CN111333842A - Synthesis method of hydroxyl silicone oil - Google Patents
Synthesis method of hydroxyl silicone oil Download PDFInfo
- Publication number
- CN111333842A CN111333842A CN202010356004.9A CN202010356004A CN111333842A CN 111333842 A CN111333842 A CN 111333842A CN 202010356004 A CN202010356004 A CN 202010356004A CN 111333842 A CN111333842 A CN 111333842A
- Authority
- CN
- China
- Prior art keywords
- solvent
- silicone oil
- hydroxyl silicone
- synthesizing
- hexamethylcyclotrisiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides a synthetic method of hydroxyl silicone oil, which comprises the following steps: 1) adding hexamethylcyclotrisiloxane, a blocking agent, a solvent and a catalyst into a reaction kettle, heating until the solvent is boiled, and reacting for 1-5 hours at the boiling point of the solvent until all the reaction is completed; 2) adding a neutralizing agent to neutralize until the pH value is 6-8, extracting the solvent, the end-capping agent and unreacted hexamethylcyclotrisiloxane under vacuum to obtain a crude product, and filtering salts in the crude product to obtain a hydroxyl silicone oil finished product; 3) analyzing the component proportions of the solvent, the end-capping reagent and unreacted hexamethylcyclotrisiloxane extracted in the step 2) by using a gas chromatograph, and adding the components into the next batch of reaction production for recycling. According to the synthetic method, no control chemical raw material is used, the process is simple, the synthesis can be completed in one reaction kettle, no wastewater or waste gas is generated in the process, only less than 10 KG/ton of salt is generated, the solvent in the reaction is recycled, the process cost is very low, the environment is protected, the process is simple, and the control is easy.
Description
Technical Field
The invention belongs to the technical field of hydroxy silicone oil synthesis, and particularly relates to a method for synthesizing hydroxy silicone oil.
Background
Low-viscosity hydroxyl-terminated silicone oil (with the viscosity of 10-100 cps) is widely used as a structure control agent of an organic silicon rubber compound and an inorganic material hydrophobic treatment agent. At present, two methods are mainly used for synthesizing the low-viscosity hydroxyl silicone oil:
the first method comprises the following steps: direct hydrolysis of dimethyldichlorosilane. Neutralization of HCl liberated upon hydrolysis of the dimethyldichlorosilane monomer with excess ammonia to form NH3-NH4Cl buffer solution. Dimethyldichlorosilane was added dropwise to ammonia (containing NH)4OH24 percent) is controlled below 30 ℃, the monomer and the dispersed phase thereof enter the reaction system by rapid stirring, and the oil phase generated by the reaction is continuously led out from the system. Drying the finished product with anhydrous calcium chloride, decolorizing with active carbon, and removing ammonia by gas stripping method.
The method has simple process, but the raw materials are not easy to obtain, and a large amount of waste water and hydrochloric acid are generated in the production process, so the method is not environment-friendly.
The second method comprises the following steps: the organosilicon ring body reacts with acetic anhydride. Reacting organosilicon ring bodies (D4 or DMC) with acetic anhydride under an acid catalyst (sulfuric acid or acid clay) at a temperature below the boiling point (125-139 ℃) of the acetic anhydride to obtain an acetyl-terminated intermediate product. And then, rapidly washing off the acid catalyst by using water, adding a sodium carbonate or sodium bicarbonate aqueous solution for neutralization and hydrolysis to obtain a crude product, and adjusting the pH value to 6-7. The product is dried by anhydrous calcium chloride, decolorized by active carbon and filtered to obtain the final product.
The method needs a large amount of acetic anhydride, a large amount of sodium carbonate or sodium bicarbonate aqueous solution for neutralization, hydrolysis and washing, and the acetic anhydride belongs to a controlled product easy to prepare virus. Therefore, the process is not environment-friendly, has high cost and easily limits raw materials.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a method for synthesizing hydroxyl silicone oil, which does not use control chemical raw materials, has a simple process, can be completed in a reaction kettle, does not produce waste water and waste gas in the process, only generates less than 10 KG/ton of salt, recycles the solvent in the reaction, has very low process cost, is environment-friendly, and has a simple process and easy control.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a synthetic method of hydroxyl silicone oil comprises the following steps:
1) adding 60-90 parts by weight of hexamethylcyclotrisiloxane, 10-40 parts by weight of end-capping agent, 30-60 parts by weight of solvent and 0.01-0.5 part by weight of catalyst into a reaction kettle, heating until the solvent is boiled, and reacting for 1-5 hours at the boiling point of the solvent until the reaction is complete;
2) adding a neutralizing agent to neutralize until the pH value is 6-8, pumping out the solvent, the end-capping reagent and unreacted hexamethylcyclotrisiloxane under the vacuum degree of less than 1000pa to obtain a crude product, and then filtering out salts in the crude product to obtain a finished product of the hydroxyl silicone oil;
3) analyzing the component proportions of the solvent, the end-capping reagent and unreacted hexamethylcyclotrisiloxane extracted in the step 2) by using a gas chromatograph, and adding the components into the next batch of reaction production for recycling.
Further, the end-capping agent is deionized water.
Further, the solvent is small molecular alcohol with the carbon number of 1-4, such as ethanol or isopropanol.
Further, the catalyst is alkali, such as NaOH and KOH, and the concentration of LiOH is 10-5000 ppm.
Further, step 1) was followed by gas chromatography of hexamethylcyclotrisiloxane until all reaction was complete.
Further, the neutralizing agent is an organic or inorganic acid, such as acetic acid or phosphoric acid.
Further, the filtration method in the step 2) is that the crude product is sequentially filtered by a bag filter, a precision filter and a membrane filter.
Further, the viscosity of the hydroxyl silicone oil finished product obtained in the step 2) is 10-100 cps.
Further, the proportion of the unreacted hexamethylcyclotrisiloxane, the solvent and the end-capping reagent in the step 3) is (5-20): (40-85): (10-15).
The invention has the beneficial effects that:
the method for synthesizing the hydroxyl silicone oil comprises the steps of reacting hexamethylcyclotrisiloxane in a system of solvent low-molecular-weight alcohol and deionized water at the boiling point of the solvent, and recycling the extracted solvent after analysis.
The method has the advantages that the method does not use control chemical raw materials, is simple in process, can be completed in a reaction kettle, does not produce waste water and waste gas in the process, only generates less than 10 KG/ton of salt, recycles the solvent in the reaction, is very low in process cost, is environment-friendly, is simple in process, and is easy to control.
Detailed Description
The invention relates to a synthetic method of hydroxyl silicone oil, which comprises the following steps:
1) adding 60-90 parts by weight of hexamethylcyclotrisiloxane, 10-40 parts by weight of end-capping agent, 30-60 parts by weight of solvent and 0.01-0.5 part by weight of catalyst into a reaction kettle, heating until the solvent is boiled, and reacting for 1-5 hours at the boiling point of the solvent until the reaction is complete;
2) adding a neutralizing agent to neutralize until the pH value is 6-8, pumping out the solvent, the end-capping reagent and unreacted hexamethylcyclotrisiloxane under the vacuum degree of less than 1000pa to obtain a crude product, and then filtering out salts in the crude product to obtain a finished product of the hydroxyl silicone oil;
3) analyzing the component proportions of the solvent, the end-capping reagent and unreacted hexamethylcyclotrisiloxane extracted in the step 2) by using a gas chromatograph, and adding the components into the next batch of reaction production for recycling.
Further, the end-capping agent is deionized water.
Further, the solvent is small molecular alcohol with the carbon number of 1-4, such as ethanol or isopropanol.
Further, the catalyst is alkali, such as NaOH and KOH, and the concentration of LiOH is 10-5000 ppm.
Further, step 1) was followed by gas chromatography of hexamethylcyclotrisiloxane until all reaction was complete.
Further, the neutralizing agent is an organic or inorganic acid, such as acetic acid or phosphoric acid.
Further, the filtration method in the step 2) is that the crude product is sequentially filtered by a bag filter, a precision filter and a membrane filter.
Further, the viscosity of the hydroxyl silicone oil finished product obtained in the step 2) is 10-100 cps.
Further, the proportion of the unreacted hexamethylcyclotrisiloxane, the solvent and the end-capping reagent in the step 3) is (5-20): (40-85): (10-15).
In examples 1 to 4 of the present invention, the ratios of the solvent, the capping agent and the unreacted hexamethylcyclotrisiloxane extracted in step 2) analyzed by a gas chromatograph are shown in table 1.
TABLE 1 (unit: wt%)
| Hexamethylcyclotrisiloxane | Solvent(s) | End-capping agents | |
| Example 1 | 20 | 70 | 10 |
| Example 2 | 10 | 80 | 10 |
| Example 3 | 45 | 40 | 45 |
| Example 4 | 5 | 85 | 10 |
In table 1, the solvent is ethanol and the capping agent is deionized water.
The method for synthesizing the hydroxyl silicone oil uses hexamethylcyclotrisiloxane to react with deionized water in a system of solvent low-molecular alcohol with carbon number of 1-4 at the boiling point of the solvent, and the extracted solvent is recycled after analysis.
The method has the advantages that the method does not use control chemical raw materials, is simple in process, can be completed in a reaction kettle, does not produce waste water and waste gas in the process, only generates less than 10 KG/ton of salt, recycles the solvent in the reaction, is very low in process cost, is environment-friendly, is simple in process, and is easy to control.
It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.
Claims (9)
1. The method for synthesizing the hydroxyl silicone oil is characterized by comprising the following steps of:
1) adding 60-90 parts by weight of hexamethylcyclotrisiloxane, 10-40 parts by weight of end-capping agent, 30-60 parts by weight of solvent and 0.01-0.5 part by weight of catalyst into a reaction kettle, heating until the solvent is boiled, and reacting for 1-5 hours at the boiling point of the solvent until the reaction is complete;
2) adding a neutralizing agent to neutralize until the pH value is 6-8, pumping out the solvent, the end-capping reagent and unreacted hexamethylcyclotrisiloxane under the vacuum degree of less than 1000pa to obtain a crude product, and then filtering out salts in the crude product to obtain a finished product of the hydroxyl silicone oil;
3) analyzing the component proportions of the solvent, the end-capping reagent and unreacted hexamethylcyclotrisiloxane extracted in the step 2) by using a gas chromatograph, and adding the components into the next batch of reaction production for recycling.
2. The method for synthesizing hydroxyl silicone oil according to claim 1, wherein the end-capping reagent is deionized water.
3. The method for synthesizing hydroxyl silicone oil according to claim 1, wherein the solvent is a small molecular alcohol, such as ethanol or isopropanol.
4. The method for synthesizing hydroxyl silicone oil according to claim 1, wherein the catalyst is alkali such as NaOH, KOH, LiOH, and the concentration is 10-5000 ppm.
5. The method for synthesizing a hydroxysilicone oil according to claim 1, wherein step 1) comprises following hexamethylcyclotrisiloxane by gas chromatography until the entire reaction is completed.
6. The method for synthesizing hydroxyl silicone oil according to claim 1, wherein the neutralizing agent is an organic acid or an inorganic acid, such as acetic acid or phosphoric acid.
7. The method for synthesizing hydroxyl silicone oil according to claim 1, wherein the filtration method in step 2) is to filter the crude product sequentially through a bag filter, a precision filter and a membrane filter.
8. The method for synthesizing the hydroxyl silicone oil according to claim 1, wherein the viscosity of the hydroxyl silicone oil finished product obtained in the step 2) is 10-100 cps.
9. The method for synthesizing the hydroxyl silicone oil according to claim 1, wherein the ratio of unreacted hexamethylcyclotrisiloxane, solvent and end-capping reagent in step 3) is (5-20): (40-85): (10-15).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010356004.9A CN111333842A (en) | 2020-04-29 | 2020-04-29 | Synthesis method of hydroxyl silicone oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010356004.9A CN111333842A (en) | 2020-04-29 | 2020-04-29 | Synthesis method of hydroxyl silicone oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111333842A true CN111333842A (en) | 2020-06-26 |
Family
ID=71179324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010356004.9A Pending CN111333842A (en) | 2020-04-29 | 2020-04-29 | Synthesis method of hydroxyl silicone oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111333842A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625241A (en) * | 2020-10-12 | 2021-04-09 | 湖北兴瑞硅材料有限公司 | Synthesis method of low-viscosity hydroxyl silicone oil |
| CN113087908A (en) * | 2021-04-29 | 2021-07-09 | 江苏众合硅基新材料有限公司 | Preparation method of low-viscosity hydroxyl silicone oil |
| CN114561014A (en) * | 2022-03-21 | 2022-05-31 | 内蒙古恒星化学有限公司 | Method for synthesizing glue 107 and glue 107 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009040807A (en) * | 2007-08-06 | 2009-02-26 | Shin Etsu Chem Co Ltd | Solid polymer electrolyte film and method for producing the same |
| CN101570601A (en) * | 2008-04-30 | 2009-11-04 | 中国石油天然气股份有限公司 | Preparation method of low-molecular-weight hydroxyl silicone oil |
| CN101885845A (en) * | 2010-07-16 | 2010-11-17 | 东莞市贝特利新材料有限公司 | Method for synthesizing vinyl phenyl silicone oil |
| CN102127227A (en) * | 2010-12-27 | 2011-07-20 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Low viscosity hydroxyl terminated polysiloxane and preparation method thereof |
| CN102504259A (en) * | 2011-10-26 | 2012-06-20 | 华南理工大学 | Low molecular weight hydroxyl silicone oil and preparation method thereof |
| CN105754102A (en) * | 2016-04-27 | 2016-07-13 | 广州道林合成材料有限公司 | Hydroxyl silicone oil and continuous preparation method thereof |
| CN106366318A (en) * | 2016-08-29 | 2017-02-01 | 枣阳市金鹏化工有限公司 | Production method of hydroxyl silicone oil |
| CN107868250A (en) * | 2016-09-27 | 2018-04-03 | 枣阳市华威硅氟材料有限公司 | The method for preparing dimethicone |
| CN109266013A (en) * | 2018-09-07 | 2019-01-25 | 苏州歌诗夫新材料有限公司 | Height refraction, color inhibition add-on type silica gel material and preparation method thereof |
-
2020
- 2020-04-29 CN CN202010356004.9A patent/CN111333842A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009040807A (en) * | 2007-08-06 | 2009-02-26 | Shin Etsu Chem Co Ltd | Solid polymer electrolyte film and method for producing the same |
| CN101570601A (en) * | 2008-04-30 | 2009-11-04 | 中国石油天然气股份有限公司 | Preparation method of low-molecular-weight hydroxyl silicone oil |
| CN101885845A (en) * | 2010-07-16 | 2010-11-17 | 东莞市贝特利新材料有限公司 | Method for synthesizing vinyl phenyl silicone oil |
| CN102127227A (en) * | 2010-12-27 | 2011-07-20 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Low viscosity hydroxyl terminated polysiloxane and preparation method thereof |
| CN102504259A (en) * | 2011-10-26 | 2012-06-20 | 华南理工大学 | Low molecular weight hydroxyl silicone oil and preparation method thereof |
| CN105754102A (en) * | 2016-04-27 | 2016-07-13 | 广州道林合成材料有限公司 | Hydroxyl silicone oil and continuous preparation method thereof |
| CN106366318A (en) * | 2016-08-29 | 2017-02-01 | 枣阳市金鹏化工有限公司 | Production method of hydroxyl silicone oil |
| CN107868250A (en) * | 2016-09-27 | 2018-04-03 | 枣阳市华威硅氟材料有限公司 | The method for preparing dimethicone |
| CN109266013A (en) * | 2018-09-07 | 2019-01-25 | 苏州歌诗夫新材料有限公司 | Height refraction, color inhibition add-on type silica gel material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SIM, HB等: "Synthesis and characterization of new positive type photosensitive poly(amic acid)s", 《POLYMER-KOREA》 * |
| 齐帆等: "羟基硅油制备技术研究进展", 《杭州师范大学学报(自然科学版)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625241A (en) * | 2020-10-12 | 2021-04-09 | 湖北兴瑞硅材料有限公司 | Synthesis method of low-viscosity hydroxyl silicone oil |
| CN113087908A (en) * | 2021-04-29 | 2021-07-09 | 江苏众合硅基新材料有限公司 | Preparation method of low-viscosity hydroxyl silicone oil |
| CN114561014A (en) * | 2022-03-21 | 2022-05-31 | 内蒙古恒星化学有限公司 | Method for synthesizing glue 107 and glue 107 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111333842A (en) | Synthesis method of hydroxyl silicone oil | |
| CN101104665B (en) | AM/NaAA/allylcyclodextrin polymer with inclusion function and synthetic method thereof | |
| CN108329239B (en) | Method for preparing taurine from sodium isethionate | |
| JP2007261990A (en) | Method for producing furan-2,5-dicarboxylic acid | |
| CN107793325B (en) | Method for preparing synthetic capsaicin | |
| WO2014092490A1 (en) | Method for preparing an anhydrosugar alcohol using hydrol | |
| KR101764477B1 (en) | Method for producing polyalkylene glycol derivative having amino group at end, with narrow molecular weight distribution | |
| CN104140420A (en) | Synthesis process of thiothiamine | |
| CN110283315B (en) | Method for producing hydroxyl silicone oil by using methyl chlorosilane by-product | |
| CN113444039B (en) | Method for preparing 2,2, 4-trimethyl-1, 2-dihydroquinoline by using ionic liquid | |
| CN114181178A (en) | Method for recovering layered water of alpha-chloro-alpha-acetyl-gamma-butyrolactone and application thereof | |
| CN103787894A (en) | Method for recovering TDA (Toluene Diamine) from residues and wastes formed in preparation process of TDI (Toluene Diisocyanate) | |
| CN110938207B (en) | Preparation method of hydrogen-containing silicone oil | |
| CN109053627A (en) | The comprehensive recovering process of 2-mercaptobenzothiazole, triethylamine and methylene chloride in Ceftriaxone Sodium methylene chloride mother liquor | |
| CN102977373A (en) | Preparation method of hydroxyfluorosilicone oil | |
| CN113087908A (en) | Preparation method of low-viscosity hydroxyl silicone oil | |
| CN114702607B (en) | Water-soluble hydroxymethyl propyl chitosan and preparation method thereof | |
| CN103044272B (en) | Preparation method of 4-nitroso-N-ethyl-N-hydroxyethyl aniline | |
| CN106632699A (en) | Preparation method of high-transparency hydroxy ethyl cellulose (HEC) | |
| CN113321681A (en) | Purification process of glufosinate-ammonium | |
| CN111518861A (en) | Novel process for preparing D-calcium pantothenate | |
| CN112898187A (en) | Method for crystallizing taurine | |
| CN112142580A (en) | Clean production method of UV-9 crystallization mother liquor | |
| CN114940666B (en) | High-yield synthesis method of N-methylmorpholine oxide aqueous solution | |
| CN113336680B (en) | Green process synthesis method of sulfanilamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |