阅读说明：本技术 一种苯基硅橡胶生胶合成工艺 (Phenyl silicone rubber raw rubber synthesis process ) 是由 唐小斗 谢琴 康乃文 朱良波 潘涛 张良 熊刚 于 2020-12-07 设计创作，主要内容包括：本发明公开了一种苯基硅橡胶生胶合成工艺,以甲基硅氧烷环体及苯基硅氧烷环体为原料,甲基硅氧烷环体经脱水后再计量,苯基硅氧烷环体经计量后再脱水,然后再将其在80℃下混合后,加入甲基乙烯基硅氧烷环体、封端剂和碱胶催化剂,制得苯基硅橡胶生胶。本发明通过控制原料的投料和混合方式,可有效抑制现有含量控制不准确、脱低效果不好、合成效率低的缺陷。(The invention discloses a process for synthesizing phenyl silicone rubber crude rubber, which comprises the steps of taking methyl siloxane ring bodies and phenyl siloxane ring bodies as raw materials, dehydrating and metering the methyl siloxane ring bodies, dehydrating the phenyl siloxane ring bodies after metering, mixing the phenyl siloxane ring bodies and the phenyl siloxane ring bodies at 80 ℃, and adding methyl vinyl siloxane ring bodies, a blocking agent and an alkali rubber catalyst to prepare the phenyl silicone rubber crude rubber. The invention can effectively inhibit the defects of inaccurate content control, poor threshing effect and low synthesis efficiency by controlling the feeding and mixing modes of the raw materials.)

1. A process for synthesizing raw phenyl silicone rubber is characterized by comprising the following steps: taking methylsiloxane ring bodies and phenylsiloxane ring bodies as raw materials, metering the methylsiloxane ring bodies after dehydration, metering the phenylsiloxane ring bodies after dehydration, mixing the phenylsiloxane ring bodies and the phenylsiloxane ring bodies at the temperature of below 80 ℃, and adding the methyl vinyl siloxane ring bodies, a blocking agent and an alkali gel catalyst to prepare the phenyl silicone rubber crude rubber.

2. The raw phenyl silicone rubber synthesis process of claim 1, wherein the synthesis process comprises the following steps: the methyl siloxane ring body is sent into a dehydration kettle (2), 10-20% of the methyl siloxane ring body is steamed out under the conditions of 50-100 ℃ and-0.07-0.09 MPa, and then the residual 80-90% of the methyl siloxane ring body is sent into a weighing and metering tank (5).

3. The raw phenyl silicone rubber synthesis process of claim 1, wherein the synthesis process comprises the following steps: and directly weighing and metering the phenyl siloxane ring body, adding the phenyl siloxane ring body into a double-planet stirring reaction kettle (3), and drying and dehydrating for 0.5-4 h under the conditions of the temperature of 120-160 ℃ and the pressure of less than or equal to-0.08 MPa.

4. The raw phenyl silicone rubber synthesis process according to claim 3, characterized in that: after the phenyl siloxane ring body is dehydrated, cooling the double-planet stirring reaction kettle (3) to be below 80 ℃, adding the dehydrated methyl siloxane ring body according to the measurement, adding the methyl vinyl siloxane ring body, the end-capping agent and the catalyst in the stirring process, and then preparing the phenyl silicone rubber crude rubber after polymerization balance, catalyst inactivation and vacuum devolatilization.

5. The raw phenyl silicone rubber synthesis process according to claim 4, wherein: methyl siloxane ring body and phenyl siloxane ring body mix and stir in double planet stirred tank reactor (3), the planet stirring rake of double planet stirred tank reactor (3) is two parallel synchronous frame stirring rakes of turning round, should turn round in the frame stirring rake inserts the flat material jar of double planet stirred tank reactor (3), both the rotation carries out the revolution again, and two turn round the rotation space mutual overlap of frame stirring rake.

6. The raw phenyl silicone rubber synthesis process according to claim 4, wherein: the polymerization balance is that the temperature is raised to 110-180 ℃ in a closed double-planet stirring reaction kettle (3) by stirring, and the polymerization reaction is carried out for 2-4 hours.

7. The raw phenyl silicone rubber synthesis process according to claim 4, wherein: the vacuum devolatilization is to perform primary devolatilization for 1 to 2 hours in a double-planet stirring reaction kettle (3) at the temperature of between 160 and 180 ℃ and under the pressure of less than or equal to-0.09 MPa, then press the material subjected to primary devolatilization into a screw extruder (4) by a rubber press machine (1), and continue devolatilization at the temperature of between 160 and 180 ℃ and under the pressure of less than or equal to-0.09 MPa to obtain the phenyl silicone rubber crude rubber.

8. The raw phenyl silicone rubber synthesis process of claim 1, wherein the synthesis process comprises the following steps: in the synthesis process, the following materials are fed according to the weight ratio:

methylsiloxane ring body: 100 parts by weight;

phenyl siloxane ring body: 2-200 parts by weight;

methylvinylsiloxane ring body: 0 to 5 parts by weight;

end-capping agent: 0-10 parts;

alkali gel catalyst: 0.1 to 1.5 parts by weight.

9. The raw phenyl silicone rubber synthesis process of claim 1, wherein the synthesis process comprises the following steps: the alkali glue catalyst comprises but is not limited to alkali metal silicon alkoxide, tetramethyl ammonium silicon alkoxide or tetrabutyl phosphonium polydimethylsiloxane silicon alkoxide, and the weight percentage of corresponding salt cations in the alkali glue is between 1 and 6 percent.

Technical Field

The invention relates to a synthesis process of phenyl silicone rubber crude rubber, in particular to an intermittent polymerization production process of the phenyl silicone rubber crude rubber, belonging to the field of polymerization production of organic silicon high polymer materials.

Background

Phenyl silicone rubber is a special variety of silicone rubber, and the performance of the phenyl silicone rubber far exceeds that of methyl silicone rubber in many aspects, so that the phenyl silicone rubber is indispensable in some special fields, and the added value of the phenyl silicone rubber is more than ten times higher than that of the methyl silicone rubber. But the varieties are numerous, and the synthesis difficulty is much higher. Due to the diversity of the application field, the product is designed to belong to a product with multiple varieties, small batch and high value, the design consideration of batch and continuity cannot be carried out on the production like a comprehensive product, and more varieties need to be switched conveniently and the batch capacity needs to be moderate. Therefore, the synthesis of the raw phenyl silicone rubber is basically produced by a batch method, and a continuous high-capacity production line is adopted unlike the methyl silicone rubber.

Therefore, the existing process device for continuously producing the raw methyl silicone rubber is not suitable. For example, the static mixer used in CN1113923C as a continuous production line of polymerization devices is not realized by changing the type of the injected raw material alone when the type needs to be switched, because a large amount of the rubber material of the former type is left in the static mixer and ejected by the switched type, and a long transition section of mixing is inevitably existed. The phenyl silicone crude rubber with different phenyl contents is insoluble, the mixed crude rubber not only has the phenyl content in the change transition, but also is completely opaque, and the mechanical strength, particularly the fatigue resistance, of the prepared silicone rubber vulcanized rubber can be greatly influenced. Because the internal mechanism of the static mixer is stationary, the replacement of the internal material can only be accomplished by means of the gradual ejection of the subsequent material from the previous batch. However, because of the variety of the phenyl silicone rubber, the required amount of each variety is not too large, the switching is frequent, and the amount of the rubber in the transition section generated by each switching can directly exceed the required amount of the rubber in one order. This waste is unacceptable as a costly phenyl silicone rubber.

For batch production processes, the conventional paddle type stirred tank is not suitable. The reason is that the high molecular weight phenyl silicone rubber raw rubber is a very viscous material, the room temperature viscosity of the raw rubber possibly exceeds ten million centipoise, the raw rubber is more viscous than methyl silicone rubber with the same molecular weight, the standing state of the raw rubber basically loses fluidity, and when a paddle type stirrer stirs the raw rubber, due to the climbing rod characteristic of a high molecular material, the rubber can wholly hold a shaft and then rotate along with a stirring shaft, and the part which can not be touched by the stirring paddle is adhered to the wall of a kettle and is completely separated from the rubber of the shaft holding on the stirring paddle, so that the stirring failure is caused. Under the conditions of no mass transfer and low heat exchange efficiency, the molecular weight of the sizing materials at each part cannot be uniform. The final de-ironing process of the process also causes the content of volatile matters to be uneven at each part because of no surface renewal. These can seriously affect product quality.

In patent CN101381459B, a planetary stirrer is used as a polymerization reaction device, which improves the mass and heat transfer in the single-paddle stirring mode to some extent, but there are several more critical problems: firstly, in the patent specification and the embodiment, only a powerful or high-load planetary stirrer is mentioned, but the form of a stirring paddle of a planetary machine is not clearly indicated, and the problems of insufficient surface renewal, insufficient efficiency and low efficiency of removal, insufficient mass transfer caused by pole climbing and shaft holding of materials and non-uniform sizing materials are still caused because the polymerization and the removal of the materials depend on the planetary machine are not mentioned. In addition, in the aspect of process, all raw materials are fed and then subjected to reduced pressure dehydration, and the problems of inaccurate control of the content of phenyl, fluctuation of the proportion of the raw materials, insufficient dehydration of the raw materials and the like also exist. Because the decompression dehydration is to distill a small part of dimethyl polysiloxane ring body (about 10-20% of the input amount) to carry out water, the boiling point of the phenyl ring body is very high, and the phenyl ring body cannot be distilled out synchronously with the methyl ring body. Therefore, the ratio of methyl ring bodies to phenyl ring bodies is changed after dehydration during feeding, and the change can not be accurately controlled to be consistent every time. The phenyl content of the phenyl silicone rubber thus manufactured is not accurately controlled.

The three groups of screw machines in the patent CN104589547 are connected in series to form a polymerization and low reaction device, which is used for the continuous production of methyl silicone rubber, can effectively improve the problems of mixing, mass transfer, heat transfer, surface renewal and the like of materials in a high-viscosity state, but is still not applicable to phenyl silicone rubber. Since, like raw diphenyl silicone rubber, one of the synthetic raw materials is octaphenylcyclotetrasiloxane, which is a solid substance, the initial charge forms two phases with the liquid raw materials DMC, VMC, etc. The two phases are mixed with stirring and an interfacial reaction occurs, so that octaphenylcyclotetrasiloxane is gradually consumed and the system gradually becomes homogeneous. The metering feeder described in patent CN104589547 is a weight-reduced weighing apparatus suitable only for liquid materials. The problems of dehydration and moisture resistance of the raw materials are not mentioned in the whole process. Moreover, for the multiphase phenyl polysiloxane ring-opening reaction with longer polymerization time, the ring-opening polymerization time in the screw is probably insufficient, and if the number of screw units is increased, the equipment investment is higher, the flow is lengthened, and the method is not suitable for frequent switching of various small-batch products.

In summary, in order to overcome the defects of low production efficiency, low product quality, difficult process control, high production cost and the like caused by improper equipment selection and process control in the preparation of the phenyl silicone rubber crude rubber in the prior art, a new synthetic process for synthesizing the phenyl silicone rubber crude rubber needs to be found urgently, the synthetic process not only needs to meet the product characteristics for intermittent production, but also needs to give consideration to stable production of the phenyl silicone rubber crude rubber, improve the product quality and smoothly realize industrial production.

Disclosure of Invention

The invention aims to provide a raw phenyl silicone rubber synthesis process, which can effectively overcome the defects of inaccurate content control, poor removal effect and low synthesis efficiency by controlling the feeding and mixing modes of raw materials.

The invention is realized by the following technical scheme: a process for synthesizing raw phenyl silicone rubber includes such steps as dewatering methylsiloxane ring and phenylsiloxane ring, metering phenylsiloxane ring, dewatering, mixing at 80 deg.C, adding methylvinylsiloxane ring, end-capping agent and alkali-type catalyst, and features high adhesion, low cost and high adhesion.

The invention mainly solves the problems of the synthesis production process flow of the phenyl silicone rubber crude rubber and the configuration and combination of corresponding equipment thereof, and particularly, the target product to be synthesized by the invention comprises a series of phenyl silicone rubber crude rubber products represented by the following chemical formula:

wherein R is₁、R₂It may be a phenyl group and a methyl group, but not both. p/(p + m + n) = 1-50%, and n/(p + m + n) = 0-1%.

And (2) feeding the methyl siloxane ring body into a dehydration kettle, steaming out a methyl siloxane ring body with the feeding amount of 10-20% under the conditions of 50-100 ℃ and-0.07-0.09 MPa, and then feeding the remaining 80-90% of the methyl siloxane ring body into a weighing and metering tank.

And directly weighing and metering the phenyl siloxane ring body, adding the phenyl siloxane ring body into a double-planet stirring reaction kettle, and drying and dehydrating for 0.5-4 hours at the temperature of 120-160 ℃ and under the pressure of less than or equal to-0.08 MPa.

After the phenyl siloxane ring body is dehydrated, cooling the double-planet stirring reaction kettle to the temperature of 80 ℃, adding the dehydrated methyl siloxane ring body according to the measurement, adding the methyl vinyl siloxane ring body, the end-capping agent and the catalyst in the stirring process, and then carrying out polymerization balance, catalyst inactivation and vacuum devolatilization to prepare the phenyl silicone rubber crude rubber.

Methyl siloxane ring body and phenyl siloxane ring body mix and stir in double planet stirring reation kettle, double planet stirring reation kettle's planet stirring rake is two parallel synchronous turn round frame formula stirring rakes, should turn round in frame formula stirring rake inserts double planet stirring reation kettle's flat feed cylinder, not only rotation but also revolution, and the rotation space of two turn round frame formula stirring rakes overlaps each other. In the actual operation process, the rotation and revolution speeds of the torsion frame type stirring paddle are adjusted simultaneously and independently, and the rotation and revolution speeds of the stirring paddle are adjustable between 0rpm and 40rpm under the common condition.

And the polymerization balance is that the mixture is stirred and heated to 110-180 ℃ in a closed double-planet stirring reaction kettle, and the polymerization reaction is carried out for 2-4 hours.

The invention adopts the twisted frame type stirring paddle of the double-planet stirring reaction kettle, and in the stirring process, the stirring speed is reasonably controlled, so that the stirring device not only can adapt to the increase of the viscosity of a polymer, but also can increase the tolerance of the torque stress of equipment, and avoid damaging the equipment.

In the polymerization balance process, when the reaction is carried out for 10-40 min, the stirring rotating speed is more than or equal to 20rpm, then the viscosity of the materials in the kettle is observed, when the viscosity is obviously thickened, the speed is adjusted, and at the moment, the stirring rotating speed is controlled to be less than or equal to 10 rpm.

And the vacuum devolatilization is to perform primary devolatilization for 1 to 2 hours in a double-planet stirring reaction kettle at the temperature of between 160 and 180 ℃ and the pressure of less than or equal to-0.09 MPa, press the material subjected to primary devolatilization into a screw extruder by a rubber press, and perform continuous devolatilization at the temperature of between 160 and 180 ℃ and the pressure of less than or equal to-0.09 MPa to obtain the phenyl silicone rubber crude rubber.

According to the invention, a mode of matching primary devolatilization with devolatilization of a screw extruder is adopted, on one hand, the materials are subjected to primary devolatilization in a material cylinder, the material cylinder can be thermally transferred after the primary devolatilization is completed, too large steam when the cylinder is opened is avoided, in the primary devolatilization process, through reasonable temperature and vacuum degree control, not only are small molecules volatilized and separated from a system as much as possible, but also the devolatilization efficiency is ensured, on the other hand, the devolatilization is continued by adopting the screw extruder, and through reasonable temperature and vacuum degree control, the small molecules are further removed and the efficiency is ensured, and meanwhile, the extrusion speed of a rubber press is required to be consistent with the extrusion speed of the screw extruder, so that the operation balance is realized and the good devolatilization effect is maintained.

In the synthesis process, the following materials are fed according to the weight ratio:

methylsiloxane ring body: 100 parts by weight of, for example, D4 (Chinese name: octamethylcyclotetrasiloxane), DMC (Chinese name: dimethylcyclosiloxane mixture in which octamethylcyclotetrasiloxane is the main component and hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, etc. are present in small amounts);

phenyl siloxane ring body: 2-200 parts by weight of a diphenyl polysiloxane ring body such as octaphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decaphenylcyclopentasiloxane or a mixture thereof, or a methylphenyl polysiloxane ring body such as trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, pentamethylpentaphenylcyclopentasiloxane or a mixture thereof;

methylvinylsiloxane ring body (VMC): 0 to 5 parts by weight;

end-capping agent: 0 to 10 parts of divinyl tetramethyl disiloxane, hexamethyldisiloxane, low viscosity vinyl silicone oil, low viscosity methyl silicone oil and the like;

alkali gel catalyst: 0.1 to 1.5 parts by weight.

The alkali glue catalyst comprises but is not limited to alkali metal silicon alkoxide, tetramethyl ammonium silicon alkoxide or tetrabutyl phosphonium polydimethylsiloxane silicon alkoxide, and the weight percentage of corresponding salt cations in the alkali glue is between 1 and 6 percent.

It is known that the polymerization and devolatilization are carried out with ordinary stirring as employed in the prior art, which is aimed at preparing a polymerization product having not very high viscosity, generally required to be less than one hundred thousand centipoise; in addition, in the preparation process of the synthetic silica raw rubber, a static mixer method is adopted, polymerization is carried out in the static mixer, devolatilization is carried out in a flash evaporator, the process belongs to continuous reaction, and the method is suitable for the condition of mass production of a certain product, such as the dimethyl silica raw rubber, the product type is not required to be frequently switched, and one product can be continuously produced by thousands of tons. Therefore, for the condition that the raw phenyl silicone rubber has high viscosity and needs to be switched frequently due to the production of products with different phenyl contents, the invention firstly provides a batch synthesis process route for preparing the raw phenyl silicone rubber by taking methyl siloxane ring bodies and phenyl siloxane ring bodies as raw materials, and has the following advantages and beneficial effects:

(1) because the prior art has low requirements on the control of the phenyl content, if the prior raw rubber synthesis equipment is adopted, the problems of inaccurate control of the phenyl content, fluctuation of raw material proportion, insufficient dehydration of raw materials and the like often occur, so that the control of the technical indexes of the product is influenced, and in order to overcome the problems, the invention provides the following operations for feeding the raw materials of methyl siloxane ring bodies and phenyl siloxane ring bodies:

A. the method comprises the steps of dehydrating methylsiloxane ring bodies, metering and feeding the methylsiloxane ring bodies, evaporating a part of methylsiloxane ring bodies through reduced pressure to bring a small amount of water out by utilizing the characteristics that the methylsiloxane ring bodies are low in boiling point and only have the temperature of 60-80 ℃ in vacuum, reducing the water content of the remaining methylsiloxane ring bodies, and meeting the polymerization requirement. In the actual operation process, the accurate measurement of the methylsiloxane ring body can improve the accuracy of the proportioning of the phenylsiloxane ring body, effectively realize the control of the technical index of the product and be beneficial to industrial production.

B. The phenyl siloxane ring body is metered and then dehydrated, and the boiling point of the phenyl siloxane ring body is very high and exceeds 400 ℃, so that no material is lost in the dehydration process, and the phenyl siloxane ring body can be metered and then dehydrated, and can also be dehydrated at higher temperature.

Based on the situation, the invention overcomes the defect of large product index difference caused by large phenyl content fluctuation in the prior art, adopts a reasonable feeding mode, effectively solves the accurate control of the phenyl content in the phenyl silicone rubber crude rubber synthesis process, and ensures the consistency of industrial batch production of phenyl silicone rubber crude rubber products.

(2) The invention adopts the matching of the double-planetary stirring reaction kettle and the screw extruder and the reasonable setting of the process parameters to realize the process of mixing, polymerizing, bottom removing and extruding materials, wherein the double-planetary stirring reaction kettle can stir low-viscosity materials (the viscosity of the materials is very low at the initial stage of reaction and is only dozens of centipoises; the viscosity of the materials is very thick at the later stage of reaction and reaches millions and tens of millions of centipoises) and can stir high-viscosity materials to force the high-viscosity materials to generate mass and heat transfer and surface updating, and the torsion frame type stirring paddle can avoid the phenomenon of climbing a high polymer material, so the torsion frame type stirring paddle can adapt to the stirring of the whole polymerization process and is also suitable for primary devolatilization. However, since the stirring speed must be reduced at the later stage, the surface renewal is still relatively slow, and the complete devolatilization efficiency is not high, so that a screw extruder is used for assistance.

(3) The index performance of the raw phenyl silicone rubber prepared by the invention meets the following requirements: the content of the phenyl can be within any range of 3-50%, and the content of the phenyl can be controlled to be less than +/-2% or even less than +/-1%; the molecular weight range covers 40-80 ten thousand, and the error can be controlled within +/-3 ten thousand.

In summary, the phenyl silicone rubber raw rubber produced by the conventional common stirring device has poor phenyl content control effect and insufficient stirring, and influences the product performance of the phenyl silicone rubber raw rubber (for example, the molecular weights of materials at different positions in a kettle may be different, and the difference can also be reflected in volatile matters).

Drawings

FIG. 1 is a flow chart of the raw phenyl silicone rubber synthesis process of the present invention.

1-a glue press, 2-a dehydration kettle, 3-a double-planet stirring reaction kettle, 4-a screw extruder, 5-a weighing tank and 6-a magnetic conveying pump.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1:

putting 200kg of dimethyl siloxane ring body into a dehydration kettle 2, decompressing to minus 0.08MPa at 58-88 ℃, stirring and dehydrating for 147 minutes, evaporating about 35kg of dimethyl siloxane ring body, and dehydrating; meanwhile, 89.8kg of octaphenylcyclotetrasiloxane was charged into a double planetary stirred autoclave 3, dehydrated for 240 minutes under reduced pressure of-0.09 MPa at 138 ℃ to 145 ℃ under vacuum, then decompressed with nitrogen, and cooled to 80 ℃ or lower. Pumping 115kg of dehydrated dimethyl siloxane ring bodies into an online metering tank (a weighing and metering tank 5, the same below), weighing 110.4kg of dimethyl siloxane ring bodies by weight reduction, putting the dimethyl siloxane ring bodies into a double-planetary stirring reaction kettle 3, starting the double-planetary stirring reaction kettle 3 to stir, setting the initial stirring rotation speed to be 20rpm, putting 634g of methyl vinyl siloxane ring bodies, 1070g of tetramethyl ammonium silanol saline-alkali glue and 160g of methyl silicone oil with the viscosity of 50 centipoises through a hand hole, stirring and heating after closing the hand hole, carrying out polymerization reaction for 125 minutes at 112-130 ℃, timing after the temperature reaches 110 ℃, stirring at 25rpm within 10 minutes, and then stirring at 4rpm within 115 minutes. Heating to 165-175 ℃ under the condition of maintaining stirring, breaking the medium for 1 hour, reducing the pressure to-0.095 MPa of vacuum degree for primary devolatilization for 1 hour, introducing nitrogen to release vacuum, transferring a material cylinder to a rubber press 1, connecting a screw extruder 4, maintaining the temperature of the material cylinder and a material barrel of the screw extruder 4 at 165-175 ℃, vacuumizing a tail gas system to below-0.095 MPa of vacuum degree, extruding and removing the material by a screw, opening condensed water at a machine head to cool the material temperature to below 100 ℃, discharging and packaging to obtain 176kg of the phenyl silicone rubber crude rubber. The raw rubber has the average molecular weight of 53 ten thousand, the phenyl content of 24 percent, the vinyl content of 0.36 percent and the volatile component of 0.94 percent.

Example 2:

putting 180kg of dimethyl siloxane ring body into a dehydration kettle 2, decompressing to-0.08 MPa at 50-78 ℃, stirring and dehydrating for 165 minutes under vacuum degree, evaporating about 30kg of dimethyl siloxane ring body, and dehydrating; meanwhile, 65.2kg of tetramethyltetraphenylcyclotetrasiloxane was charged into a double planetary stirred tank reactor 3, dehydrated by stirring at 120 ℃ to 146 ℃ under reduced pressure to-0.09 MPa vacuum for 180 minutes, then decompressed by nitrogen gas, and cooled to 80 ℃ or lower. Pumping 45kg of dehydrated dimethyl siloxane ring bodies into an online metering tank, weighing 39.7kg of dimethyl siloxane ring bodies by weight reduction, putting the dimethyl siloxane ring bodies into a double-planet stirring reaction kettle 3, starting the double-planet stirring reaction kettle 3 to stir, setting the initial stirring rotation speed to be 20rpm, putting 93g of methyl vinyl siloxane ring bodies and 362g of tetramethyl ammonium silanol saline-alkali glue through a hand hole, sealing the hand hole, stirring and heating, carrying out polymerization reaction for 134 minutes at 114-126 ℃, timing after reaching 110 ℃, stirring at 20rpm within 40 minutes, and stirring at 6rpm within 94 minutes. Heating to 160-175 ℃ under the condition of maintaining stirring, breaking the medium for 1 hour, reducing the pressure to-0.099 MPa of vacuum degree for primary devolatilization for 1 hour, introducing nitrogen to release vacuum, transferring a material cylinder to a rubber press 1, connecting a screw extruder 4, maintaining the temperature of the material cylinder and a material barrel of the screw extruder 4 at 173-177 ℃, vacuumizing a tail gas system to below-0.094 MPa of vacuum degree for screw extrusion and removing, opening condensed water at a machine head to cool the material temperature to below 100 ℃, discharging and packaging to obtain 95kg of the phenyl silicone rubber crude rubber. The test shows that the raw adhesive has an average molecular weight of 47 ten thousand, a phenyl content of 49 percent, a vinyl content of 0.11 percent and a volatile component of 1.5 percent.

Example 3:

putting 230kg of dimethyl siloxane ring body into a dehydration kettle 2, decompressing to-0.08 MPa at 50-71 ℃, stirring and dehydrating for 67 minutes under vacuum degree, and evaporating about 35kg of dimethyl siloxane ring body to complete dehydration; at the same time, 66.3kg of tetramethyltetraphenylcyclotetrasiloxane was charged into a double planetary stirred tank reactor 3, dehydrated by stirring at 140 ℃ to 147 ℃ under reduced pressure to-0.09 MPa of vacuum for 240 minutes, then decompressed with nitrogen and cooled to 80 ℃ or lower. 188kg of dehydrated dimethyl siloxane ring bodies are pumped into an online metering tank, 181kg of dimethyl siloxane ring bodies are weighed by losing weight and placed into a double-planet stirring reaction kettle 3, the double-planet stirring reaction kettle 3 is started to stir, the initial stirring rotation speed is set to be 25rpm, 1010g of methyl vinyl siloxane ring bodies, 588g of methyl silicone oil with the viscosity of 50 centipoises and 1824g of potassium polysiloxane saline-alkali glue are placed into a hand hole, the hand hole is sealed, stirring and temperature rising are carried out, polymerization reaction is carried out for 183 minutes at the temperature of 141-173 ℃, in the period, the time is counted after the temperature reaches 140 ℃, the stirring speed is 25rpm within 18 minutes, and then the stirring speed is 7rpm within 165 minutes. Then adding 412g of silicon-based phosphate ester under the condition of maintaining stirring for 1 hour, reducing the pressure to-0.098 MPa of vacuum degree for primary devolatilization for 2 hours, introducing nitrogen to release vacuum, transferring a material cylinder to a rubber press 1, connecting a screw extruder 4, maintaining the temperature of the material cylinder and a material barrel of the screw extruder at 150-170 ℃, vacuumizing a tail gas system to-0.09 MPa of vacuum degree for screw extrusion and removing, opening condensed water at a machine head to cool the material temperature to below 100 ℃, discharging and packaging to obtain 213kg of the phenyl silicone rubber crude rubber. The test shows that the raw adhesive has an average molecular weight of 77 ten thousand, a phenyl content of 19 percent, a vinyl content of 0.30 percent and a volatile component of 1.5 percent.

Example 4:

putting 180kg of dimethyl siloxane ring body into a dehydration kettle 2, decompressing to-0.08 MPa at 57-64 ℃, stirring and dehydrating for 79 minutes under vacuum degree, and evaporating about 30kg of dimethyl siloxane ring body to complete dehydration; meanwhile, 11.3kg of octaphenylcyclotetrasiloxane was charged into a double planetary stirred tank reactor 3, dehydrated under reduced pressure at 133 ℃ to 140 ℃ to-0.09 MPa of vacuum degree for 177 minutes with stirring, then decompressed with nitrogen, and cooled to 80 ℃ or lower. Pumping 115kg of dehydrated dimethyl siloxane ring bodies into an online metering tank, weighing 112.7kg of dimethyl siloxane ring bodies by weight reduction, putting the dimethyl siloxane ring bodies into a double-planet stirring reaction kettle 3, starting the double-planet stirring reaction kettle 3 to stir, setting the initial stirring rotation speed to be 20rpm, putting 520g of methyl vinyl siloxane ring bodies, 300g of methyl silicone oil with the viscosity of 50 centipoises and 580g of tetramethyl ammonium silanol saline-alkali glue through hand holes, stirring and heating after closing the hand holes, carrying out polymerization reaction for 75 minutes at the temperature of 96-115 ℃, timing after reaching the temperature of 100 ℃, stirring at the speed of 20rpm within 13 minutes, and stirring at the speed of 10rpm within 62 minutes. Heating to 158-170 ℃ under the condition of maintaining stirring, breaking the medium for 1 hour, reducing the pressure to-0.097 MPa of vacuum degree for primary devolatilization for 1 hour, introducing nitrogen to release vacuum, transferring a material cylinder to a rubber press 1, connecting a screw extruder 4, maintaining the temperature of the material cylinder and a material barrel of the screw extruder 4 at 160-175 ℃, vacuumizing a tail gas system to below-0.098 MPa of vacuum degree, extruding and removing the material by a screw, opening condensed water at a machine head to cool the material temperature to below 100 ℃, discharging and packaging to obtain 100kg of the phenyl silicone rubber crude rubber. The weight average molecular weight of the raw rubber is 83 ten thousand, the phenyl content is 3.8 percent, the vinyl content is 0.38 percent, and the volatile component is 0.4 percent.

Example 5:

putting 200kg of dimethyl siloxane ring body into a dehydration kettle 2, decompressing to-0.078 MPa at 80-100 ℃, stirring and dehydrating for 120 minutes under vacuum degree, and evaporating about 40kg of dimethyl siloxane ring body to complete dehydration; meanwhile, 8.5kg of octaphenylcyclotetrasiloxane was charged into a double planetary stirred tank reactor 3, and the mixture was dehydrated for 30 minutes under reduced pressure at 153 ℃ to 160 ℃ to-0.09 MPa of vacuum degree, then pressure was released with nitrogen gas, and the mixture was cooled to 80 ℃ or lower. Pumping 135kg of dehydrated dimethyl siloxane ring bodies into an online metering tank, weighing 125kg of dimethyl siloxane ring bodies by reducing weight, putting the dimethyl siloxane ring bodies into a double-planet stirring reaction kettle 3, starting the double-planet stirring reaction kettle 3 to stir, setting the initial stirring rotation speed to be 20rpm, putting 260g of methyl vinyl siloxane ring bodies, 400g of methyl silicone oil with the viscosity of 50 centipoises and 360g of tetramethyl ammonium silanol saline-alkali adhesive through a hand hole, stirring and heating after closing the hand hole, carrying out polymerization reaction for 120 minutes at 150-175 ℃, timing after reaching 100 ℃, stirring at 20rpm within 40 minutes, and then stirring at 10rpm within 65 minutes. Heating to 168-175 ℃ under the condition of maintaining stirring, breaking medium for 1 hour, reducing the pressure to-0.097 MPa of vacuum degree for primary devolatilization for 1 hour, introducing nitrogen to release vacuum, transferring a material cylinder to a rubber press 1, connecting a screw extruder 4, maintaining the temperature of the material cylinder and a material barrel of the screw extruder 4 at 175-180 ℃, vacuumizing a tail gas system to below-0.098 MPa of vacuum degree, extruding and removing by a screw, cooling the material to below 100 ℃ by opening condensed water at a machine head, discharging and packaging to obtain 108kg of the raw phenyl silicone rubber. The weight average molecular weight of the raw rubber is 65 ten thousand, the phenyl content is 3 percent, the vinyl content is 0.2 percent, and the volatile component is 1.4 percent.

Example 6:

putting 250kg of dimethyl siloxane ring body into a dehydration kettle 2, decompressing to-0.09 MPa at 63-75 ℃, stirring and dehydrating for 80 minutes under vacuum degree, evaporating about 25kg of dimethyl siloxane ring body, and dehydrating; meanwhile, 85.2kg of tetramethyltetraphenylcyclotetrasiloxane was charged into a double planetary stirring reaction tank 3, dehydrated by stirring at 130 ℃ to 145 ℃ under reduced pressure to-0.09 MPa of vacuum degree for 120 minutes, then decompressed with nitrogen gas, and cooled to 80 ℃ or lower. Pumping 200kg of dehydrated dimethyl siloxane ring bodies into an online metering tank, weighing 160kg of dimethyl siloxane ring bodies by reducing weight, putting the dimethyl siloxane ring bodies into a double-planet stirring reaction kettle 3, starting the double-planet stirring reaction kettle 3 to stir, setting the initial stirring rotation speed to be 25rpm, putting 800g of methyl vinyl siloxane ring bodies, 320g of methyl silicone oil with the viscosity of 50 centipoises and 160g of potassium polysiloxane saline-alkali adhesive through a hand hole, stirring and heating after closing the hand hole, carrying out polymerization reaction for 240 minutes at 110-122 ℃, timing after reaching the temperature of 140 ℃, stirring at the speed of 25rpm within 20 minutes, and then stirring at the speed of 7rpm within 120 minutes. Then adding 388g of silicon-based phosphate ester as a breaking medium for 1 hour under the condition of maintaining stirring, reducing the pressure to-0.095 MPa of vacuum degree for primary devolatilization for 2 hours, introducing nitrogen to release vacuum, transferring a material cylinder to the rubber press 1, connecting a screw extruder 4, maintaining the temperature of the material cylinder and a material barrel of the screw extruder 4 at 160-168 ℃, vacuumizing a tail gas system to below-0.09 MPa of vacuum degree for screw extrusion and reduction, opening condensed water at a machine head to cool the material temperature to below 100 ℃, discharging and packaging to obtain 201 kg of the phenyl silicone rubber crude rubber. The weight average molecular weight of the raw rubber is 69 ten thousand, the phenyl content is 27.4 percent, the vinyl content is 0.34 percent, and the volatile component is 1.2 percent.

Example 7:

this example is a complete set of equipment for the above-described phenyl silicone rubber crude rubber synthesis process.

The equipment system comprises 1 300L stainless steel dehydration kettle and 1 displacement 1.5m³A magnetic delivery pump 6 of per hour, 1 weighing and metering tank 5 of 300L, 1 double planetary stirring reaction kettle 3 of 600L, 1 gum pressing machine 1 of 600L, 1 three screw extruder and 1 second-stage Roots vacuum unit, wherein the dehydration kettle 2 is provided with an anchor stirrer, jacket steam heating and 5m of Roots vacuum unit²A shell and tube condenser and a 100L receiver tank; the stirrer of the double-planet stirring reaction kettle 3 is two torsion frame type same-direction clockwise-rotation stirrers with adjustable speed, the material cylinder is heated by hot oil with a jacket, and a tail gas port is provided with 2m²A shell and tube condenser and a 50L receiver tank; the barrel of the three-screw devolatilization machine is heated by hot oil of a jacket to control the temperature, the barrel is provided with three or more devolatilization tail gas ports, and the tail gas ports are connected in parallel by pipelines and then are connected into a 2m barrel²A tube train condenser and a 50L condensate receiver tank; the heating of the double-planet reaction kettle and the screw extruder 4 is realized by hot oil provided by a 60kW hot oil furnace; condenser tail gas port and condenser tail gas port of dehydration kettle 2The condenser tail gas port of the planet stirring reaction kettle 3 and the condenser exhaust port of the tail gas of the screw extruder 4 are connected with the gas inlet of the second-stage Roots vacuum pump through the buffer tank in a parallel connection mode, and the vacuum pump can respectively vacuumize the three devices. The material inlet and outlet pipelines of the weighing and metering tank 5 are connected by a 15-30 cm hose respectively, so that the weighing is not influenced; the material cylinder heat conducting oil inlet and outlet pipelines of the double-planet stirring reaction kettle 3 are also connected through a section of metal corrugated hose of 2-3 m, so that the material cylinder can be conveniently moved.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.