CN103408582B - A kind of preparation method of 3-mercaptopropyltriethoxysilane coupling agent - Google Patents
A kind of preparation method of 3-mercaptopropyltriethoxysilane coupling agent Download PDFInfo
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- CN103408582B CN103408582B CN201310396681.3A CN201310396681A CN103408582B CN 103408582 B CN103408582 B CN 103408582B CN 201310396681 A CN201310396681 A CN 201310396681A CN 103408582 B CN103408582 B CN 103408582B
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Abstract
The present invention relates to a kind of preparation method of 3-mercaptopropyltriethoxysilane coupling agent, belong to technical field of organic chemistry.The present invention is for raw material with Sodium sulfhydrate, 3-chloropropyl triethoxysilane, take water as solvent, under the effect of phase-transfer catalyst, heated and stirred is obtained by reacting silane crude product, and crude product obtains 3-mercaptopropyltriethoxysilane coupling agent product through super-dry, filtration, distillation.Present invention process is simple, production cost compared with low, product yield is high, stink is little, safety, environmental protection, easily realize large-scale industrial and produce.
Description
Technical field
The present invention relates to a kind of preparation method of 3-mercaptopropyltriethoxysilane coupling agent, belong to technical field of organic chemistry.
Background technology
3-mercaptopropyltriethoxysilane coupling agent is a kind of silane coupler containing sulfur with sulfydryl functional group.It is for the metal finishing such as gold and silver, copper, can strengthen the rotproofness on its surface, oxidation-resistance and increase the high molecular cementabilities such as itself and resin.In rubber industry, be usually used in the mineral fillers such as process white carbon black, carbon black, glass fibre, mica, effectively can improve mechanical property and the wear resisting property of rubber.Weaving can be used for the shrink proof finish of fabric.
At present, the production method of domestic 3-mercaptopropyltriethoxysilane mainly contains two kinds of techniques.A kind of technique is: utilize the dried thiocarbamide of baking and the 3-chloropropyl triethoxysilane stirring reaction that heats up under catalyst action to generate amidino groups salt intermediate, this intermediate generates guanidinesalt and 3-mercaptopropyltriethoxysilane product again with ammonia react.Then filtering separation guanidinesalt, filtrate obtains 3-mercaptopropyltriethoxysilane product by underpressure distillation.
Another kind of technique is: ethanolic soln reaction hydrogen sulfide being passed into sodium ethylate generates the ethanolic soln of Sodium sulfhydrate, add 3-chloropropyl triethoxysilane again, reaction generates sodium-chlor and 3-mercaptopropyltriethoxysilane, filters sodium-chlor, filtrate by distilling and obtaining 3-mercaptopropyltriethoxysilane product.
The main shortcoming of above-mentioned two kinds of modes of production is: the amount that front a kind of technique produces by product guanidinesalt is larger, guanidinesalt and product stink greatly, larger to the pollution of environment; The gas that the hydrogen sulfide used in rear a kind of technique is a kind of severe toxicity, its production safety risk is high, potential safety hazard is large.
Summary of the invention
The object of the invention is to: providing one with Sodium sulfhydrate solid, 3-chloropropyl triethoxysilane for raw material, take water as solvent, the method for Reactive Synthesis 3-mercaptopropyltriethoxysilane coupling agent under phase-transfer catalyst effect.
Technical scheme of the present invention:
A preparation method for 3-mercaptopropyltriethoxysilane coupling agent, is characterized in that: it comprises the following steps:
1), first by mass content be 70 ~ 73% Sodium sulfhydrate solid mix by 1:1 ~ 1:2 mass ratio with tap water, under normal temperature, stirring and dissolving forms the Sodium sulfhydrate aqueous solution of yellow transparent, is then warmed up to 60 ~ 85 DEG C.
2), add sodium bicarbonate powder stirring and dissolving, after continuing to be warmed up to 80 ~ 90 DEG C, add benzyl tributyl ammonium chloride or palmityl trimethyl ammonium chloride as phase-transfer catalyst.Then at 80 ~ 90 DEG C, drip 3-chloropropyl triethoxysilane stirring reaction, the time for adding of 3-chloropropyl triethoxysilane is 2 ~ 3 hours, dropwises rear continuation reaction 8 ~ 12 hours.Wherein, the mass ratio of Sodium sulfhydrate and 3-chloropropyl triethoxysilane is 1:2.95 ~ 1:3.05, sodium bicarbonate and Sodium sulfhydrate mass ratio are 1:4 ~ 1:5, and the add-on of benzyl tributyl ammonium chloride or palmityl trimethyl ammonium chloride is 3 ~ 5% of 3-chloropropyl triethoxysilane quality;
3), after completion of the reaction, get the analysis of upper organic phase crude product gas chromatographic detection, when 3-chloropropyl triethoxysilane content drops to stopped reaction after below 2.0%, then reduce the temperature to room temperature; Again material is transferred to separating funnel stratification, time of repose 2 ~ 6 hours, separate the organic phase crude product that lower floor's aqueous phase obtains upper strata yellow.
4), in organic phase crude product, add the anhydrous magnesium sulfate of 5% ~ 10% of crude product quality or anhydrous sodium sulphate carries out drying as siccative, 8 ~ 10 hours time of drying, after filtration, obtain dried crude product.
5), by dried crude product at 80 ~ 110 DEG C, under 2 ~ 3mmHg vacuum degree condition, carry out underpressure distillation, obtain water white 3-mercaptopropyltriethoxysilane coupling agent product.Product yield 85 ~ 95%, through gas chromatographic detection, the content of its product is greater than 98.0%.
Advantage of the present invention is:
1) utilize Sodium sulfhydrate and 3-chloropropyl triethoxysilane Reactive Synthesis 3-mercaptopropyltriethoxysilane coupling agent product under taking water as solvent, catalyst action, its reactions steps is short, and production technique is simple.
2) main raw material that reaction adopts is Sodium sulfhydrate and 3-chloropropyltriethylsilane, and its raw material is easy to get, low price, therefore production cost is lower.
3) yield of product is higher, purity is high, production process safety, environmental protection, and product stink is little.
The present invention prepares 3-mercaptopropyltriethoxysilane product, and compared with the 3-mercaptopropyltriethoxysilane product prepared with other processing method, each index is as follows:
Embodiment
Embodiment 1:
In the four-hole boiling flask of 3000ml, load onto prolong, mechanical stirring, thermometer and heating in water bath pot.By mass content be 70% flak sodium hydrosulfide solid 480g and tap water 600g drop in flask, stirring at normal temperature 10 minutes, makes Sodium sulfhydrate dissolve and forms the Sodium sulfhydrate aqueous solution of yellow transparent.Then be warmed up to 60 ~ 65 DEG C, drop into 95g sodium bicarbonate powder and stir 5 minutes in flask, after its sodium bicarbonate dissolves, the PH of reaction system is 9 ~ 10.Continue to be warmed up to 80 ~ 85 DEG C, the benzyl tributyl ammonium chloride adding 45g, as phase-transfer catalyst, drips the 3-chloropropyl triethoxysilane stirring reaction of 1450g under 80 ~ 85 DEG C of conditions, and the time for adding of 3-chloropropyl triethoxysilane is 2 hours.Drip rear continuation reaction 8 hours, get upper organic phase crude product gas chromatographic detection, now 3-chloropropyl triethoxysilane content is 1.8%.Then continue insulated and stirred and react stopped reaction after 1 hour, temperature drops to room temperature; Material is transferred to separating funnel stratification, time of repose 2 hours, separate the organic phase crude product that lower floor's aqueous phase obtains upper strata yellow.In organic phase crude product, add the anhydrous magnesium sulfate drying 8 hours of 75g, obtain 1402g dried 3-mercaptopropyltriethoxysilane coupling agent crude product.
3-mercaptopropyltriethoxysilane coupling agent crude product is carried out underpressure distillation at 90 ~ 100 DEG C, under 2mmHg vacuum degree condition, obtains 1280g water white 3-mercaptopropyltriethoxysilane coupling agent product (finished product), the high boiling material do not distilled out is 150g.3-mercaptopropyltriethoxysilane coupling agent product yield is 88.9%, and through gas chromatographic detection, in product, the content of 3-mercaptopropyltriethoxysilane coupling agent is 98.2%.
Embodiment 2:
In the four-hole boiling flask of 3000ml, load onto prolong, mechanical stirring, thermometer and heating in water bath pot.By 480g mass content be 73% Sodium sulfhydrate and tap water 700g drop in flask, stirring at normal temperature 10 minutes, makes Sodium sulfhydrate dissolve and forms the Sodium sulfhydrate aqueous solution of yellow transparent.Then be warmed up to 70 ~ 75 DEG C, drop into 110g sodium bicarbonate powder and stir 5 minutes in flask, after its sodium bicarbonate dissolves, the PH of reaction system is 9 ~ 10; Continue to be warmed up to 85 ~ 90 DEG C, add the benzyl tributyl ammonium chloride of 50g as phase-transfer catalyst, under 85 ~ 90 DEG C of conditions, drip the 3-chloropropyl triethoxysilane stirring reaction of 1450g, the time for adding of 3-chloropropyl triethoxysilane is 2.5 hours.Drip rear continuation reaction 10 hours, get upper organic phase crude product gas chromatographic detection and detect, now 3-chloropropyl triethoxysilane content is 1.4%.Then continue to stir insulation reaction stopped reaction after 1 hour.After temperature drops to room temperature, material is transferred to separating funnel stratification, time of repose 4 hours, separate the organic phase crude product that lower floor's aqueous phase obtains upper strata yellow.The anhydrous magnesium sulfate adding 75g in organic phase crude product carries out drying, 9 hours time of drying.Obtain 1400g dried 3-mercaptopropyltriethoxysilane coupling agent crude product.
3-mercaptopropyltriethoxysilane coupling agent crude product is carried out underpressure distillation at 90 ~ 95 DEG C, under 2.5mmHg vacuum degree condition, obtains 1320g water white 3-mercaptopropyltriethoxysilane coupling agent product (finished product), the high boiling material do not distilled out is 75g.3-mercaptopropyltriethoxysilane coupling agent product yield 91.5%, through gas chromatographic detection, in product, the content of 3-mercaptopropyltriethoxysilane coupling agent is 98.5%.
Embodiment 3:
In the four-hole boiling flask of 3000ml, load onto prolong, mechanical stirring, thermometer and heating in water bath pot.By mass content be 73% Sodium sulfhydrate solid 480g and tap water 800g drop in flask, stirring at normal temperature 10 minutes, makes Sodium sulfhydrate dissolve and forms the Sodium sulfhydrate aqueous solution of yellow transparent.Then be warmed up to 80 ~ 85 DEG C, drop into 120g sodium bicarbonate powder and stir 5 minutes in flask, after sodium bicarbonate dissolves, the PH of reaction system is 9 ~ 10; After continuing to be warmed up to 88 ~ 90 DEG C, add the palmityl trimethyl ammonium chloride of 50g as phase-transfer catalyst, under 88 ~ 90 DEG C of conditions, drip the 3-chloropropyl triethoxysilane stirring reaction of 1450g, the time for adding of 3-chloropropyl triethoxysilane is 3 hours.Dropwise rear continuation reaction 12 hours, get the analysis of upper organic phase crude product gas chromatographic detection, now 3-chloropropyl triethoxysilane content is 0.9%, then continues to stir insulation reaction stopped reaction after 1 hour.After temperature drops to room temperature, material is transferred to separating funnel stratification, time of repose 6 hours, separate the organic phase crude product that lower floor's aqueous phase obtains upper strata yellow.The anhydrous sodium sulphate adding 100g in organic phase crude product carries out drying, 10 hours time of drying, obtains 3-mercaptopropyltriethoxysilane coupling agent crude product after 1400g drying.
3-mercaptopropyltriethoxysilane coupling agent crude product is carried out underpressure distillation at 100 ~ 110 DEG C, under 3mmHg vacuum degree condition, obtain 1350g water white 3-mercaptopropyltriethoxysilane coupling agent coupling agent product (finished product), the high boiling material do not distilled out is 45g.3-mercaptopropyltriethoxysilane coupling agent coupling agent product yield is 93.7%, and through gas chromatographic detection, in product, the content of 3-mercaptopropyltriethoxysilane coupling agent is 98.8%.
Claims (1)
1. a preparation method for 3-mercaptopropyltriethoxysilane coupling agent, is characterized in that: it comprises the following steps:
1), first by mass content be 70 ~ 73% Sodium sulfhydrate solid mix by 1:1 ~ 1:2 mass ratio with tap water, under normal temperature, stirring and dissolving forms the Sodium sulfhydrate aqueous solution of yellow transparent, is then warmed up to 60 ~ 85 DEG C;
2), add sodium bicarbonate powder stirring and dissolving, after continuing to be warmed up to 80 ~ 90 DEG C, add benzyl tributyl ammonium chloride or palmityl trimethyl ammonium chloride as phase-transfer catalyst; Then at 80 ~ 90 DEG C, drip 3-chloropropyl triethoxysilane stirring reaction, the time for adding of 3-chloropropyl triethoxysilane is 2 ~ 3 hours, dropwises rear continuation reaction 8 ~ 12 hours; Wherein, the mass ratio of Sodium sulfhydrate and 3-chloropropyl triethoxysilane is 1:2.95 ~ 1:3.05, sodium bicarbonate and Sodium sulfhydrate mass ratio are 1:4 ~ 1:5, and the add-on of benzyl tributyl ammonium chloride or palmityl trimethyl ammonium chloride is 3 ~ 5% of 3-chloropropyl triethoxysilane quality;
3), after completion of the reaction, get the analysis of upper organic phase crude product gas chromatographic detection, when 3-chloropropyl triethoxysilane content drops to after below 2.0%, reduce the temperature to room temperature; Again material is transferred to separating funnel stratification, time of repose 2 ~ 6 hours, separate the organic phase crude product that lower floor's aqueous phase obtains upper strata yellow;
4), in organic phase crude product, add the anhydrous magnesium sulfate of 5% ~ 10% of crude product quality or anhydrous sodium sulphate carries out drying as siccative, 8 ~ 10 hours time of drying, after filtration, obtain dried crude product;
5), dried crude product is carried out underpressure distillation at 80 ~ 110 DEG C, under 2 ~ 3mmHg vacuum degree condition, obtain water white 3-mercaptopropyltriethoxysilane coupling agent product, product yield 85 ~ 95%, through gas chromatographic detection, the content of its product is greater than 98.0%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104926854B (en) * | 2014-03-23 | 2018-05-11 | 浙江新安化工集团股份有限公司 | A kind of method that atmospheric low-temperature water mutually prepares mercaptopropyltriethoxysilane |
| CN104926857B (en) * | 2015-06-25 | 2017-10-31 | 嘉兴学院 | The synthetic method of 3 mercaptopropyltriethoxysilanes |
| CN107513076A (en) * | 2015-11-12 | 2017-12-26 | 青岛惠国新材料科技有限公司 | A kind of method that γ mercaptopropyltriethoxysilanes are synthesized using multicomponent catalyst |
| CN107522730A (en) * | 2017-08-31 | 2017-12-29 | 永修县艾科普新材料有限公司 | A kind of preparation method of γ mercaptopropyltriethoxysilanes |
| CN109776593B (en) * | 2017-11-14 | 2023-05-09 | 河北圣泰材料股份有限公司 | Preparation method of 1, 3-dimethyl-1, 3-tetraethylenedisiloxane |
| CN107936053A (en) * | 2017-12-25 | 2018-04-20 | 荆州市江汉精细化工有限公司 | A kind of preparation method of mercapto propyl group alkoxy silane |
| CN110003266B (en) * | 2019-04-28 | 2021-11-05 | 南京曙光精细化工有限公司 | Environment-friendly production method of high-quality 3-octanoyl thio-1-propyltriethoxysilane |
| CN110483566B (en) * | 2019-07-31 | 2022-03-25 | 湖南正量工程技术有限公司 | Method for preparing mercaptosilane coupling agent by using phase transfer catalyst |
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