CN108409775B - Preparation method of 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane - Google Patents
Preparation method of 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane Download PDFInfo
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- CN108409775B CN108409775B CN201810246857.XA CN201810246857A CN108409775B CN 108409775 B CN108409775 B CN 108409775B CN 201810246857 A CN201810246857 A CN 201810246857A CN 108409775 B CN108409775 B CN 108409775B
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
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Abstract
The invention relates to a preparation method of 1-vinyl-1, 1,3,3, 3-pentamethyl disiloxane, which takes 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane and 1,1,1,3,3, 3-hexamethyl disiloxane as raw materials, carries out rearrangement reaction under the catalytic action of a complex catalyst KOH/18-crown ether-6, then neutralizes the catalyst, filters and rectifies filtrate to prepare a product. The invention adopts the macromolecular cyclic compound 18-crown ether-6 and KOH to form a complex catalyst, improves the activity of the catalyst through complex reaction, and can efficiently catalyze rearrangement reaction. Meanwhile, the preparation method is simple, the reaction is fast and stable, and the method has the advantages of high yield, good safety, environmental protection and the like.
Description
Technical Field
The invention belongs to the field of synthesis of organic silicon chemistry, and particularly relates to a preparation method of 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane.
Background
1-vinyl-1, 1,3,3, 3-pentamethyl disiloxane is an important organosilicon intermediate, and is characterized in that functional groups on two silicon are asymmetric, and a molecular structure has an active ethylene group, so that the structure can be used as a monomer for synthesizing an organosilicon compound to perform hydrosilylation with other hydrogen-containing compounds to prepare products with different properties, and the organosilicon intermediate has important functions in the fields of organosilicon chemistry and organic synthesis. Meanwhile, the 1-vinyl-1, 1,3,3, 3-pentamethyl disiloxane can also be used as a sealing head agent for synthesizing organosilicon polymers such as fluorosilicone oil, crude fluorosilicone rubber and the like, one end of a high polymer prepared from the polysiloxane is an inert methyl group, and the other end of the high polymer is an active vinyl group, so that the vinyl group and other crude rubber molecules form a bridging structure in the vulcanization process of the fluorosilicone rubber, and methyl end molecules are dissociated outside the system to form a semi-interpenetrating winding structure, thereby being more beneficial to the fluorosilicone rubber to resist the invasion of foreign small molecules and improving the oil resistance of the rubber. Therefore, the 1-vinyl-1, 1,3,3, 3-pentamethyl disiloxane has important industrial utilization value and good application prospect, and the invention of the high-efficiency preparation method has important significance.
In the prior art, a preparation method of vinyl pentamethyl disiloxane is mainly obtained by carrying out cohydrolysis on vinyl dimethylchlorosilane and trimethylchlorosilane in equal moles at a low temperature and then condensing. The preparation method has complex reaction and is difficult to control, and due to different hydrolysis rates of the vinyl dimethylchlorosilane and the trimethylchlorosilane, the products obtained mainly comprise divinyl tetramethyldisiloxane and hexamethyldisiloxane by hydrolysis condensation in the cohydrolysis process, and the selectivity and the yield of the vinyl pentamethyldisiloxane are low. In addition, the method adopts chlorosilane as a reaction raw material, so that the stability is poor, hydrochloric acid vapor is easily generated in the operation process, the physical health and the environmental safety are seriously harmed, and a large amount of acid water generated after the hydrolysis is finished further generates environmental protection pressure.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the 1-vinyl-1, 1,3,3, 3-pentamethyl disiloxane, which has the advantages of simple preparation method, stable and efficient reaction and short reaction time. The method solves the problems of environmental protection, poor selectivity and the like caused by using chlorosilane in the prior art, and has the advantages of high yield, good safety, environmental protection and the like.
The technical scheme of the invention is as follows:
a method for preparing 1-vinyl-1, 1,3,3, 3-pentamethyl disiloxane comprises the following steps:
uniformly mixing 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 1,1,1,3,3, 3-hexamethyldisiloxane, adding a complexing catalyst KOH/18-crown ether-6, stirring, heating to 70-90 ℃ for rearrangement reaction, adding a neutralizing agent into the system for neutralization reaction, cooling, filtering, collecting filtrate, and rectifying to obtain the 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane.
According to the present invention, it is preferred that the 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and the 1,1,1,3,3, 3-hexamethyldisiloxane are mixed in a molar ratio of 1: (1.1-1.5) mixing uniformly.
According to the invention, preferably, the complex catalyst KOH/18-crown-6 is formed by the complex reaction of 18-crown-6 and KOH;
preferably, in the complex catalyst KOH/18-crown ether-6, the feeding amount of KOH is 0.1-1% to 1% of the total mass of 1, 3-divinyl-1, 1,3,3, -tetramethyldisiloxane and 1,1,1,3,3, 3-hexamethyldisiloxane;
preferably, in the complex catalyst KOH/18-crown ether-6, the feeding amount of 18-crown ether-6 is 20-80% of the feeding amount of KOH.
According to the invention, the rearrangement reaction time is preferably 0.5-2 h.
According to the invention, preferably, the neutralizing agent is anhydrous acetic acid, and the neutralizing reaction is carried out until the system is neutral.
According to the invention, preferably, the temperature is reduced to room temperature (20-25 ℃) after the neutralization reaction is finished.
According to the invention, preferably, the rectification conditions are that the pressure is-0.082 MPa to-0.096 MPa, and the kettle temperature is 50-80 ℃;
preferably, the reflux ratio of the rectification is preferably 8-10: 1.
The present invention has not been described in detail, but is in accordance with conventional techniques in the art.
Compared with the prior art, the invention has the following technical characteristics and beneficial effects:
1. the invention adopts a macromolecular cyclic compound 18-crown ether-6 and KOH to form a complex catalyst, in the catalyst, the 18-crown ether-6 and potassium ions carry out complex reaction, the potassium ions are complexed into an inner space of a ring and are dissolved in a reaction system in an ion pair form, the activity of the catalyst is improved, and the catalyst can efficiently catalyze 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 1,1,1,3,3, 3-hexamethyldisiloxane to carry out rearrangement reaction at lower temperature, and has the characteristics of high reaction speed, high catalysis efficiency and the like.
2. The invention adopts an anhydrous rearrangement reaction system, avoids the defect of disordered and complex products caused by a hydrolysis reaction system, and has the advantages of mild reaction conditions and high product selectivity.
3. The method does not use chlorosilane raw materials, solves the problems of a large amount of acid water and environmental pollution caused by a chlorosilane process in the prior art, and reduces the pressure of environmental protection.
4. The preparation method is simple and easy to control, and the product has high yield and high purity.
Drawings
FIG. 1 is a diagram of 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane, a product prepared in example 1 of the present invention1H-NMR spectrum.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The starting materials described in the examples are conventional and are commercially available or prepared according to the prior art.
Example 1
Adding 744g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 712.8g of 1,1,1,3,3, 3-hexamethyldisiloxane into a 2L three-neck flask provided with a stirrer, a thermometer and a condenser, uniformly mixing, then adding a mixture of 4.37g of KOH and 2.19g of 18-crown ether-6 into the flask, violently stirring, starting heating and slowly heating to 80 ℃ for rearrangement reaction, maintaining the reaction for 1h, then adding 4.96g of anhydrous acetic acid into the system for neutralization reaction, cooling the reaction mixture to room temperature, filtering, collecting filtrate, rectifying under the conditions of pressure of-0.082 MPa to-0.096 MPa and kettle temperature of 50-80 ℃, wherein the reflux ratio of rectification is 10: 1; 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane is prepared, the purity is 99.32 percent, and the yield is 95.7 percent.
Example 2
Adding 744g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 712.8g of 1,1,1,3,3, 3-hexamethyldisiloxane into a 2L three-neck flask provided with a stirrer, a thermometer and a condenser, uniformly mixing, then adding a mixture of 7.28g of KOH and 2.19g of 18-crown ether-6 into the flask, violently stirring, starting heating and slowly heating to 80 ℃ for rearrangement reaction, maintaining the reaction for 1h, then adding 8.08g of anhydrous acetic acid into the system for neutralization reaction, cooling the reaction mixture to room temperature, filtering, collecting filtrate, rectifying under the conditions of pressure of-0.082 MPa to-0.096 MPa and kettle temperature of 50-80 ℃, wherein the reflux ratio of rectification is 10: 1; 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane is prepared, the purity is 99.25 percent, and the yield is 95.2 percent.
Example 3
Adding 744g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 712.8g of 1,1,1,3,3, 3-hexamethyldisiloxane into a 2L three-neck flask provided with a stirrer, a thermometer and a condenser, uniformly mixing, then adding a mixture of 7.28g of KOH and 3.64g of 18-crown ether-6 into the flask, violently stirring, starting heating and slowly heating to 80 ℃ for rearrangement reaction, maintaining the reaction for 1h, then adding 8.08g of anhydrous acetic acid into the system for neutralization reaction, cooling the reaction mixture to room temperature, filtering, collecting filtrate, rectifying under the conditions of pressure of-0.082 MPa to-0.096 MPa and kettle temperature of 50-80 ℃, wherein the reflux ratio of rectification is 9: 1; 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane is prepared, the purity is 99.58 percent, and the yield is 96.2 percent.
Example 4
Adding 744g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 712.8g of 1,1,1,3,3, 3-hexamethyldisiloxane into a 2L three-neck flask provided with a stirrer, a thermometer and a condenser, uniformly mixing, then adding a mixture of 7.28g of KOH and 5.09g of 18-crown ether-6 into the flask, violently stirring, starting heating and slowly heating to 80 ℃ for rearrangement reaction, maintaining the reaction for 1h, then adding 8.08g of anhydrous acetic acid into the system for neutralization reaction, cooling the reaction mixture to room temperature, filtering, collecting filtrate, rectifying under the conditions of pressure of-0.082 MPa to-0.096 MPa and kettle temperature of 50-80 ℃, wherein the reflux ratio of rectification is 10: 1; 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane is prepared, the purity is 99.45 percent, and the yield is 94.8 percent.
Example 5
Adding 744g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 712.8g of 1,1,1,3,3, 3-hexamethyldisiloxane into a 2L three-neck flask provided with a stirrer, a thermometer and a condenser, uniformly mixing, then adding a mixture of 11.66g of KOH and 5.83g of 18-crown ether-6 into the flask, violently stirring, starting heating and slowly heating to 80 ℃ for rearrangement reaction, maintaining the reaction for 1h, then adding 12.77g of anhydrous acetic acid into the system for neutralization reaction, cooling the reaction mixture to room temperature, filtering, collecting filtrate, rectifying under the conditions of pressure of-0.082 MPa to-0.096 MPa and kettle temperature of 50-80 ℃, wherein the reflux ratio of rectification is 8: 1; 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane is prepared, the purity is 99.08 percent, and the yield is 94.6 percent.
Comparative example 1
Adding 744g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 712.8g of 1,1,1,3,3, 3-hexamethyldisiloxane into a 2L three-neck flask provided with a stirrer, a thermometer and a condenser, uniformly mixing, then adding only 4.37g of KOH into the flask, vigorously stirring, starting heating, slowly heating to 80 ℃ for reaction, maintaining the reaction for 1h, analyzing by gas chromatography, generating no 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane, continuously prolonging the reaction time to 5h, generating no product, and prolonging the reaction time to 12h, wherein the product is still generated; the reaction system was maintained, KOH was added to the flask to 11.66g, and the reaction was maintained for 5 hours, and by gas chromatography, no 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane was produced in the system.
Comparative example 1 the procedure of the example was repeated, but the catalyst was KOH, and the reaction progress was analyzed by gas chromatography, and it was found that no 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane was produced in the system, and no product was produced even if the reaction time was prolonged and the amount of KOH added was increased.
Comparative example 2
Adding 1000g of distilled water into a 2L four-neck flask provided with a stirrer, a thermometer and a condenser, synchronously dropwise adding 108.5g of trimethylchlorosilane and 120.5g of vinyldimethylchlorosilane through two constant-pressure dropping funnels to carry out cohydrolysis reaction, keeping the dropwise adding speed consistent as much as possible, cooling the system by adopting an ice water bath, maintaining the dropwise adding temperature at 0-10 ℃, continuing stirring for 2 hours after dropwise adding is finished, then standing for layering, washing an upper organic phase to be neutral, and drying to obtain a cohydrolysate.
The co-hydrolysate was analyzed by gas chromatography, the components in the product were very complex, the main products were divinyltetramethyldisiloxane and hexamethyldisiloxane, and the yield of 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane was very low.
Claims (6)
1. A method for preparing 1-vinyl-1, 1,3,3, 3-pentamethyl disiloxane comprises the following steps:
uniformly mixing 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 1,1,1,3,3, 3-hexamethyldisiloxane, adding a complexing catalyst KOH/18-crown ether-6, stirring, heating to 70-90 ℃, carrying out rearrangement reaction for 0.5-2 h, adding a neutralizing agent into the system for neutralization reaction, cooling, filtering, collecting filtrate, and rectifying to obtain 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane; in the complex catalyst KOH/18-crown ether-6, the feeding amount of KOH is 0.1-1 percent of the total mass of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane and 1,1,1,3,3, 3-hexamethyldisiloxane, and the feeding amount of 18-crown ether-6 is 20-80 percent of the feeding amount of KOH.
2. The method of preparing 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane according to claim 1, wherein the molar ratio of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane to 1,1,1,3,3, 3-hexamethyldisiloxane is 1: (1.1-1.5) mixing uniformly.
3. The method for preparing 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane as claimed in claim 1, wherein the neutralizing agent is anhydrous acetic acid, and the neutralizing reaction is carried out until the system is neutral.
4. The method for producing 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane according to claim 1, wherein the temperature is reduced to room temperature after the completion of the neutralization reaction.
5. The method for preparing 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane as claimed in claim 1, wherein the rectification conditions are-0.082 MPa to-0.096 MPa of pressure and 50-80 ℃ of kettle temperature.
6. The method for preparing 1-vinyl-1, 1,3,3, 3-pentamethyldisiloxane as claimed in claim 1, wherein the reflux ratio of the rectification is 8-10: 1.
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| CN106986890A (en) * | 2017-06-07 | 2017-07-28 | 威海新元化工有限公司 | A kind of environment-friendly preparation method of the pentamethyl cyclotrisiloxane of 2 vinyl 2,4,4,6,6 |
| CN107235996A (en) * | 2017-06-16 | 2017-10-10 | 壮铭新材料科技江苏有限公司 | A kind of preparation method and application of trimethyl silicane alkoxide |
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| CN106986890A (en) * | 2017-06-07 | 2017-07-28 | 威海新元化工有限公司 | A kind of environment-friendly preparation method of the pentamethyl cyclotrisiloxane of 2 vinyl 2,4,4,6,6 |
| CN107235996A (en) * | 2017-06-16 | 2017-10-10 | 壮铭新材料科技江苏有限公司 | A kind of preparation method and application of trimethyl silicane alkoxide |
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