Preparation method of silane containing sulfydryl and trimethylsilyl

Abstract

The invention relates to the technical field of compound synthesis, and particularly discloses a preparation method of silane containing sulfydryl and trimethylsilyl, which comprises the following steps: reacting sulfydryl alkoxy silane with trimethylsilanol in an organic solvent, adding a catalyst, and reacting to obtain the silane containing sulfydryl and trimethylsilanol. Stirring and mixing, heating and reacting for 24-72 hours, layering to obtain a crude product of silane containing sulfydryl and trimethylsilyl, distilling at normal pressure to recover the organic solvent, and rectifying at reduced pressure to obtain a colorless and transparent finished product. The synthesized silane containing sulfydryl and trimethylsilyl is free of VOC emission, olefin, unsaturated ester, polyester and metal treated by the silane have high hydrophobicity and weather resistance, the silane has huge development prospects in the application field, and the synthesis method is simple in process, short in synthesis time, high in synthesis efficiency, high in finished product yield and beneficial to industrial mass production.

Description

Technical Field

[0001] The invention relates to the technical field of compound synthesis, and in particular to a method for preparing mercapto- and trimethylsilyl-silane-containing compounds. Background Art

[0002] The silane containing mercapto and trimethylsilyl is a reactive sulfur-containing silane coupling agent, containing mercapto and trimethylsilyl, without VOC emission, and its processed olefins, unsaturated fats, polyesters, and metals are highly hydrophobic and weather-resistant. The synthesis of the silane containing mercapto and trimethylsilyl in the prior art, such as patent CN104610337A, is to put the silane coupling agent containing active groups and trialkyl chlorosilane into the reactor in proportion, add methanol aqueous solution dropwise under stirring for cold water bath reaction, and then introduce the materials in the reactor into a conical container for static stratification, the upper layer is the crude product, and the upper layer crude product is washed, neutralized, dried, and vacuum-pulled to obtain the product after low-boiling substances are removed. The main disadvantage is that the raw material is chlorosilane, the yield of trimethylsilanol hydrolyzed in the reaction system is too low, and hexamethylsiloxane is easily produced. The reaction is easy to hydrolyze when water silane coupling agent liquid is added, and hydrochloric acid needs to be washed off in the later stage, which has high pollution and low yield. Summary of the invention

[0003] The present invention provides a method for preparing mercapto- and trimethylsilylsilane-containing compounds, which has mild reaction conditions, is easy to operate, has a short reaction time, a large safety factor, has low requirements on equipment, and has a high product yield and content, so as to solve the problems raised in the above-mentioned background technology.

[0004] The present invention provides a method for preparing a thiol- and trimethylsilylsilane-containing compound, the synthesis method comprising the following steps:

[0005] Add mercaptoalkoxysilane, trimethylsilanol, solvent and catalyst into a reaction kettle, raise the temperature to 50-100°C, react for 24-72h, then cool and separate the layers, take the organic layer, add it into a distillation tower for distillation, recover the solvent under reduced pressure, and obtain mercaptotrimethylsilylsilane by distillation.

[0006] Preferably, the mercaptoalkoxysilane includes: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyldimethylethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyldimethylethoxysilane.

[0007] Preferably, the solvent includes: petroleum ether (60-90° C.), cyclohexane, benzene, toluene, xylene and other hydrophobic solvents.

[0008] Preferably, the catalyst includes: tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin dioctoate, bismuth isooctanoate, bismuth laurate, and bismuth neodecanoate.

[0009] Preferably, the trimethylsilanol includes: trimethylsilanol (acidic) and trimethylsilanol (basic).

[0010] Preferably, the delamination temperature is 30-60°C, the distillation temperature is 30-210°C, the desolventizing pressure is 0-0.08MP, and the distillation pressure is 0-0.1MP.

[0011] Preferably, the amount of the catalyst is 0.1%-5% of the mercaptoalkoxysilane.

[0012] Preferably, the mass ratio of the amount of the solvent to the amount of the mercaptoalkoxysilane is 1-3:1.

[0013] Preferably, the molar ratio of the mercaptoalkoxysilane and trimethylsilanol during synthesis is 1:6-10.

[0014] The structural formula of the product is HS(CH2)nSi(CH3)m[OSi(CH3)3]3-m, where m is 0 to 2 and n is 1 or 3.

[0015] The chemical reaction equation of the present invention is:

[0016] HS(CH2)nSi(CH3)m(OR)3-m+HOSi(CH3)3→HS(CH2)nSi(CH3)m[OSi(CH3)3]3-m+ROH;

[0017] Wherein m is 0 to 2, n is 1 or 3; R is CH3 or CH2CH3.

[0018] The beneficial effects of the present invention are as follows: the present invention synthesizes mercapto-containing groups and trimethylsilyl silane without VOC emission, and the olefins, unsaturated fats, polyesters and metals treated by the present invention have strong hydrophobicity and weather resistance, and have great development prospects in the application field. The synthesis method has a simple process, short synthesis time, high synthesis efficiency, high yield of finished products, and is conducive to industrial mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Schematic diagram of the main reaction of 3-mercaptopropyltris(trimethylsilyloxy)silane;

[0020] Figure 2 Schematic diagram of the side reaction of 3-mercaptopropyltris(trimethylsiloxy)silane;

[0021] Figure 3This is a schematic diagram of the main reaction of mercaptomethyltris(trimethylsiloxy)silane;

[0022] Figure 4 Schematic diagram of the side reaction of mercaptomethyltris(trimethylsiloxy)silane;

[0023] Figure 5 Schematic diagram of the main reaction of 3-mercaptopropylmethylbis(trimethylsilyloxy)silane;

[0024] Figure 6 Schematic diagram of the side reaction of 3-mercaptopropylmethylbis(trimethylsilyloxy)silane. DETAILED DESCRIPTION

[0025] The present invention will be further described below in conjunction with specific embodiments.

[0026] Example 1

[0027] The present invention provides a preparation method of a thiol- and trimethylsilyl-containing silane, specifically a synthesis method of 3-mercaptopropyltris(trimethylsiloxy)silane, comprising the following steps:

[0028] 39.3g cyclohexane, 39.3g 3-mercaptopropyltrimethoxysilane (0.2mol), 90.2g trisilanol (acidic) (1mol), 0.5g dibutyltin dilaurate were added to the kettle, stirred and reacted at 70°C for 60 hours, then cooled to 30°C, separated and the upper layer was taken. The crude product was then distilled to obtain 68.3g of 3-mercaptopropyltris(trimethylsiloxy)silane.

[0029] The main reaction of this synthetic method is Figure 1 For side reactions, please refer to Figure 2 The synthesis method has a simple process and high synthesis efficiency, a yield of 92%, and a purity of up to 98.7%, which is conducive to industrial mass production.

[0030] Example 2

[0031] The present invention provides a method for preparing a thiol- and trimethylsilyl-containing silane, specifically a method for synthesizing mercaptomethyltris(trimethylsiloxy)silane, comprising the following steps:

[0032] 67.4g petroleum ether, 67.4g mercaptomethyl trimethoxysilane (0.4mol), 252.5g trisilanol (acidic) (2.8mol), and 0.8g tetrabutyl titanate were added to the kettle, stirred and reacted at 70°C for 48 hours, then cooled to 30°C, separated, and the upper layer was taken. The crude product was then distilled to obtain 123.4g of mercaptomethyl tris(trimethylsiloxy)silane.

[0033] The main reaction of this synthetic method is Figure 3 For side reactions, please refer to Figure 4 The synthetic method is easy to operate, has a short reaction time, a high safety factor, a yield of 90%, a purity of 98.3%, and has a high development prospect.

[0034] Example 3

[0035] The present invention provides a preparation method of a thiol- and trimethylsilyl-containing silane, specifically a method for synthesizing 3-mercaptopropylmethylbis(trimethylsiloxy)silane, comprising the following steps:

[0036] 41.4g of benzene, 41.4g of 3-mercaptopropylmethyldiethoxysilane (0.2mol), 0.4mol of trisilanol (basic), and 0.5g of dibutyltin dioctanoate were added to the kettle, and stirred at 70°C for 72 hours, then cooled to 30°C, separated, and the upper layer was taken. The crude product was then distilled to obtain 55.7g of the product 3-mercaptopropylmethylbis(trimethylsiloxy)silane.

[0037] The main reaction of this synthetic method is Figure 5 For side reactions, please refer to Figure 6 Compared with the traditional synthesis method, the yield of this synthesis method is as high as 94%, the purity is 98.5%, the reaction conditions are mild, the operation is easy, the equipment requirements are low, and it is conducive to industrial promotion.

[0038] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a mercapto- and trimethylsilylsilane-containing compound, characterized in that: The synthesis method comprises the following steps: Add mercaptoalkoxysilane, trimethylsilanol, solvent and catalyst into a reaction kettle, raise the temperature to 50-100°C, react for 24-72h, then cool and separate the layers, take the organic layer, add it into a distillation tower for distillation, recover the solvent under reduced pressure, and obtain mercaptotrimethylsilylsilane by distillation.

2. The method for preparing the mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The mercaptoalkoxysilane includes: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyldimethylethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyldimethylethoxysilane.

3. The method for preparing the mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The solvent includes: petroleum ether (60-90° C.), cyclohexane, benzene, toluene, xylene and other hydrophobic solvents.

4. The method for preparing the mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The catalyst includes: tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dibutyltin dioctoate, bismuth isooctanoate, bismuth laurate, and bismuth neodecanoate.

5. The method for preparing the mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The trimethylsilanol includes: trimethylsilanol (acidic) and trimethylsilanol (alkaline).

6. The method for preparing the mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The delamination temperature is 30-60°C, the distillation temperature is 30-210°C, the desolventizing pressure is 0-0.08MP, and the distillation pressure is 0-0.1MP.

7. The method for preparing a mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The amount of the catalyst used is 0.1%-5% of the mercaptoalkoxysilane.

8. The method for preparing a mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The mass ratio of the amount of the solvent to the amount of the mercaptoalkoxysilane is 1-3:

1.

9. The method for preparing a mercapto- and trimethylsilylsilane-containing compound according to claim 1, wherein: The molar ratio of the mercaptoalkoxysilane and trimethylsilanol during synthesis is 1:6-10.

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