Process and device for synthesizing hydroxyl silicone oil through efficient polycondensation

Abstract

The invention belongs to the technical field of synthesis of hydroxyl silicone oil, and discloses a process for synthesizing hydroxyl silicone oil through efficient polycondensation and a device used in the process. A falling film reactor is used as a reactor, a linear body and modified linear phosphonitrile chloride are mixed and then are pumped into the reactor from the upper part of the reactor for reaction, and the hydroxyl silicone oil is prepared. According to the invention, the falling-film reactor is used as a reactor, and the high-temperature environment of the falling-film reactor and the greatly increased cavity type thermal contact surface are utilized to realize rapid and efficient polymerization film formation of a linear body; meanwhile, through blowing of nitrogen, a large amount of water which is rapidly generated in a linear body polymerization reaction is rapidly brought away, and the problems that in a traditional linear body reaction system, water in a reaction kettle cannot be discharged in time, so that a catalyst is inactivated, and a large amount of ring bodies are generated are solved; through gravity falling film, the reaction is continuously and rapidly carried out, continuous and efficient production of hydroxyl silicone oil is achieved, the process is simple and efficient, and the obtained product is low in ring content and good in stability.

Description

Technical Field

[0001] This invention belongs to the field of hydroxyl silicone oil synthesis technology, and specifically relates to a process for high-efficiency cavity falling film polymerization to synthesize hydroxyl silicone oil and the apparatus used in this process. Background Technology

[0002] 107 silicone rubber is a base rubber for two-component and one-component condensation silicone rubbers. It is a colorless, transparent, viscous liquid at room temperature and can be used directly as a commodity or processed into silicone rubber products. It is widely used in building sealing, electronic packaging, new energy vehicles, and photovoltaic modules.

[0003] Existing production methods mainly include batch and continuous processes: the batch process involves the equilibrium polymerization of cyclosiloxanes under alkaline catalysis, followed by hydrolysis and rearrangement, neutralization with silica or phosphoric acid-polysiloxane solution, and then removal of volatiles; the continuous process utilizes three static mixers in series to sequentially complete polymerization hydrolysis, phosphoric acid neutralization, and desulfurization. These production methods are cumbersome, inefficient, energy-intensive, and exhibit poor batch-to-batch stability. They cannot achieve continuous production, and the rapid reaction and large water production result in a large amount of cyclic compounds (D4, D5, etc.) remaining in the product. Furthermore, these cyclic compounds have been found to be toxic in recent years and easily accumulate in higher organisms, causing persistent environmental and biological hazards. Therefore, there is a need to develop an efficient, continuous production process for hydroxyl silicone oil with low cyclic compound content to meet market demands. Summary of the Invention

[0004] In order to overcome the shortcomings and deficiencies of the prior art, the primary objective of this invention is to provide a process for the efficient condensation polymerization of hydroxyl silicone oil using a cavity falling film method.

[0005] The process of this invention uses hydroxyl-terminated polydimethylsiloxane (linear body) as raw material and a cavity falling film reactor as reactor. It utilizes rapid heat transfer and large cavity reaction area to achieve high-efficiency polycondensation, while avoiding the generation of a large number of cyclic bodies (D4, D5, etc.) during the polymerization process. Gravity self-falling film is used to achieve continuous production to obtain hydroxyl silicone oil.

[0006] Another object of the present invention is to provide an apparatus for use in the above-described process.

[0007] The objective of this invention is achieved through the following solution:

[0008] The first aspect is a process for high-efficiency condensation polymerization of hydroxyl silicone oil using a falling film reactor. The process involves mixing a linear polymer and a modified linear phosphazene chloride, and then injecting the mixture into the reactor from the top to react and prepare hydroxyl silicone oil.

[0009] The process of this invention uses a falling film reactor as the reactor. Under the action of gravity, the raw materials are heated and reacted rapidly as they descend from the inner wall of the reactor, and the reaction products can be obtained from the bottom of the reactor.

[0010] Traditional methods using linear polymers as raw materials in reactors suffer from several drawbacks. The rapid polymerization process leads to a large volume of water that cannot be promptly drained, catalyst deactivation upon contact with water, and the generation of numerous cyclic compounds, resulting in products that fail to meet practical application requirements. Therefore, cyclic compounds are currently commonly used as raw materials, but these have a low ring-opening rate of only 85%, resulting in a high residual cyclic compound content in the product. This invention utilizes low-viscosity linear polymers as raw materials and employs a cavity falling film reactor. This process allows for rapid heat transfer and efficient water removal during the film-forming reaction, resulting in a fast reaction rate and continuous production. This cavity falling film reactor enables highly efficient condensation polymerization of hydroxyl silicone oil, producing a product with low cyclic compound content and good stability.

[0011] As a preferred embodiment of the present invention, the linear body may be a small molecule hydroxyl-terminated polydimethylsiloxane with a viscosity of 80-120 CPS.

[0012] As a preferred embodiment of the present invention, the amount of the modified linear phosphazene chloride can be 10-100 ppm, more preferably 10-30 ppm.

[0013] As a preferred embodiment of the present invention, the modified linear phosphazene chloride is prepared with reference to CN118406080A. The modified linear phosphazene chloride structure improves stability by replacing chlorine with low-activity groups. Using it as a catalyst overcomes the problems of excessively rapid reaction and excessive molecular weight growth of hydroxyl silicone oil in falling film reactors, which prevents self-falling film formation, and excessive viscosity leading to catalyst deactivation and hindering continuous production. By utilizing a specific low-activity catalyst, the falling film reactor device suitable for the process of this invention can achieve excellent polymerization effects for the continuous, rapid, efficient, and stable synthesis of hydroxyl silicone oil. Simultaneously, virtually no cyclic compounds are generated during the reaction, making the linear product obtained from the polymerization more suitable for practical applications.

[0014] As a preferred embodiment of the present invention, the modified linear phosphazene chloride is prepared by the following method: mixing linear phosphazene chloride with an active substitute at a mass ratio of 0.8:1-1:0.8 and reacting at 50-120°C for 1-5 hours; the active substitute is trifluoroethanol or hexafluoroisopropanol, dimethyl phosphate or diethyl phosphate.

[0015] Furthermore, the mass ratio of linear phosphazene chloride to the active substitute can be 0.9:1 to 1:0.9.

[0016] The molecular formula of the linear phosphazene chloride is Cl(PCl2 =N)3PCl3.

[0017] As a preferred embodiment of the present invention, the modified linear chlorinated phosphazene is a highly substituted linear chlorinated phosphazene. This is because the polymerization reaction of hydroxyl silicone oil is a rapid condensation reaction. Without a capping agent, the reaction process is difficult to control. Furthermore, molecular weight is related to catalyst activity; the higher the activity and the faster the reaction rate, the faster the molecular weight of the resulting product increases. In the process of the present invention, the cavity falling film reactor used results in rapid heat transfer and rapid reaction, leading to a rapid increase in molecular weight. Excessive reaction speed can cause an increase in cyclicity, and excessively rapid growth can lead to excessively high product viscosity, preventing self-falling film formation and thus affecting continuous production. The present invention, by using highly substituted linear chlorinated phosphazene, significantly reduces catalyst activity while ensuring rapid reaction and easy control of the reaction process, enabling continuous and efficient production without the formation of cyclicity.

[0018] As a preferred technical solution of the present invention, the reaction time of the material in the reactor can be controlled by controlling the flow rate of the material fed into the reactor, such as 1-10 min, more preferably 1-5 min.

[0019] In the process of this invention, the molecular weight of hydroxyl silicone oil is related to the reaction time; the longer the time, the larger the molecular weight under the same reaction conditions. The cavity falling film reactor used in this invention allows for rapid heat transfer and rapid reaction, necessitating strict control of the reaction time to control the molecular weight of the product. This prevents the product from becoming too viscous, which would hinder self-falling film formation and thus affect the continuous production process.

[0020] As a preferred embodiment of the present invention, the heat preservation temperature of the reactor can be 40-130℃, more preferably 60-100℃.

[0021] In the process of this invention, hydroxyl silicone oil rapidly polymerizes under heating catalysis, and the higher the temperature, the faster the reaction rate and the faster the molecular weight increase. The cavity falling film reactor used in this process allows for rapid heat transfer and reaction, requiring strict control of the heating temperature to control the molecular weight of the product. This prevents the product from becoming too viscous, hindering self-falling film formation and thus affecting continuous production. Simultaneously, to ensure that the large amount of water generated during the rapid reaction is promptly removed, the reaction system temperature must not be too low.

[0022] As a preferred embodiment of the present invention, the vacuum degree in the reactor can be -0.10 to -0.05 MPa.

[0023] As a preferred embodiment of the present invention, the bubbling rate of the inert gas in the reactor can be 0.1-2 kg / h. The inert gas can be nitrogen or the like.

[0024] As a preferred embodiment of the present invention, the mixing of the linear body and the modified linear phosphazene chloride can be carried out at room temperature.

[0025] In the method of the present invention, the hydroxyl silicone oil obtained by the reaction in the falling film reactor can be purified into a purified product after neutralization and de-lowering treatment.

[0026] Furthermore, the neutralization can be achieved by adding a neutralizing agent. The neutralizing agent can be any conventionally used neutralizing agent, such as, but not limited to, at least one selected from, but not limited to, methyldivinyldisilazane (vinylsilazane), hexamethyldisilazane (silazane), diethylamine, triethylamine, etc.

[0027] Furthermore, the neutralization can be carried out at 40-130°C.

[0028] Furthermore, the neutralization reaction time can be 10-60 minutes.

[0029] Furthermore, the neutralization can be carried out in a reaction vessel, a static balancer, or a dynamic reactor.

[0030] Furthermore, the amount of the neutralizing agent is 1.1-1.5 times the amount of catalyst-modified linear phosphazene chloride in the reaction system.

[0031] Furthermore, the aforementioned degradation can be carried out using conventional methods, such as molecular evaporators, or at a vacuum of -0.10 to -0.05 MPa and a temperature of 140-200°C.

[0032] Furthermore, it is preferable to adjust the temperature of the material exiting the falling film reactor before neutralization. The temperature can be adjusted to 20-50℃.

[0033] Furthermore, the temperature adjustment can be achieved by adding the material to a temperature control device such as a heat exchanger.

[0034] Secondly, the present invention also provides an apparatus for the above-described process, comprising a falling film reactor, a temperature control device, and a neutralization reactor connected in sequence.

[0035] The temperature control device is connected to the lower outlet of the falling film reactor.

[0036] The temperature control device is connected to one or more neutralization reactors.

[0037] The feed inlet at the top of the falling film reactor is connected to a static mixer via a pipe. The reactants are mixed in the static mixer and then pumped into the falling film reactor through the feed inlet for further reaction.

[0038] Furthermore, the temperature control device is used to adjust the temperature of the material obtained from the falling film reactor reaction. Any device that can achieve temperature control can be used in this device, such as a heat exchanger.

[0039] Furthermore, a static mixer can be provided between the temperature control device and the neutralization reactor. The hydroxyl silicone oil and neutralizing agent, after temperature adjustment, can be added to the static mixer and mixed evenly before being added to the neutralization reactor for reaction.

[0040] Furthermore, the neutralization reactor is used to carry out the neutralization reaction. Any device that can perform this function can be used as a neutralization reactor, such as a reaction vessel, a static balancer, or a dynamic reactor.

[0041] Furthermore, the neutralization reactor can be connected to a descaling device. The material after the neutralization reaction can be descaled to remove small molecules. The descaling device can be any device conventionally used in the art, such as a molecular evaporator.

[0042] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0043] 1. This invention uses linear bodies as raw materials and employs a cavity falling film reactor. Through rapid heat transfer via a large cavity area, it achieves rapid reaction while quickly removing water generated during the condensation process. Moreover, production is continuous, greatly improving production efficiency.

[0044] 2. The process of this invention uses modified linear phosphazene chloride as a catalyst. By controlling the reaction temperature, reaction time and other conditions, it achieves a high-efficiency reaction while effectively avoiding the generation of a large number of cyclic compounds (D4, D5, etc.). It also avoids the problems of hydroxyl silicone oil reacting too quickly in the falling film reactor, resulting in excessive molecular weight growth and failure to fall film on its own, and excessive viscosity causing water to be unable to be discharged in time, leading to catalyst deactivation and affecting continuous reaction production.

[0045] 3. The synthesis process based on the falling film reactor of this invention can synthesize hydroxyl silicone oil continuously, rapidly and efficiently, effectively solving the problems of cumbersome synthesis process, low production efficiency, high energy consumption and poor batch stability of hydroxyl silicone oil in the prior art. Attached Figure Description

[0046] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0047] Figure 1 This is a schematic diagram of the process flow of the present invention. Detailed Implementation

[0048] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto. Unless otherwise specified, all materials involved in the following embodiments are commercially available. Unless otherwise specified, all methods described are conventional methods.

[0049] This invention provides a process for the efficient condensation polymerization of hydroxyl silicone oil using a cavity falling film polymerization method, wherein... Figure 1 This is a schematic diagram of the process flow of the present invention. The falling film reactor is typically arranged vertically, with the liquid forming a thin film flowing along the inner wall of the cavity. The cavity has a temperature control system, which allows for heat transfer to the liquid on the inner wall. Simultaneously, internal vacuum ventilation removes small molecules and moisture, commonly used in industrial processes for dewatering. In this invention, the material undergoes rapid polymerization during the falling film process along the inner wall of the reactor, and the vacuum ventilation quickly removes the large amount of water rapidly generated during the linear polymerization reaction. Gravity-induced film falling allows the reaction to continue rapidly. Therefore, existing conventional falling film reactors can be used in this invention's process, and equipment with simple modifications to the interior of the cavity that does not affect the heat transfer, falling film, and vacuum ventilation functions required for the production process of this invention can also be used.

[0050] The following embodiments use a hinged falling film reactor as an example to implement the process of the present invention. Different types of falling film reactors do not affect their applicability to the process of the present invention.

[0051] The modified linear phosphazene chloride used in the following examples was prepared by the following specific methods: Ten parts by mass of linear phosphazene chloride (with the structure [Cl(PCl2=N)3PCl3]) were added to ten parts by mass of hexafluoroisopropanol, and the mixture was reacted at 80-100°C for 1-3 hours. Under vacuum conditions (e.g., -0.09 MPa), the reaction was continued at 50-60°C for 0.5-1 hours to remove unreacted hexafluoroisopropanol, yielding the modified linear phosphazene chloride. Other highly substituted modified linear phosphazene chlorides with a linear phosphazene chloride to active substitute ratio of 0.9:1 to 1:0.9 can be applied in this application and all have the same or similar technical effects. Example 1

[0052] A process for high-efficiency condensation polymerization of hydroxyl silicone oil using cavity falling film polymerization includes the following steps:

[0053] (1) The modified linear phosphazene chloride and the linear hydroxyl-terminated polydimethylsiloxane (viscosity 80-120 CPS) were mixed evenly in a static mixer, and the amount of catalyst was 20 ppm.

[0054] (2) The above-mentioned mixed material is injected into the cavity falling film reactor from the top through the pressure valve and the reaction product is obtained from the bottom outlet; wherein, in the falling film reactor, the vacuum degree is -0.10~-0.05MPa, the nitrogen bubbling speed is 0.2Kg / h, the oil temperature is 70℃, and the flow rate is controlled so that the material reacts in the reactor for 3min.

[0055] (3) The reaction product flows out from the bottom of the falling film reactor. After GPC testing, the linear conversion rate is 98.6%. It is pumped into the heat exchanger and the temperature is adjusted to 40°C. Based on the amount of catalyst in the raw materials, the amount of neutralizing agent required is calculated. The neutralizing agent and the hydroxyl silicone oil after temperature adjustment are added to the static mixer and mixed. The mixture is neutralized for 20 min in a static balancer (or dynamic reactor) at 50°C. The mixture is then de-lowered through a molecular evaporator at 190°C with a vacuum of -0.10 to -0.05 MPa to obtain 5100 mm / s hydroxyl silicone oil with a yield of 97% and a cyclic content of 320 ppm. Example 2

[0056] A process for high-efficiency condensation polymerization of hydroxyl silicone oil using cavity falling film polymerization includes the following steps:

[0057] (1) The modified linear phosphazene chloride and the linear hydroxyl-terminated polydimethylsiloxane (viscosity 80-120 CPS) were mixed evenly in a static mixer, and the amount of catalyst was 15 ppm.

[0058] (2) The above-mentioned mixed material is injected into the cavity falling film reactor from the top through the pressure valve and the reaction product is obtained from the bottom outlet; wherein, in the falling film reactor, the vacuum degree is -0.10~-0.05MPa, the nitrogen bubbling speed is 0.2Kg / h, the oil temperature is 80℃, and the flow rate is controlled so that the material reacts in the reactor for 4min.

[0059] (3) The reaction product flows out from the bottom of the falling film reactor. After GPC testing, the linear conversion rate is 98.8%. It is pumped into the heat exchanger and the temperature is adjusted to 40°C. Based on the amount of catalyst in the raw materials, the amount of neutralizing agent required is calculated. The neutralizing agent and the hydroxyl silicone oil after temperature adjustment are added to the static mixer and mixed. The mixture is neutralized for 20 min in a static balancer (or dynamic reactor) at 70°C. The mixture is then de-lowered through a molecular evaporator at 190°C and a vacuum of -0.10 to -0.05 MPa to obtain 4900 mm / s hydroxyl silicone oil with a yield of 98% and a cyclic content of 310 ppm. Example 3

[0060] A process for high-efficiency condensation polymerization of hydroxyl silicone oil using cavity falling film polymerization includes the following steps:

[0061] (1) The modified linear phosphazene chloride and the linear hydroxyl-terminated polydimethylsiloxane (viscosity 80-120 CPS) were mixed evenly in a static mixer, and the amount of catalyst was 10 ppm.

[0062] (2) The above-mixed material is injected into the cavity falling film reactor from the top through the pressure valve and the reaction product is obtained from the bottom outlet; wherein, in the falling film reactor, the vacuum degree is -0.10~-0.05MPa, the nitrogen bubbling speed is 0.2Kg / h, the oil temperature is 65℃, and the flow rate is controlled so that the material reacts in the reactor for 5min.

[0063] (3) The reaction product flows out from the bottom of the falling film reactor. After GPC testing, the linear conversion rate is 98.9%. It is pumped into the heat exchanger and the temperature is adjusted to 40°C. Based on the amount of catalyst in the raw materials, the amount of neutralizing agent required is calculated. The neutralizing agent and the hydroxyl silicone oil after temperature adjustment are added to the static mixer and mixed. The mixture is neutralized for 20 min in a static balancer (or dynamic reactor) at 80°C. The mixture is then de-lowered through a molecular evaporator at 190°C with a vacuum of -0.10 to -0.05 MPa to obtain 5280 mm / s hydroxyl silicone oil with a yield of 97.8% and a cyclic content of 330 ppm. Example 4

[0064] A process for high-efficiency condensation polymerization of hydroxyl silicone oil using cavity falling film polymerization includes the following steps:

[0065] (1) The modified linear phosphazene chloride and the linear hydroxyl-terminated polydimethylsiloxane (viscosity 80-120 CPS) were mixed evenly in a static mixer, and the amount of catalyst was 25 ppm.

[0066] (2) The above-mixed material is injected into the chamber-type falling film reactor from the top through the pressure valve and the reaction product is obtained from the bottom outlet; wherein, in the falling film reactor, the vacuum degree is -0.10~-0.05MPa, the nitrogen bubbling speed is 0.2Kg / h, the oil temperature is 65℃, and the flow rate is controlled so that the material reacts in the reactor for 3.5min.

[0067] (3) The reaction product flows out from the bottom of the falling film reactor. After GPC testing, the linear conversion rate is 98.6%. It is pumped into the heat exchanger and the temperature is adjusted to 40°C. Based on the amount of catalyst in the raw materials, the amount of neutralizing agent required is calculated. The neutralizing agent and the hydroxyl silicone oil after temperature adjustment are added to the static mixer and mixed. The mixture is neutralized for 20 min in a static balancer (or dynamic reactor) at 60°C. The mixture is then de-lowered through a molecular evaporator at 190°C with a vacuum of -0.10 to -0.05 MPa to obtain 6300 mm / s hydroxyl silicone oil with a yield of 96.9% and a cyclic content of 350 ppm. Comparative Example 1: Hydroxyl silicone oil prepared from DMC (dimethylsiloxane mixed cyclic compound, commercially available) via a batch reactor.

[0068] First, 3880 kg (measured by a mass flow meter) of DMC was pumped into a DMC metering tank and then added to the reactor. The reactor was stirred, the heat transfer oil valve was opened, and the temperature was raised. When the temperature reached 120°C, 24 g of potassium hydroxide alkali gel catalyst was added. The reaction temperature was controlled at 150°C, and the reaction was allowed to proceed for 2 hours. Once the kinematic viscosity of the reactants reached above 50,000 mm / s, water was added to initiate the degradation reaction. 12.81 kg of water was added at a uniform rate over 150-180 minutes. During this process, the reactant temperature was controlled between 130°C and 150°C, and the kinematic viscosity gradually decreased to 3500-4500 mm / s. After the water addition was completed, heating was immediately stopped, and the temperature was lowered to below 100°C. 36g of phosphate-based silicone gum was added as a neutralizing agent and neutralized at 150℃ for 1 hour. GPC testing showed a DMC conversion rate of 86%. After neutralization, vacuum distillation was performed. The descaling temperature was controlled at 170℃, the vacuum degree at 300Pa, and the descaling time was 4 hours until no liquid flowed out of the sight glass of the receiving vessel, yielding hydroxyl silicone oil, of which 580 kg was produced at low boiling point. The kinematic viscosity of the product reached 4300 mm / s, the yield was 85%, and the cyclic content was 1500 ppm. Comparative Example 2

[0069] A process for high-efficiency condensation polymerization of hydroxyl silicone oil using cavity falling film polymerization includes the following steps:

[0070] (1) The linear hydroxyl-terminated polydimethylsiloxane (viscosity 80-120 CPS) and linear phosphazene chloride were mixed evenly in a static mixer, and the amount of catalyst was 20 ppm.

[0071] (2) The above-mentioned mixed material is fed into the cavity falling film reactor through the pressure valve and the reaction product is obtained from the lower outlet. The vacuum degree is -0.10~-0.05MPa, the nitrogen bubbling speed is 0.2Kg / h, the oil temperature is 70℃, and the flow rate is controlled so that the material reacts in the reactor for 3min.

[0072] Because linear phosphazene chloride has high catalytic activity, as the material is fed into the falling film reactor, the hydroxyl silicone oil reacts rapidly and produces a large amount of water. Due to the fast reaction rate and rapid molecular weight increase, the resulting hydroxyl silicone oil has an excessively large molecular weight and viscosity, making it unable to fall into the film and thus production cannot proceed. Comparative Example 3

[0073] A process for high-efficiency condensation polymerization of hydroxyl silicone oil using cavity falling film polymerization includes the following steps:

[0074] (1) The linear hydroxyl-terminated polydimethylsiloxane (viscosity 80-120 CPS) and the modified linear phosphazene chloride were mixed evenly in a static mixer, and the amount of catalyst was 15 ppm.

[0075] (2) The above-mentioned mixed material is injected into the cavity falling film reactor through the pressure valve for reaction. The vacuum degree is -0.10~-0.05MPa, the nitrogen bubbling speed is 0.2Kg / h, the oil temperature is 150℃, and the flow rate is controlled so that the material reacts in the reactor for 3min.

[0076] Due to the high reaction temperature, the hydroxyl silicone oil reacts rapidly as the material is fed into the falling film reactor. The dehydration rate is too fast, and the molecular weight increases too quickly, resulting in an excessively large molecular weight and viscosity of the hydroxyl silicone oil. This makes it unable to fall film on its own, and production cannot proceed.

[0077] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A process for high-efficiency condensation polymerization to form hydroxyl silicone oil, characterized in that: Using a falling film reactor as the reactor, linear polymers and modified linear phosphazene chlorides were mixed and injected into the reactor from the top to react, thus preparing hydroxyl silicone oil.

2. The process according to claim 1, characterized in that: The amount of the modified linear phosphazene chloride used is 10-100 ppm.

3. The process according to claim 1, characterized in that... The modified linear phosphazene chloride is prepared by the following method: a linear phosphazene chloride is mixed with an active substitute at a mass ratio of 0.8:1-1:0.8 and reacted at 50-120℃ for 1-5 hours; the active substitute is trifluoroethanol or hexafluoroisopropanol, dimethyl phosphate or diethyl phosphate; the molecular formula of the linear phosphazene chloride is Cl(PCl2=N)3PCl3.

4. The process according to claim 1, characterized in that... The reaction time of the material in the reactor is controlled by adjusting the flow rate of the material fed into the reactor, which is 1-10 minutes.

5. The process according to claim 1, characterized in that: The reactor is kept at a temperature of 40-130℃.

6. The process according to claim 1, characterized in that: The vacuum degree in the reactor is -0.10 to -0.05 MPa; the bubbling speed of the inert gas in the reactor is 0.1-2 kg / h.

7. The process according to claim 1, characterized in that... The hydroxyl silicone oil obtained by the falling film reactor reaction is neutralized and de-lowered to obtain a purified product.

8. An apparatus for the process according to any one of claims 1-7, characterized in that: It includes a falling film reactor, a temperature control device, and a neutralization reactor connected in sequence; the temperature control device is connected to the lower outlet of the falling film reactor; the temperature control device is connected to one or more neutralization reactors respectively.

9. The apparatus according to claim 8, characterized in that: A static mixer is provided between the temperature control device and the neutralization reactor.

10. The apparatus according to claim 8, characterized in that: The neutralization reactor is connected to the de-lowering device.

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