Preparation method of γ-methacryloxypropyl alkoxysilane

Abstract

The invention discloses a method for preparing γ-methacryloxypropyl alkoxysilane, and relates to the technical field of preparing γ-methacryloxypropyl alkoxysilane. The invention utilizes potassium methacrylate or sodium methacrylate to react with chloroalkane silane, and the raw materials are easily available; the reaction process is solvent-free, and solvent recovery is not required, thereby avoiding contact with personnel and causing personal injury, and the process route is shortened and the operation is simpler; the water washing process is used, and the product recovery is more thorough, and the yield is relatively high, with an input of 2400kg per batch and an output of 2750-2780kg per batch, and an average of about 80kg more products are produced per batch than the original process; an efficient organic amine catalyst is used, and the reaction time is short and the crude product content is high.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of gamma-methacryloxypropyl alkoxy silane, and in particular to a preparation method of gamma-methacryloxypropyl alkoxy silane. Background Art

[0002] The prior art mostly adopts trimethoxysilane (TMS) and allyl methacrylate (AMA) to directly hydrosilylate to prepare γ-methacryloxypropyl alkoxysilane, such as the Chinese patent with publication number CN101121727A. Although the process route is simple and environmentally friendly, due to the use of a Pt catalyst with too high activity, the reaction is too intense, the product is easy to gel, and the hydrosilylation reaction is accompanied by the generation of isomers, so the product purity is not high, the color is difficult to meet customer requirements, and the water solubility of the product is also affected.

[0003] Potassium or sodium methacrylate reacts with chloroalkane silane in an organic solvent environment and under the action of a catalyst, and potassium chloride or sodium chloride is removed to obtain γ-methacryloxypropyl alkoxysilane. The product has high purity, good water solubility and stable quality. However, the organic solvent in the reaction system needs to be recovered, and the organic solvent has hazards such as carcinogenicity, flammability and explosion. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a method for preparing γ-methacryloxypropyl alkoxysilane, the reaction process is solvent-free, no solvent recovery is required, the process route is shortened, and the operation is simpler.

[0005] To achieve this technical purpose, the present invention adopts the following scheme:

[0006] The preparation method of γ-methacryloxypropyl alkoxysilane is carried out according to the following steps:

[0007] S1. Synthesizing crude γ-methacryloxypropyl alkoxysilane by direct reaction of sodium methacrylate or potassium methacrylate with chloroalkylsilane under catalyst conditions;

[0008] S2, the synthesized γ-methacryloxypropyl alkoxysilane crude product is stirred and mixed with water, and then allowed to stand for stratification, the lower salt-containing phase is sent to sewage treatment, and the upper oil phase is dehydrated;

[0009] S3. The crude product after dehydration is distilled to obtain the refined product of γ-methacryloxypropyl alkoxysilane.

[0010] Compared with the prior art, the present invention has the following beneficial effects:

[0011] 1. Potassium methacrylate or sodium methacrylate is used to react with chloroalkylsilane, and the raw materials are easy to obtain;

[0012] 2. The reaction process does not involve solvents, and no solvent recovery is required, which avoids contact with personnel and personal injury. The process route is shortened and the operation is simpler;

[0013] 3. Using the water washing process, the product recovery is more thorough and the yield is relatively high. The input of each batch is 2400kg, and the output is 2750~2780kg. On average, each batch produces about 80kg more products than the original process.

[0014] 4. Use highly efficient organic amine catalysts, short reaction time and high crude product content.

[0015] The preferred embodiment of the present invention is:

[0016] The synthesis reaction temperature in S1 is 100~180°C and the pressure is 0~0.3Mpa.

[0017] The chloroalkylsilane in S1 is any one or more of chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chloromethylmethyldimethoxysilane and chloropropylmethyldiethoxysilane.

[0018] A highly efficient acylation catalyst.

[0019] S3 distillation is carried out under the conditions of vacuum degree -0.07Mpa~0.1Mpa and temperature 150~200℃. DETAILED DESCRIPTION

[0020] In order to fully understand the purpose, features and effects of the present invention, the present invention is described in detail through the following specific implementation methods, but the present invention is not limited thereto. Example 1

[0021] The preparation method of γ-methacryloxypropyl alkoxysilane is carried out according to the following steps:

[0022] S1. At a temperature of 150°C and a pressure of 0-0.3 MPa, 480 g of chloropropyltrimethoxysilane (Z2 for short, wherein the effective ingredient content of chloropropyltrimethoxysilane in the raw material is 99.34%), 260 g of sodium methacrylate, 1.8 g of a catalyst (tetrabutylammonium bromide) and 0.8 g of a polymerization inhibitor (p-hydroxyanisole) were directly reacted to obtain a crude product of γ-methacryloyloxypropyl alkoxysilane, the crude product content of which was 97.92%.

[0023] S2, the synthesized γ-methacryloxypropyl alkoxysilane crude product was stirred and mixed with water (the mass ratio of water to the input amount of Z2 was 1:1), and then allowed to stand for 10 minutes to separate the layers. The lower salty water phase was sent for sewage treatment, and the upper oil phase was dehydrated. The mass of the crude product after dehydration was 596.6g.

[0024] S3, the crude product after dehydration was distilled under the conditions of vacuum degree -0.07Mpa~0.1Mpa and temperature 150~200℃ to obtain the fine product of γ-methacryloxypropyl alkoxysilane. The mass of the fine product was 572g, and the yield based on the amount of Z2 (i.e. the mass of the distilled product / the amount of Z2 input) was 1.1917. Example 2

[0025] The preparation method of γ-methacryloxypropyl alkoxysilane is carried out according to the following steps:

[0026] S1. At a temperature of 150°C and a pressure of 0-0.3 MPa, 480 g of chloropropyltrimethoxysilane (Z2 for short, wherein the effective ingredient content of chloropropyltrimethoxysilane in the raw material is 99.34%), 260 g of sodium methacrylate, 1.8 g of a catalyst (pyridine) and 0.8 g of a polymerization inhibitor (p-tert-butylcatechol) were directly reacted to obtain a crude product of γ-methacryloxypropyl alkoxysilane, the crude product content of which was 97.86%.

[0027] S2, the synthesized γ-methacryloxypropyl alkoxysilane crude product was stirred and mixed with water (the mass ratio of water to the input amount of Z2 was 1:1), and then allowed to stand for 10 minutes to separate the layers. The lower salty water phase was sent for sewage treatment, and the upper oil phase was dehydrated. The mass of the crude product after dehydration was 585g.

[0028] S3, the crude product after dehydration was distilled under the conditions of vacuum degree -0.07Mpa~0.1Mpa and temperature 150~200°C to obtain the refined product of γ-methacryloxypropyl alkoxysilane. The mass of the refined product was 563g, and the yield was 1.1729 based on the amount of Z2. Example 3

[0029] The preparation method of γ-methacryloxypropyl alkoxysilane is carried out according to the following steps:

[0030] S1. At a temperature of 150°C and a pressure of 0-0.3 MPa, 480 g of chloropropyltrimethoxysilane (Z2 for short, wherein the effective ingredient content of chloropropyltrimethoxysilane in the raw material is 99.34%), 260 g of sodium methacrylate, 1.8 g of a catalyst (quaternary ammonium base) and 0.8 g of a polymerization inhibitor (2,5-di-tert-butylhydroquinone) were directly reacted to obtain a crude product of γ-methacryloyloxypropyl alkoxysilane, the crude product content of which was 98.37%.

[0031] S2, the synthesized γ-methacryloxypropyl alkoxysilane crude product was mixed with water (the mass ratio of water to the input amount of Z2 was 1:1), and then allowed to stand to separate into layers. The lower salty water phase was sent for sewage treatment, and the upper oil phase was dehydrated. The mass of the crude product after dehydration was 588g.

[0032] S3, the crude product after dehydration was distilled under the conditions of vacuum degree -0.07Mpa~0.1Mpa and temperature 150~200°C to obtain the refined product of γ-methacryloxypropyl alkoxysilane. The mass of the refined product was 568g, and the yield was 1.1809 based on the amount of Z2. Example 4

[0033] The preparation method of γ-methacryloxypropyl alkoxysilane is carried out according to the following steps:

[0034] S1. At a temperature of 130°C and a pressure of 0-0.3 MPa, 480 g of chloropropyltrimethoxysilane (Z2 for short, wherein the effective ingredient content of chloropropyltrimethoxysilane in the raw material is 99.34%), 260 g of sodium methacrylate, 1.8 g of a catalyst (tetrabutylammonium bromide) and 0.8 g of a polymerization inhibitor (p-hydroxyanisole) were directly reacted to obtain a crude product of γ-methacryloxypropyl alkoxysilane, the crude product content of which was 96.18%.

[0035] S2, the synthesized γ-methacryloxypropyl alkoxysilane crude product was stirred and mixed with water (the mass ratio of water to the input amount of Z2 was 1:1), and then allowed to stand for 10 minutes to separate the layers. The lower salty water phase was sent for sewage treatment, and the upper oil phase was dehydrated. The mass of the crude product after dehydration was 585.8g.

[0036] S3, the crude product after dehydration was distilled under the conditions of vacuum degree -0.07Mpa~0.1Mpa and temperature 150~200℃ to obtain the refined product of γ-methacryloxypropyl alkoxysilane. The mass of the refined product was 545.6g, and the yield based on the amount of Z2 (i.e. the mass of the distilled product / the amount of Z2 input) was 1.1367.

[0037] Comparative Example 1

[0038] S1. At a temperature of 138°C and a pressure of 0-0.3 MPa, 480 g of chloropropyltrimethoxysilane (Z2 for short, wherein the effective ingredient content of chloropropyltrimethoxysilane in the raw material is 99.34%), 260 g of sodium methacrylate, 1.8 g of a catalyst (tetrabutylammonium bromide) and 0.8 g of a polymerization inhibitor (p-hydroxyanisole) were directly reacted to obtain a crude product of γ-methacryloyloxypropyl alkoxysilane, the crude product content of which was 96.52%.

[0039] S2. Add 96 g of DMF solvent to the synthesized crude product of γ-methacryloxypropylalkoxysilane. After filtration, the mass of the crude product is 508.4 g.

[0040] S3, the filtered crude product was distilled under vacuum degree -0.07Mpa~0.1Mpa and temperature 150~200°C to obtain γ-methacryloxypropyl alkoxysilane fine product. The mass of the fine product was 465.8g, and the yield was 0.97 based on Z2 amount.

[0041] Finally, it should be noted that the above are only preferred embodiments of the present invention. Of course, those skilled in the art can make changes and modifications to the present invention. If these modifications and variations fall within the scope of the claims of the present invention and their equivalent technologies, they should be considered to be within the scope of protection of the present invention.

Claims

1. A method for preparing γ-methacryloxypropyl alkoxysilane, characterized in that: Proceed as follows: S1. Synthesizing crude γ-methacryloxypropyl alkoxysilane by direct reaction of sodium methacrylate or potassium methacrylate with chloropropyltrimethoxysilane under catalyst conditions; S2, the synthesized γ-methacryloxypropyl alkoxysilane crude product was stirred and mixed with water, and then allowed to stand for stratification, the lower salt-containing phase was sent to sewage treatment, and the upper oil phase was dehydrated; the mass ratio of water to chloropropyltrimethoxysilane was 1:1; S3, distilling the dehydrated crude product to obtain γ-methacryloxypropyl alkoxysilane fine product; A polymerization inhibitor is also added to S1, and the polymerization inhibitor is any one of p-hydroxyanisole, p-tert-butylcatechol, 2,5-di-tert-butylhydroquinone, and 2-tert-butylhydroquinone; S3 distillation is carried out under the conditions of vacuum degree -0.07Mpa~0.1Mpa and temperature 150~200℃; The catalyst is any one of tetrabutylammonium bromide, tetrapropylammonium bromide, pyridine, quaternary ammonium base, and benzyltriethylammonium chloride.

2. The method for preparing γ-methacryloxypropyl alkoxysilane according to claim 1, characterized in that: The synthesis reaction temperature in S1 is 100~180°C and the pressure is 0~0.3Mpa.