Preparation method of 3-octanoyl thiopropyltriethoxysilane
By dissolving sodium hydrosulfide and sodium hydroxide solids in water and adding a phase transfer catalyst, a two-step substitution reaction and post-treatment were carried out, solving the problem of low purity of 3-octanoylthiopropyltriethoxysilane in the prior art. This enabled the preparation of high-purity products, meeting the application requirements of photovoltaic and high-end manufacturing fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANDONG GUIKE NEW MATERIAL CO LTD
- Filing Date
- 2026-01-27
- Publication Date
- 2026-05-12
AI Technical Summary
Existing methods for preparing 3-octanoylthiopropyltriethoxysilane yield products with low purity, which cannot meet the requirements for high purity, especially for applications in the photovoltaic industry and high-end manufacturing.
High-purity 3-octanoylthiopropyltriethoxysilane was prepared by dissolving solid sodium hydrosulfide and solid sodium hydroxide in water under a protective atmosphere, adding a phase transfer catalyst, and undergoing a two-step substitution reaction and post-treatment steps, including settling, washing, dehydration, and distillation at low boiling point.
It improved product purity and yield, reduced impurity generation and sodium hydrosulfide loss, lowered production costs, solved the problem of hydrogen sulfide spillage, and met the demand for high-purity products.
Smart Images
Figure CN122011008A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic compound technology, specifically relating to a method for preparing 3-octanoylthiopropyltriethoxysilane. Background Technology
[0002] 3-Octanoylthiopropyltriethoxysilane and its derivatives, as organosilicon compounds, are widely used in surface treatment, sealants, and adhesives. They form a silicon-oxygen bond network through hydrolysis and condensation reactions, providing waterproofing, corrosion protection, and enhanced adhesion. With the increasing demands for new materials technology and environmental protection, the application scope of organosilicon compounds such as 3-octanoylthiopropyltriethoxysilane may gradually expand into the field of green chemicals, particularly in the areas of high-efficiency catalysts and biodegradation research, thereby increasing the demand for 3-octanoylthiopropyltriethoxysilane.
[0003] As the photovoltaic industry raises its requirements for the performance of crosslinking agents, the demand for high-purity 3-octanoylthiopropyltriethoxysilane has also increased. For example, in the production of photovoltaic EVA films, high-purity 3-octanoylthiopropyltriethoxysilane can ensure uniform crosslinking reaction and improve the light transmittance and aging resistance of the adhesive. In the modification of electronic-grade plastics, high-purity 3-octanoylthiopropyltriethoxysilane can avoid the influence of impurities on the insulation performance of materials and meet the needs of high-end manufacturing.
[0004] However, the existing methods for preparing 3-octanoylthiopropyltriethoxysilane result in 3-octanoylthiopropyltriethoxysilane with low purity, mostly around 90%. Summary of the Invention
[0005] In view of this, the present invention provides a method for preparing 3-octanoylthiopropyltriethoxysilane, which can be prepared with high purity 3-octanoylthiopropyltriethoxysilane according to the preparation method provided by the present invention.
[0006] To address the aforementioned technical problems, this invention provides a method for preparing 3-octanoylthiopropyltriethoxysilane, comprising the following steps: Sodium hydrosulfide solid and sodium hydroxide solid were dissolved in water under a protective atmosphere, and a first phase transfer catalyst was added to obtain a first mixture. Octanoyl chloride was added dropwise to the first mixture to carry out a first substitution reaction, yielding an intermediate; After adding a second phase transfer catalyst to the system following the first substitution reaction, chloropropyltriethoxysilane was added dropwise to carry out a second substitution reaction, and the 3-octanoylthiopropyltriethoxysilane was obtained after post-treatment. The post-processing includes the following steps: cooling the system after the second substitution reaction and allowing it to stand for separation, taking the organic phase; washing the organic phase with water and then performing dehydration and distillation at low boiling point to obtain the 3-octanoylthiopropyltriethoxysilane.
[0007] Preferably, the molar ratio of sodium hydrosulfide solid to sodium hydroxide solid is 0.8~1.2:1, and the dissolution temperature is 45~50℃.
[0008] Preferably, the first phase transfer catalyst is tetrabutylammonium bromide, and the molar ratio of the first phase transfer catalyst to octanoyl chloride is 0.16~0.18:100.
[0009] Preferably, the molar ratio of octanoyl chloride to sodium hydrosulfide is 0.8~1.2:1, the dropping rate of octanoyl chloride is 20~22 mL / min, the dropping of octanoyl chloride is accompanied by stirring, the temperature of the first substitution reaction is 20~30℃, and the time of the first substitution reaction is 0.5~1 h.
[0010] Preferably, the acidic gas generated during the first substitution reaction is absorbed by water or sodium hydroxide solution.
[0011] Preferably, the second phase transfer catalyst is tetrabutylammonium bromide, and the molar ratio of the second phase transfer catalyst to chloropropyltriethoxysilane is 1.15~1.17:100.
[0012] Preferably, the molar ratio of chloropropyltriethoxysilane to octanoyl chloride is 0.9~1.1:1; the time for adding chloropropyltriethoxysilane is 0.4~0.6 h; the temperature of the second substitution reaction is 88~92 °C; and the time of the second substitution reaction is 4~6 h.
[0013] Preferably, the temperature after cooling is 25~35℃; the volume ratio of organic phase to water during the washing process is 0.8~1.2:1; and the number of washing cycles is 2~3.
[0014] Preferably, the dehydration conditions include: a negative pressure vacuum of 700~730 mmHg and a temperature of 99~101℃.
[0015] Preferably, the distillation temperature for low boiling is 150~160℃.
[0016] This invention provides a method for preparing 3-octanoylthiopropyltriethoxysilane, comprising the following steps: dissolving sodium hydrosulfide solid and sodium hydroxide solid in water under a protective atmosphere, adding a first phase transfer catalyst to obtain a first mixture; adding octanoyl chloride dropwise to the first mixture to carry out a first substitution reaction to obtain an intermediate; adding a second phase transfer catalyst to the system after the first substitution reaction, and then adding chloropropyltriethoxysilane dropwise to carry out a second substitution reaction, and obtaining the 3-octanoylthiopropyltriethoxysilane after post-treatment; the post-treatment includes the following steps: cooling the system after the second substitution reaction and allowing it to stand for separation, taking the organic phase; washing the organic phase with water and then performing dehydration and distillation at low boiling point to obtain the 3-octanoylthiopropyltriethoxysilane. This invention directly uses solid sodium hydrosulfide and solid sodium hydroxide as raw materials, dissolving them simultaneously in water. This stabilizes the reaction environment, reduces impurity formation, and improves product purity. It also maximizes the reactivity of sodium hydrosulfide, minimizes its loss, and reduces the release of acidic gases and hydrogen sulfide during the reaction. The preparation method provided by this invention is simple and easy to operate, and the resulting 3-octanoylthiopropyltriethoxysilane exhibits high purity and yield. Attached Figure Description
[0017] Figure 1 The gas chromatogram of the 3-octanoylthiopropyltriethoxysilane product prepared in Example 1; Figure 2 The mass spectrometry chromatogram shows the 3-octanoylthiopropyltriethoxysilane product prepared in Example 1. Detailed Implementation
[0018] This invention provides a method for preparing 3-octanoylthiopropyltriethoxysilane, comprising the following steps: Sodium hydrosulfide solid and sodium hydroxide solid were dissolved in water under a protective atmosphere, and a first phase transfer catalyst was added to obtain a first mixture. Octanoyl chloride was added dropwise to the first mixture to carry out a first substitution reaction, yielding an intermediate; After adding a second phase transfer catalyst to the system following the first substitution reaction, chloropropyltriethoxysilane was added dropwise to carry out a second substitution reaction, and the 3-octanoylthiopropyltriethoxysilane was obtained after post-treatment. The post-processing includes the following steps: cooling the system after the second substitution reaction and allowing it to stand for separation, taking the organic phase; washing the organic phase with water and then performing dehydration and distillation at low boiling point to obtain the 3-octanoylthiopropyltriethoxysilane.
[0019] This invention involves dissolving solid sodium hydrosulfide and solid sodium hydroxide in water under a protective atmosphere, and then adding a first phase transfer catalyst to obtain a first mixture. In one specific embodiment, the protective atmosphere can be nitrogen or argon; the sodium hydrosulfide can be industrial grade, with a purity of 70-72%, specifically 71.83%; the molar ratio of solid sodium hydrosulfide to solid sodium hydroxide can be 0.8-1.2:1, specifically 1:1; the dissolution temperature can be 45-50°C, and stirring can accompany the dissolution process. This invention does not have special requirements for stirring, as long as complete dissolution is achieved. This invention does not have special requirements for the amount of water used, as long as complete dissolution is achieved. In this invention, the dissolution of solid sodium hydrosulfide and solid sodium hydroxide in water is exothermic, requiring the temperature of the mixed system to be controlled at 45-50°C; in this invention, sodium hydroxide can react with the acidic gas generated by the first substitution reaction, such as HCl or H₂S, to promote the forward reaction.
[0020] In this invention, the sulfide ions in sodium hydrosulfide have strong reducing properties. When sodium hydrosulfide solution is left standing for a long time, it is easily oxidized to elemental sulfur by oxygen in the air, leading to a decrease in sulfide ion concentration and affecting reactivity. Simultaneously, sodium hydrosulfide may decompose in aqueous solution, releasing hydrogen sulfide gas, which also reduces the sulfide ion concentration in the solution, affecting reactivity. Sodium hydrosulfide may also undergo hydrolysis in aqueous solution, generating other compounds that further affect reactivity. This invention directly uses solid sodium hydrosulfide as a raw material, simultaneously dissolving solid sodium hydrosulfide and solid sodium hydroxide in water to maximize the reactivity of sodium hydrosulfide, thereby reducing the loss of raw material sodium hydrosulfide and minimizing the release of acidic gases and hydrogen sulfide during the reaction process.
[0021] In one specific embodiment of the present invention, the first phase transfer catalyst can be tetrabutylammonium bromide, and the molar ratio of the first phase transfer catalyst to octanoyl chloride can be 0.16~0.18:100, specifically 0.17:100. The addition of the first phase transfer catalyst can be accompanied by stirring. The present invention has no special requirements for the stirring, as long as the mixture is homogeneous.
[0022] As a specific embodiment of the present invention, after obtaining the first mixture, the present invention can cool the first mixture to 15~25℃, specifically 20℃; the present invention has no special requirements for the cooling method, as long as the required temperature can be achieved.
[0023] After obtaining the first mixture, the present invention adds octanoyl chloride dropwise to the first mixture to carry out a first substitution reaction, thereby obtaining an intermediate. In one specific embodiment of the present invention, the molar ratio of octanoyl chloride to sodium hydrosulfide can be 0.8~1.2:1, specifically 1:1; the dropping rate of octanoyl chloride can be 20~22 mL / min, specifically 21 mL / min; the dropping of octanoyl chloride can be accompanied by stirring, and the present invention has no special requirements for the stirring, as long as the mixture is homogeneous.
[0024] In one specific embodiment of the present invention, the temperature of the first substitution reaction can be 20~30℃, or 18~23℃, specifically 20℃; the time of the first substitution reaction can be 0.5~1h; the time of the first substitution reaction starts after the addition of octanoyl chloride is completed; the first substitution reaction is carried out under a protective atmosphere, which can be nitrogen or argon.
[0025] In this invention, the equation for the first substitution reaction is shown in Formula 1: Formula 1.
[0026] In one specific embodiment of the present invention, the acidic gas generated during the first substitution reaction can be absorbed by water or sodium hydroxide solution; the acidic gas can be hydrogen chloride or hydrogen sulfide; the sodium sulfide or sodium hydrosulfide generated after the sodium hydroxide solution absorbs the acidic gas can provide reactants for the first substitution reaction, promote the forward reaction, and at the same time reduce the extra leakage of tail gas.
[0027] Following the first substitution reaction, the present invention adds a second phase transfer catalyst to the system after the first substitution reaction and then drops chloropropyltriethoxysilane to carry out a second substitution reaction, obtaining the 3-octanoylthiopropyltriethoxysilane after post-treatment. In one specific embodiment of the present invention, the second phase transfer catalyst can be tetrabutylammonium bromide; the molar ratio of the second phase transfer catalyst to chloropropyltriethoxysilane can be 1.15~1.17:100, specifically 1.16:100. In another specific embodiment of the present invention, the molar ratio of chloropropyltriethoxysilane to octanoyl chloride can be 0.9~1.1:1, specifically 1:1; the time for dropping chloropropyltriethoxysilane can be 0.4~0.6 h, specifically 0.5 h; stirring can accompany the dropping of chloropropyltriethoxysilane, and the present invention has no special requirements for the stirring, as long as the mixture is homogeneous.
[0028] In one specific embodiment of the present invention, the temperature of the second substitution reaction can be 88~92℃, specifically 90℃; the time of the second substitution reaction can be 4~6h or 4.5~5h.
[0029] In this invention, the equation for the second substitution reaction using tetrabutylammonium bromide as the second phase transfer catalyst is shown in Formula 2: Equation 2.
[0030] In this invention, the post-processing includes the following steps: cooling the system after the second substitution reaction and allowing it to stand for separation, taking the organic phase; washing the organic phase with water and then sequentially dehydrating and distilling at low boiling point to obtain the 3-octanoylthiopropyltriethoxysilane. As a specific embodiment of this invention, the cooling temperature can be 25~35℃, specifically 30℃; the water used for washing can be distilled water; the volume ratio of the organic phase to water during washing can be 0.8~1.2:1, specifically 1:1; and the number of water washes can be 2~3 times. This invention can remove the catalyst from the organic phase through water washing.
[0031] In one specific embodiment of the present invention, the dehydration conditions may include: a negative pressure vacuum of 700-730 mmHg and a temperature of 99-101°C, or a negative pressure vacuum of 710-720 mmHg and a temperature of 100°C; the low-boiling temperature of the distillation may be 150-160°C. The present invention can remove pre-boiling fractions such as ethanol and chloropropyltriethoxysilane through distillation; and can retain 3-octanoylthiopropyltriethoxysilane at the bottom of the vessel through distillation.
[0032] The preparation method provided by this invention can effectively solve the problem of hydrogen sulfide overflow during the synthesis process and the problem of the strong taste of the finished product. This invention ensures that sodium hydrosulfide is in a highly active state during the reaction process, reduces the amount of sodium hydrosulfide used, and thus reduces production costs.
[0033] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0034] Example 1 Under N2 protection, 1716.5 mL of water was first added to the reactor. Then, while stirring, 1 mol of sodium hydrosulfide solid and 1 mol of sodium hydroxide solid were added (dissolution is exothermic, so pay attention to temperature control. After dissolution, the temperature inside the reactor is about 50°C). After stirring and dissolving, 1.7 mmol of tetrabutylammonium bromide (as a phase transfer catalyst) was added and stirred evenly to obtain the first mixture. Under N2 protection, the first mixture was cooled to 20°C, and 1 mol of octanoyl chloride was added dropwise at a rate of 20 mL / min. The first substitution reaction was carried out at 20°C for 0.5 h. The acidic gases (hydrogen chloride and hydrogen sulfide) generated during the first substitution reaction were absorbed by sodium hydroxide solution. Under N2 protection, 11.6 mmol of tetrabutylammonium bromide (as a phase transfer catalyst) was added to the system after the first reaction, the temperature was raised to 90 °C, and 1 mol of chloropropyltriethoxysilane was added dropwise over 0.5 h; after the addition was completed, the second substitution reaction was carried out at 90 °C for 4 h. Under N2 protection, the system after the second substitution reaction was cooled to about 30°C, allowed to stand, and the organic phase was separated. The organic phase and distilled water were mixed at a volume ratio of 1:1 and washed twice. The mixture was separated, and then the organic phase was dehydrated using a water pump under negative pressure (vacuum degree of 720 mmHg, temperature of 100°C). The dehydrated phase was then distilled under negative pressure using an oil pump (distillation temperature of 150~160°C) to obtain 3-octanoylthiopropyltriethoxysilane.
[0035] The yield of 3-octanoylthiopropyltriethoxysilane was 77%, and the purity was 99.17% as determined by gas chromatography.
[0036] The product 3-octanoylthiopropyltriethoxysilane prepared in Example 1 was analyzed by gas chromatography and mass spectrometry to obtain... Figure 1 and Figure 2 ;in Figure 1 The gas chromatogram of the product 3-octanoylthiopropyltriethoxysilane prepared in Example 1 is shown below. Figure 2 The mass spectrometry spectrum of the product 3-octanoylthiopropyltriethoxysilane prepared in Example 1 is shown. Figure 1 and Figure 2 It can be seen that the product obtained in Example 1 is 3-octanoylthiopropyltriethoxysilane.
[0037] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.
Claims
1. A method for preparing 3-octanoylthiopropyltriethoxysilane, characterized in that, Includes the following steps: Sodium hydrosulfide solid and sodium hydroxide solid were dissolved in water under a protective atmosphere, and a first phase transfer catalyst was added to obtain a first mixture. Octanoyl chloride was added dropwise to the first mixture to carry out a first substitution reaction, yielding an intermediate; After adding a second phase transfer catalyst to the system following the first substitution reaction, chloropropyltriethoxysilane was added dropwise to carry out a second substitution reaction, and the 3-octanoylthiopropyltriethoxysilane was obtained after post-treatment. The post-processing includes the following steps: cooling the system after the second substitution reaction and allowing it to stand for separation, taking the organic phase; washing the organic phase with water and then performing dehydration and distillation at low boiling point to obtain the 3-octanoylthiopropyltriethoxysilane.
2. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The molar ratio of sodium hydrosulfide solid to sodium hydroxide solid is 0.8~1.2:1, and the dissolution temperature is 45~50℃.
3. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The first phase transfer catalyst is tetrabutylammonium bromide, and the molar ratio of the first phase transfer catalyst to octanoyl chloride is 0.16~0.18:
100.
4. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The molar ratio of octanoyl chloride to sodium hydrosulfide is 0.8~1.2:1, the dropping rate of octanoyl chloride is 20~22 mL / min, the dropping of octanoyl chloride is accompanied by stirring, the temperature of the first substitution reaction is 20~30℃, and the time of the first substitution reaction is 0.5~1 h.
5. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1 or 4, characterized in that, In the first substitution reaction, the acidic gas generated is absorbed by water or sodium hydroxide solution.
6. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The second phase transfer catalyst is tetrabutylammonium bromide, and the molar ratio of the second phase transfer catalyst to chloropropyltriethoxysilane is 1.15~1.17:
100.
7. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The molar ratio of chloropropyltriethoxysilane to octanoyl chloride is 0.9~1.1:1; the time for adding chloropropyltriethoxysilane is 0.4~0.6 h; the temperature of the second substitution reaction is 88~92 °C; and the time of the second substitution reaction is 4~6 h.
8. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The temperature after cooling is 25~35℃; the volume ratio of organic phase to water during the washing process is 0.8~1.2:1, and the number of times the water is washed is 2~3.
9. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The dehydration conditions include: a negative pressure vacuum of 700~730 mmHg and a temperature of 99~101℃.
10. The method for preparing 3-octanoylthiopropyltriethoxysilane according to claim 1, characterized in that, The distillation temperature for low boiling is 150~160℃.