CN102875588A - Preparation method of sulfhydryl silane coupling agent - Google Patents
Preparation method of sulfhydryl silane coupling agent Download PDFInfo
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- CN102875588A CN102875588A CN2012104003476A CN201210400347A CN102875588A CN 102875588 A CN102875588 A CN 102875588A CN 2012104003476 A CN2012104003476 A CN 2012104003476A CN 201210400347 A CN201210400347 A CN 201210400347A CN 102875588 A CN102875588 A CN 102875588A
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Abstract
The invention relates to a preparation method of a sulfhydryl silane coupling agent, belonging to the field of organic chemistry. According to the invention, the reaction is firstly completed partially under reduced pressure, and a small amount of acid absorbent is added to complete the reaction, thereby reducing the generation of amine hydrochloride and the generation of the byproduct. The sulfhydryl silane coupling agent product prepared by the method has the advantages of high and stable quality, high yield and fewer impurities. The invention does not discharge waste water or pollute the environment, and can easily implement industrial production. The invention solves the problems of complex after-treatment, difficulty in control of product quality, unstable product quality, high energy consumption in the synthetic process, and high waste water discharge amount in the existing complex synthesis technique. The sulfhydryl silane coupling agent prepared by the method can lower the viscosity of rubber, reduce the number of stages of milling, improve the working properties of the rubber, accelerate the dispersion of the reinforcing agent, enhances the dynamic mechanical properties of the rubber and the ageing resistance of the tread rubber, and prolong the storage time of the rubber.
Description
Technical field
The present invention relates to a kind of preparation method of mercaptosilane coupling agents, belong to organic chemistry filed.
Background technology
At present, the silane coupling agent used in the tire builder industry is almost silane coupler containing sulfur entirely, and wherein the most frequently used have two kinds of two (the silica-based propyl group of triethoxy) tetrasulfides (TESPT) and pair (the silica-based propyl group of triethoxy) disulphide (TESPD).Within 1973, Degussa company is used as tackifier by TESPT first, uses it for afterwards the earth-grasping force of finding to significantly improve tire in tire, when within 1976, Degussa company starts the TESPT suitability for industrialized production in Belgium first, just by its called after Si69.After entering the nineties in 20th century, along with the rise of green tire technology, this product uses in a large number rapidly in tire industry.
Si69 reacts with the filler such as white carbon black in rubber mixing process, and in sulfidation with rubber molecule chain formation coupling key, keep the sulfuration balance to using and improve reversion resistance and make it obtain good heat aging performance as vulcanizing agent.Si69 can improve the tensile strength of cross-linked rubber, reduces tire drag, compression heat generation, abrasion and tension set, and improves dynamic property, reduces swelling property, water-absorbent and hysteresis quality to polar solvent.Two (the silica-based propyl group of triethoxy) disulphide (TESPD) is s-generation multi-sulfur silane coupling agent product, also referred to as Si75, with Si69, compares, and the viscosity that it can reduce sizing material, improve processing characteristics.After the nineties in 20th century, tire industry has entered green tire technological revolution period, requires to use various power-saving technologies, wherein also comprises adopting and uses green tire, thereby also will inevitably widely apply the multi-sulfur silane coupling agent.
Although Si69 has been used more than 30 year, the relative Si69 of Si75 is some advantage also, and also there is shortcomings in they when synthetic and use; As: (1), synthesis technique complexity, aftertreatment is loaded down with trivial details, the more difficult control of quality product, quality is unstable.(2), building-up process power consumption is large, wastewater discharge is large.(3), Si69 and Si75 in use polysulfidic bond may rupture, easily cause that sizing material burns, need repeatedly mixing.(4), the ethanol that produces in use of Si69 and Si75, during high-temperature mixing, because its Quick-gasifying causes the rubber void content, increase.(5) easily produce when, mixing and reunite and compound viscosity increases.Therefore, research and develop a kind of building-up process easy, consume energy little, the mercaptosilane coupling agents production method of the few and product with stable quality of wastewater discharge, be our task urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to, provide a kind of synthetic method simple, can improve the quality of products and the stability of product quality, improve product yield, greatly reduce the preparation method of the mercaptosilane coupling agents of discharge of wastewater.
Technical scheme of the present invention is:
A kind of synthetic method of mercaptosilane coupling agents, it comprises the steps:
(1), drop into the sad and dimethylbenzene of a certain amount of sulfo-in the four-hole reaction flask with mechanical stirring, constant pressure funnel and condenser, drop into a certain amount of chloropropyl organoalkoxysilane in constant pressure funnel, start vacuum pump using circulatory water, start dropwise reaction under the mechanical stirring turned at per minute 100-500, the time for adding of chloropropyl organoalkoxysilane is 2.5-5 hours, after dropwise reaction completes, the continuation reaction is 0.5-1 hour, and the hydrogen chloride gas that reaction generates is absorbed by water; Sulfo-sad with the mol ratio chloropropyl organoalkoxysilane be 1:1, the add-on of dimethylbenzene be sulfo-sad with chloropropyl organoalkoxysilane total mass 50%-100%, temperature of reaction is controlled at 80-150 ℃, the whole reaction times is controlled at 3-6 hours.
(2), after 0.5-1 hour, reaction system cools to 40 ℃, to dripping a certain amount of triethylamine alkaline solution in the four-hole reaction flask, (alkali can be triethylamine or tripropyl amine again, or Tributylamine), absorb remaining hydrogenchloride and reaction thoroughly completes discharged hydrogenchloride, be precipitated out with the form of triethylamine hydrochloride, time for adding is 0.5-1 hour, proceed to react 0.5-1 hour after being added dropwise to complete, drip reacting temperature is controlled at 40-100 ℃.
(3), to dissolve amine hydrochlorate, in mechanical stirring speed, be then, after triethylamine alkaline solution dropwise reaction finishes, to reaction system, add a small amount of water, strong stirring stratification after 5 minutes under the condition that turns of per minute 670.
(4), stratification is after 10 minutes, reaction system is divided into significantly two-layer up and down, the crude product that upper strata is mercaptosilane coupling agents, the aqueous solution that lower floor is triethylamine hydrochloride.Then be transferred in separating funnel and carry out layering, after isolating lower floor's hydrochloride aqueous solution, by thick transferred product to the three mouthful round-bottomed flask of upper strata, according to 1%-3% of thick quality product, add anhydrous magnesium sulfate to carry out drying.Obtain the mercaptosilane coupling agents product after filtration under diminished pressure, distillation.
The isolated triethylamine hydrochloride aqueous solution can carry out next production cycle after being neutralized, recycle with the aqueous sodium hydroxide solution of 20% concentration.
Chemical equation of the present invention is as follows:
The molecular structural formula of mercaptosilane coupling agents is:
Wherein
R
1mean C
1-C
17straight or branched, saturated or undersaturated alkyl;
R
2mean methyl or ethyl.
Principle of the present invention
The present invention joins in reactor by sulfo-organic carboxyl acid, chloropropyl organoalkoxysilane and solvent according to a certain percentage, in vacuum systems, reacted, solvent is immiscible with the hydrogenchloride that reacts generation, the hydrogen chloride gas that reaction generates like this is easy effusion reaction system under the effect of solvent stripping, and minimizing contacts with product.Then add a certain amount of basic amine solution to continue reaction, reaction is thoroughly completed.Directly add a small amount of water in the most backward system, dissolve the part amine hydrochlorate of generation, carry out multi_layer extraction.Two be separated after, upper strata crude product drying is filtered, underpressure distillation obtains product except after desolventizing.The aqueous solution of the amine hydrochlorate of lower floor can carry out neutralizing treatment by the aqueous sodium hydroxide solution of 20% concentration, reclaims amine, and salt brine solution can recycle.
The present invention contrasts with reporting other patents:
The present invention's advantage compared with prior art is:
The present invention is by first under reduced pressure, allowing and reacted a part, and then makes it to react completely after adding a small amount of acid absorber, thereby reduces the generation of the hydrochloride of amine, has also reduced the generation of by product simultaneously.The mercaptosilane coupling agents product quality prepared by the present invention is high and stable, and yield is high, and impurity is few.The yield of its reaction reach 96.9% and more than, product purity reaches more than 98%, chloride ion content is lower than 20ppm, and material can fully recycle, non-wastewater discharge is free from environmental pollution, easily suitability for industrialized production.The mercaptosilane coupling agents product simultaneously prepared by the present invention can reduce compound viscosity, reduces mixing hop count, improves the sizing material processing characteristics, promotes strengthening agent to disperse, and improves the dynamic properties of sizing material.In addition, can also improve the ageing-resistant performance of tread rubber, extend the sizing material storage time, also reduce the content of the volatile organic matter in finished tire simultaneously.Therefore, compare Si69 and Si75, it can reach reduces the silane consumption, does not need repeatedly the better effect such as mixing, as to reduce costs, improve tire physicals.
Embodiment
Embodiment 1:
Drop into the sad 647.6g of sulfo-and dimethylbenzene 1000g in the 5000ml four-hole reaction flask with mechanical stirring, constant pressure funnel and condenser, drop into 3-chloropropyl triethoxysilane 972.9g simultaneously in constant pressure funnel.Sulfo-sad with the mol ratio 3-chloropropyl triethoxysilane be 1:1, the add-on of dimethylbenzene be sulfo-sad with 3-chloropropyl triethoxysilane total mass 50%-100%
.then start vacuum pump using circulatory water, start dropwise reaction under the mechanical stirring turned at per minute 400, temperature of reaction system is 80 ℃, the time for adding of 3-chloropropyl triethoxysilane is 4 hours, be added dropwise to complete rear continuation reaction 0.5 hour, the hydrogen chloride gas that reaction generates is absorbed by water, and now system reaction has completed major part.
0.5 after hour, system cools to 40 ℃, by constant pressure funnel, drips triethylamine solution 171g again in the four-hole reaction flask, time for adding is 1 hour, and triethylamine solution is added dropwise to complete rear continuation reaction 0.5 hour, and temperature of reaction is controlled at 80 ℃.After reaction finishes, to reaction system, adding 210g water, to dissolve the triethylamine hydrochloride generated, is then strong stirring after 5 minutes under the condition that turns of per minute 670 in mechanical stirring speed, stratification 10 minutes.
After stratification 10 minutes, reaction system is divided into significantly two-layer up and down, the crude product that upper strata is mercaptosilane coupling agents, the aqueous solution that lower floor is triethylamine hydrochloride.Then be transferred in separating funnel and separated, after lower floor's triethylamine hydrochloride aqueous solution is isolated, by thick transferred product to the three mouthful round-bottomed flask of upper strata, by 2% of mercaptosilane coupling agents crude product quality, add the 52g anhydrous magnesium sulfate to carry out drying simultaneously.Then obtain mercaptosilane coupling agents product 1421g after filtration under diminished pressure, distillation, product yield is 97.4%, and purity is 98.0%, and chloride ion content is 15ppm.The isolated triethylamine hydrochloride aqueous solution can carry out next production cycle after being neutralized, recycle with the aqueous sodium hydroxide solution of 20% concentration.
Embodiment 2:
Drop into the sad 647.6g of sulfo-and dimethylbenzene 1150g in the 5000ml four-hole reaction flask with mechanical stirring, constant pressure funnel and condenser, drop into 3-chloropropyl triethoxysilane 972.9g simultaneously in constant pressure funnel.Sulfo-sad with the mol ratio 3-chloropropyl triethoxysilane be 1:1, the add-on of dimethylbenzene be sulfo-sad with 3-chloropropyl triethoxysilane total mass 50%-100%.Then start vacuum pump using circulatory water, start dropwise reaction under under the mechanical stirring turned at per minute 450, temperature of reaction system is 100 ℃, the time for adding of 3-chloropropyl triethoxysilane is 3.5 hours, be added dropwise to complete rear continuation reaction 0.5 hour, the hydrogen chloride gas that reaction generates is absorbed by water, and now reaction has nearly completed most.
Then reaction system is cooled to 40 ℃, by constant pressure funnel, drip triethylamine solution 129g again in the four-hole reaction flask, time for adding is 1 hour, and triethylamine solution is added dropwise to complete rear continuation reaction 0.5 hour, and temperature of reaction is controlled at 80 ℃.After reaction finishes, to reaction system, adding 165g water, to dissolve the triethylamine hydrochloride generated, is strong stirring after 5 minutes under the condition that turns of per minute 670 in mechanical stirring speed, stratification 10 minutes.
After stratification 10 minutes, reaction system is divided into significantly two-layer up and down, the crude product that upper strata is mercaptosilane coupling agents, the aqueous solution that lower floor is triethylamine hydrochloride.Then transfer them in separating funnel and separated, after lower floor's triethylamine hydrochloride aqueous solution is isolated, by thick transferred product to the three mouthful round-bottomed flask of upper strata, by 2% of mercaptosilane coupling agents crude product quality, add the 52g anhydrous magnesium sulfate to carry out drying simultaneously.Dried mercaptosilane coupling agents crude product obtains mercaptosilane coupling agents product 1419.5g after filtration under diminished pressure, distillation, and product yield is 97.3%, and purity is 98.1%, and chloride ion content is 16ppm.The isolated triethylamine hydrochloride aqueous solution can carry out next production cycle after being neutralized, recycle with the aqueous sodium hydroxide solution of 20% concentration.
Embodiment 3:
Drop into the sad 647.6g of sulfo-and dimethylbenzene 1300g in the 5000ml four-hole reaction flask with mechanical stirring, constant pressure funnel and condenser, drop into 3-chloropropyl triethoxysilane 972.9g in constant pressure funnel simultaneously, sulfo-sad with the mol ratio 3-chloropropyl triethoxysilane be 1:1, the add-on of dimethylbenzene be sulfo-sad with 3-chloropropyl triethoxysilane total mass 50%-100%.Then start vacuum pump using circulatory water, start dropwise reaction under under the mechanical stirring turned at per minute 400, temperature of reaction system is 135 ℃, the time for adding of 3-chloropropyl triethoxysilane is 3 hours, be added dropwise to complete rear continuation reaction 0.5 hour, the hydrogen chloride gas that reaction generates is absorbed by water, and now reaction has nearly completed most.
Then reaction system is cooled to 40 ℃, by constant pressure funnel, drip triethylamine 86g again in the four-hole reaction flask, time for adding is 0.5 hour, and triethylamine solution is added dropwise to complete rear continuation reaction 0.5 hour, and temperature of reaction is controlled at 80 ℃.After reaction finishes, to reaction system, adding 110g water, to dissolve the triethylamine hydrochloride generated, is then strong stirring after 5 minutes under 670 rev/mins of conditions in mechanical stirring speed, then stratification 10 minutes.
After stratification 10 minutes, reaction system is divided into significantly two-layer up and down, the crude product that upper strata is mercaptosilane coupling agents, the aqueous solution that lower floor is triethylamine hydrochloride.Then transfer them in separating funnel and separated, after lower floor's triethylamine hydrochloride aqueous solution is isolated, by thick transferred product to the three mouthful round-bottomed flask of upper strata, by 2% of mercaptosilane coupling agents crude product quality, add the 52g anhydrous magnesium sulfate to carry out drying simultaneously.Dried mercaptosilane coupling agents crude product obtains mercaptosilane coupling agents product 1413.3g after filtration under diminished pressure, distillation, and product yield is 96.9%, and purity is 98.5%, and chloride ion content is 20ppm.The isolated triethylamine hydrochloride aqueous solution can carry out next production cycle after being neutralized, recycle with the aqueous sodium hydroxide solution of 20% concentration.
The content be not described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (1)
1. the synthetic method of a mercaptosilane coupling agents, it is characterized in that: it comprises the steps:
(1), drop into the sad and dimethylbenzene of a certain amount of sulfo-in the four-hole reaction flask with mechanical stirring, constant pressure funnel and condenser, drop into a certain amount of chloropropyl organoalkoxysilane in constant pressure funnel, start vacuum pump using circulatory water, start dropwise reaction under the mechanical stirring turned at per minute 100-500, the time for adding of chloropropyl organoalkoxysilane is 2.5-5 hours, after dropwise reaction completes, the continuation reaction is 0.5-1 hour, and the hydrogen chloride gas that reaction generates is absorbed by water; Sulfo-sad with the mol ratio chloropropyl organoalkoxysilane be 1:1, the add-on of dimethylbenzene be sulfo-sad with chloropropyl organoalkoxysilane total mass 50%-100%, temperature of reaction is controlled at 80-150 ℃, the whole reaction times is controlled at 3-6 hours;
(2), after 0.5-1 hour, reaction system cools to 40 ℃, drip a certain amount of triethylamine alkaline solution again in the four-hole reaction flask, absorb remaining hydrogenchloride and react and thoroughly complete discharged hydrogenchloride, form with triethylamine hydrochloride is precipitated out, time for adding is 0.5-1 hour, after being added dropwise to complete, proceeds to react 0.5-1 hour, and drip reacting temperature is controlled at 40-100 ℃;
(3), to dissolve amine hydrochlorate, in mechanical stirring speed, be then, after triethylamine alkaline solution dropwise reaction finishes, to reaction system, add a small amount of water, strong stirring stratification after 5 minutes under the condition that turns of per minute 670;
(4), stratification is after 10 minutes, reaction system is divided into significantly two-layer up and down, the crude product that upper strata is mercaptosilane coupling agents, the aqueous solution that lower floor is triethylamine hydrochloride;
Then be transferred in separating funnel and carry out layering, after isolating lower floor's hydrochloride aqueous solution, by thick transferred product to the three mouthful round-bottomed flask of upper strata, according to 1%-3% of thick quality product, add anhydrous magnesium sulfate to carry out drying;
Obtain the mercaptosilane coupling agents product after filtration under diminished pressure, distillation;
The isolated triethylamine hydrochloride aqueous solution can carry out next production cycle after being neutralized, recycle with the aqueous sodium hydroxide solution of 20% concentration.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104926855A (en) * | 2015-05-08 | 2015-09-23 | 广州市博兴化工科技有限公司 | Silane coupling agent intermediate and application thereof in light-cured silica sol |
| CN108948072A (en) * | 2018-08-28 | 2018-12-07 | 山东省宁津县浩润科技有限公司 | A kind of preparation method of peroxidating silane coupling agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926855A (en) * | 2015-05-08 | 2015-09-23 | 广州市博兴化工科技有限公司 | Silane coupling agent intermediate and application thereof in light-cured silica sol |
| CN104926855B (en) * | 2015-05-08 | 2017-08-22 | 广东博兴新材料科技有限公司 | A kind of silane coupler intermediate and its application in photocuring Ludox |
| CN108948072A (en) * | 2018-08-28 | 2018-12-07 | 山东省宁津县浩润科技有限公司 | A kind of preparation method of peroxidating silane coupling agent |
| CN108948072B (en) * | 2018-08-28 | 2020-07-28 | 山东省宁津县浩润科技有限公司 | Preparation method of peroxide silane coupling agent |
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