CN110156826B - Diphenyl cyclotrisiloxane and preparation method and application thereof - Google Patents
Diphenyl cyclotrisiloxane and preparation method and application thereof Download PDFInfo
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- CN110156826B CN110156826B CN201910536793.1A CN201910536793A CN110156826B CN 110156826 B CN110156826 B CN 110156826B CN 201910536793 A CN201910536793 A CN 201910536793A CN 110156826 B CN110156826 B CN 110156826B
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- C07F7/02—Silicon compounds
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- 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
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- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
Abstract
The invention relates to diphenyl cyclotrisiloxane and a preparation method and application thereof, wherein trisiloxane with two ends being chlorine is prepared by reacting trifluoropropyl methyl dichlorosilane and diphenyl silanediol, and then the trisiloxane is subjected to hydrolytic condensation to cause intramolecular cyclization, and a target product is prepared directionally through two-step reaction. The method not only inhibits the occurrence of side reaction, but also greatly improves the yield of the cyclotrisiloxane, and has the advantages of high efficiency, simple and convenient operation, high product purity and the like.
Description
Technical Field
The invention belongs to the field of synthesis of organic silicon compounds, and particularly relates to 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane and a preparation method and application thereof.
Background
The fluorosilicone rubber is a special synthetic material with a main chain of a silica structure and side chains of methyl and trifluoropropyl structures, and is mainly prepared by 1,3, 5-trimethyl-1, 3, 5-tri (3,3, 3-trifluoropropyl) cyclotrisiloxane (D)3F) Ring-opening polymerization. The special chemical structure of the material enables the material to have a plurality of unique functions, the flexibility and the thermal stability of the fluorosilicone rubber are endowed by the Si-O-Si structure of the main chain, and the good oil resistance and the solvent resistance of the fluorosilicone rubber are endowed by the side chain structure of trifluoropropyl. However, trifluoropropyl groups are more easily decomposed at high temperatures than methyl groups, and fluoride is formed, so that the heat resistance is not as good as that of methyl vinyl silicone rubber, and the application is limited to a certain extent.
With the continuous development of the application field of the fluorosilicone rubber, higher requirements are provided for the heat resistance of the fluorosilicone rubber, and how to improve the heat resistance and the aging resistance of the fluorosilicone rubber is an important development direction of the fluorosilicone rubber. The phenyl silicone rubber has good thermal oxidation stability, and due to the introduction of phenyl, the internal rotation resistance of a silicone rubber molecular chain is increased, and free radicals generated in a high-temperature process can be stabilized, so that the high-temperature resistance of the material is improved.
At present, there are data indicating that phenyl-containing cyclosiloxane and 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D) are used to address the heat resistance problem of fluorosilicone rubber3F) By means of copolymerization, the product has excellent heat resistanceThe sexual phenyl is introduced into the molecular chain of the fluorosilicone rubber, so that the heat resistance of the fluorosilicone rubber is improved. However, in the copolymerization process, due to the difference of different ring structures and side chain groups of the two monomers, the difference of ring-opening activities of the two monomers is large, the copolymerization effect is poor, and the problem of poor heat resistance of the fluorosilicone rubber cannot be effectively solved. Thus, a compound was invented which reacts with 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D)3F) Cyclosiloxanes with close ring-opening activity and containing phenyl groups are of particular importance.
Chinese patent CN1181081C discloses a fluorine-containing mixed cyclosiloxane, which is prepared by reacting a mixed raw material of fluorine-containing alkyl methyl dichlorosilane and dialkyl dichlorosilane with a metal oxide or an alkali metal carbonate at the temperature of between 20 ℃ below zero and 80 ℃ for dechlorination. The structural formula of the fluorine-containing cyclosiloxane is as follows:
wherein R is1＝C1～4Alkyl, phenyl of (a); r2Methyl, phenyl; m is 0, 1, 2; n is an integer of 3-10; x is 2, 3; and Y is an integer of 0-11. The cyclosiloxane can form cyclotrisiloxane only when m is 0 and n is 3, but the cyclotrisiloxane only has a fluorine-containing group and cannot form a mixed structure; when m is 1 or 2 and n is an integer of 3-10, the cyclosiloxane contains at least four siloxane units, namely, the cyclosiloxane is minimum, and the cyclotrisiloxane with a mixed structure can not be obtained.
Chinese patent CN105085567A discloses a preparation method of polyfunctional group co-substituted cyclosiloxane and cyclosiloxane mixture. Adding weak base or metal oxide or metal carbonate into a mixed system consisting of water and an organic solvent by using methyldichlorosilane or methyldiphenylsilane, maintaining the temperature of the system at 0-80 ℃, and carrying out a cohydrolysis reaction to obtain a mixture of cyclosiloxane. According to the method, a plurality of chlorosilanes are subjected to co-hydrolysis reaction to obtain different cyclosiloxanes, the selectivity of the cyclosiloxanes with specific structures is poor, the total product is a mixture of various cyclosiloxanes, and the target product cannot be efficiently obtained.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane and a preparation method thereof. The invention firstly prepares trisiloxane with the end group of chlorine, then hydrolyzes and condenses the trisiloxane to make the trisiloxane cyclize in the molecule, and prepares the target product directionally through two steps of reactions.
The technical scheme of the invention is as follows:
1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane having the structure:
according to the present invention, the above-mentioned 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane is prepared by the steps of:
dropwise adding an organic solvent system of diphenyl silanediol and triethylamine into an organic solvent system of trifluoropropylmethyldichlorosilane, and stirring for reaction;
after the reaction is finished, the obtained 1, 5-dichloro-1, 5-dimethyl-1, 5-di (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution is dripped into water for hydrolytic cyclization reaction, and then the 1, 3-dimethyl-1, 3-di (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane is obtained.
According to the present invention, it is preferable that the organic solvent system of diphenylsilanediol and triethylamine is the same as the organic solvent system of trifluoropropylmethyldichlorosilane; the feeding amount of the organic solvent in the organic solvent system of the diphenyl silanediol and the triethylamine is 2-3 times of the feeding amount of the diphenyl silanediol, and the feeding amount of the organic solvent in the organic solvent system of the trifluoropropylmethyl dichlorosilane is 2-3 times of the feeding amount of the trifluoropropylmethyl dichlorosilane;
the preferred organic solvent is ethyl acetate.
According to the invention, the preferred mixed reaction of the organic solvent system of diphenyl silanediol and triethylamine and the organic solvent system of trifluoropropylmethyl dichlorosilane is carried out under the protection of protective gas, and the preferred protective gas is nitrogen or argon;
preferably, the reaction temperature is 0-20 ℃, and the reaction time is 1-3 h;
preferably, the feeding molar ratio of the diphenyl silicon glycol to the trifluoropropylmethyl dichlorosilane is 1: (2.0-2.2), the feeding molar ratio of triethylamine to trifluoropropylmethyldichlorosilane is 1: (1.0-1.2).
According to the invention, after the reaction is completed, the system is filtered to remove triethylamine hydrochloride, and 1, 5-dichloro-1, 5-dimethyl-1, 5-di (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution is obtained;
preferably, the temperature of the hydrolytic cyclization reaction is 0-10 ℃, and the reaction time is 1-2 h;
preferably, the feeding amount of the water is 2 to 5 times of the feeding mass of the trifluoropropylmethyldichlorosilane.
According to the invention, after the hydrolytic cyclization reaction is finished, the system is stood for layering, and the organic phase is taken out and washed to be neutral;
rectifying the organic phase under vacuum condition to obtain purified 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane;
preferably, the washing temperature is 20-50 ℃, and the washing time is 0.5-1 h;
preferably, the rectification conditions are-0.099 MPa pressure and 174-176 ℃; namely, the fraction with the temperature of 174-; further preferably, the reflux ratio of the rectification process is controlled to be (8-10): 1.
according to the present invention, a method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane comprises the steps of:
(1) under the protection of inert gas, uniformly mixing an organic solvent, diphenyl silanediol and triethylamine to form a transparent solution, slowly dropwise adding the transparent solution into a system of trifluoropropyl methyl dichlorosilane and the same organic solvent, quickly stirring, maintaining the reaction at 0-20 ℃, and after dropwise adding, keeping the temperature of 0-20 ℃ and continuously stirring for 1-3 hours;
(2) after the reaction is completed, filtering the system to remove triethylamine hydrochloride, and obtaining 1, 5-dichloro-1, 5-dimethyl-1, 5-di (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution;
(3) dropwise adding the 1, 5-dichloro-1, 5-dimethyl-1, 5-di (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution obtained in the step (2) into water at 0-10 ℃ to perform hydrolytic cyclization reaction, and after dropwise adding is completed, keeping the temperature of 0-10 ℃ and continuing stirring for 1-2 hours;
(4) standing and layering, taking out an organic phase and washing the organic phase to be neutral;
(5) the organic phase was rectified under vacuum to give 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane.
According to the invention, 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane is used for preparing high temperature resistant fluoro-silicone rubber, in particular for preparing high temperature resistant fluoro-silicone rubber by ring-opening copolymerization with 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane.
The reaction equation of the invention is as follows:
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 utilizes the reaction of trifluoropropylmethyl dichlorosilane and diphenyl silanediol to prepare the trisiloxane with chlorine at two ends, and then the trisiloxane is subjected to hydrolysis reaction at low temperature, compared with dichlorosilane, the trisiloxane with chlorine at two ends is easier to perform intramolecular condensation, the generation of linear polymers is reduced, the cyclotrisiloxane is beneficial to generating, and the target product is directionally prepared by two steps of reaction, so that the efficiency is high.
2. Compared with various chlorosilane cohydrolysis reactions, the method avoids the defects of complex products and poor selectivity of target products caused by the difference of respective hydrolysis activities of different chlorosilanes, and has the advantages of less impurities, high purity and clear target.
3. The preparation method has the advantages of simple and convenient process, simple and convenient operation, recyclable solvent, reduced production cost and easy realization of industrial production.
4.1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to the invention and 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D)3F) The ring-opening activity is close to that of the fluorine-silicon rubber, the fluorine-silicon rubber contains phenyl, the copolymerization reaction effect of the phenyl and the fluorine-silicon rubber is good, and the obtained fluorine-silicon rubber has excellent heat resistance.
Drawings
FIG. 1 shows the product obtained by reactive distillation in example 1 of the present invention1H-NMR spectrum.
FIG. 2 is a TGA graph of the fluorosilicone raw rubber prepared in application example 1 of the present invention and a common fluorosilicone raw rubber.
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
A method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane, comprising the steps of:
(1) under the protection of nitrogen, adding 1055g of trifluoropropylmethyldichlorosilane and 540g of ethyl acetate into a 5L four-neck flask provided with a mechanical stirrer, a thermometer, a constant-pressure dropping funnel and a vent pipe, uniformly mixing 1080g of ethyl acetate, 540g of diphenylsilanediol and 555.5g of triethylamine to form a transparent solution, then adding the transparent solution into the constant-pressure dropping funnel, starting stirring, slowly dropping the materials in the constant-pressure dropping funnel into the flask, cooling the system by adopting an ice-water bath, maintaining the reaction at 0-20 ℃ until the dropping of the materials is finished, and then keeping the temperature of 0-20 ℃ to continue stirring for 2 hours;
(2) after the reaction is completed, filtering the system to remove triethylamine hydrochloride, wherein a filter cake is washed by 200g of ethyl acetate, and collecting filtrate to obtain a 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution;
(3) 4220g of water is added into another 10L four-neck flask which is provided with a mechanical stirrer, a thermometer, a constant pressure dropping funnel and a vent pipe, the 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution obtained in the step (2) is dropped into water through the constant pressure dropping funnel for hydrolysis cyclization reaction, the system is cooled by adopting an ice water bath, the dropping temperature is maintained at 0-10 ℃ until the dropping of the materials is finished, and then the stirring is continued for 1 hour under the temperature of 0-10 ℃;
(4) standing and layering, separating a lower organic phase, washing the organic phase with water at 20-30 ℃ for 1h until the system becomes neutral, and obtaining an organic phase crude product;
(5) collecting an organic phase, separating and recovering ethyl acetate under the condition of negative pressure, then rectifying and purifying by adopting a reflux ratio of 10:1, and intercepting a fraction with 174-fold and 176 ℃/-0.099MPa, namely the product 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane with the purity of 99.12 percent and the yield of 82.4 percent.
The nuclear magnetic hydrogen spectrum of the product is shown in figure 1, chemical shift peaks of hydrogen in a typical silicon phenyl group are at 7.41-7.67ppm, wherein chemical shifts of H at ortho-position of carbon connected with silicon are at 7.64-7.67ppm, the integrated area is 1, chemical shifts of H at meta-position and para-position of carbon connected with silicon are at 7.41-7.51ppm, the integrated area is 1.5, and the two represent hydrogen in the phenyl group; Si-CH at 2.00-2.13ppm2CH2CF3Middle near-CF3The integrated area of the chemical shift of methylene H of (2) is 1, and Si-CH is present at 0.87-0.95ppm2CH2CF3The integral area of the chemical shift of methylene H close to Si is 1;Si-CH at 0.20-0.33ppm3Chemical shift of medium H, integrated area 1.5; the integrated area ratio of H in the three groups is 2:3:2:2:3, and the product can be determined to be 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane.
Example 2
A method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane, comprising the steps of:
(1) under the protection of nitrogen, 1107.8g of trifluoropropylmethyldichlorosilane and 540g of ethyl acetate are added into a 5L four-neck flask provided with a mechanical stirrer, a thermometer, a constant-pressure dropping funnel and a vent pipe, 1080g of ethyl acetate, 540g of diphenylsilanediol and 583.3g of triethylamine are uniformly mixed to form a transparent solution, then the transparent solution is added into the constant-pressure dropping funnel, stirring is started, the materials in the constant-pressure dropping funnel are slowly dropped into the flask, the system is cooled by adopting an ice-water bath, the reaction is maintained at 0-20 ℃ until the dropping of the materials is finished, and then the stirring is continued for 2 hours at 0-20 ℃;
(2) after the reaction is completed, filtering the system to remove triethylamine hydrochloride, wherein a filter cake is washed by 200g of ethyl acetate, and collecting filtrate to obtain a 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution;
(3) adding 4432g of water into another 10L four-neck flask provided with a mechanical stirrer, a thermometer, a constant pressure dropping funnel and a vent pipe, dropping the 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution obtained in the step (2) into water through the constant pressure dropping funnel for hydrolysis cyclization reaction, cooling the system by adopting an ice water bath, maintaining the dropping temperature at 0-10 ℃ until the dropping of the materials is finished, and then keeping the temperature at 0-10 ℃ and continuing stirring for 1 h;
(4) standing and layering, separating a lower organic phase, washing the organic phase with water at 20-30 ℃ for 1h until the system becomes neutral, and obtaining an organic phase crude product;
(5) collecting an organic phase, separating and recovering ethyl acetate under the condition of negative pressure, then rectifying and purifying by adopting a reflux ratio of 10:1, and intercepting a fraction with 174-fold and 176 ℃/-0.099MPa, namely the product 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane with the purity of 99.08 percent and the yield of 81.5 percent.
Example 3
A method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane, comprising the steps of:
(1) under the protection of nitrogen, 1160.5g of trifluoropropylmethyldichlorosilane and 540g of ethyl acetate are added into a 5L four-neck flask provided with a mechanical stirrer, a thermometer, a constant-pressure dropping funnel and a vent pipe, 1080g of ethyl acetate, 540g of diphenylsilanediol and 611.1g of triethylamine are uniformly mixed to form a transparent solution, then the transparent solution is added into the constant-pressure dropping funnel, stirring is started, the materials in the constant-pressure dropping funnel are slowly dropped into the flask, the system is cooled by adopting an ice-water bath, the reaction is maintained at 5-15 ℃ until the dropping of the materials is finished, and then the stirring is continued for 2 hours at 5-15 ℃;
(2) after the reaction is completed, filtering the system to remove triethylamine hydrochloride, wherein a filter cake is washed by 200g of ethyl acetate, and collecting filtrate to obtain a 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution;
(3) adding 4642g of water into another 10L four-neck flask provided with a mechanical stirrer, a thermometer, a constant pressure dropping funnel and a vent pipe, dropping the 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution obtained in the step (2) into water through the constant pressure dropping funnel to perform hydrolytic cyclization reaction, cooling the system by adopting an ice water bath, maintaining the dropping temperature at 0-10 ℃ until the dropping of the materials is finished, and then keeping the temperature at 0-10 ℃ to continue stirring for 2 hours;
(4) standing and layering, separating a lower organic phase, washing the organic phase with water at 20-30 ℃ for 1h until the system becomes neutral, and obtaining an organic phase crude product;
(5) collecting an organic phase, separating and recovering ethyl acetate under the condition of negative pressure, then rectifying and purifying by adopting a reflux ratio of 10:1, and intercepting a fraction with 174-fold and 176 ℃/-0.099MPa, namely the product 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane with the purity of 99.25 percent and the yield of 80.8 percent.
Example 4
A method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane, comprising the steps of:
(1) under the protection of nitrogen, 1107.8g of trifluoropropylmethyldichlorosilane and 540g of ethyl acetate are added into a 5L four-neck flask provided with a mechanical stirrer, a thermometer, a constant-pressure dropping funnel and a vent pipe, 1080g of ethyl acetate, 540g of diphenylsilanediol and 636.3g of triethylamine are uniformly mixed to form a transparent solution, then the transparent solution is added into the constant-pressure dropping funnel, stirring is started, the material in the constant-pressure dropping funnel is slowly dropped into the flask, the system is cooled by adopting an ice-water bath, the reaction is maintained at 0-10 ℃ until the material is dropped completely, and then stirring is continued for 2 hours at 0-10 ℃;
(2) after the reaction is completed, filtering the system to remove triethylamine hydrochloride, wherein a filter cake is washed by 200g of ethyl acetate, and collecting filtrate to obtain a 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution;
(3) adding 4432g of water into another 10L four-neck flask provided with a mechanical stirrer, a thermometer, a constant pressure dropping funnel and a vent pipe, dropping the 1, 5-dichloro-1, 5-dimethyl-1, 5-bis (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution obtained in the step (2) into water through the constant pressure dropping funnel for hydrolysis cyclization reaction, cooling the system by adopting an ice water bath, maintaining the dropping temperature at 0-10 ℃ until the dropping of the materials is finished, and then keeping the temperature at 0-10 ℃ for stirring for 2 hours;
(4) standing and layering, separating a lower organic phase, washing the organic phase with water at 20-30 ℃ for 1h until the system becomes neutral, and obtaining an organic phase crude product;
(5) collecting an organic phase, separating and recovering ethyl acetate under the condition of negative pressure, then rectifying and purifying by adopting a reflux ratio of 10:1, and intercepting a fraction with 174-fold and 176 ℃/-0.099MPa, namely the product 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane with the purity of 99.32 percent and the yield of 82.6 percent.
Comparative example
Under the protection of nitrogen, 4220g of water and 540g of ethyl acetate are added into a 10L four-neck flask provided with a mechanical stirrer, a thermometer, a constant-pressure dropping funnel and a vent pipe, 1080g of ethyl acetate, 1055g of trifluoropropylmethyldichlorosilane and 632.5g of diphenyldichlorosilane are uniformly mixed and added into the constant-pressure dropping funnel, stirring is started, the materials in the constant-pressure dropping funnel are slowly dropped into the flask for cohydrolysis reaction, the system is cooled by adopting an ice water bath, the reaction is maintained at 0-10 ℃ until the dropping of the materials is finished, and the stirring is continued for 1-2 hours at 0-10 ℃. Then standing for layering, separating out the lower organic phase, washing with water to neutrality, and drying to obtain co-hydrolysate.
The product contains various cyclosiloxanes and linear polysiloxanes with different chain numbers by GC-MS analysis, the components are numerous and disordered, and the selectivity of the target product 1, 3-dimethyl-1, 3-di (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane is poor and the yield is low.
Application example 1
1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D) was added to a 1L four-necked flask equipped with a mechanical stirrer, a thermometer, a condenser and a snorkel under nitrogen protection3F)530.4g of 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane prepared in example 1, 7.2g of 1-vinyl-3-hydroxy-1, 1,3, 3-tetramethyldisiloxane (purity: 96%) and 0.48g of sodium hydroxide silanolate (NaOH content: 4.05%), and the mixture was stirred uniformly; heating, raising the temperature of the kettle to 125 ℃, maintaining the copolymerization reaction for 3 hours after small bubbles appear in the system, and maintaining the pressure between-0.04 MPa and-0.08 MPa in the copolymerization reaction process; and after the reaction is completed, adding 0.6g of silicon-based phosphate ester neutralization catalyst into the bottle, heating the system to 200-220 ℃ under the pressure of-0.099 MPa, removing low-boiling-point micromolecules, and cooling to room temperature to obtain the phenyl-containing fluorosilicone raw rubber.
The product appearance is as follows: clear and transparent, yield: 96.5%, viscosity: 21600cp (25 ℃), volatile matter: 1.02% (200 ℃ C. times.4 h), vinyl mass fraction: 0.138 percent.
Application example 2
Under the protection of nitrogen, 1,3, 5-trimethyl-1, 3, 5-plus-material is added into a 1L four-neck flask which is provided with a mechanical stirring device, a thermometer, a condensation tube and a vent pipeTris (3,3, 3-trifluoropropyl) cyclotrisiloxane (D)3F)530.4g of methylphenylcyclosiloxane (D)nPh, n is 3-5) 102g, 1-vinyl-3-hydroxy-1, 1,3, 3-tetramethyldisiloxane (purity 96%) 7.2g and sodium hydroxide silicon alkoxide (NaOH content 4.05%) 0.48g, and stirring uniformly; heating is started, the temperature of the kettle is raised to 125 ℃ and maintained for 3 hours, the system is very thin, and no reaction sign exists; the temperature of the kettle is raised to 160 ℃, the kettle is continuously maintained for 3 hours, and the system still has no reaction sign; and (4) turning off the heating, cooling the system to room temperature, wherein the material is very thin and the appearance is milky turbid.
In the course of the reaction, D3F and DnThe relative ring opening rates of Ph are very different and copolymerization cannot be well carried out; even if the reaction temperature is raised to 160 ℃, D cannot be solved3F and DnPh reactivity ratio difference problem, and D is hardly initiated in the catalytic systemnPh ring opening polymerization.
The phenyl group-containing fluorosilicone raw rubber (sample 1) prepared in application example 1 and the ordinary fluorosilicone raw rubber (sample 2) were placed in an air drying oven to be subjected to a heat resistance test under the experimental conditions of 260 ℃ for 5 hours, and the test results are shown in table 1.
TABLE 1
When the phenyl-containing fluorosilicone raw gum (sample 1) prepared in application example 1 and the ordinary fluorosilicone raw gum (sample 2) were subjected to thermogravimetric analysis in an oxygen atmosphere, the initial decomposition temperature of sample 1 was 394.1 ℃, the initial decomposition temperature of sample 2 was 343.2 ℃, and the initial decomposition temperature of sample 1 was increased by 50.9 ℃ as compared to sample 2, as shown in fig. 2.
By combining the test results, in the molecular structure of the fluorosilicone raw rubber, due to the introduction of phenyl groups, the thermal oxidative degradation of the raw rubber is inhibited, the overall heat resistance of the polymer is improved, and the initial decomposition temperature of the fluorosilicone raw rubber is greatly increased; in addition, the raw rubber is stable at 260 ℃, is not crosslinked or caked and still has fluidity, which shows that the 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane of the invention has obvious improvement effect on the high temperature resistance of the fluorosilicone rubber.
Claims (15)
1.1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane having the structure:
2. a method of preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 1, comprising the steps of:
dropwise adding an organic solvent system of diphenyl silanediol and triethylamine into an organic solvent system of trifluoropropylmethyldichlorosilane, and stirring for reaction;
after the reaction is finished, the obtained 1, 5-dichloro-1, 5-dimethyl-1, 5-di (3,3, 3-trifluoropropyl) -3, 3-diphenyl trisiloxane solution is dripped into water for hydrolytic cyclization reaction, and then the 1, 3-dimethyl-1, 3-di (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane is obtained.
3. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the organic solvent system of diphenylsilanediol and triethylamine is the same kind of organic solvent as that of trifluoropropylmethyldichlorosilane; the dosage of the organic solvent in the organic solvent system of the diphenyl silanediol and the triethylamine is 2-3 times of the dosage of the diphenyl silanediol, and the dosage of the organic solvent in the organic solvent system of the trifluoropropylmethyl dichlorosilane is 2-3 times of the dosage of the trifluoropropylmethyl dichlorosilane.
4. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the organic solvent is ethyl acetate.
5. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the mixing reaction of the organic solvent system of diphenylsilanediol and triethylamine and the organic solvent system of trifluoropropylmethyldichlorosilane is carried out under a protective gas atmosphere.
6. The method of claim 5, wherein the protective gas is nitrogen or argon.
7. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the reaction temperature is 0-20 ℃ and the reaction time is 1-3 h.
8. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the molar ratio of the diphenylsilanediol to the trifluoropropylmethyldichlorosilane fed is 1: (2.0-2.2), the feeding molar ratio of triethylamine to trifluoropropylmethyldichlorosilane is 1: (1.0-1.2).
9. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the hydrolytic cyclization reaction temperature is 0-10 ℃ and the reaction time is 1-2 h.
10. The process for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the amount of water used for the hydrolytic cyclization reaction is 2-5 times the amount of trifluoropropylmethyldichlorosilane used.
11. The process for producing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 2, wherein the hydrolytic cyclization reaction is completed, and the system is allowed to stand for layering, and the organic phase is taken out and washed with water to be neutral;
and rectifying the organic phase under vacuum to obtain the purified 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenyl cyclotrisiloxane.
12. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 11, wherein the washing temperature is 20-50 ℃ and the washing time is 0.5-1 h.
13. The method for preparing 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane as claimed in claim 11, wherein the distillation conditions are-0.099 MPa pressure, 174 ℃ and 176 ℃, and the reflux ratio of the distillation process is controlled to be (8-10): 1.
14. use of 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 1 in the preparation of high temperature resistant fluorosilicone rubber.
15. Use of 1, 3-dimethyl-1, 3-bis (3,3, 3-trifluoropropyl) -5, 5-diphenylcyclotrisiloxane according to claim 1 for the preparation of high temperature resistant fluorosilicone rubber by ring-opening copolymerization with 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane.
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| JPH09221489A (en) * | 1996-02-14 | 1997-08-26 | Shin Etsu Chem Co Ltd | Organohydrogen cyclotetrasiloxane containing fluorine |
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