a 1000ml three-neck flask, adding 10.54 g of an end sealing agent MDM, uniformly stirring, adding 2g of tetramethylammonium hydroxide alkali gel with the alkali content of 2%, stirring and reacting for 2h at 110 ℃, heating to 160 ℃ after polymerization is finished, breaking the medium for 30min, removing the solvent for 3h at 180 ℃ and 0.098MPa to obtain a methyl fluorosilicone oil product, wherein the viscosity is 13657cp, the volatile component is 0.38%, the conversion rate is 82.7%, and the appearance is colorless and transparent.
Claims (6)
1. The preparation method of methyl fluorosilicone oil is characterized by comprising the following steps:
(1) respectively drying siloxane ring bodies and trifluoropropyl methyl cyclotrisiloxane by blowing dry nitrogen at the temperature of 70-90 ℃ and dehydrating for 1-2 hours under negative pressure, and uniformly mixing the siloxane ring bodies and the trifluoropropyl methyl cyclotrisiloxane according to a certain proportion after dehydration;
(2) adding a sealing agent and a catalyst under a stirring state, stirring and reacting for 1-1.5 h at the temperature of 60-80 ℃, and then heating to 100-110 ℃ for reacting for 2-4 h;
(3) heating to 150-160 ℃ for 0.5-1 h, and then reducing the vacuum degree at 160-180 ℃ for 3-5 h under the vacuum degree lower than 0.095 MPa.
2. The method for preparing methyl fluorosilicone oil according to claim 1, wherein the siloxane ring body in step (1) is one or a mixture of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) … D12.
3. The method for preparing methyl fluorosilicone oil according to claim 2, wherein the mass ratio of the dried siloxane ring body to the trifluoropropyl methylcyclotrisiloxane in the step (1) is 0.2-5: 1.
4. the method for preparing methyl fluorosilicone oil according to claim 1, wherein in the step (1), the dehydration pressure is-0.095 MPa to-0.01 MPa; the purity of the nitrogen is more than or equal to 99.999 percent.
5. The method for preparing methyl fluorosilicone oil according to claim 1, wherein the end capping agent in step (2) is hexamethyldisiloxane (MM), low viscosity methyl silicone oil (MDM), and the amount of the end capping agent is 0.1% to 5% of the total amount of the siloxane ring bodies and D3F.
6. The method for preparing methyl fluorosilicone oil according to claim 1, wherein two stages of reaction temperatures are adopted in the step (2), wherein the first stage temperature is 60-80 ℃, the second stage temperature is 100-110 ℃, the catalyst is tetramethylammonium hydroxide alkali glue, and the dosage of the catalyst is 100-150 ppm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690417A (en) * | 2012-06-13 | 2012-09-26 | 江苏宏达新材料股份有限公司 | Preparation method of crude liquid fluorosilicone rubber by means of room temperature vulcanization |
| CN107151325A (en) * | 2017-06-22 | 2017-09-12 | 湖北兴瑞化工有限公司 | A kind of production technology of methyl vinyl silicone rubber |
| CN107522863A (en) * | 2017-09-15 | 2017-12-29 | 湖北兴瑞化工有限公司 | A kind of method that trifluoro propyl silicone oil is produced using ion exchange resin |
| CN110698675A (en) * | 2019-11-01 | 2020-01-17 | 浙江新安化工集团股份有限公司 | Hydroxyl fluorosilicone oil and preparation method and application thereof |
| CN111621017A (en) * | 2020-06-16 | 2020-09-04 | 湖北兴瑞硅材料有限公司 | Ternary polymerization fluorosilicone rubber and preparation method thereof |
-
2020
- 2020-11-20 CN CN202011314331.4A patent/CN112358618A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102690417A (en) * | 2012-06-13 | 2012-09-26 | 江苏宏达新材料股份有限公司 | Preparation method of crude liquid fluorosilicone rubber by means of room temperature vulcanization |
| CN107151325A (en) * | 2017-06-22 | 2017-09-12 | 湖北兴瑞化工有限公司 | A kind of production technology of methyl vinyl silicone rubber |
| CN107522863A (en) * | 2017-09-15 | 2017-12-29 | 湖北兴瑞化工有限公司 | A kind of method that trifluoro propyl silicone oil is produced using ion exchange resin |
| CN110698675A (en) * | 2019-11-01 | 2020-01-17 | 浙江新安化工集团股份有限公司 | Hydroxyl fluorosilicone oil and preparation method and application thereof |
| CN111621017A (en) * | 2020-06-16 | 2020-09-04 | 湖北兴瑞硅材料有限公司 | Ternary polymerization fluorosilicone rubber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 冯新德: "《高分子辞典》", 30 June 1998 * |
| 易玲敏等: "1,3,5-三甲基-1,3,5-三（3′,3′,3′-三氟丙基）环三硅氧烷的阴离子开环（共）聚合研究进展", 《高分子材料科学与工程》 * |
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