CN102659831A - Synthesis method of gamma-thiopropyl trimethoxy silane - Google Patents
Synthesis method of gamma-thiopropyl trimethoxy silane Download PDFInfo
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- CN102659831A CN102659831A CN2012101245435A CN201210124543A CN102659831A CN 102659831 A CN102659831 A CN 102659831A CN 2012101245435 A CN2012101245435 A CN 2012101245435A CN 201210124543 A CN201210124543 A CN 201210124543A CN 102659831 A CN102659831 A CN 102659831A
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Abstract
The invention discloses a synthesis method of gamma-thiopropyl trimethoxy silane, comprising the following steps of: (1) dissolving NaHS into water and adjusting a pH (Potential of Hydrogen) value to be less than 7.0; (2) uniformly mixing gamma-chloropropyl trimethoxy silane, ethanol, a phase transfer catalyst and a stabilizing agent to react; (3) vacuumizing a synthesis reaction kettle and introducing mixed gas of N2 and CO2; adjusting a kettle temperature of the synthesis reaction kettle to 65-70 DEG C; then respectively feeding a mixed solution obtained by the step (1) and a mixed solution obtained by the step (2) into the synthesis reaction kettle in a flowing way to carry out synthesis reaction; and (4) layering reaction products and distilling an upper-layer oil phase to obtain the product gamma-thiopropyl trimethoxy silane. The synthesis reaction can be carried out under a stable low-pressure condition; in a synthesis process, two raw materials are fed into the reaction kettle in a flowing way to react, so that the mixing uniformity and the reaction uniformity of the materials are reinforced, the reaction conversion rate is improved, the reaction time is shortened and the product purity is improved.
Description
Technical field
The present invention relates to the synthetic technology of γ-mercaptopropyl trimethoxysilane, relate in particular to a kind of use phase transfer method and carry out the synthetic method.
Background technology
γ-mercaptopropyl trimethoxysilane is a kind of multi-functional silane coupler containing sulfur with bifunctional of reactive and crosslinkable property; Its mercapto propyl group functional group (SH) can with unsaturated lipid, polyester effect; Trimethoxy functional group hydrolysis simultaneously generate silanol can with effect such as inorganics, organic polymer and mineral filler are bonded together securely.In glass fiber industry, as reinforcement material,, can also effectively alleviate the cohesive force that causes owing to moisture intrusion and degenerate except improving the composite material strength, effectively keep or improve the hygrometric state mechanical property and the stability of matrix material; At rubber industry, be usually used in mineral fillers such as treated carbon black, WHITE CARBON BLACK, mica, spun glass, can significantly improve the mechanical property and the wear resisting property of rubber; As tackifier, be widely used in urethane, epoxy resin, polyester, styrene-butadiene rubber(SBR) and tree elastomer etc., can effectively improve rubber resin and all kinds of base materials comprised dry state bounding forces such as glass, concrete, building stones; γ-mercaptopropyl trimethoxysilane is incorporated in propenoate, epoxy and the polyurethane coating, can obviously improves the cohesive force and the ageing resistance of coating; Produce mercapto propyl group modified silicon oil and be widely used as the antiseized barrier coat of paper, optical fiber coats coating etc.; Aspect household chemicals, can give hair wet fastness and persistence behind the adding agent for permanent hair waving, and hair style is fixed; Also useful as surfactants, organic synthesis intermediate; And as metal conditioner, can strengthen its surperficial rotproofness, oxidation-resistance and increase it and high molecular cementability such as resin etc.
In recent years, along with the further investigation that γ-mercaptopropyl trimethoxysilane is used, this product had become the focus that the expert pays close attention in the research and the application in following field, mainly concentrated on the following aspects.
1, preparation silicon hydrogen addition catalyst
With the mercaptopropyl trimethoxysilane is starting raw material, synthesizes 4, and 7-dithia alkyl trimethoxysilane is used for the synthetic silicon monomer that contains multiple tooth dentate, and the title complex of its polymkeric substance and platinum is one type of good alkene silicon hydrogen addition catalyst.
2, medically handle as the silylanization on stainless steel stent surface
Percutaneous coronary artery intervention (PCI); Be to be widely used in clinical coronary heart disease to rebuild one of most effectual way of blood fortune; But early stage bare bracket restenosis rate is higher, though the bracket for eluting medicament restenosis rate of wide clinical application obviously descends at present, is easy to form thrombus.In thrombotic process, the physics-chem characteristic of material surface and the blood compatibility of material also are important factors.With mercaptopropyl trimethoxysilane the naked metal support surface of 316L stainless steel is carried out silylanization and handle, its contact angle mercaptopropyl trimethoxysilane hydrophilic coating support is 40 °, has obtained good antithrombotic characteristic.
3, preparation unitary film
Adopt numerator self-assembly technique to prepare 3-mercaptopropyl trimethoxysilane unitary film at hydroxylated glass substrate surface; Result of study shows; Behind this unitary film of assembling; The coefficient of friction of substrate surface 0.85 during by no film dropped to 0.19, and explanation can reduce the frictional coefficient of substrate, and under low load, has wear resisting property preferably.
4, preparative hplc stationary phase
3-mercaptopropyl trimethoxysilane and vinyltrimethoxy silane generation addition reaction, synthetic a kind of pair of siloxanes coupling agent makes a kind of novel chromatographic stationary phase that contains the thioether abutment.This stationary phase has tangible reverse-phase chromatography performance, aspect the pre-treatment (like polycyclic aromatic hydrocarbons, polar substituted arene, purine class and anthraquinone analog compound) of chromatographic separation and sample application promise in clinical practice is being arranged.
5, red copper surface is handled
Red copper is conducted electricity, thermal conductivity is good, be widely used, but in moist and corrosive medium, red copper is prone to be corroded, and serious discoloration can take place on the surface, makes its performance reduction.At its surface preparation one deck organosilicone film is a kind of effective protection against corrosion surface treatment way.(SH) functional group, sulfydryl can directly act on the copper substrate and form the Cu-S key mercaptopropyltriethoxysilane, thereby can significantly improve silane molecule and copper substrate caking power and the gained Silan-based Thin Films protection efficient to the copper substrate because of containing sulfydryl in its molecular structure.With the organic inhibition agent film; Compare like benzotriazole, organosilicone film not only has excellent Corrosion Protection, and as the pre-treatment before the organic coat; Can significantly improve silane molecule combines with the copper substrate; And environmental friendliness can substitute pretreatment processs such as traditional chromic acid salt, phosphoric acid salt, with the environmental regulation of reply increasingly stringent.
6, the efficient selective sorbent material of preparation precious metal palladium
The noble metal catalyst that with the palladium is representative has been widely used in the synthetic of medicine and midbody thereof, because the genotoxic potential of precious metal, the removal technology of palladium is an important topic in the pharmaceutical industry in the research and development medicine.The silica gel absorber of mercapto functional groupization is because the loading capacity of its outstanding adsorption selectivity receives people's attention.Technique for atomic layer deposition is the method for manufacturing thin film that extensively adopts in the microelectronics industry; It utilizes the chemisorption reaction of precursor steam at material surface; Can generate the film with high step coverage rate and good thickness evenness, the surface bond rate of its part all is higher than the organic solvent medium method.Adopt technique for atomic layer deposition, make gasifications such as γ-mercaptopropyl trimethoxysilane, and under the katalysis of triethylamine, respectively it is bonded to the porous silica gel surface, make the high-efficiency adsorbent of precious metal palladium.
The expansion of Application Areas requires also to improve constantly to quality product; Especially industry such as medical use, chromatographic separation is particularly harsh to the gamma-mercaptopropyltriethoxysilane specification of quality, and the gamma-mercaptopropyltriethoxysilane of high purity, low impurity, minimizing impurity kind is the product summarys of the urgent expectation of numerous Application Areass.
The compound method of existing γ-mercaptopropyl trimethoxysilane according to the difference of reaction system, simply is divided into two kinds of anhydrous synthesis method and water methods; According to working pressure, be divided into non-pressure process and low-pressure process (pressure is lower than 0.2MPa).
(1) anhydrous synthesis method
1, thiocarbamide method
With anhydrous methanol or absolute ethyl alcohol is solvent, is promotor with KI or NaI, and r-chloropropyl trimethoxyl silane and thiocarbamide reaction make finished product.
This method advantage is: easy to operate, product yield reaches about 80%; Side reaction is few, and product purity reaches 98%.Weak point is: necessary drying was at least four hours before raw material γ-chloropropyl triethoxysilane, thiocarbamide, potassiumiodide or Soiodin used, and had increased operation sequence; Reaction time is long; Content requirement to raw material γ-chloropropyl triethoxysilane, aqueous solvent is harsh, and is strict to water-content in the conversion unit; Raw material γ-chloropropyl triethoxysilane transformation efficiency is not high, and product cost is higher.
2, hydrogen sulfide method
Hydrogen sulfide and reacting ethylenediamine generate the ethylenediamine salt of hydrogen sulfide, in the presence of solvent, react with r-chloropropyl trimethoxyl silane.Remove by filter ethylenediamine-hydrochloride, filtrating is obtained finished product through cut under distillation removal solvent (solvent recovery cycle use), the intercepting certain temperature.React as follows:
H
2N-CH
2CH
2-NH
2H
2S+(CH
3O)
3SiCH
2CH
2H
2Cl→(CH
3O)
3SiCH
2CH
2CH
2SH+H
2N-CH
2CH
2NH
2.HCl↓
This method advantage is: product purity higher (content is more than 98%), and the reaction times is short, and ethylenediamine-hydrochloride is prone to filter, and product cost is low.Weak point is: H
2S toxicity is big, and operational safety is high, and is high to equipment material and sealing requirements, and identical industrial scale investment is bigger, and the operation site environment is relatively poor.
3, the sodium polysulphide method is (with Na
2S
2Be main ingredient)
The sodium polysulphide method is (with Na in the presence of solvent
2S
2Be main ingredient) generate 3 with r-chloropropyl trimethoxyl silane reaction, two (the silica-based propyl group of the trimethoxy)-disulphide of 3-reduce and get.This method advantage is: the reaction times is short, and flow process is short, and production cost is low.Weak point is: no matter be with hydrogen reducing or use NaBH
4Reduction because free hydrogen is active high, is easy to cause product purity low the methoxyl group reduction, and by product is many; In addition, sodium polysulphide Na
2S
nIn the numerical value of n very wide, a plurality of reduction reactions take place in from 2 to 7 skewness, final product complicated component and be difficult to separate.
(2) water method
Use phase-transfer catalyst, make at aqueous phase γ-chloropropyl triethoxysilane and the reaction of metal sulfohydrate.The metal sulfohydrate can be NaHS, KHS, NH
4HS one of them, type reaction is:
(CH
3CH
2O)
3SiCH
2CH
2CH
2Cl+NaHS→(CH
3O)
3SiCH
2CH
2CH
2SH+NaCl
Existing method advantage is: be reflected at aqueous phase and carry out, the reaction times is short, easy to operate, SF is big, low for equipment requirements, temperature of reaction is low.Weak point is: raw material γ-chloropropyl triethoxysilane hydrolysis is serious, and the jello parcel raw material of generation makes reaction carry out difficulty, and the product foreign matter content that makes is high, and separating difficulty is big, so product cost is higher.
Gamma-mercaptopropyltriethoxysilane is many characteristics such as industry is many, usage quantity big, applied range because of using; More to this product research both at home and abroad; With improve product yield, reduce production costs, optimization production technology, selection appropriate catalyst is research contents, obtained interim breakthrough.
See that from production technique the water method of using phase-transfer catalyst is a synthetic developing direction from now on.Phase-transfer catalyst be can help reactant from a phase transition to can react another quite, thereby accelerate one type of catalyzer of outphasing system speed of reaction.Generally have the reaction of phase-transfer catalysis, all exist the aqueous solution and organic solvent two mutually, reaction of ionic type thing often dissolves in water, is insoluble to organic phase, and organic substrates then dissolves among the organism.When not having phase-transfer catalyst, two isolate each other, and several reactants can't contact, and reaction is carried out very slowly.The existence of phase-transfer catalyst can combine with the ion of aqueous phase, and utilizes self to organic affinity, in organic phase, impels reaction to take place the reactant transfer of aqueous phase.Phase-transfer-catalyzed reactions, because productive rate is high, reaction conditions is gentle, and selectivity is high, and by product is few, and catalyst consumption is also fewer, and is simple to operate, reduced the use of harmful organic solvent, become a kind of widely used compound method.
Summary of the invention
Technical problem to be solved by this invention is: to the deficiency that prior art exists, the compound method of a kind of sufficient reacting, feed stock conversion is high, product purity is high, production cost is low γ-mercaptopropyl trimethoxysilane is provided.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of compound method of γ-mercaptopropyl trimethoxysilane may further comprise the steps:
(1) NaHS is added in the entry dissolving fully after, adding the pH regulator agent, to regulate the pH value be below 7.0.
(2) γ-r-chloropropyl trimethoxyl silane, ethanol, phase-transfer catalyst and stablizer are mixed.
(3) synthesis reaction vessel being evacuated to steady pressure is 0.96～0.098Mpa, feeds N
2And CO
2Mixed gas, stabilize to 0.1～0.12MPa to reacting kettle inner pressure, stop to feed N
2And CO
2, the opening plunger pump is opened the jacket steam valve simultaneously; Synthesis reaction vessel still temperature is transferred to 65～70 ℃; The mixing solutions that then step (1) and step (2) is obtained flows respectively and is added in the synthesis reaction vessel, and two kinds of mixture stream add and finish, and continue reaction 3.5～4.5 hours again.
(4) the reactant layering that step (3) is obtained, at vacuum tightness >=0.099MPa, distillation obtains product γ-mercaptopropyl trimethoxysilane during 80～85 ℃ of gas phase temperatures with upper oil phase.
Preferably, said pH regulator agent is adjusted to the mixture of hydrochloric acid, Hydrocerol A and Trisodium Citrate, and the consumption of said pH regulator agent is respectively hydrochloric acid 5～8 weight parts, Hydrocerol A 3～6 weight parts and Trisodium Citrate 2～6 weight parts of 30wt%.
Preferably, said phase-transfer catalyst is DTAC and Tetrabutyl amonium bromide, and the consumption of said DTAC and Tetrabutyl amonium bromide is respectively 6～16 weight parts and 8～12 weight parts.
Preferably, said stablizer is thiophene piperazine and Ucar 35, and consumption is respectively 1.5～2 weight parts and 0.5～1.5 weight part.
Preferably, in the step (1), the consumption of NaHS and water is respectively 135～160 weight parts and 130～150 weight parts.
Preferably, in the step (2), γ-r-chloropropyl trimethoxyl silane and consumption of ethanol are respectively 300～350 weight parts and 8～20 weight parts.
Flow when the mixing solutions that preferably, step (1) and step (2) is obtained flows respectively and is added to synthesis reaction vessel is 0.3～0.35m
3/ h.
Preferably, said N
2And CO
2The volume ratio of mixed gas be 1: 0.3～0.5.
As a kind of improvement, use activated carbon decolorizing also to distill after the filtration organic phase before the said distillation.
As further improvement, before the said mixing solutions that step (1) and step (2) are obtained flows respectively and is added to synthesis reaction vessel, earlier through a mixing kettle, after two kinds of mixed solutions are mixed again stream be added to reaction kettle.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention charges into N in reaction system when building-up reactions
2And CO
2Mixed gas, CO
2PH value in can the conditioned reaction process can consume a part in the reaction process, therefore adds with N
2Mixed gas, can avoid because of CO
2Consumption makes the on the low side or pressure surge considerable influence reaction process of system reaction pressure, and the assurance building-up reactions is carried out under the stabilizing low voltage condition.In addition; The present invention is added to two kinds of feedstreams in the reaction kettle when synthetic and reacts; The mixture homogeneity of having strengthened material and reaction homogeneity, so reaction conversion ratio height when reacting after in the prior art raw material being mixed in reaction kettle react more abundant; Reaction times shortens more than 2 hours than prior art, and the product purity of preparation is more than 99.0wt%.
2, owing in the NaHS solution under acidic conditions, minor N a
2S
x(x=1-4) exist with the NaHS form mostly, and under alkaline condition, Na
2S
xWith Na
2S is that principal mode exists, but under high temperature or heating state, NaHS can be decomposed into Na
2S, H
2S etc. cause the NaHS loss.And when temperature of reaction is too high, can impel the alkoxyl group hydrolysis rate in the organoalkoxysilane to increase, and can make and take off ether between the alkoxyl group, generate the polymer of siliceous-oxygen-silicon bound.The present invention adopts three components and the CO of hydrochloric acid, Hydrocerol A and Trisodium Citrate
2As the pH regulator agent; Can be under the solutions of weak acidity by guarantee system; Guarantee besides under stable low pressure condition, to carry out, make temperature of reaction can be controlled at below 70 ℃, avoided the decomposition of NaHS and alkoxyl group hydrolysis to generate polymeric phenomenon; And need not before using γ-chloropropyl triethoxysilane is neutralized or pre-treatment such as distillation, simplified production process.
3, owing to there is big water gaging to exist in the reaction system; Water can cause the methoxyl group in r-chloropropyl trimethoxyl silane, the mercaptopropyl trimethoxysilane to be hydrolyzed into silanol; Intermolecular condensation forms and contains the condenses of Si-O-Si key under heating condition, thereby generates a large amount of high boiling material.Because these high boiling material majorities are linear dimer or trimer, wherein also remaining has methoxy functional group, and at high temperature these remaining functional groups can further condensations form the polymkeric substance that build intersects.The present invention adds thiophene piperazine and Ucar 35 as one package stabilizer, has significantly reduced the generation of hydrolysis, condensation and the jello of γ-r-chloropropyl trimethoxyl silane, makes building-up reactions carry out smoothly according to theory orientation.And the present invention adopts two kinds of phase-transfer catalysts, disposable adding reaction system, and two kinds of catalyzer promote mutually, have accelerated the synthesising reacting speed of γ-r-chloropropyl trimethoxyl silane and NaHS.
4, the present invention is before carrying out building-up reactions, with two kinds of mixing solutionss earlier through a mixing kettle, after two kinds of mixed solutions are mixed again stream be added to reaction kettle, further strengthened the mixed effect and the reaction uniformity of raw material.
Embodiment
Below in conjunction with concrete embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) 140Kg solid industrial goods NaHS is added dissolution kettle; Added 137Kg water stirring and dissolving again 20 minutes; 67 rev/mins of stirring velocitys after the dissolving fully, add hydrochloric acid 5Kg, Hydrocerol A 4Kg and the Trisodium Citrate 2.5Kg of 30wt%; Stirring and regulating the pH value in 25 minutes is below 7.0, squeezes into header tank then.
(2) with γ-r-chloropropyl trimethoxyl silane 300Kg, ethanol 8Kg, phase-transfer catalyst DTAC 7Kg and Tetrabutyl amonium bromide 8.5Kg, stablizer thiophene piperazine 1.5Kg and Ucar 35 0.8Kg; Stir and mixed in 25 minutes, squeeze into header tank then.
(3) synthesis reaction vessel being evacuated to steady pressure is 0.98Mpa, keeps 12 minutes, and the feeding volume ratio is 1: 0.35 N
2And CO
2Mixed gas, stabilize to 0.1MPa to reacting kettle inner pressure, stop to feed N
2And CO
2The opening plunger pump; Open the jacket steam valve simultaneously, synthesis reaction vessel still temperature is transferred to 66 ℃, the mixing solutions that then step (1) and step (2) is obtained flows respectively from header tank separately to be added in the mixing kettle; After two kinds of mixed solutions are mixed again stream be added in the synthesis reaction vessel, flow is 0.3m
3/ h, temperature of reaction is 66 ℃, two kinds of mixture stream add and finish, and continue reaction 4.5 hours again.
(4) reactant that step (3) is obtained is put into the separator layering; Upper oil phase is used activated carbon decolorizing and filtered, and filtrating is squeezed into the still kettle heating, treats that gas phase temperature surpasses 100 ℃ and when the ascendant trend of continuation is arranged; Open Roots-water ring vacuum unit; First control vacuum tightness 0.096MPa continues to be heated to gas phase temperature and reaches 90 ℃ and when the ascendant trend of continuation is arranged, and opens the whole lobe pumps of Roots's water ring vacuum unit; At vacuum tightness >=0.099MPa, the phlegma when the collection gas phase temperature is 82～85 ℃ is specification product γ-mercaptopropyl trimethoxysilane then.
Embodiment 2
(1) 160Kg solid industrial goods NaHS is added dissolution kettle; Added 145Kg water stirring and dissolving again 30 minutes; 80 rev/mins of stirring velocitys after the dissolving fully, add hydrochloric acid 5.5Kg, Hydrocerol A 5Kg and the Trisodium Citrate 3.2Kg of 30wt%; Stirring and regulating the pH value in 25 minutes is below 7.0, squeezes into header tank then.
(2) with γ-r-chloropropyl trimethoxyl silane 320Kg, ethanol 9.5Kg, phase-transfer catalyst DTAC 7.5Kg and Tetrabutyl amonium bromide 9.5Kg, stablizer thiophene piperazine 1.6Kg and Ucar 35 0.9Kg; Stir and mixed in 25 minutes, squeeze into header tank then.
(3) synthesis reaction vessel being evacuated to steady pressure is 0.96Mpa, keeps 15 minutes, and the feeding volume ratio is 1: 0.37 N
2And CO
2Mixed gas, stabilize to 0.11MPa to reacting kettle inner pressure, stop to feed N
2And CO
2, the opening plunger pump is opened the jacket steam valve simultaneously, and synthesis reaction vessel still temperature is transferred to 70 ℃, and the mixing solutions that then step (1) and step (2) is obtained flows respectively from header tank separately and is added in the synthesis reaction vessel, and flow is 0.31m
3/ h, temperature of reaction is 70 ℃, two kinds of mixture stream add and finish, and continue reaction 3.5 hours again.
(4) reactant that step (3) is obtained is put into the separator layering; Upper oil phase is used activated carbon decolorizing and filtered, and filtrating is squeezed into the still kettle heating, treats that gas phase temperature surpasses 101 ℃ and when the ascendant trend of continuation is arranged; Open Roots-water ring vacuum unit; First control vacuum tightness 0.097MPa continues to be heated to gas phase temperature and reaches 90 ℃ and when the ascendant trend of continuation is arranged, and opens the whole lobe pumps of Roots's water ring vacuum unit; At vacuum tightness >=0.099MPa, the phlegma when the collection gas phase temperature is 80～83 ℃ is specification product γ-mercaptopropyl trimethoxysilane then.
Embodiment 3
(1) 150Kg solid industrial goods NaHS is added dissolution kettle, added 160Kg water stirring and dissolving again 30 minutes, 90 rev/mins of stirring velocitys; After the dissolving fully; Add hydrochloric acid 6Kg, Hydrocerol A 5.5Kg and the Trisodium Citrate 3.5KgpH regulator of 30wt%, stirred 30 minutes, squeeze into header tank then.
(2) with γ-r-chloropropyl trimethoxyl silane 350Kg, ethanol 11Kg, phase-transfer catalyst DTAC 8.2Kg and Tetrabutyl amonium bromide 10.5Kg, stablizer thiophene piperazine 1.7Kg and Ucar 35 1.2Kg; Stir and mixed in 30 minutes, squeeze into header tank then.
(3) synthesis reaction vessel being evacuated to steady pressure is 0.97Mpa, keeps 10 minutes, and the feeding volume ratio is 1: 0.4 N
2And CO
2Mixed gas, stabilize to 0.12MPa to reacting kettle inner pressure, stop to feed N
2And CO
2The opening plunger pump; Open the jacket steam valve simultaneously, synthesis reaction vessel still temperature is transferred to 68 ℃, the mixing solutions that then step (1) and step (2) is obtained flows respectively from header tank separately to be added in the mixing kettle; After two kinds of mixed solutions are mixed again stream be added in the synthesis reaction vessel, flow is 0.32m
3/ h, temperature of reaction is 68 ℃, two kinds of mixture stream add and finish, and continue reaction 4.2 hours again.
(4) reactant that step (3) is obtained is put into the separator layering; Upper oil phase is used activated carbon decolorizing and filtered, and filtrating is squeezed into the still kettle heating, treats that gas phase temperature surpasses 100 ℃ and when the ascendant trend of continuation is arranged; Open Roots-water ring vacuum unit; First control vacuum tightness 0.096MPa continues to be heated to gas phase temperature and reaches 90 ℃ and when the ascendant trend of continuation is arranged, and opens the whole lobe pumps of Roots's water ring vacuum unit; At vacuum tightness >=0.099MPa, the phlegma when the collection gas phase temperature is 80～83 ℃ is specification product γ-mercaptopropyl trimethoxysilane then.
Embodiment 4
(1) 145Kg solid industrial goods NaHS is added dissolution kettle, added 145Kg water stirring and dissolving again 20 minutes, 75 rev/mins of stirring velocitys after the dissolving fully, add the pH regulator agent, and regulating the pH value is below 7.0, squeezes into header tank then.
(2) with γ-r-chloropropyl trimethoxyl silane 340Kg, ethanol 12Kg, phase-transfer catalyst and stablizer, stir and mixed in 25 minutes, squeeze into header tank then.
(3) synthesis reaction vessel being evacuated to steady pressure is 0.96Mpa, keeps 12 minutes, and the feeding volume ratio is 1: 0.5 N
2And CO
2Mixed gas, stabilize to 0.1MPa to reacting kettle inner pressure, stop to feed N
2And CO
2, the opening plunger pump is opened the jacket steam valve simultaneously, and synthesis reaction vessel still temperature is transferred to 69 ℃, and the mixing solutions that then step (1) and step (2) is obtained flows respectively from header tank separately and is added in the synthesis reaction vessel, and flow is 0.33m
3/ h, temperature of reaction is 69 ℃, two kinds of mixture stream add and finish, and continue reaction 4.5 hours again.
(4) the reactant layering that step (3) is obtained; Upper oil phase is used activated carbon decolorizing and filtered, and filtrating is squeezed into the still kettle heating, treats that gas phase temperature surpasses 100 ℃ and when the ascendant trend of continuation is arranged; Open Roots-water ring vacuum unit; First control vacuum tightness 0.096MPa continues to be heated to gas phase temperature and reaches 90 ℃ and when the ascendant trend of continuation is arranged, and opens the whole lobe pumps of Roots's water ring vacuum unit; At vacuum tightness >=0.099MPa, the phlegma when the collection gas phase temperature is 80～85 ℃ is specification product γ-mercaptopropyl trimethoxysilane then.
The product quality indicator for preparing among each embodiment is seen table 1.
Table 1
Claims (10)
1. the compound method of a γ-mercaptopropyl trimethoxysilane is characterized in that may further comprise the steps:
(1) NaHS is added in the entry dissolving fully after, adding the pH regulator agent, to regulate the pH value be below 7.0;
(2) γ-r-chloropropyl trimethoxyl silane, ethanol, phase-transfer catalyst and stablizer are mixed;
(3) synthesis reaction vessel being evacuated to steady pressure is 0.96～0.098Mpa, feeds N
2And CO
2Mixed gas; Stabilize to 0.1～0.12MPa to reacting kettle inner pressure, synthesis reaction vessel still temperature is transferred to 65～70 ℃, the mixing solutions that then step (1) and step (2) is obtained flows respectively and is added in the synthesis reaction vessel; Two kinds of mixture stream add and finish, and continue reaction 3.5～4.5 hours again;
(4) the reactant layering that step (3) is obtained, at vacuum tightness >=0.099MPa, distillation obtains product γ-mercaptopropyl trimethoxysilane during 80～85 ℃ of gas phase temperatures with upper oil phase.
2. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 1; It is characterized in that: said pH regulator agent is adjusted to the mixture of hydrochloric acid, Hydrocerol A and Trisodium Citrate, and the consumption of said pH regulator agent is respectively hydrochloric acid 5～8 weight parts, Hydrocerol A 3～6 weight parts and Trisodium Citrate 2～6 weight parts of 30wt%.
3. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 1; It is characterized in that: said phase-transfer catalyst is DTAC and Tetrabutyl amonium bromide, and the consumption of said DTAC and Tetrabutyl amonium bromide is respectively 6～16 weight parts and 8～12 weight parts.
4. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 1, it is characterized in that: said stablizer is thiophene piperazine and Ucar 35, consumption is respectively 1.5～2 weight parts and 0.5～1.5 weight part.
5. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 1, it is characterized in that: in the step (1), the consumption of NaHS and water is respectively 135～160 weight parts and 130～150 weight parts.
6. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 1, it is characterized in that: in the step (2), γ-r-chloropropyl trimethoxyl silane and consumption of ethanol are respectively 300～350 weight parts and 8～20 weight parts.
7. like the compound method of described any the γ-mercaptopropyl trimethoxysilane of claim 1 to 6, it is characterized in that: the flow the when mixing solutions that step (1) and step (2) are obtained flows respectively and is added to synthesis reaction vessel is 0.3～0.35m3/h.
8. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 7, it is characterized in that: the volume ratio of the mixed gas of said N2 and CO2 is 1: 0.3～0.5.
9. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 7 is characterized in that: use activated carbon decolorizing also to distill after the filtration organic phase before the said distillation.
10. the compound method of γ-mercaptopropyl trimethoxysilane as claimed in claim 7; It is characterized in that: before the said mixing solutions that step (1) and step (2) are obtained flows respectively and is added to synthesis reaction vessel; Earlier through a mixing kettle, after two kinds of mixed solutions are mixed again stream be added to reaction kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101245435A CN102659831A (en) | 2012-04-25 | 2012-04-25 | Synthesis method of gamma-thiopropyl trimethoxy silane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104926854A (en) * | 2014-03-23 | 2015-09-23 | 浙江新安化工集团股份有限公司 | Method for preparing mercaptopropyltriethoxysilane through constant-pressure low-temperature aqueous phase |
| CN105153216A (en) * | 2015-08-07 | 2015-12-16 | 荆州市江汉精细化工有限公司 | Preparation method of 3-mercaptopropyl-trimethoxy silane |
| CN115215898A (en) * | 2022-07-29 | 2022-10-21 | 上海橡实化学有限公司 | Method for producing mercaptopropyltriethoxysilane |
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| CN102241701A (en) * | 2011-05-25 | 2011-11-16 | 郭学阳 | Method for synthesizing gamma-mercaptopropyltriethoxysilane |
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| CN102241701A (en) * | 2011-05-25 | 2011-11-16 | 郭学阳 | Method for synthesizing gamma-mercaptopropyltriethoxysilane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926854A (en) * | 2014-03-23 | 2015-09-23 | 浙江新安化工集团股份有限公司 | Method for preparing mercaptopropyltriethoxysilane through constant-pressure low-temperature aqueous phase |
| 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 |
| CN105153216A (en) * | 2015-08-07 | 2015-12-16 | 荆州市江汉精细化工有限公司 | Preparation method of 3-mercaptopropyl-trimethoxy silane |
| CN115215898A (en) * | 2022-07-29 | 2022-10-21 | 上海橡实化学有限公司 | Method for producing mercaptopropyltriethoxysilane |
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