Continuous synthesis method of phenyl silicone resin

Abstract

The invention provides a continuous synthesis method and device of phenyl silicone resin, which innovatively adopts a turntable tubular reactor, integrates a hydrolytic condensation reaction and a dynamic layering process driven by a centrifugal force into the same device, is different from a traditional static layering mode depending on gravity, and realizes continuous synthesis of the phenyl silicone resin by virtue of the centrifugal force generated by high-speed rotation. The rapid and efficient separation of water and oil phases is realized, the layering time is greatly shortened, and the upstream continuous synthesis rhythm is effectively matched. According to the design, the equipment investment and operation links are remarkably reduced, the production efficiency is improved, the stability and the consistency of product batches are ensured, and the device is particularly suitable for a continuous production process.

Description

Technical Field

[0001] This invention belongs to the field of polymer silicone resins, and specifically relates to a continuous synthesis method for phenyl silicone resin. Background Technology

[0002] In the field of heat-resistant coatings, modifying organic resins with silicone resins is one of the core strategies for improving the thermal stability of the substrate and extending its service life. Its key advantage lies in the excellent thermal oxidation stability and extremely high Si-O bond energy inherent in silicone resins themselves.

[0003] Currently, most mainstream heat-resistant coatings on the market use phenyl silicone resins. However, these resins are typically prepared using a batch process, which often suffers from problems such as uneven mixing, long separation times, high equipment investment, and difficulty in controlling batch stability. Therefore, to overcome the shortcomings of existing technologies, this invention aims to provide a continuous synthesis method for phenyl silicone resins. Summary of the Invention

[0004] This invention addresses the aforementioned technical problems by providing a continuous synthesis method for phenyl silicone resin. This method employs a rotating tubular reactor to simultaneously integrate monomer polymerization and water-oil phase extraction and separation, thereby achieving continuous preparation of phenyl silicone resin. Compared to traditional batch reaction processes, this invention eliminates multiple reaction vessels and extraction / separation equipment, simplifying the synthesis process while significantly improving product stability and production efficiency.

[0005] The technical solution adopted in this invention is as follows:

[0006] 1) Mix chlorosilane and solvent to obtain mixture A;

[0007] 2) Mix the co-solvent and water to obtain mixture B;

[0008] 3) Mixture A is injected through the upper feed port of the rotary tube reactor, and mixture B is injected through the lower feed port of the rotary tube reactor to carry out hydrolysis and condensation reactions. After the reaction is completed, the polymerization solution is collected from the bottom discharge port and the acidic wastewater is discharged from the top discharge port.

[0009] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0010] 5) The resin mother liquor is filtered and dried sequentially to finally obtain phenyl silicone resin.

[0011] Furthermore, in step 1), the chlorosilane in mixture A contains at least one T-type monomer or a combination of at least one T-type monomer and at least one D-type monomer;

[0012] Furthermore, the T-type monomer is selected from methyltrichlorosilane, propyltrichlorosilane, and phenyltrichlorosilane;

[0013] Furthermore, the D-type monomer is selected from dimethyldichlorosilane, methylphenyldichlorosilane, and diphenyldichlorosilane;

[0014] Furthermore, in step 1), the chlorosilane in mixture A is preferably a combination of phenyltrichlorosilane and propyltrichlorosilane in a molar ratio of 1:1 to 3:1.

[0015] Furthermore, the solvent of mixture A in step 1) includes at least one of toluene and xylene.

[0016] Furthermore, in step 1), the amount of solvent added to mixture A is 0.5 to 2 times the total mass of chlorosilane.

[0017] Furthermore, in step 2), the amount of water added to mixture B is 1 to 5 times the total mass of the chlorosilane.

[0018] Furthermore, the co-solvent for mixture B in step 2) includes at least one of methanol, ethanol, isopropanol, n-butanol, tert-butanol, and acetone.

[0019] Furthermore, in step 2), the amount of cosolvent added to mixture B is 5-30% of the water mass.

[0020] Furthermore, in step 3), the rotating disc reactor is a jacketed tubular structure with an inner wall material resistant to acid corrosion and is equipped with an acid-resistant disc agitator.

[0021] Furthermore, the disc-shaped stirring paddle has 20-40 layers.

[0022] Furthermore, in step 3), the reaction temperature is 15–60°C, the material residence time is 30–60 minutes, and the rotation speed is 150–300 rpm.

[0023] Furthermore, the water washing temperature in step 4) is 15–50°C.

[0024] Furthermore, the drying temperature in step 5) is 40–70°C.

[0025] Furthermore, the weight-average molecular weight of the phenyl silicone resin obtained in step 5) is 1500–10000 g / mol.

[0026] The present invention also provides a continuous synthesis apparatus for phenyl silicone resin, comprising:

[0027] The premixing tank V101 for chlorosilane and solvent, the premixing tank V102 for cosolvent and water, the rotary tube reactor R201, the water washing device R301, the wastewater storage device V201, the filtration device and the drying device.

[0028] Furthermore, the outlet of the premix tank V101 is connected to the upper inlet of the rotary tube reactor via a pipeline, and the outlet of the premix tank V102 is connected to the lower inlet of the rotary tube reactor R201 via a pipeline.

[0029] Furthermore, the upper outlet of the rotary tube reactor R201 is connected to the wastewater storage device V201, and the lower outlet is connected to the upper inlet of the washing device R301.

[0030] Furthermore, water is introduced into the lower inlet of the washing device R301, the upper outlet is connected to the wastewater storage device V201, and the discharge outlet is connected to the filter device and the drying device.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) This invention innovatively employs a rotating tube reactor, integrating the hydrolysis-condensation reaction with a dynamic layering process driven by centrifugal force into the same device. Unlike the traditional method of static layering relying on gravity, this invention utilizes the centrifugal force generated by high-speed rotation to achieve rapid and efficient separation of the water and oil phases, greatly shortening the layering time and effectively matching the upstream continuous synthesis rhythm.

[0033] (2) This design not only significantly reduces equipment investment and operation, but also helps to improve production efficiency and ensure the stability and consistency of product batches, especially suitable for continuous production processes. Attached Figure Description

[0034] Figure 1 This is a schematic diagram of a continuous synthesis apparatus for phenyl silicone resin.

[0035] In the diagram, V101 is a premixing tank for chlorosilane and solvent; V102 is a premixing tank for cosolvent and water; R201 is a rotary tube reactor; R301 is a water washing device; and V201 is a wastewater storage device.

[0036] Figure 2 This is a schematic diagram of a rotating tube reactor.

[0037] Figure 3 For example 2, phenyl silicone resin 1 H NMR spectrum.

[0038] Figure 4 The image shows the GPC chromatogram of phenyl silicone resin from Example 2. Detailed Implementation

[0039] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0040] The raw materials used in the examples were all selected from commercially available conventional products.

[0041] Example 1

[0042] Constructing a continuous synthesis apparatus for phenyl silicone resin:

[0043] The premixing tank V101 for chlorosilane and solvent and the premixing tank V102 for cosolvent and water are made of acid-resistant material;

[0044] The rotary tube reactor R201 has a jacketed tubular structure with an inner wall material resistant to acid corrosion and is equipped with an acid-resistant disc agitator, which is connected to the drive motor.

[0045] The discharge port of V101 is connected to the upper inlet of R201 via a pipeline, and the discharge port of V102 is connected to the lower inlet of R201 via a pipeline. The upper and lower discharge ports of R201 are respectively connected to the upper inlets of the wastewater storage device V201 and the washing device R301. Water is introduced into the lower inlet of R301, the upper discharge port is connected to the wastewater storage tank V201, and the lower discharge port is connected to the filtration and drying device.

[0046] Example 2

[0047] 1) Add 211.6g of phenyltrichlorosilane, 65.8g of propyltrichlorosilane and 166.4g of toluene to V101 and mix to obtain mixture A;

[0048] 2) Add 27.7g of isopropanol and 277.3g of water to V102 and mix to obtain mixture B;

[0049] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (24-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 15℃, the rotation speed is 150rpm, and the residence time is 45 minutes. After the reaction is completed, 328.4g of polymerization solution is collected from the bottom outlet and acidic wastewater is discharged from the top outlet.

[0050] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 30°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0051] 5) The resin mother liquor was successively filtered, dried (40℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 2800 g / mol.

[0052] Example 3

[0053] 1) Add 211.6g of phenyltrichlorosilane, 55.4g of methyltrichlorosilane, and 152.1g of toluene to V101 and mix to obtain mixture A;

[0054] 2) Add 26.7g of isopropanol and 267.0g of water to V102 and mix to obtain mixture B;

[0055] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (20-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 15℃, the rotation speed is 200rpm, and the residence time is 45 minutes. After the reaction is completed, the polymerization solution is collected from the bottom outlet and the acidic wastewater is discharged from the top outlet.

[0056] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 30°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0057] 5) The resin mother liquor was successively filtered, dried (40℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 3500 g / mol.

[0058] Example 4

[0059] 1) Add 211.6g of phenyltrichlorosilane, 177.5g of propyltrichlorosilane and 194.5g of toluene to V101 and mix to obtain mixture A;

[0060] 2) Add 19.5g of isopropanol and 389.1g of water to V102 and mix to obtain mixture B;

[0061] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (30-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 15℃, the rotation speed is 150rpm, and the residence time is 60 minutes. After the reaction is completed, the polymerization solution is collected from the bottom outlet and the acidic wastewater is discharged from the top outlet.

[0062] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 50°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0063] 5) The resin mother liquor was successively filtered, dried (40℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 5600 g / mol.

[0064] Example 5

[0065] 1) Add 211.6g of phenyltrichlorosilane, 177.5g of propyltrichlorosilane and 778.2g of toluene to V101 and mix to obtain mixture A;

[0066] 2) Add 583.6g of acetone and 1945.4g of water to V102 and mix to obtain mixture B;

[0067] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (40-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 60℃, the rotation speed is 300rpm, and the residence time is 30 minutes. After the reaction is completed, the polymerization solution is collected from the bottom outlet and the acidic wastewater is discharged from the top outlet.

[0068] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 15°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0069] 5) The resin mother liquor was successively filtered, dried (40℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 9000 g / mol.

[0070] Example 6

[0071] 1) Add 211.6g of phenyltrichlorosilane and 211.6g of xylene to V101 and mix to obtain mixture A;

[0072] 2) Add 63.5g of methanol and 634.7g of water to V102 and mix to obtain mixture B;

[0073] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (24-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 30℃, the rotation speed is 200rpm, and the residence time is 45 minutes. After the reaction is completed, the polymerization solution is collected from the bottom outlet and the acidic wastewater is discharged from the top outlet.

[0074] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 30°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0075] The resin mother liquor was successively filtered, dried (70℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 6300 g / mol.

[0076] Example 7

[0077] 1) Add 211.6g of phenyltrichlorosilane, 64.5g of dimethyldichlorosilane, and 165.6g of toluene to V101 and mix to obtain mixture A;

[0078] 2) Add 82.8g of ethanol and 828.2g of water to V102 and mix to obtain mixture B;

[0079] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (40-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 40℃, the rotation speed is 200rpm, and the residence time is 45 minutes. After the reaction is completed, the polymerization solution is collected from the bottom outlet and the acidic wastewater is discharged from the top outlet.

[0080] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 30°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0081] 5) The resin mother liquor was successively filtered, dried (70℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 8500 g / mol.

[0082] Example 8

[0083] 1) Add 211.6g of phenyltrichlorosilane, 95.6g of methylphenyldichlorosilane and 184.3g of xylene to V101 and mix to obtain mixture A;

[0084] 2) Add 30.7g of n-butanol and 307.1g of water to V102 and mix to obtain mixture B;

[0085] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (24-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 15℃, the rotation speed is 200rpm, and the residence time is 45 minutes. After the reaction is completed, the polymerization solution is collected from the bottom outlet and the acidic wastewater is discharged from the top outlet.

[0086] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 30°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0087] 5) The resin mother liquor was successively filtered, dried (70℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 6300 g / mol.

[0088] Example 9

[0089] 1) Add 211.6g of phenyltrichlorosilane, 126.6g of diphenyldichlorosilane, and 202.9g of xylene to V101 and mix to obtain mixture A;

[0090] 2) Add 33.8 g of tert-butanol and 338.1 g of water to V102 and mix to obtain mixture B;

[0091] 3) Mixture A is injected through the upper inlet of the rotary tube reactor, and mixture B is injected through the lower inlet of the rotary tube reactor (24-layer disc agitator) to carry out hydrolysis and condensation reactions. The reaction temperature is controlled at 15℃, the rotation speed is 200rpm, and the residence time is 45 minutes. After the reaction is completed, the polymerization solution is collected from the bottom outlet and the acidic wastewater is discharged from the top outlet.

[0092] 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. The washing temperature is 30°C. After washing until neutral, the resin mother liquor is obtained from the bottom outlet.

[0093] 5) The resin mother liquor was successively filtered, dried (70℃) and pulverized to finally obtain phenyl silicone resin with a molecular weight of 3100 g / mol.

Claims

1. A continuous synthesis method for phenyl silicone resin, characterized in that, Includes the following steps: 1) Mix chlorosilane and solvent to obtain mixture A; 2) Mix the co-solvent and water to obtain mixture B; 3) Mixture A is injected through the upper feed port of the rotary tube reactor, and mixture B is injected through the lower feed port of the rotary tube reactor to carry out hydrolysis and condensation reactions. After the reaction is completed, the polymerization solution is collected from the bottom discharge port and the acidic wastewater is discharged from the top discharge port. 4) The polymerization solution is fed into the top inlet of the washing device, and water is simultaneously introduced into the bottom inlet for washing. After washing until neutral, the resin mother liquor is obtained from the bottom outlet. 5) The resin mother liquor is filtered and dried sequentially to finally obtain phenyl silicone resin.

2. The continuous synthesis method of phenyl silicone resin according to claim 1, characterized in that, The chlorosilane comprises at least one T-type monomer or a combination of at least one T-type monomer and at least one D-type monomer; The T-type monomer is selected from methyltrichlorosilane, propyltrichlorosilane and phenyltrichlorosilane; The D-type monomer is selected from dimethyldichlorosilane, methylphenyldichlorosilane, and diphenyldichlorosilane; The chlorosilane is preferably a combination of phenyltrichlorosilane and propyltrichlorosilane in a molar ratio of 1:1 to 3:

1.

3. The continuous synthesis method of phenyl silicone resin according to claim 1, characterized in that, The solvent contains at least one of toluene and xylene, and the amount added is 0.5 to 2 times the total mass of the chlorosilane.

4. The continuous synthesis method of phenyl silicone resin according to claim 1, characterized in that, The amount of water added is 1 to 5 times the total mass of the chlorosilane; The co-solvent comprises at least one of methanol, ethanol, isopropanol, n-butanol, tert-butanol, and acetone, and is added in an amount of 5-30% of the water mass.

5. The continuous synthesis method of phenyl silicone resin according to claim 1, characterized in that, The rotary tube reactor is a jacketed tubular structure with an inner wall material resistant to acid corrosion and is equipped with an acid-resistant disc agitator. The disc-shaped agitator has 20-40 layers.

6. The continuous synthesis method of phenyl silicone resin according to claim 1, characterized in that, In step 3), the reaction temperature is 15~60℃, the material residence time is 30~60 minutes, and the rotation speed is 150~300rpm.

7. The continuous synthesis method of phenyl silicone resin according to claim 1, characterized in that, The water washing temperature in step 4) is 15~50℃; The drying temperature in step 5) is 40~70℃.

8. The continuous synthesis method of phenyl silicone resin according to claim 1, characterized in that, The weight-average molecular weight of the phenyl silicone resin obtained in step 5) is 1500~10000 g / mol.

9. A continuous synthesis apparatus for phenyl silicone resin, characterized in that, The continuous synthesis method according to any one of claims 1-8 includes a premixing tank V101 for chlorosilane and solvent, a premixing tank V102 for cosolvent and water, a rotating tube reactor R201, a water washing device R301, a wastewater storage device V201, a filtration device, and a drying device.

10. The continuous synthesis apparatus for phenyl silicone resin according to claim 9, characterized in that, The outlet of the premix tank V101 is connected to the upper inlet of the rotary tube reactor via a pipeline, and the outlet of the premix tank V102 is connected to the lower inlet of the rotary tube reactor R201 via a pipeline. The upper outlet of the rotary tube reactor R201 is connected to the wastewater storage device V201, and the lower outlet is connected to the upper inlet of the washing device R301; Water is introduced into the lower inlet of the washing device R301, the upper outlet is connected to the wastewater storage device V201, and the discharge outlet is connected to the filter and drying devices.

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