CN111393649B - Low-cost environment-friendly method for preparing epoxy silicone rubber - Google Patents
Low-cost environment-friendly method for preparing epoxy silicone rubber Download PDFInfo
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Abstract
The invention discloses a low-cost environment-friendly method for preparing epoxidized silicone rubber, which comprises the following steps: taking 1-10 parts of high vinyl silicone rubber, 100 parts of organic peroxy acid poor solvent and 0.5-12 parts of epoxidation reagent, mixing the high vinyl silicone rubber and the organic peroxy acid poor solvent, adding the epoxidation reagent after the high vinyl silicone rubber and the organic peroxy acid poor solvent are completely dissolved to react to obtain epoxidized silicone rubber, storing the obtained solution at low temperature to separate out a deoxidation product of the epoxidation reagent and unreacted epoxidation reagent, then precipitating the epoxidized silicone rubber, washing and drying to obtain the epoxidized silicone rubber. The preparation method is more scientific and reasonable, can ensure that the produced epoxidized silicone rubber has the molecular weight of the original high-vinyl silicone rubber and has no gel content, so that the epoxidized silicone rubber has more stable performance and higher strength, and is more suitable for mass production when the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-cost environment-friendly method for preparing epoxidized silicone rubber.
Background
The silicone rubber molecule has main chain with siloxane bond as repeating unit and two organic groups connected to silicon atom. Ordinary silica gel is mainly connected with methyl and other organic groups. The silicon-oxygen bond has certain bond length and bond energy, so that the silicon rubber has small molecular chain interaction, good flexibility and thermal stability and better high and low temperature resistance. The Si-O bond distance was 1.64A, shorter than the sum of the covalent radii (1.76A), suggesting that the Si-O bond is characterized as a partial double bond. In fact, siloxanes are less basic than ethers. However, the barrier to rotation about the Si — O bond axis and the linearization barrier of SiOSi are both very low. Thus, the polysiloxane chain is extremely compliant. The silicone rubber has excellent low temperature resistance, oil resistance, chemical reagent resistance and biocompatibility, so that the silicone rubber can be applied to various fields, such as aerospace, automobiles and medical materials. However, although the glass transition temperature of the conventional methyl vinyl silicone rubber is below-100 ℃, the rubber loses elasticity and becomes hard when used below-50 ℃, and the silicone rubber is crystallized. To this end, it has been proposed that methyl vinyl silicone rubber can increase the polarity of methyl vinyl silicone rubber to improve oil resistance, and can suppress the occurrence of crystallization at-50 ℃ and has a low glass transition temperature by increasing the vinyl content and then converting the vinyl group into an epoxy group by adding an epoxy reagent, so that silicone rubber can be used at-100 ℃, but the preparation method thereof is not suitable for industrial scale-up. Therefore, finding a suitable method for preparing the low-temperature-resistant and oil-resistant epoxidized silicone rubber has great significance and has practical value for industrial production.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides a low-cost environment-friendly method for preparing epoxidized silicone rubber. The invention adopts the poor solvent of organic peroxy acid, and achieves the conditions required by the reaction and the purpose of separating organic acid by adjusting the temperature, thereby simplifying the production process.
One of the purposes of the invention is to provide a low-cost and environment-friendly method for preparing epoxidized silicone rubber, which comprises the following steps:
1) taking 1-10 parts by weight of high vinyl silicone rubber, 100 parts by weight of organic peroxy acid poor solvent and 0.5-12 parts by weight of epoxidation reagent, wherein the vinyl chain segment molar content of the high vinyl silicone rubber is 5-60%;
2) mixing high vinyl silicone rubber and an organic peroxy acid poor solvent, and stirring and dissolving for 3-6 hours at the temperature of 30-60 ℃;
3) after the high vinyl silicone rubber is completely dissolved, adding an epoxidation reagent, and stirring and reacting for 30-96 hours at 25-60 ℃ to obtain epoxidized silicone rubber;
4) storing the solution obtained in the step 3) at low temperature, and separating out a deoxidation product of the epoxidation reagent and an unreacted epoxidation reagent;
5) separating the deoxygenated product of the epoxidizing agent precipitated in step 4) from unreacted epoxidizing agent;
6) adding ethanol with the volume 1.8-2.2 times of the volume of the solution into the solution obtained after separation in the step 5) under the condition of stirring, and then adding water with the mass 1/12-1/9 of that of the ethanol while stirring, so that the epoxidized silicone rubber can be precipitated;
7) washing the epoxidized silicone rubber obtained in the step 6) with absolute ethyl alcohol under the stirring condition, adding water under the stirring condition to extract the ethyl alcohol in the epoxidized silicone rubber, and finally drying.
Preferably, in the method for preparing epoxidized silicone rubber of the present invention,
1-6 parts of high vinyl silicone rubber and 1-8 parts of an epoxidation reagent;
the high-vinyl silicone rubber has a vinyl chain segment molar content of 20-40%;
the epoxidation reagent is m-chloroperoxybenzoic acid or peroxybenzoic acid;
the poor organic peroxyacid solvent is chlorobenzene or carbon tetrachloride;
in the step 2), the stirring speed is 100-200 r/min;
in the step 3), the stirring speed is 150-300 r/min;
in the step 3), stirring and reacting for 32-56 h at 45-55 ℃;
in the step 4), the low-temperature storage is carried out for 2-20 h under the condition of-30 ℃ to 10 ℃, and more preferably for 12-20 h under the condition of-30 ℃ to 5 ℃;
separating the epoxidation reagent from the solution in the step 5), wherein the specific separation method comprises centrifuging to obtain supernatant, filtering, suction filtering and the like;
in the step 7), the volume of the absolute ethyl alcohol is 0.5-20 times that of the epoxidized silicon rubber solution obtained in the step 3), and then the volume of the absolute ethyl alcohol with the volume of 0.5-50% of that of water is added.
The high vinyl silicone rubber can be synthesized by a method generally used in the field, and can be prepared by the following method: octamethylcyclotetrasiloxane (D4), tetramethyltetravinylcyclotetrasiloxane (D4Vi), catalyst and end-capping agent are used as raw materials to react to obtain the methyl vinyl silicone rubber.
Specifically, the method of the present invention can be carried out by the following steps:
(1): weighing high vinyl silicone rubber, an organic peroxy acid poor solvent and an epoxidizing agent organic acid;
(2): setting the heating temperature of a water bath kettle to be 30-60 ℃, setting the mechanical stirring speed to be 100-200 r/min, and adding high vinyl silicone rubber and an organic peroxy acid poor solvent into a three-neck flask for dissolving for 3-6 h;
(3): after the high vinyl silicone rubber is completely dissolved, adding an epoxidation reagent, adjusting the temperature of a water bath to 25-60 ℃, continuously reacting for 30-96 hours at a mechanical stirring speed of 150-300 r/min to obtain the epoxidized high vinyl silicone rubber in the three-neck flask;
(4): storing the epoxy silicone rubber solution obtained by the reaction at a certain temperature for a period of time at a low temperature to separate out unreacted organic peroxy acid and organic acid;
(5): separating unreacted organic peroxy acid and organic acid which are separated out after freezing, wherein the mass of the removed organic peroxy acid and organic acid is 40-85% of the mass of the added organic peroxy acid;
(6): adding ethanol into the obtained solution, and then adding water while stirring to precipitate the gel;
(7): washing the obtained glue with a certain amount of absolute ethyl alcohol, then adding a certain amount of water to separate the glue from the ethyl alcohol, and then drying.
Another object of the present invention is to provide an epoxidized silicone rubber obtained according to the method.
The invention has the beneficial effects that:
(1) the invention adopts the poor solvent of the organic peroxy acid to replace the good solvent adopted by the prior epoxidation, and most of the deoxidation products of the epoxidation reagent and the unreacted epoxidation reagent are separated out during low-temperature storage, thereby greatly reducing the post-treatment time.
(2) The organic acid is separated out by cooling, the content of the organic acid in the subsequent glue solution is effectively reduced, and the pressure is reduced for the subsequent glue deposition and washing processes.
(3) In the process of depositing the gel, the solution is diluted by ethanol to reduce the acid concentration in the solution, and then water is added to deposit the gel from the mixed solution of the solvent and the ethanol, so that the acid concentration in the initially deposited gel is reduced.
(4) Washing the process of gluing is earlier washed with absolute ethyl alcohol, because the epoxy glue has certain solubility in the ethanol, remain a small amount of chlorobenzene in gluing in addition for glue dispersion in the ethanol is fine, the hardening phenomenon of cohesion can not appear, through adding water after the washing, extract the separation to the ethanol in gluing, make glue cohesion harden not only reduce the content of inside acid but also improved greatly and washed the gluey productivity of in-process of gluing, washed the time of gluing the process and shortened greatly for methyl alcohol moreover.
(5) The reagents used in the glue precipitation and washing processes are replaced by conventional methanol into ethanol, so that the effect is improved, and the key point is that the ethanol is relatively similar to the methanol, the toxicity of the ethanol is very low, and the blindness can be caused by eating a small amount of methanol by mistake.
(6) A small amount of generated organic peroxy acid is quickly reduced into organic acid in the environment, so that the final organic acid product is a pure product and can be directly sold, the separation difficulty and cost are greatly reduced, and the feasibility of the technology is proved.
The preparation method is more scientific and reasonable, can ensure that the produced epoxidized silicone rubber has the molecular weight of the original high-vinyl silicone rubber and has no gel content, so that the epoxidized silicone rubber has more stable performance and higher strength, reduces the production cost and is more suitable for mass production.
Drawings
FIG. 1 shows the infrared absorption spectrum of m-chlorobenzoic acid precipitated in example by potassium bromide tabletting method.
FIG. 2 is an infrared transmission spectrum of a pure m-chlorobenzoic acid product.
FIG. 3 shows the mass percentage of m-chlorobenzoic acid precipitated at different temperatures.
FIG. 3 shows the process conditions of the process for producing epoxidized silicone rubber in example 1, and it can be seen from FIG. 3 that the mass of precipitated m-chlorobenzoic acid is increased gradually as the temperature is decreased, and that the mass fraction precipitated when the temperature is about-10 ℃ is about 62% by calculating the variance by measuring three values at one temperature and then calculating the confidence interval.
FIG. 4 is a graph showing the effect of temperature on the solubility of organic acids in a mixed solvent.
As can be seen from FIG. 4, the ethanol-water mixed solution containing 10% by mass of water has a solubility of 15% or more at 15 ℃ and increases in solubility at elevated temperatures.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the examples, the raw material sources are as follows:
high vinyl silicone rubber: synthesized according to the general method;
chlorobenzene: brand macklin, distributed by yinaoka technologies ltd, beijing;
ethanol: absolute ethanol, branded alatin, distributed by shanghai alatin Biochemical technologies, Inc.;
m-chloroperoxybenzoic acid: the brand mieire, distributed by shanghai mieire chemical technology limited.
Example 1
1525g of octamethylcyclotetrasiloxane and 443g of tetramethyltetravinylcyclotetrasiloxane are added into a 5L strong dispersion reaction kettle, the vacuum degree is below 0.1MPa at 45 ℃, water is removed for 1 hour under the condition of introducing a small amount of nitrogen, then 9.77g of catalyst and 1.62g of end-capping agent are added, and water is removed for 1.5 hours under the condition of introducing a small amount of nitrogen at 45 ℃ below 0.1 MPa. After the dehydration is finished and the normal pressure is recovered, the temperature is set to be 110 ℃, and the reaction is carried out for 3 hours in the nitrogen atmosphere. After the reaction is finished, the temperature is set to be 170 ℃, meanwhile, the low molecules are removed by vacuumizing under the condition of introducing a small amount of nitrogen and under the pressure of-0.1 MPa, and the time for removing the low molecules is 6 hours. And after low molecules are removed, the high vinyl silicone rubber with the vinyl chain segment molar content of 20 percent is obtained.
3g of high vinyl silicone rubber with the vinyl content of 20 percent is taken and added with 100g of chlorobenzene in a 250ml three-neck flask, and the mixture is dissolved for 3 hours at the temperature of 45 ℃ and the stirring speed is 200 r/min. After the high vinyl silicone rubber is completely dissolved, 4.16g of m-chloroperoxybenzoic acid is added, the stirring speed is 200r/min, after 40 hours of reaction at 55 ℃, the solution is placed in an environment at-10 ℃ for 20 hours, then crystallized organic peroxy acid and organic acid are filtered, and the mass of crystallized educt is 65 percent of the mass of the added peroxy acid. Adding 2 times of ethanol in volume into the obtained solution, uniformly mixing, adding water with the mass being 1/10 of that of the ethanol, and stirring to precipitate the gel. The gel was then washed with 80ml absolute ethanol to remove chlorobenzene and organic acids, and then 2ml water was added to de-ethanol the gel from chlorobenzene. And finally, drying the obtained glue, and removing residual ethanol, chlorobenzene and water in the glue.
After the solution obtained after the reaction is placed in an environment with the temperature of minus 10 ℃ for 20 hours, the solution is found to be opaque from the transparency before freezing, which indicates that a large amount of organic acid is separated out, and the organic acid and the chlorobenzene solution can be separated by filtering or centrifuging, so that the pressure is reduced for the subsequent processes of depositing and washing the glue.
The absolute ethyl alcohol is added in the process of depositing the glue, the glue cannot be deposited due to certain solubility of the ethyl alcohol to the glue, the ethyl alcohol, the chlorobenzene and the epoxy glue are completely mutually dissolved, and the solution is colorless and transparent. Water was then added and the solution was found to be cloudy, i.e. a gel was precipitated.
Since water is a poor solvent for organic acids, there is a fear that the solution becomes cloudy due to precipitation of acids. Therefore, the solubility curve of the aqueous 10% ethanol mixture to m-chlorobenzoic acid was prepared, as shown in FIG. 4.
The excessive acid content in the epoxy glue can not occur in the glue depositing process through the glue depositing process.
The glue washing process is firstly carried out by absolute ethyl alcohol, and the epoxy glue has certain solubility in the ethyl alcohol, and in addition, a small amount of chlorobenzene remains in the glue, so that the glue is well dispersed in the ethyl alcohol, and the phenomenon of conglomeration and hardening cannot occur. After washing, water is added to harden the cohesive gel for convenient separation.
Example 2
1525g of octamethylcyclotetrasiloxane and 443g of tetramethyltetravinylcyclotetrasiloxane are added into a 5L strong dispersion reaction kettle, the vacuum degree is below 0.1MPa at 45 ℃, water is removed for 1 hour under the action of a small amount of nitrogen, then 9.77g of catalyst and 1.62g of end-capping agent are added, and water is removed for 1.5 hours under the action of a small amount of nitrogen at 45 ℃ below 0.1 MPa. After the dehydration is finished and the normal pressure is recovered, the temperature is set to be 110 ℃, and the reaction is carried out for 3 hours in the nitrogen atmosphere. After the reaction is finished, the temperature is set to be 170 ℃, meanwhile, the low molecules are removed by vacuumizing under the condition of introducing a small amount of nitrogen and under the pressure of-0.1 MPa, and the time for removing the low molecules is 6 hours. And after low molecules are removed, the high vinyl silicone rubber with the vinyl chain segment molar content of 20 percent is obtained.
3g of high vinyl silicone rubber with the vinyl content of 20 percent is taken and added with 100g of chlorobenzene in a 250ml three-neck flask, and the mixture is dissolved for 3 hours at the temperature of 45 ℃ and the stirring speed is 200 r/min. After the high vinyl silicone rubber is completely dissolved, 4.16g of m-chloroperoxybenzoic acid is added, the stirring speed is 200r/min, after 40 hours of reaction at 55 ℃, the solution is placed in an environment at minus 20 ℃ for 20 hours, then centrifugation is carried out to obtain an upper layer solution, and the mass of a crystallized precipitate is 72 percent of the mass of the added peroxy acid. Adding 2 times of ethanol in volume into the obtained solution, uniformly mixing, adding water with the mass being 1/10 of that of the ethanol, and stirring to precipitate the gel. The gel was then washed with 80ml absolute ethanol to remove chlorobenzene and organic acids, and then 2ml water was added to de-ethanol the gel from chlorobenzene. And finally, drying the obtained glue, and removing residual ethanol, chlorobenzene and water in the glue.
Example 3
Adding 1335g of octamethylcyclotetrasiloxane and 662.4g of tetramethyltetravinylcyclotetrasiloxane into a 5L strong dispersion reaction kettle, removing water at 45 ℃ under vacuum degree of-0.1 MPa under the action of a small amount of nitrogen for 1 hour, then adding 9.74g of catalyst and 1.60g of end-capping agent, and removing water at-0.1 MPa at 45 ℃ under the action of a small amount of nitrogen for 1.5 hours. After the dehydration is finished and the normal pressure is recovered, the temperature is set to be 110 ℃, and the reaction is carried out for 3 hours in the nitrogen atmosphere. After the reaction is finished, the temperature is set to be 170 ℃, meanwhile, the low molecules are removed by vacuumizing under the condition of introducing a small amount of nitrogen and under the pressure of-0.1 MPa, and the time for removing the low molecules is 6 hours. And after low molecules are removed, the high vinyl silicone rubber with the vinyl chain segment molar content of 30 percent is obtained.
3g of high vinyl silicone rubber with the vinyl content of 30 percent is taken and added with 100g of chlorobenzene in a 250ml three-neck flask, and the mixture is dissolved for 3 hours at the temperature of 45 ℃ and the stirring speed is 200 r/min. After the high vinyl silicone rubber is completely dissolved, 5.88g of m-chloroperoxybenzoic acid is added, the stirring speed is 200r/min, after the reaction is carried out for 36h at the temperature of 55 ℃, the solution is placed in the environment of-10 ℃ for 20h, then the crystallized organic peroxy acid and the organic acid are filtered, and the mass of the crystallized educt is 75 percent of the mass of the added peroxy acid. Adding 2 times of ethanol in volume into the obtained solution, uniformly mixing, adding water with the mass being 1/10 of that of the ethanol, and stirring to precipitate the gel. The gum was then washed with 120ml absolute ethanol to remove chlorobenzene and organic acids, and then 2ml water was added to de-ethanol the gum from chlorobenzene. And finally, drying the obtained glue, and removing residual ethanol, chlorobenzene and water in the glue.
Example 4
Adding 1142g of octamethylcyclotetrasiloxane and 883.1g of tetramethyltetravinylcyclotetrasiloxane into a 5L strong dispersion reaction kettle, removing water at 45 ℃ under vacuum degree of-0.1 MPa under the condition of introducing a small amount of nitrogen for 1 hour, then adding 9.75g of catalyst and 1.50g of end-capping agent, and removing water at-0.1 MPa at 45 ℃ under the condition of introducing a small amount of nitrogen for 1.5 hours. After the dehydration is finished and the normal pressure is recovered, the temperature is set to be 110 ℃, and the reaction is carried out for 3 hours in the nitrogen atmosphere. After the reaction is finished, the temperature is set to be 170 ℃, meanwhile, the low molecules are removed by vacuumizing under the condition of introducing a small amount of nitrogen and under the pressure of-0.1 MPa, and the time for removing the low molecules is 6 hours. And after low molecules are removed, the high vinyl silicone rubber with the vinyl chain segment molar content of 40 percent is obtained.
3g of high vinyl silicone rubber with the vinyl content of 40 percent is taken and added with 100g of chlorobenzene in a 250ml three-neck flask, and the mixture is dissolved for 3 hours at the temperature of 45 ℃ and the stirring speed is 200 r/min. After the high vinyl silicone rubber is completely dissolved, 7.98g of m-chloroperoxybenzoic acid is added, the stirring speed is 200r/min, after the reaction is carried out for 32h at the temperature of 55 ℃, the solution is placed in the environment of-10 ℃ for 20h, then the crystallized organic peroxy acid and the organic acid are filtered, and the mass of the crystallized educt is 82 percent of the mass of the added peroxy acid. Adding 2 times of ethanol in volume into the obtained solution, uniformly mixing, adding water with the mass being 1/10 of that of the ethanol, and stirring to precipitate the gel. The gel was then washed with 80ml absolute ethanol to remove chlorobenzene and organic acids, and then 2ml water was added to de-ethanol the gel from chlorobenzene. And finally, drying the obtained glue, and removing residual ethanol, chlorobenzene and water in the glue.
Example 5
1525g of octamethylcyclotetrasiloxane and 443g of tetramethyltetravinylcyclotetrasiloxane are added into a 5L strong dispersion reaction kettle, the vacuum degree is below 0.1MPa at 45 ℃, water is removed for 1 hour under the condition of introducing a small amount of nitrogen, then 9.77g of catalyst and 1.62g of end-capping agent are added, and water is removed for 1.5 hours under the condition of introducing a small amount of nitrogen at 45 ℃ below 0.1 MPa. After the dehydration is finished and the normal pressure is recovered, the temperature is set to be 110 ℃, and the reaction is carried out for 3 hours in the nitrogen atmosphere. After the reaction is finished, the temperature is set to be 170 ℃, meanwhile, the low molecules are removed by vacuumizing under the condition of introducing a small amount of nitrogen and under the pressure of-0.1 MPa, and the time for removing the low molecules is 6 hours. And after low molecules are removed, the high vinyl silicone rubber with the vinyl chain segment molar content of 20 percent is obtained.
1g of high vinyl silicone rubber with 20 percent of vinyl content and a 250ml three-neck flask are taken, 100g of chlorobenzene is added, and the mixture is dissolved for 3 hours at the temperature of 45 ℃ and the stirring speed is 200 r/min. After the high vinyl silicone rubber is completely dissolved, 1.35g of m-chloroperoxybenzoic acid is added, the stirring speed is 200r/min, after 40 hours of reaction at 55 ℃, the solution is placed in an environment at-30 ℃ for 5 hours, then crystallized organic peroxy acid and organic acid are filtered, and the mass of crystallized educt is 45 percent of the mass of the added peroxy acid. Adding 2 times of ethanol in volume into the obtained solution, uniformly mixing, adding water with the mass being 1/10 of that of the ethanol, and stirring to precipitate the gel. The gel was then washed with 80ml absolute ethanol to remove chlorobenzene and organic acids, and then 2ml water was added to de-ethanol the gel from chlorobenzene. And finally, drying the obtained glue, and removing residual ethanol, chlorobenzene and water in the glue.
Example 6
1525g of octamethylcyclotetrasiloxane and 443g of tetramethyltetravinylcyclotetrasiloxane are added into a 5L strong dispersion reaction kettle, the vacuum degree is below 0.1MPa at 45 ℃, water is removed for 1 hour under the condition of introducing a small amount of nitrogen, then 9.77g of catalyst and 1.62g of end-capping agent are added, and water is removed for 1.5 hours under the condition of introducing a small amount of nitrogen at 45 ℃ below 0.1 MPa. After the dehydration is finished and the normal pressure is recovered, the temperature is set to be 110 ℃, and the reaction is carried out for 3 hours in the nitrogen atmosphere. After the reaction is finished, the temperature is set to be 170 ℃, meanwhile, the low molecules are removed by vacuumizing under the condition of introducing a small amount of nitrogen and under the pressure of-0.1 MPa, and the time for removing the low molecules is 6 hours. And after low molecules are removed, the high vinyl silicone rubber with the vinyl chain segment molar content of 20 percent is obtained.
5g of high vinyl silicone rubber with 20 percent of vinyl content and a 250ml three-neck flask are taken, 100g of chlorobenzene is added, and the mixture is dissolved for 3 hours at the temperature of 45 ℃ and the stirring speed is 200 r/min. After the high vinyl silicone rubber is completely dissolved, 6.93g of m-chloroperoxybenzoic acid is added, the stirring speed is 200r/min, after 40 hours of reaction at 55 ℃, the solution is placed in an environment at-5 ℃ for 20 hours, then crystallized organic peroxy acid and organic acid are filtered, and the mass of crystallized educt is 80.1 percent of the mass of the added peroxy acid. Adding 2 times of ethanol in volume into the obtained solution, uniformly mixing, adding water with the mass being 1/10 of that of the ethanol, and stirring to precipitate the gel. The gum was then washed with 120ml absolute ethanol to remove chlorobenzene and organic acids, and then 2ml water was added to de-ethanol the gum from chlorobenzene. And finally, drying the obtained glue, and removing residual ethanol, chlorobenzene and water in the glue.
Claims (7)
1. The method for preparing the epoxidized silicone rubber with low cost and environmental protection is characterized by comprising the following steps:
1) taking 1-10 parts by weight of high vinyl silicone rubber, 100 parts by weight of organic peroxy acid poor solvent and 0.5-12 parts by weight of epoxidation reagent, wherein the vinyl chain segment molar content of the high vinyl silicone rubber is 5-60%;
2) mixing high vinyl silicone rubber and an organic peroxy acid poor solvent, and stirring and dissolving for 3-6 hours at the temperature of 30-60 ℃;
3) after the high vinyl silicone rubber is completely dissolved, adding an epoxidation reagent, and stirring and reacting for 30-96 hours at 25-60 ℃ to obtain an epoxidized silicone rubber solution;
4) storing the solution obtained in the step 3) at low temperature, and separating out a deoxidation product of the epoxidation reagent and an unreacted epoxidation reagent;
5) separating the deoxygenated product of the epoxidizing agent precipitated in step 4) from unreacted epoxidizing agent;
6) adding ethanol with the volume 1.8-2.2 times of the volume of the solution into the solution obtained after separation in the step 5) under the condition of stirring, and then adding water with the mass 1/12-1/9 of that of the ethanol while stirring, so that the epoxidized silicone rubber can be precipitated;
7) washing the epoxidized silicone rubber obtained in the step 6) by absolute ethyl alcohol under the stirring condition, then adding water under the stirring condition, and finally drying;
the epoxidation reagent is m-chloroperoxybenzoic acid or peroxybenzoic acid; the poor organic peroxyacid solvent is chlorobenzene or carbon tetrachloride;
in the step 4), the low-temperature storage is carried out for 2-20 h under the condition of-30 ℃ to 10 ℃.
2. The method for producing an epoxidized silicone rubber according to claim 1, characterized in that:
in the step 1), 1-6 parts of high vinyl silicone rubber, 1-8 parts of an epoxidation reagent and 20-40% of vinyl chain segment molar content of the high vinyl silicone rubber.
3. The method for producing an epoxidized silicone rubber according to claim 1, characterized in that:
in the step 2), the stirring speed is 100-200 r/min;
in the step 3), the stirring speed is 150-300 r/min.
4. The method for producing an epoxidized silicone rubber according to claim 1, characterized in that:
in the step 3), stirring and reacting for 32-56 h at 45-55 ℃.
5. The method for producing an epoxidized silicone rubber according to claim 1, characterized in that:
the low-temperature storage is carried out for 12-20 h at the temperature of-30 ℃ to 5 ℃.
6. The method for producing an epoxidized silicone rubber according to claim 1, characterized in that:
in the step 7), the volume of the absolute ethyl alcohol is 0.5-20 times that of the epoxidized silicon rubber solution obtained in the step 3), and the volume of the water is 0.5-50% of the volume of the absolute ethyl alcohol.
7. An epoxidized silicone rubber obtained by the method according to any one of claims 1 to 6.
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| US4788268A (en) * | 1987-05-05 | 1988-11-29 | Hughes Aircraft Company | Method for preparation of epoxysilicone compounds and allyl-terminated silicone compounds |
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2019
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| US4788268A (en) * | 1987-05-05 | 1988-11-29 | Hughes Aircraft Company | Method for preparation of epoxysilicone compounds and allyl-terminated silicone compounds |
| CN1322713A (en) * | 2001-04-27 | 2001-11-21 | 宜兴市第二化学试剂厂 | Prepn of m-chlorobenzoyl hydroperoxide |
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| 《苯基硅橡胶的溶解性与溶液聚合研究》;吴蓁等;《弹性体》;20130225;第23卷(第1期);第10页2.1苯基硅橡胶的溶解性研究，具体参见第11页表5 * |
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