CN106977721B - Hydrolysis method of silicone oil monomer - Google Patents
Hydrolysis method of silicone oil monomer Download PDFInfo
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- CN106977721B CN106977721B CN201710283016.1A CN201710283016A CN106977721B CN 106977721 B CN106977721 B CN 106977721B CN 201710283016 A CN201710283016 A CN 201710283016A CN 106977721 B CN106977721 B CN 106977721B
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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 a hydrolysis method of a silicone oil monomer, which comprises the following steps: sequentially adding a catalyst, a ring body and a silicone oil monomer into water, and hydrolyzing to obtain a branched silicone oil hydrolysate; the ring body comprises an octamethylcyclotetrasiloxane and/or a dimethylcyclosiloxane mixture; the silicone oil monomer comprises one or more of monomethyltriethoxysilane, monomethyltrimethoxysilane, monophenyltriethoxysilane and monophenyltrimethoxysilane. The invention adopts a specific feeding sequence and a slow feeding method, and improves the hydrolysis efficiency of the branched silicone oil monomer by matching with specific raw material types. In the examples of the present invention, the hydrolysis yield using the hydrolysis method of the present invention can reach 91.0%.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a hydrolysis method of a silicone oil monomer.
Background
Silicone oil is polyorganosiloxane with chain structures of different polymerization degrees, belongs to an organic silicon compound, is developed from the eighteenth century, and is one of the synthetic lubricants which are initially obtained industrially. Silicone oils have a number of excellent properties: 1) excellent viscosity-temperature performance; 2) excellent thermal stability; 3) excellent thermal oxidation stability; 4) excellent electrical insulation; 5) excellent shear stability; 6) is nontoxic. And thus have found applications in many fields.
The branched silicone oil is one of silicone oils, and due to the introduction of a branch chain, the branched silicone oil has the following more excellent properties while maintaining various excellent properties of the silicone oil: 1. the low-temperature performance is more excellent, and the lowest freezing point can be as low as about-90 ℃; 2. improving the compatibility of the additive and other oil products. Therefore, the branched silicone oil is mainly used for base oil of lubricating grease at extremely low temperature.
The production flow of the branched silicone oil is as follows:
hydrolyzing a branched silicone oil monomer to obtain a silicone oil hydrolysate, then carrying out polymerization reaction and equilibrium reaction under acidic or alkaline conditions, and then sequentially distilling and filtering to obtain the branched silicone oil. Since various chain links forming the silicone oil are obtained by hydrolyzing corresponding organosilicon monomers, the hydrolysis of the branched silicone oil monomer is an important step for preparing the branched silicone oil. The branched silicone oil is generally prepared by hydrolyzing alkyl triethoxysilane or alkyl trichlorosilane serving as a branched silicone oil monomer to obtain a hydrolysate, but the hydrolysis process has the following technical problems: 1) the branched silicone oil monomer has strong activity, the hydrolysis speed is too high, and the hydrolysis process is not easy to control; 2) when the amount of the branched silicone oil monomer added is too large, a crosslinking reaction may occur to form a gum. Therefore, the branched silicone oil monomer has high hydrolysis difficulty.
Disclosure of Invention
The invention aims to provide a hydrolysis method of a silicone oil monomer, which can hydrolyze a branched silicone oil monomer and has high hydrolysis yield.
The invention provides a hydrolysis method of a silicone oil monomer, which comprises the following steps:
sequentially adding a catalyst, a ring body and a silicone oil monomer into water, and hydrolyzing to obtain a branched silicone oil hydrolysate;
the ring body comprises an octamethylcyclotetrasiloxane and/or a dimethylcyclosiloxane mixture;
the silicone oil monomer comprises one or more of monomethyltriethoxysilane, monomethyltrimethoxysilane, monophenyltriethoxysilane and monophenyltrimethoxysilane.
Preferably, the mass ratio of the silicone oil monomer to the ring body is (3-10): (90-97).
Preferably, the mass ratio of the silicone oil monomer to the ring body is (6-8): (92-94).
Preferably, the mass ratio of the total mass of the silicone oil monomer and the ring body to the water is 1: (1-1.5).
Preferably, the catalyst comprises hydrochloric acid and/or sulfuric acid.
Preferably, the mass ratio of the total mass of the silicone oil monomer and the ring body to the catalyst is 1: (0.04-0.12).
Preferably, the hydrolysis temperature is 30-50 ℃;
the hydrolysis time is 3-5 hours.
Preferably, the feeding time of the silicone oil monomer is 1-2 hours.
Preferably, the method further comprises the following steps after the hydrolysis:
and standing the product obtained by hydrolysis, removing acid water, and washing with water until the pH value is 6-8 to obtain the branched silicone oil hydrolysate.
Preferably, the temperature of the washing water is 50-70 ℃.
The invention provides a hydrolysis method of a silicone oil monomer, which comprises the following steps: sequentially adding a catalyst, a ring body and a silicone oil monomer into water, and hydrolyzing to obtain a branched silicone oil hydrolysate; the ring body comprises an octamethylcyclotetrasiloxane and/or a dimethylcyclosiloxane mixture; the silicone oil monomer comprises one or more of monomethyltriethoxysilane, monomethyltrimethoxysilane, monophenyltriethoxysilane and monophenyltrimethoxysilane. The invention adopts a specific feeding sequence and a slow feeding method, and improves the hydrolysis efficiency of the branched silicone oil monomer by matching with specific raw material types. In the examples of the present invention, the hydrolysis yield using the hydrolysis method of the present invention can reach 91.0%.
Furthermore, the branched silicone oil synthesized by the branched silicone oil hydrolysate obtained by hydrolysis according to the invention has excellent low-temperature performance and additive compatibility, and is mainly used for lubricating grease base oil at extremely low temperature.
Detailed Description
The invention provides a hydrolysis method of a silicone oil monomer, which comprises the following steps:
sequentially adding a catalyst, a ring body and a silicone oil monomer into water, and hydrolyzing to obtain a branched silicone oil hydrolysate;
the ring body comprises an octamethylcyclotetrasiloxane and/or a dimethylcyclosiloxane mixture;
the silicone oil monomer comprises one or more of monomethyltriethoxysilane, monomethyltrimethoxysilane, monophenyltriethoxysilane and monophenyltrimethoxysilane.
The hydrolysis method of the invention can hydrolyze the branched silicone oil monomer, and the obtained hydrolysate is used for synthesizing the branched silicone oil.
In the present invention, the catalyst preferably comprises hydrochloric acid and/or sulfuric acid, the ring body comprises octamethylcyclotetrasiloxane and/or a Dimethylcyclosiloxane Mixture (DMC) mainly comprising hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6); the ring body can increase the chain length of the hydrolysate; the silicone oil monomer comprises one or more of monomethyltriethoxysilane, monomethyltrimethoxysilane, monophenyltriethoxysilane and monophenyltrimethoxysilane.
In the invention, the mass ratio of the silicone oil monomer to the ring body is preferably (3-10): (90-97), more preferably (6-8): (92-94), specifically, in the embodiment of the invention, the ratio of the total weight of the components can be 8:92, 6:94 or 10: 90; the mass ratio of the total mass of the silicone oil monomer and the ring body to the water is preferably 1: (1 to 1.5), more preferably 1: (1.1-1.4), specifically, in the embodiment of the invention, the ratio of 1:1.15 or 1: 1.5; the mass ratio of the total mass of the silicone oil monomer and the ring body to the catalyst is preferably 1: (0.04 to 0.12), more preferably 1: (0.05 to 0.1), specifically, in an embodiment of the present invention, the ratio may be 1: 0.08, 1:0.1 or 1: 0.12.
according to the invention, the silicone oil monomer is preferably slowly dripped, the dripping time is preferably 1-2 hours, and the hydrolysis temperature is preferably 30-50 ℃, and more preferably 35-45 ℃; the hydrolysis time is preferably 3 to 5 hours, and more preferably 4 hours.
Preferably, the hydrolyzed product is stood, acid water is removed, and then the product is washed by water at the temperature of 50-70 ℃ until the pH value of the product is 6-8, so that the branched silicone oil hydrolysate is obtained.
The invention provides a hydrolysis method of a silicone oil monomer, which comprises the following steps: sequentially adding a catalyst, a ring body and a silicone oil monomer into water, and hydrolyzing to obtain a branched silicone oil hydrolysate; the ring body comprises an octamethylcyclotetrasiloxane and/or a dimethylcyclosiloxane mixture; the silicone oil monomer comprises one or more of monomethyltriethoxysilane, monomethyltrimethoxysilane, monophenyltriethoxysilane and monophenyltrimethoxysilane. The invention adopts a specific feeding sequence and a slow feeding method, and improves the hydrolysis efficiency of the branched silicone oil monomer by matching with specific raw material types. In the examples of the present invention, the hydrolysis yield using the hydrolysis method of the present invention can reach 91.0%.
Furthermore, the branched silicone oil synthesized by the branched silicone oil hydrolysate obtained by hydrolysis according to the invention has excellent low-temperature performance and additive compatibility, and is mainly used for lubricating grease base oil at extremely low temperature.
In order to further illustrate the present invention, the following will describe the hydrolysis method of a silicone oil monomer in detail with reference to the examples, but it should not be construed as limiting the scope of the present invention.
Example 1
Adding 600g of water, 40g of concentrated sulfuric acid and 460g of octamethylcyclotetrasiloxane in sequence into a reaction vessel, slowly dropwise adding 40g of monomethyltriethoxysilane for 1 hour, reacting at 40 +/-5 ℃ for 3 hours after adding, standing to remove acid water, and washing with 50 ℃ water for three times to obtain the branched-chain silicone oil hydrolysate. The hydrolysis yield was calculated to be 91.0%.
Example 2
Adding 750g of water, 50g of concentrated sulfuric acid and 470g of octamethylcyclotetrasiloxane in sequence into a reaction vessel, slowly dropwise adding 30g of monomethyltrimethoxysilane for 1.5 hours, reacting at 40 +/-5 ℃ for 4 hours after the addition is finished, standing, removing acid water, and washing with 60 ℃ water for three times to obtain the branched-chain silicone oil hydrolysate. The hydrolysis yield was calculated to be 89.8%.
Example 3
Adding 750g of water, 60g of concentrated sulfuric acid and 450g of octamethylcyclotetrasiloxane into a reaction container, slowly dropwise adding 50g of monophenyl triethoxysilane for 2 hours, reacting at 45 +/-5 ℃ for 5 hours after adding, standing to remove acid water, and washing with 60 ℃ water for three times to obtain the branched-chain silicone oil hydrolysate. The hydrolysis yield was calculated to be 90.5%.
Comparative example 1:
500g of methylphenyldiethoxysilane and 30g of hydrochloric acid were added to a reaction vessel, 318g of water was slowly added dropwise over 1 hour, 1000g of water was then added thereto, and the mixture was reacted at 80 ℃ for 4 hours, left to stand to remove acid water, and washed three times with water at 60 ℃ to obtain a tolylene silicone oil hydrolysate. The hydrolysis rate was calculated to be 84.5%.
Comparative example 2:
600g of water, 40g of concentrated sulfuric acid, 300g of octamethylcyclotetrasiloxane and 200g of monomethyltriethoxysilane were added in sequence to a reaction vessel for 2 hours, and after the addition was completed, the reaction was carried out at 40. + -. 5 ℃ for 3 hours to obtain a non-flowable gel.
The properties of the silicone oils synthesized by using the hydrolysates in examples 1 to 3 and comparative example 1 are shown in table 1, and table 1 shows the properties of the silicone oils synthesized by using the hydrolysates in examples 1 to 3 and comparative example 1.
Table 1 properties of the silicone oils synthesized from the hydrolysates in inventive examples 1 to 3 and comparative example 1.
As can be seen from Table 1, the hydrolysis method of the present invention has high hydrolysis yield, and the silicone oil synthesized from the hydrolysate obtained by hydrolysis has excellent high and low temperature properties, especially outstanding low temperature properties.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for hydrolyzing a silicone oil monomer comprises the following steps:
sequentially adding a catalyst and a ring body into water, slowly dropwise adding a silicone oil monomer, and hydrolyzing to obtain a branched chain silicone oil hydrolysate;
the catalyst comprises hydrochloric acid and/or sulfuric acid; the mass ratio of the total mass of the silicone oil monomer and the ring body to the catalyst is 1: (0.04 to 0.12);
the charging time of the silicone oil monomer is 1-2 hours;
the ring body is octamethylcyclotetrasiloxane or a dimethyl cyclosiloxane mixture;
the silicone oil monomer comprises one or more of methyl triethoxysilane, methyl trimethoxysilane, phenyl triethoxysilane and phenyl trimethoxysilane;
the mass ratio of the silicone oil monomer to the ring body is (3-10): (90-97);
the mass ratio of the total mass of the silicone oil monomer and the ring body to the water is 1: (1-1.5);
the hydrolysis temperature is 30-50 ℃; the hydrolysis time is 3-5 hours.
2. The hydrolysis method according to claim 1, wherein the mass ratio of the silicone oil monomer to the ring body is (6-8): (92-94).
3. The hydrolysis method according to any one of claims 1 to 2, further comprising the following steps after the hydrolysis:
and standing the product obtained by hydrolysis, removing acid water, and washing with water until the pH value is 6-8 to obtain the branched silicone oil hydrolysate.
4. The hydrolysis method according to claim 3, wherein the temperature of the washing water is 50 to 70 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834133A (en) * | 2006-04-17 | 2006-09-20 | 广州天赐有机硅科技有限公司 | Branched benzene siliconic oil |
| CN103936997A (en) * | 2014-04-29 | 2014-07-23 | 东莞兆舜有机硅新材料科技有限公司 | Organopolysiloxane, and preparation method and application thereof |
| CN103952079A (en) * | 2014-05-15 | 2014-07-30 | 桂林电器科学研究院有限公司 | Photo-cured fluorine-containing organosilicone optical fiber coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000072968A (en) * | 1998-08-28 | 2000-03-07 | Dow Corning Toray Silicone Co Ltd | Aqueous silicone emulsion composition |
| DE102004022406A1 (en) * | 2004-05-06 | 2005-12-15 | Wacker-Chemie Gmbh | Polysiloxane graft polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834133A (en) * | 2006-04-17 | 2006-09-20 | 广州天赐有机硅科技有限公司 | Branched benzene siliconic oil |
| CN103936997A (en) * | 2014-04-29 | 2014-07-23 | 东莞兆舜有机硅新材料科技有限公司 | Organopolysiloxane, and preparation method and application thereof |
| CN103952079A (en) * | 2014-05-15 | 2014-07-30 | 桂林电器科学研究院有限公司 | Photo-cured fluorine-containing organosilicone optical fiber coating and preparation method thereof |
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