CN104910202A - Method for preparing sulfur-containing silane coupling agent - Google Patents
Method for preparing sulfur-containing silane coupling agent Download PDFInfo
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- CN104910202A CN104910202A CN201410089165.0A CN201410089165A CN104910202A CN 104910202 A CN104910202 A CN 104910202A CN 201410089165 A CN201410089165 A CN 201410089165A CN 104910202 A CN104910202 A CN 104910202A
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Abstract
The invention discloses a method for preparing a sulfur-containing silane coupling agent from an aqueous polysulfide solution and 3-halogenopropyltrialkoxy silane through using a supported quaternary ammonium salt phase-transfer catalyst. Compared with biphasic phase-transfer catalysts adopted by present technologies for preparing the sulfur-containing silane coupling agent, the supported quaternary ammonium salt phase-transfer catalyst is insoluble in water, acids, alkalis and organic solvents, and can be directly filtered, washed, dried and recycled after use. The method for preparing the sulfur-containing silane coupling agent has the advantages of has the advantages of recycling of the catalyst, no influences on the yield or quality of the above product, easy separation of the product, low production cost, no residual of the catalyst in a water phase or an organic phase, and environmental protection.
Description
Technical field
The present invention relates to technical field of organic chemistry, in particular to a kind of preparation method of silane coupler containing sulfur.
Background technology
Enter the nineties in 20th century, along with the rise of green tire technology, silane coupler containing sulfur uses in a large number rapidly in green tire technology.Silane coupler containing sulfur is a kind of traditional silane coupling agents, the main additive being used as rubber tyre, tire, the wear resistance of glue goods and ageing-resistant performance can be improved, generally carry out coupling, to reach the improvement of performance by use mineral filler or fiber and rubber matrix.At present, the silane coupler containing sulfur used in tire industry, mainly: two (triethoxysilylpropyl) tetrasulfide (being also called Si69), two (triethoxysilylpropyl) disulphide (being also called Si75), γ mono-mercaptopropyl trimethoxysilane.Wherein, the consumption of Si69, Si75 silane coupler containing sulfur is maximum.
The catalyzer adopted when preparing silane coupling agent is at present mainly two-phase phase-transfer catalyst, although it is high to adopt two-phase phase-transfer catalyst to have catalytic efficiency, and the advantage that reaction conversion ratio is also high, but there is following shortcoming in two-phase phase-transfer catalyst: 1) two-phase phase-transfer catalyst can not be reused, and adds production cost; 2) two-phase phase-transfer catalyst can be partly dissolved in the product, affects the application performance of product, also has partially catalyzed agent to be dissolved in aqueous phase, causes contaminated wastewater.
Therefore, be necessary to improve further the existing method preparing silane coupler containing sulfur, to obtain, a kind of cost is low, product is easily separated, catalyzer is recyclable applies mechanically, simultaneously again can the green preparation process of silane coupler containing sulfur of energy-saving consumption-reducing.
Summary of the invention
The present invention aims to provide a kind of preparation method of silane coupler containing sulfur, and this preparation method's energy consumption is little, cost is low, product is easily separated and catalyzer recoverable.
To achieve these goals, according to an aspect of the present invention, provide a kind of preparation method of silane coupler containing sulfur, under the effect of loading type quaternary ammonium salt phase transfer catalyst, to the polysulfide aqueous solution and the process of 3-halogen propyl trialkoxy silane Hybrid Heating.
Further, loading type quaternary ammonium salt phase transfer catalyst is polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst or silicon dioxide carried type quaternary ammonium salt phase transfer catalyst.
Further, comprise the following steps: S1, in the polysulfide aqueous solution, add loading type quaternary ammonium salt phase transfer catalyst, stir, be heated to preset temperature, obtain the first mixed solution; S2, at a predetermined temperature, in the first mixed solution, add 3-halogen propyl trialkoxy silane, constant temperature stirring reaction, obtains silane coupler containing sulfur.
Further, the polysulfide aqueous solution is one or more in aqueous sodium polysulfide, the potassium polysulfide aqueous solution and the ammonium polysulfide aqueous solution.
Further, the concentration of the polysulfide aqueous solution is 1.6 ~ 2.8mol/L.
Further, the concentration of the polysulfide aqueous solution is 2.1 ~ 2.4mol/L.
Further, in the polysulfide aqueous solution, the mol ratio of polysulfide and 3-halogen propyl trialkoxy silane is 1:1.6 ~ 1:2.2.
Further, in loading type quaternary ammonium salt phase transfer catalyst, the molar weight of effective quaternary ammonium salt accounts for 0.5% ~ 10% of 3-halogen propyl trialkoxy silane molar weight.
Further, in loading type quaternary ammonium salt phase transfer catalyst, the molar weight of effective quaternary ammonium salt accounts for 5% ~ 9% of 3-halogen propyl trialkoxy silane molar weight.
Further, 3-halogen propyl trialkoxy silane is selected from one or more in 3-chloropropyl triethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-bromopropyl triethoxyl silane and 3-bromopropyl Trimethoxy silane.
Further, step S2 comprises: S21, be dissolved in organic solvent by 3-halogen propyl trialkoxy silane, forms the organic solution containing 3-halogen propyl trialkoxy silane; And S22, will join in the first mixed solution with the speed of 3.5 ~ 10g/ minute containing the organic solution of 3-halogen propyl trialkoxy silane; Organic solution is one or more in benzene, toluene and xylene solution.
Further, the concentration containing the organic solution of 3-halogen propyl trialkoxy silane is 20wt% ~ 98wt%.
Further, the concentration containing the organic solution of 3-halogen propyl trialkoxy silane is 30wt% ~ 50wt%.
Technical scheme of the present invention be with the polysulfide aqueous solution and 3-halogen propyl trialkoxy silane for raw material, utilize loading type quaternary ammonium salt phase transfer catalyst to prepare the process of silane coupler containing sulfur.Active centre due to loading type quaternary ammonium salt phase transfer catalyst is grafted on carrier by certain way, forms the solid-carrying type phase-transfer catalyst being not only insoluble to organic phase but also being insoluble to aqueous phase; In catalytic process, the 3-halogen propyl trialkoxy silane in organic phase and the polysulfide in aqueous phase can enter the active sites heart place of loading type quaternary ammonium salt phase transfer catalyst in the mode of diffusion, and then the active centre of catalyzer is played a role preferably.Therefore, compared with preparing with prior art the two-phase phase-transfer catalyst that silane coupler containing sulfur adopts, loading type quaternary ammonium salt phase transfer catalyst has the feature of water insoluble, sour, alkali and organic solvent, can directly by catalyst filtration, washing, oven dry, i.e. recoverable after using.Adopt method provided by the present invention to prepare silane coupler containing sulfur and there is catalyzer recoverable, and the yield of product and quality is unaffected, product is easily separated, production cost is low, catalyzer environment-friendly advantage such as equal noresidue in aqueous phase or organic phase.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
When preparing silane coupler containing sulfur to solve in prior art, two-phase phase-transfer catalyst can not be reused, and catalyzer can be partly dissolved in product and aqueous phase, bring the problems such as contaminated wastewater, the invention provides a kind of preparation method of silane coupler containing sulfur, under the effect of loading type quaternary ammonium salt phase transfer catalyst, to the polysulfide aqueous solution and the process of 3-halogen propyl trialkoxy silane Hybrid Heating.
Technical scheme of the present invention be with the polysulfide aqueous solution and 3-halogen propyl trialkoxy silane for raw material, utilize loading type quaternary ammonium salt phase transfer catalyst to prepare the process of silane coupler containing sulfur.Active centre due to loading type quaternary ammonium salt phase transfer catalyst is grafted on carrier by certain way, forms the solid-carrying type phase-transfer catalyst being not only insoluble to organic phase but also being insoluble to aqueous phase; In catalytic process, the 3-halogen propyl trialkoxy silane in organic phase and the polysulfide in aqueous phase can enter the active sites heart place of loading type quaternary ammonium salt phase transfer catalyst in the mode of diffusion, and then the active centre of catalyzer is played a role preferably.Therefore, compared with preparing with prior art the two-phase phase-transfer catalyst that silane coupler containing sulfur adopts, loading type quaternary ammonium salt phase transfer catalyst has the feature of water insoluble, sour, alkali and organic solvent, can directly by catalyst filtration, washing, oven dry, i.e. recoverable after using.Adopt method provided by the present invention to prepare silane coupler containing sulfur and there is catalyzer recoverable, and the yield of product and quality is unaffected, product is easily separated, production cost is low, catalyzer environment-friendly advantage such as equal noresidue in aqueous phase or organic phase.
Preferably, loading type quaternary ammonium salt phase transfer catalyst is polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst or silicon dioxide carried type quaternary ammonium salt phase transfer catalyst.Loading type quaternary ammonium salt phase transfer catalyst of the present invention has following general formula:
Wherein,
for polystyrene-divinylbenzene interpolymer or the micron silica particulate being grafted with polystyrene, R
1, R
2for the straight chained alkyl containing 1 ~ 10 carbon atom; R
3for the straight chained alkyl containing 1 ~ 20 carbon atom.
The raw material of loading type quaternary ammonium salt phase transfer catalyst be tertiary amine and
represent chloromethylated polystyrene-divinylbenzene interpolymer or be grafted with the micron silica particulate of Chloromethyl polystyrene.Wherein the kind of tertiary amine is more, selects different tertiary amines can obtain different loading type quaternary ammonium salt phase transfer catalysts, and its catalytic effect in the reaction also can be different.As the R of selected tertiary amine
3for during containing the straight chained alkyl of carbon number higher than 20, because its steric hindrance is comparatively large, be difficult to be grafted on large polymer support.Therefore, the present invention is by R
3be defined as the straight chained alkyl containing 1 ~ 20 carbon atom.Preferably, tertiary amine is tri-n-butylamine, tri-n-amyl amine, three normal hexyl Amines, three positive heptyl amice, tri-n-octyl amine, tri-n-nonylamines.
A preferred embodiment of the invention, in silicon dioxide carried type quaternary ammonium salt phase transfer catalyst, the particle diameter of silicon-dioxide is 30 ~ 200 μm.If the particle diameter of silicon-dioxide is less than 30 μm, then can cause prepared catalyzer not easily filtered and recycled; If particle diameter is too large, then can causes contained active group very little, affect the activity of catalyzer.Further preferably, in silicon dioxide carried type quaternary ammonium salt phase transfer catalyst, the particle diameter of silicon-dioxide is 50 ~ 100 μm.
The synthetic method of two class loading type quaternary ammonium salt phase transfer catalysts above-mentioned in the present invention is prior art.The invention provides a kind of preferred method preparing polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, comprise: select aperture be the polystyrene-divinylbenzene chloromethylation interpolymer (be called for short chlorine ball) of 100 ~ 300nm with tertiary amine as raw material, swelling agent is made with ethylene dichloride (or ethylene dichloride and alcohol mixed solvent), wherein the chlorinity of chlorine ball is 4mmol/g, and the mol ratio of chlorine and amine is 1:1.0 ~ 1.2.In reaction, polystyrene-divinylbenzene chloromethylation interpolymer used (being called for short chlorine ball) can be selected from D201 type, D203 type.
Present invention also offers a kind of preferred method preparing micron silica loading type quaternary ammonium salt phase transfer catalyst, comprise: select to be grafted with the micron silica particulate of Chloromethyl polystyrene and tertiary amine as raw material, using chloroform as solvent, wherein the chlorinity of micron silica particulate is 0.4mmol/g, and the mol ratio of chlorine and amine is 1:1.0 ~ 1:1.2.After benzyl cl radical on tertiary amine and polystyrene macromolecular chain reacts, form quaternary amine also immobilized on grafting particulate, the phase-transfer catalyst of obtained micron silica loading type quaternary amine.
Prepare in silane coupler containing sulfur process in the present invention, two kinds of loading type quaternary ammonium salt phase transfer catalysts all can adopt free type and fixed two kinds of types of feed.Wherein, free type refers to and is directly joined in reaction flask by loading type quaternary ammonium salt phase transfer catalyst, and the loading type quaternary ammonium salt phase transfer catalyst wrapped with filter screen is fixed on the dividing plate of reaction flask by fixed referring to.Loading type quaternary ammonium salt phase transfer catalyst is joined in sodium polysulphide system, after stirring 10 ~ 30min, temperature is risen to 50 ~ 90 DEG C, add the toluene solution of 3-halogen propyl trialkoxy silane again, maintain this temperature of reaction, after stirring reaction 4 ~ 12h, reaction generates the crude mixture of silane coupler containing sulfur.
If loading type quaternary ammonium salt phase transfer catalyst is added in reaction system with free type, reaction terminates rear system and is down to room temperature, crude mixture is filtered, leach the loading type quaternary ammonium salt phase transfer catalyst of dispersion, with sodium-chlor or the Sulfothiorine of a small amount of deionized water wash removing catalyst surface, post-drying catalyzer is in order to reusing next time.Filtrate is separated organic phase with separating funnel, washing and drying, underpressure distillation also reclaims reaction solvent toluene and the complete 3-halogen propyl trialkoxy silane of unreacted respectively, after obtain sterling silane coupler containing sulfur.If add loading type quaternary ammonium salt phase transfer catalyst in a position-stable manner in reaction system, question response terminates rear system and is down to room temperature, is directly taken out by catalyzer, and by a small amount of deionized water wash, dry for standby.Reaction solution separating funnel separates organic phase, and washing and drying removes under reduced pressure, and reclaims reaction solvent toluene and unreacted 3-halogen propyl trialkoxy silane respectively, obtains sterling silane coupler containing sulfur afterwards.
The loading type quaternary ammonium salt phase transfer catalyst adopted in the present invention can for fresh preparation or the catalyzer of recovery.Loading type quaternary ammonium salt phase transfer catalyst after a procedure, only needs to be isolated, and with a small amount of deionized water wash, oven dry, namely recyclablely repeatedly to apply mechanically, it generally can apply mechanically 1 ~ 10 time.If it is too many to apply mechanically number of times, then can affects catalytic effect, because the mechanical wear of catalyzer is aggravated, cause a large amount of breakages of catalyzer, destroy the structure of superpolymer, thus cause reaction yield to decline; In addition, catalyzer is in the process preparing silane coupler containing sulfur, and along with applying mechanically increasing of number of times, the sulphur being adsorbed on catalyst surface can constantly increase, and causes the catalytic efficiency of loading type quaternary ammonium salt phase transfer catalyst to reduce.
Particularly, the method preparing silane coupler containing sulfur comprises the following steps: S1, in the polysulfide aqueous solution, add loading type quaternary ammonium salt phase transfer catalyst, stirs, is heated to preset temperature, obtain the first mixed solution; S2, at a predetermined temperature, in the first mixed solution, add 3-halogen propyl trialkoxy silane, constant temperature stirring reaction, obtains silane coupler containing sulfur.Follow-uply by being separated the crude product of silane coupler containing sulfur obtained above, purifying, pure silane coupler containing sulfur can be obtained.This preparation method's technique is simple, easy to operate.
Preferably, preset temperature is 50 DEG C ~ 90 DEG C, and churning time is 10 ~ 40 minutes.Heating temperature and churning time are controlled to control the catalytic rate of catalyzer and the speed of reaction of reactant better in above-mentioned scope, and then obtain highly purified silane coupler containing sulfur.In order to control speed of reaction preferably, preferably, step S2 comprises: S21, be dissolved in organic solvent by 3-halogen propyl trialkoxy silane, forms the organic solution containing 3-halogen propyl trialkoxy silane; And S22, will join in the first mixed solution with the speed of 3.5 ~ 10g/ minute containing the organic solution of 3-halogen propyl trialkoxy silane; Organic solution is one or more in benzene, toluene and xylene solution.
A preferred embodiment of the invention, 3-halogen propyl trialkoxy silane be selected from 3-chloropropyl triethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-bromopropyl triethoxyl silane and 3-bromopropyl Trimethoxy silane one or more.Further preferably, 3-halogen propyl trialkoxy silane is 3-chloropropyl triethoxysilane.In actually operating, generally reaction raw materials 3-halogen propyl trialkoxy silane is dissolved in non-polar solvent benzene, toluene or dimethylbenzene, for the selection of non-polar solvent, the preferred above-mentioned listed non-polar solvent of the present invention, but be not limited thereto, as long as reaction raw materials 3-halogen propyl trialkoxy silane can fully dissolve by selected organic solvent.
Preferably, the concentration containing the organic solution of 3-halogen propyl trialkoxy silane is 20wt% ~ 98wt%, if concentration is lower than 20wt%, then solvent load can be caused too large because concentration is too low, increase production cost, post-processed also comparatively bothers simultaneously.Further preferably, the concentration containing the organic solution of 3-halogen propyl trialkoxy silane is 30wt% ~ 50wt%.
The polysulfide aqueous solution adopted in the present invention is one or more in aqueous sodium polysulfide, the potassium polysulfide aqueous solution and the ammonium polysulfide aqueous solution, is preferably aqueous sodium polysulfide.
The step preparing aqueous sodium polysulfide comprises: in the reaction vessel with mechanical stirring, thermometer and prolong; add sodium sulphite or sodium hydroxide, water, sulphur powder; under high pure nitrogen protection; controlling stirring velocity is 500 ~ 1500 revs/min; react 0.5 ~ 5 hour at 50 DEG C ~ 100 DEG C, obtain aqueous sodium polysulfide.Wherein, when adopting sodium sulphite as raw material, the mass ratio of sodium sulphite, sulphur and water is 1:0.3 ~ 3.5:0.8 ~ 8.When adopting sodium hydroxide as raw material, the mass ratio of sodium hydroxide, sulphur and water is 1:0.3 ~ 1.3:2 ~ 8.
Wherein, the concentration of the polysulfide aqueous solution is 1.6 ~ 2.8mol/L.If the volumetric molar concentration of the polysulfide aqueous solution is higher than 2.8mol/L, then dissolving can be caused insufficient, be unfavorable for that reaction is carried out; If the volumetric molar concentration of the polysulfide aqueous solution is lower than 1.6mol/L, then speed of reaction is slower; Therefore, through considering, the volumetric molar concentration of the polysulfide aqueous solution controls, in above-mentioned scope, to control speed of reaction preferably by the present invention, also can not cause and dissolve insufficient problem.Preferably, the concentration of the polysulfide aqueous solution is 2.1 ~ 2.4mol/L.
According to a kind of exemplary embodiment of the present invention, in the polysulfide aqueous solution, the mol ratio of polysulfide and 3-halogen propyl trialkoxy silane is 1:1.6 ~ 1:2.2.The mol ratio of polysulfide and 3-halogen propyl trialkoxy silane is controlled in above-mentioned scope, 3-halogen propyl trialkoxy silane can be made fully to react, to improve the transformation efficiency of 3-halogen propyl trialkoxy silane.In the loading type quaternary ammonium salt phase transfer catalyst added, the molar weight of effective quaternary ammonium salt accounts for 0.5% ~ 10% of 3-halogen propyl trialkoxy silane molar weight.If the molar weight of effective quaternary ammonium salt accounts for the molar weight of 3-halogen propyl trialkoxy silane lower than 0.5% in the loading type quaternary ammonium salt phase transfer catalyst added, then can because of catalyst levels very little, catalytic efficiency reduce; If consumption is higher than 10%, although reaction efficiency can be improved, add cost significantly.Preferably, in the loading type quaternary ammonium salt phase transfer catalyst added, the molar weight of effective quaternary ammonium salt accounts for 5% ~ 9% of 3-halogen propyl trialkoxy silane molar weight.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment.
(1) preparation of polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst
The polystyrene-divinylbenzene chloromethylation interpolymer (being called for short chlorine ball) of to be 4mmol/g aperture by 1000 grams of chlorinity be 500nm adds in reaction vessel, with ethylene dichloride as swelling agent.Add 755 grams of tri-n-butylamines afterwards, reflux 48 hours, stopped reaction is also down to room temperature, filters and obtains crude product.Gained crude product is filtered through methanol wash, then soaks half an hour with 5wt% dilute hydrochloric acid, to filter and with deionized water wash to pH=7, be placed in 50 DEG C of vacuum drying ovens and dry, obtain 4mol polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst.
(2) preparation of micron silica loading type quaternary ammonium salt phase transfer catalyst
Be that 0.4mmol/g is grafted with Chloromethyl polystyrene micron order aerosil particles and adds in reaction vessel, with chloroform give solvent by 1000 grams of chlorinity.After add 76 grams of tri-n-butylamines, reflux 48 hours, stopped reaction is also down to room temperature, filter obtain crude product.Gained crude product filters through methanol wash, then soaks half an hour with 5wt% dilute hydrochloric acid, filters and with deionized water wash to PH=7, is placed in 50 DEG C of vacuum drying ovens and dries, obtaining 0.4mol micron silica loading type quaternary ammonium salt phase transfer catalyst.Wherein the particle diameter of carrier silicas is 50 μm.
Utilize above-mentioned loading type quaternary ammonium salt phase transfer catalyst to prepare silane coupler containing sulfur below, specific as follows:
Embodiment 1
1) aqueous sodium polysulfide is prepared
In the there-necked flask of 2.0L with mechanical stirring, thermometer, prolong, add 240 gram of nine water cure sodium (78 grams, Containing Sulfur sodium), 182 grams of water and 32 grams of sulphur powder, obtain mixed solution.Under high pure nitrogen protection, mixed solution is warming up to 85 DEG C, stirs and treat that solid dissolves gradually, maintain this temperature and continue stirring 1.5 hours, be cooled to 60 DEG C after reaction, obtain the aqueous sodium polysulfide of 2.8mol/L.Wherein, the mass ratio of raw material sodium sulphite, sulphur and water is 1:0.4:4.4.
2) in above-mentioned there-necked flask, add 16g above-mentioned self-control macroporous polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, be warming up to 85 DEG C, stir 15 minutes, obtain the first mixed solution.Then in the first mixed solution, add the toluene solution of the 3-chloropropyl triethoxysilane that 688g concentration is 71wt% with the speed of 3.5g/ minute, drip off this temperature of rear maintenance and continue stirring 5.5 hours, stopped reaction, obtains silane coupling agent mixed solution.Wherein, the mol ratio of the sodium polysulphide added and 3-chloropropyl triethoxysilane is 1:2, and in loading type quaternary ammonium salt phase transfer catalyst, the effective molar weight of quaternary ammonium salt accounts for 2% of the molar weight of 3-chloropropyl triethoxysilane.
3) after question response stops, to the silane coupling agent mixed solution filtered while hot obtained, with appropriate amount of deionized water cleaning polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, dry afterwards in order to using next time.Gained filtrate uses separating funnel separatory, and lower floor is water white salt aqueous phase, and upper strata is shallow amber yellow product and toluene phase.Organic phase, through removed under reduced pressure solvent toluene, obtains crude product.By high-vacuum installation, residual toluene and unreacted raw material 3-chloropropyl triethoxysilane in removing crude product, finally obtain 308.5 grams of silane coupler containing sulfurs.
Embodiment 2
1) the potassium polysulfide aqueous solution is prepared
In the there-necked flask of 2.0L with mechanical stirring, thermometer, prolong, add 110 grams of potassium sulphides, 482 grams of water and 33 grams of sulphur powder, obtain mixed solution.Under high pure nitrogen protection, mixed solution is warming up to 100 DEG C, stirs and treat that solid dissolves gradually, maintain this temperature and continue stirring 2.0 hours, be cooled to 60 DEG C after reaction, obtain the potassium polysulfide aqueous solution of 2.1mol/L.Wherein, the mass ratio of raw material potassium sulphide, sulphur and water is 1:0.3:3.9.
2) in above-mentioned there-necked flask, add 22g above-mentioned self-control macroporous polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, be warming up to 90 DEG C, stir 30 minutes, obtain the first mixed solution.Then in the first mixed solution, add the toluene solution of the 3-chloropropyl triethoxysilane that 498g concentration is 98wt% with the speed of 3.5g/ minute, drip off this temperature of rear maintenance and continue stirring 5.5 hours, stopped reaction, obtains silane coupling agent mixed solution.Wherein, the mol ratio of the potassium polysulfide added and 3-chloropropyl triethoxysilane is 1:2, and in loading type quaternary ammonium salt phase transfer catalyst, the effective molar weight of quaternary ammonium salt accounts for 5% of the molar weight of 3-chloropropyl triethoxysilane.
3) after question response stops, to the silane coupling agent mixed solution filtered while hot obtained, with appropriate amount of deionized water cleaning polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, dry afterwards in order to using next time.Gained filtrate uses separating funnel separatory, and lower floor is water white salt aqueous phase, and upper strata is shallow amber yellow product and toluene phase.Organic phase, through removed under reduced pressure solvent toluene, obtains crude product.By high-vacuum installation, residual toluene and unreacted raw material 3-chloropropyl triethoxysilane in removing crude product, finally obtain 297.5 grams of silane coupler containing sulfurs.
Embodiment 3
1) aqueous sodium polysulfide is prepared
In the there-necked flask of 2.0L with mechanical stirring, thermometer, prolong, add 240 gram of nine water cure sodium (78 grams, Containing Sulfur sodium), 462 grams of water and 32 grams of sulphur powder, obtain mixed solution.Under high pure nitrogen protection, mixed solution is warming up to 90 DEG C, stirs and treat that solid dissolves gradually, maintain this temperature and continue stirring 1.5 hours, be cooled to 60 DEG C after reaction, obtain the aqueous sodium polysulfide of 1.6mol/L.Wherein, the mass ratio of raw material sodium sulphite, sulphur and water is 1:0.4:8.
2) in above-mentioned there-necked flask, add 4.4g above-mentioned self-control macroporous polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, be warming up to 90 DEG C, stir 15 minutes, obtain the first mixed solution.Then in the first mixed solution, add the toluene solution of the 3-chloropropyl triethoxysilane that 688g concentration is 71wt% with the speed of 4.0g/ minute, drip off this temperature of rear maintenance and continue stirring 5.5 hours, stopped reaction, obtains silane coupling agent mixed solution.Wherein, the mol ratio of the sodium polysulphide added and 3-chloropropyl triethoxysilane is 1:1.6, and in loading type quaternary ammonium salt phase transfer catalyst, the effective molar weight of quaternary ammonium salt accounts for 0.5% of the molar weight of 3-chloropropyl triethoxysilane.
3) after question response stops, to the silane coupling agent mixed solution filtered while hot obtained, with appropriate amount of deionized water cleaning polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, dry afterwards in order to using next time.Gained filtrate uses separating funnel separatory, and lower floor is water white salt aqueous phase, and upper strata is shallow amber yellow product and toluene phase.Organic phase, through removed under reduced pressure solvent toluene, obtains crude product.By high-vacuum installation, residual toluene and unreacted raw material 3-chloropropyl triethoxysilane in removing crude product, finally obtain 278.5 grams of silane coupler containing sulfurs.
Embodiment 4
1) aqueous sodium polysulfide is prepared
In the there-necked flask of 2.0L with mechanical stirring, thermometer, prolong, add 60 grams of sodium hydroxide, 205 grams of water, 80 grams of sulphur powder, obtain mixed solution.Under high pure nitrogen protection, mixed solution is warming up to 85 DEG C, stirs and treat that solid dissolves gradually, maintain this temperature and continue stirring 1.0 hours, be cooled to 60 DEG C after reaction, obtain the aqueous sodium polysulfide of 2.4mol/L.Wherein, the mass ratio of feed hydrogen sodium oxide, sulphur and water is 1:1.3:3.4.
2) in above-mentioned there-necked flask, add 22g above-mentioned self-control macroporous polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, stir and be warming up to 85 DEG C after 25 minutes, obtain the first mixed solution.Then in the first mixed solution, add the toluene solution of the 3-chloropropyl triethoxysilane that 483g concentration is 50wt% with the speed of 5.0g/ minute, drip off this temperature of rear maintenance and continue stirring 4.5 hours, stopped reaction, obtains silane coupling agent mixed solution.Wherein, the mol ratio of the sodium polysulphide added and 3-chloropropyl triethoxysilane is 1:2, and the molar weight of loading type quaternary ammonium salt phase transfer catalyst accounts for 5% of the molar weight of 3-chloropropyl triethoxysilane.
3) after question response stops, to the silane coupling agent mixed solution filtered while hot obtained, with appropriate amount of deionized water cleaning polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst, dry afterwards in order to using next time.Gained filtrate uses separating funnel separatory, and lower floor is water white salt aqueous phase, and upper strata is shallow amber yellow product and toluene phase.Organic phase, through removed under reduced pressure solvent toluene, obtains crude product.By high-vacuum installation, residual toluene and unreacted raw material 3-chloropropyl triethoxysilane in removing crude product, finally obtain 202.8 grams of silane coupler containing sulfurs.
Embodiment 5
1) aqueous sodium polysulfide is prepared
At 1.5L with mechanical stirring, thermometer, prolong, and be equipped with in the stainless steel reactor of dividing plate, add 60 grams of sodium hydroxide, 205 grams of water, 80 grams of sulphur powder, obtain mixed solution.Under high pure nitrogen protection, mixed solution is warming up to 85 DEG C, stirs and treat that solid dissolves gradually; maintain this temperature and continue stirring 45 minutes; be cooled to 40 DEG C after reaction, obtain the aqueous sodium polysulfide of 2.4mol/L, wherein the mass ratio of feed hydrogen sodium oxide, sulphur powder and water is 1:1.3:3.4.
2) on reactor dividing plate, place 4 bag (weight per package is 10 grams) wrap up with filter screen self-control macroporous polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalysts, stir after 15 minutes, after be warming up to 85 DEG C, obtain the first mixed solution.Then in the first mixed solution, add the toluene solution of the 3-chloropropyl triethoxysilane that 305.7g concentration is 87wt% with the speed of 3.5g/ minute, drip off this temperature of rear maintenance and continue stirring 4.0 hours, stopped reaction, obtains silane coupling agent mixed solution.Wherein, the mol ratio of the sodium polysulphide added and 3-chloropropyl triethoxysilane is 1:2.2, and the molar weight of loading type quaternary ammonium salt phase transfer catalyst accounts for 9% of the molar weight of 3-chloropropyl triethoxysilane.
3), after question response stops, the loading type quaternary ammonium salt phase transfer catalyst that taking-up is wrapped up with filter screen, with deionized water wash, dries in order to experiment use next time.Gained filtrate uses separating funnel separatory, and lower floor is water white salt aqueous phase, and upper strata is shallow amber yellow product and toluene phase.Organic phase, through removed under reduced pressure solvent toluene, obtains crude product.By high-vacuum installation, residual toluene and unreacted raw material 3-chloropropyl triethoxysilane in removing crude product, finally obtain 215.0 grams of silane coupler containing sulfurs.
Embodiment 6
1) aqueous sodium polysulfide is prepared
At 1.5L with mechanical stirring, thermometer, prolong, and be equipped with in the stainless steel reactor of dividing plate, add 60 grams of sodium hydroxide, 405 grams of water, 80 grams of sulphur powder, obtain mixed solution.Under high pure nitrogen protection, mixed solution is warming up to 85 DEG C, stirs and treat that solid dissolves gradually, maintain this temperature and continue stirring 1 hour, be cooled to 40 DEG C after reaction, obtain the aqueous sodium polysulfide of 1.2mol/L.Wherein, the mass ratio of raw material sodium sulphite, sulphur and water is 1:1.3:6.8.
2) on reactor dividing plate, place 5 bag (weight per package is 52 grams) wrap up with filter screen self-control micron order particles of silicon quaternary ammonium salt loading type type phase-transfer catalysts, stir after 30 minutes, after be warming up to 85 DEG C, obtain the first mixed solution.Then in the first mixed solution, add the toluene solution of the 3-chloropropyl triethoxysilane that 829g concentration is 30wt% with the speed of 8.0g/ minute, drip off this temperature of rear maintenance and continue stirring 7.0 hours, stopped reaction, obtains silane coupling agent mixed solution.Wherein, the mol ratio of the sodium polysulphide added and 3-chloropropyl triethoxysilane is 1:2.1, and the molar weight of loading type quaternary ammonium salt phase transfer catalyst accounts for 9% of the molar weight of 3-chloropropyl triethoxysilane.
3), after question response stops, the loading type quaternary ammonium salt phase transfer catalyst that taking-up is wrapped up with filter screen, with deionized water wash, dries in order to experiment use next time.Gained filtrate uses separating funnel separatory, and lower floor is water white salt aqueous phase, and upper strata is shallow amber yellow product and toluene phase.Organic phase, through removed under reduced pressure solvent toluene, obtains crude product.By high-vacuum installation, residual toluene and unreacted raw material 3-chloropropyl triethoxysilane in removing crude product, finally obtain 202.2 grams of silane coupler containing sulfurs.
Embodiment 7
1) aqueous sodium polysulfide is prepared
At 1.5L with mechanical stirring, thermometer, prolong, and be equipped with in the stainless steel reactor of dividing plate, add 60 grams of sodium hydroxide, 205 grams of water, 80 grams of sulphur powder, obtain mixed solution.Under high pure nitrogen protection, mixed solution is warming up to 85 DEG C, stirs and treat that solid dissolves gradually, maintain this temperature and continue stirring 45 minutes, be cooled to 40 DEG C after reaction, obtain 2.4m
othe aqueous sodium polysulfide of l/L.Wherein, the mass ratio of feed hydrogen sodium oxide, sulphur and water is 1:1.3:3.4.
2) on reactor dividing plate, place the homemade macroporous polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst of recovery that 4 bags (weight per package is 11 grams) wrap up with filter screens 5 times, stir after 15 minutes, after be warming up to 85 DEG C, obtain the first mixed solution.Then in the first mixed solution, add the toluene solution of the 3-chloropropyl triethoxysilane that 1207.5g concentration is 20wt% with the speed of 10.0g/ minute, drip off this temperature of rear maintenance and continue stirring 4.5 hours, stopped reaction, obtains silane coupling agent mixed solution.Wherein, the mol ratio of the sodium polysulphide added and 3-chloropropyl triethoxysilane is 1:2, and the molar weight of loading type quaternary ammonium salt phase transfer catalyst accounts for 10% of the molar weight of 3-chloropropyl triethoxysilane.
3), after question response stops, the loading type quaternary ammonium salt phase transfer catalyst that taking-up is wrapped up with filter screen, with deionized water wash, dries in order to experiment use next time.Gained filtrate uses separating funnel separatory, and lower floor is water white salt aqueous phase, and upper strata is shallow amber yellow product and toluene phase.Organic phase, through removed under reduced pressure solvent toluene, obtains crude product.By high-vacuum installation, residual toluene and unreacted raw material 3-chloropropyl triethoxysilane in removing crude product, finally obtain 212.6 grams of silane coupler containing sulfurs.
Wherein, self-control macroporous polystyrene-divinylbenzene loading type the quaternary ammonium salt phase transfer catalyst of recovery 5 times is adopted in embodiment 7, data show that its its catalytic effect of catalyzer reclaimed is also better, thus can production cost be reduced, decrease in prior art the catalyzer using two-phase phase-transfer catalyst to bring cannot recycle, and produce a large amount of discharges of waste liquid.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. a preparation method for silane coupler containing sulfur, is characterized in that, under the effect of loading type quaternary ammonium salt phase transfer catalyst, to the polysulfide aqueous solution and the process of 3-halogen propyl trialkoxy silane Hybrid Heating.
2. preparation method according to claim 1, is characterized in that, described loading type quaternary ammonium salt phase transfer catalyst is polystyrene-divinylbenzene loading type quaternary ammonium salt phase transfer catalyst or silicon dioxide carried type quaternary ammonium salt phase transfer catalyst.
3. the preparation method according to any one of claim 1 or 2, is characterized in that, comprises the following steps:
S1, in the described polysulfide aqueous solution, add described loading type quaternary ammonium salt phase transfer catalyst, stir, be heated to preset temperature, obtain the first mixed solution; And
S2, under described preset temperature, in described first mixed solution, add 3-halogen propyl trialkoxy silane, constant temperature stirring reaction, obtains silane coupler containing sulfur.
4. preparation method according to claim 3, is characterized in that, the described polysulfide aqueous solution be aqueous sodium polysulfide,
One or more in the potassium polysulfide aqueous solution and the ammonium polysulfide aqueous solution.
5. preparation method according to claim 3, is characterized in that, the concentration of the described polysulfide aqueous solution is 1.6 ~ 2.8mol/L.
6. preparation method according to claim 5, is characterized in that, the concentration of the described polysulfide aqueous solution is 2.1 ~ 2.4mol/L.
7. preparation method according to claim 3, is characterized in that, in the described polysulfide aqueous solution, the mol ratio of polysulfide and described 3-halogen propyl trialkoxy silane is 1:1.6 ~ 1:2.2.
8. preparation method according to claim 3, is characterized in that, in described loading type quaternary ammonium salt phase transfer catalyst, the molar weight of effective quaternary ammonium salt accounts for 0.5% ~ 10% of described 3-halogen propyl trialkoxy silane molar weight.
9. preparation method according to claim 8, is characterized in that, in described loading type quaternary ammonium salt phase transfer catalyst, the molar weight of effective quaternary ammonium salt accounts for 5% ~ 9% of described 3-halogen propyl trialkoxy silane molar weight.
10. preparation method according to claim 1, it is characterized in that, described 3-halogen propyl trialkoxy silane be selected from 3-chloropropyl triethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-bromopropyl triethoxyl silane and 3-bromopropyl Trimethoxy silane one or more.
11. preparation methods according to claim 3, is characterized in that, described step S2 comprises:
S21, described 3-halogen propyl trialkoxy silane is dissolved in organic solvent, forms the organic solution containing 3-halogen propyl trialkoxy silane; And
S22, the described organic solution containing 3-halogen propyl trialkoxy silane is joined in described first mixed solution with the speed of 3.5 ~ 10g/ minute;
Described organic solution is one or more in benzene, toluene and xylene solution.
12. preparation methods according to claim 11, is characterized in that, the concentration of the described organic solution containing 3-halogen propyl trialkoxy silane is 20wt% ~ 98wt%.
13. preparation methods according to claim 12, is characterized in that, the concentration of the described organic solution containing 3-halogen propyl trialkoxy silane is 30wt% ~ 50wt%.
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