CN112028925A - Preparation method of acetoxypropyl alkoxysilane - Google Patents
Preparation method of acetoxypropyl alkoxysilane Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
Abstract
The invention discloses a preparation method of acetoxypropyl alkoxysilane, belonging to the technical field related to organic synthesis. The preparation method comprises the following steps: mixing and heating chloropropyl alkoxy silane and a solvent, adding a polymerization inhibitor when the temperature is raised to 60-70 ℃, continuously raising the temperature to 90-100 ℃, adding acetate and a catalyst, uniformly stirring, and keeping the temperature at 100-110 ℃ for 60-70 min; and cooling the obtained product, introducing the product into a centrifugal machine, filtering to obtain a crude product, and carrying out reduced pressure distillation on the crude product to collect a finished product of acetoxypropyl alkoxy silane, wherein the catalyst is one or more of tetrabutylammonium bromide, benzyltributylammonium chloride, 1-butylpyridinium bromide, tetrabutylphosphonium bromide and dodecyl triphenyl phosphonium bromide. The preparation method has simple process, low production cost and little pollution, and meets the requirements of improving the adhesive force, durability, mechanical strength, electrical performance and the like of the material at present.
Description
Technical Field
The invention belongs to the technical field related to organic synthesis, and particularly relates to a preparation method of acetoxypropyl alkoxysilane.
Background
Acetoxypropyl alkoxysilane contains 1 acetoxy functional group with an unsaturated double bond structure and 1-3 hydrolyzable alkoxy groups, can improve the glass fiber reinforcement and the mechanical and electrical properties of thermosetting and thermoplastic resins containing inorganic fillers, particularly thermosetting resins (such as unsaturated polyester, polyurethane and acrylate) cured by a reactive free radical mechanism reaction, peroxide vulcanized rubber (EPR, EPDM, silicon rubber and the like) and thermoplastic resins (including polyolefin and thermoplastic polyurethane); the dry and wet mechanical strength and electrical performance of the unsaturated polyester composite material (such as casting type or die-casting type artificial quartz stone and the like) filled with the inorganic filler can be obviously improved; the modified silane polymer can be copolymerized with vinyl acetate, acrylic acid or methacrylic acid monomers to synthesize a silane modified polymer capable of being crosslinked and cured at room temperature, and the polymer is widely applied to coatings, adhesives and sealants and provides excellent bonding force and durability.
At present, through search, the industrial synthesis process routes of acetoxypropyl alkoxysilane mainly comprise: an industrial synthesis method of acetoxypropyl trimethoxy silane is disclosed in a patent application with the Chinese patent application number of 201711422451.4 and the application publication date of 2018, 5 and 22. The patent firstly carries out hydrosilylation reaction with trichlorosilane and allyl acetate under the catalyst to obtain acetoxypropyl trichlorosilane, and then esterifies the acetoxypropyl trichlorosilane with methanol to obtain acetoxypropyl trimethoxysilane and hydrochloric acid. The industrial preparation method is complex in process and long in time consumption, chloroplatinic acid is used as a catalyst and is expensive, hydrogen chloride as a byproduct generated in the reaction is difficult to treat, the environment is polluted and the like, and in the method, trichlorosilane and allyl acetate are subjected to hydrosilylation reaction under the catalyst to obtain acetoxypropyl trichlorosilane, only products with the same silane substituent can be prepared, if products with different substituents are required to be prepared, for example, acetoxypropyl methoxydiethoxysilane and acetoxypropyl monomethoxydiethoxysilane need to be esterified by methanol and ethanol, the reaction is uncontrollable, and a target product is difficult to obtain.
In 2011, 2 months, 165 th page 168 of Hangzhou chemical engineering, No. 4, old age ahead, Shaoyangci and Tanghongding disclose an article named 'synthesis research of gamma-methacryloxypropyl trimethoxysilane', which adopts allyl methacrylate and trichlorosilane as raw materials to obtain methacryloxypropyl trichlorosilane through hydrosilylation, and then the methacryloxypropyl trichlorosilane is subjected to alcoholysis reaction with methanol to prepare the methacryloxypropyl trimethoxysilane. The reaction is similar to the preparation method, the process is complicated, the time consumption is long, the catalyst adopts chloroplatinic acid, the price is high, the byproduct hydrogen chloride generated by the reaction is difficult to treat, the environment is polluted, and the like.
Therefore, in order to improve the production efficiency of enterprises, the development of a preparation method of acetoxypropyl alkoxysilane is urgently needed.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of complex process and more byproducts of the existing method for synthesizing acetoxypropyl alkoxysilane, the invention provides a method for synthesizing acetoxypropyl alkoxysilane, which simplifies the process flow and reduces the byproducts by a substitution method to obtain high-purity acetoxypropyl alkoxysilane.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of acetoxy propyl alkoxy silane comprises the following steps: mixing and heating chloropropyl alkoxy silane and a solvent, adding a polymerization inhibitor when the temperature is raised to 60-70 ℃, continuously raising the temperature to 90-100 ℃, adding acetate and a catalyst, uniformly stirring, and keeping the temperature at 100-110 ℃ for 60-70 min; and cooling the obtained product, introducing the product into a centrifugal machine, filtering to obtain a crude product, and carrying out reduced pressure distillation on the crude product to collect a finished product of acetoxypropyl alkoxy silane, wherein the catalyst is one or more of tetrabutylammonium bromide, benzyltributylammonium chloride, 1-butylpyridinium bromide, tetrabutylphosphonium bromide and dodecyl triphenyl phosphonium bromide.
Furthermore, the water content of the acetate is less than or equal to 0.2%, and the acetate has high water content, namely the acetate has low purity and poor stability, so that the prepared finished product acetoxypropyl alkoxysilane has a yellowing phenomenon.
Further, the acetate is sodium acetate, potassium acetate, ammonium acetate, magnesium acetate, or zinc acetate.
Further, the acetoxypropyl alkoxysilane has a general structural formula:
wherein: r represents an alkyl group having 1 to 8 carbon atoms, R1Represents methoxy or ethoxy or methoxyethoxy.
Further, the solvent is N, N-dimethylformamide or toluene or xylene or N-heptane.
Further, the polymerization inhibitor is p-hydroxyanisole or 2, 6-di-tert-butyl-p-cresol or hydroquinone.
Furthermore, the mass ratio of the chloropropyl alkoxy silane to the solvent is 1 (0.5-1).
Further, the mass of the polymerization inhibitor is 0.01-0.02% of the total mass of the chloropropyl alkoxy silane and the solvent.
Further, the mass of the catalyst is 0.2-0.3% of the total mass of the chloropropyl alkoxy silane and the solvent.
Furthermore, the molar ratio of the addition amount of the acetate to the addition amount of the chloropropyl alkoxy silane is (1.0-1.1): 1.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the acetoxy propyl alkoxy silane has the advantages of simple process, low production cost and little pollution, and meets the requirements of improving the adhesive force, durability, mechanical strength, electrical performance and the like of materials in the industrial application of inorganic materials, rubber, plastics, resin, textile assistants and the like at present;
(2) the method adopts a common substitution method to prepare the acetoxy propyl alkoxy silane, has simple preparation method, easily obtained catalyst, high product purity and few byproducts, and avoids the problems of high synthesis difficulty and expensive catalyst in the existing hydrosilylation method and esterification method for preparing the acetoxy propyl alkoxy silane;
(3) the preparation method of the invention adopts the solvent, increases the contact area of reactants, can ensure that acetate is dissolved more uniformly and more quickly, is beneficial to the more thorough reaction, and has high yield and purity of the obtained product and short reaction time;
(4) the catalyst is a salt catalyst, comprises tetrabutylammonium bromide, benzyltributylammonium chloride, 1-butylpyridinium bromide, tetrabutylphosphonium bromide or dodecyltriphenylphosphonium bromide, and is a phase transfer catalyst, so that the reaction rate of an out-of-phase system is accelerated, the liquid-solid contact area is increased, the dissolution and reaction of solid salt are accelerated, and the reaction is promoted to occur; when the phase transfer catalyst does not exist, the two phases are mutually isolated, a plurality of reactants cannot contact, the reaction is carried out very slowly, the existence of the phase transfer catalyst can be combined with ions in a water phase, and the reactants in the water phase are transferred to an organic phase by utilizing the affinity of the phase transfer catalyst to an organic solvent, so that the reaction is promoted to occur, wherein the 1-butyl pyridine bromide is alkalescent, the generation of haloalkane is prevented, and the forward progress of the reaction is promoted;
(5) the water content of the acetate is controlled within 0.2 percent, which is found by the inventor in the experimental process that a reaction product using industrial grade acetate can be yellowed, because the water content of most industrial grade acetates reaches more than 1 percent, the water content of the acetate is required to be less than 0.2 percent, the appearance quality of the product is improved, the yellowing phenomenon is avoided, and the obtained product is colorless and transparent.
Drawings
FIG. 1 is a GC spectrum of acetoxypropyltrimethoxysilane obtained in example 1;
FIG. 2 is a GC spectrum of acetoxypropyltriethoxysilane obtained in example 2;
FIG. 3 is a GC spectrum of acetoxypropylmethyldimethoxysilane obtained in example 3;
FIG. 4 is a GC spectrum of acetoxypropyl dimethoxymethoxyethoxysilane obtained in example 4;
FIG. 5 is a GC spectrum of acetoxypropyldimethylmethoxysilane obtained in example 5;
FIG. 6 is a GC spectrum of acetoxypropyltrimethoxysilane obtained in example 6;
FIG. 7 is a GC spectrum of acetoxypropyltrimethoxysilane obtained in example 7.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
the specific preparation method is as follows:
198g of gamma-chloropropyltrimethoxysilane and 100g of DMF are put into a 500ml three-neck flask with a stirring device, stirring is started, 0.04g of p-hydroxyanisole polymerization inhibitor is put into the flask when the temperature is raised to 60 ℃, 86g of sodium acetate (reagent grade, water content is less than or equal to 0.2%) and 0.6g of tetrabutylammonium bromide catalyst are put into the flask when the temperature is raised to 90 ℃, the mixture is uniformly stirred, the reaction time is controlled to be 60min when the reaction temperature is stabilized at 105 ℃, after the heat preservation is finished, the mixture is cooled to below 60 ℃, a centrifuge is introduced into the flask for filtering to obtain a crude product, 320g of acetoxypropyltrimethoxysilane crude product, and finally the crude product is subjected to reduced pressure distillation to obtain 200g of acetoxypropyltrimethoxysilane finished product.
The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
Through GC chromatographic detection, the content of the finished acetoxypropyl trimethoxy silane product obtained after rectification is 99.12 percent, the color number is 15, and the refractive index is as follows: 1.4153(25 ℃), density: 1.010(20 ℃), free chlorine: 2.60ppm, water solubility: as shown in FIG. 1, the GC spectrum of the acetoxypropyltrimethoxysilane synthesized in this example is acceptable.
It is worth to say that the filtrate after centrifugation is led into a fine distillation kettle for distillation, and the solvent is recovered according to different boiling points to obtain a product; the filter cake after centrifugation can be recrystallized to obtain sodium chloride with higher purity.
It can be seen that under the condition that DMF is taken as a solvent, p-hydroxyanisole is taken as a polymerization inhibitor and tetrabutylammonium bromide is taken as a catalyst, the sodium salt reaction is carried out completely, the yield of the obtained product reaches 90 percent, the product purity is more than 99 percent, and all indexes are qualified.
Example 2
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
the specific preparation method is as follows:
adding 240g of gamma-chloropropyltriethoxysilane and 120g of toluene into a 500ml three-neck flask with a stirring device, starting stirring, heating to 60 ℃, adding 0.04g of 2, 6-di-tert-butyl-p-cresol polymerization inhibitor, heating to 100 ℃, adding 103g of potassium acetate (reagent grade, water content is less than or equal to 0.2%) and 1.0g of tetrabutyl phosphonium bromide catalyst, uniformly stirring, controlling the reaction time to be 60min when the reaction temperature is stabilized at 105 ℃, cooling to below 60 ℃ after heat preservation, introducing into a centrifuge for filtering to obtain 360g of crude acetoxypropyl triethoxysilane, and finally carrying out reduced pressure distillation on the crude product to obtain 224g of finished acetoxypropyl triethoxysilane, wherein the product yield is 85%.
The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
Through GC chromatographic detection, the content of the finished acetoxypropyl triethoxysilane obtained after rectification is 97.53%, the color number is 15, and the refractive index is as follows: 1.4156(25 ℃), density: 1.019(20 ℃), free chlorine: 2.50ppm, water solubility: as shown in FIG. 2, the GC spectrum of the acetoxypropyltriethoxysilane synthesized in this example is acceptable.
It is worth to say that the filtrate after centrifugation is led into a fine distillation kettle for distillation, and the solvent is recovered according to different boiling points to obtain a product; and (4) recrystallizing the centrifuged filter cake to obtain the potassium chloride salt with higher purity.
It can be seen that, under the condition of taking toluene as a solvent, 2, 6-di-tert-butyl-p-cresol as a polymerization inhibitor and tetrabutyl phosphonium bromide as a catalyst, the potassium salt reaction is thorough, the yield of the obtained product reaches 85%, the product purity is higher than 97%, and all indexes are qualified.
Example 3
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
the specific preparation method is as follows:
putting 182g of gamma-chloropropyl dimethoxy methylsilane and 100g of n-heptane into a 500ml three-neck flask with a stirring device, starting stirring, heating to 60 ℃, adding 0.04g of benzenediol polymerization inhibitor, heating to 90 ℃, adding 81g of ammonium acetate (reagent grade, water content is less than or equal to 0.2%) and 0.6g of benzyl tributyl ammonium chloride catalyst, uniformly stirring, controlling the reaction time to be 60min when the reaction temperature is stabilized at 105 ℃, cooling to below 60 ℃ after heat preservation, introducing into a centrifuge for filtering to obtain 300g of crude acetoxypropyl dimethoxy methylsilane, and finally carrying out reduced pressure distillation on the crude product to obtain 179g of finished acetoxypropyl dimethoxy methylsilane with the product yield of 87%.
The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
Through GC chromatographic detection, the content of the finished acetoxypropyl dimethoxy methylsilane after rectification is 98.60%, the color number is 15, and the refractive index is as follows: 1.4142(25 ℃), density: 1.009(20 ℃), free chlorine: 2.52ppm, water solubility: as shown in FIG. 3, the GC spectrum of the acetoxypropyl methyldimethoxysilane synthesized in this example is acceptable.
It is worth to say that the filtrate after centrifugation is led into a fine distillation kettle for distillation, and the solvent is recovered according to different boiling points to obtain a product; and (4) recrystallizing the centrifuged filter cake to obtain the ammonium chloride with higher purity.
It can be seen that under the condition of using n-heptane as solvent, benzenediol as polymerization inhibitor and benzyltributylammonium chloride as catalyst, the ammonium salt reaction is completely carried out, the yield of the obtained product reaches 87%, the product purity is greater than 98%, and all indexes are qualified.
Example 4
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
the specific preparation method is as follows:
putting 242g of gamma-chloropropyl dimethoxy methoxy ethoxy silane and 130g of xylene into a 500ml three-neck flask with a stirring device, starting stirring, heating to 60 ℃, adding 0.04g of p-hydroxyanisole polymerization inhibitor, heating to 90 ℃, adding 112g of magnesium acetate (reagent grade, water content is less than or equal to 0.2%) and 0.8g of 1-butyl pyridine bromide, uniformly stirring, controlling the reaction time to be 60min when the reaction temperature is stabilized at 105 ℃, cooling to below 60 ℃ after heat preservation, introducing into a centrifuge for filtering to obtain 400g of crude acetoxypropyl dimethoxy methoxy ethoxy silane, and finally carrying out reduced pressure distillation on the crude product to obtain 255g of finished acetoxypropyl dimethoxy methoxy ethoxy silane, wherein the product yield is more than 95%.
The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
And detecting by GC chromatography, wherein the content of the finished acetoxypropyl dimethoxymethoxyethoxysilane after rectification is 97.22%, the color number is 20, and the refractive index is as follows: 1.4156(25 ℃), density: 1.013(20 ℃), free chlorine: 2.83ppm, water solubility: FIG. 4 shows a GC spectrum of acetoxypropyl dimethoxymethoxyethoxysilane, which is a product synthesized in this example, as a pass product.
It is worth to say that the filtrate after centrifugation is led into a fine distillation kettle for distillation, and the solvent is recovered according to different boiling points to obtain a product; the filter cake after centrifugation can be recrystallized and extracted to obtain the magnesium chloride salt with higher purity.
It can be seen that under the condition that dimethylbenzene is used as a solvent, p-hydroxyanisole is used as a polymerization inhibitor and 1-butylpyridinium bromide is used as a catalyst, wherein the 1-butylpyridinium bromide is alkalescent, so that the generation of haloalkane is prevented, the forward reaction is promoted, the magnesium salt reaction is thorough, the yield of the obtained product is more than 95%, the purity of the product is more than 97%, and all indexes are qualified.
Example 5
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
the specific preparation method is as follows:
166g of gamma-chloropropyldimethylmethoxysilane and 100g of n-heptane are put into a 500ml three-neck flask with a stirring device, stirring is started, 0.04g of p-hydroxyanisole polymerization inhibitor is put into the flask when the temperature is raised to 60 ℃, 96g of zinc acetate (reagent grade, water content is less than or equal to 0.2%) and 0.6g of dodecyltriphenylphosphonium bromide catalyst are put into the flask when the temperature is raised to 90 ℃, the mixture is uniformly stirred, the reaction time is controlled to be 60min when the reaction temperature is stabilized at 105 ℃, after the heat preservation is finished, the mixture is cooled to below 60 ℃, a centrifuge is introduced into the flask for filtering to obtain 280g of crude acetoxypropyldimethylmethoxysilane, and finally the crude product is subjected to reduced pressure distillation to obtain 152g of finished acetoxypropyldimethylmethoxysilane with the product yield of 80. The catalyst obtained by filtering can be dried for reuse.
The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
Through GC chromatographic detection, the content of the finished acetoxypropyl dimethylmethoxysilane product obtained after rectification is 97.05 percent, the color number is 20, and the refractive index is as follows: 1.4162(25 ℃), density: 1.015(20 ℃), free chlorine: 2.93ppm, water solubility: FIG. 5 shows a GC spectrum of the acetoxypropyldimethylmethoxysilane synthesized in this example.
It is worth to say that the filtrate after centrifugation is led into a fine distillation kettle for distillation, and the solvent is recovered according to different boiling points to obtain a product; and (4) recrystallizing the centrifuged filter cake to obtain the zinc chloride salt with higher purity.
It can be seen that under the condition of using n-heptane as solvent, p-hydroxyanisole as polymerization inhibitor and dodecyl triphenyl phosphonium bromide as catalyst, the zinc salt reaction is completely carried out, the yield of the obtained product reaches 80%, the product purity is greater than 97%, and all indexes are qualified.
Example 6
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
the specific preparation method is as follows:
198g of gamma-chloropropyltrimethoxysilane and 100g of DMF are put into a 500ml three-neck flask with a stirring device, stirring is started, 0.04g of p-hydroxyanisole polymerization inhibitor is put into the flask when the temperature is raised to 60 ℃, 86g of sodium acetate (reagent grade, water content is less than or equal to 0.2%), 0.47g of dodecyltriphenyl phosphonium bromide and 0.13g of 1-butylpyridinium bromide catalyst are put into the flask when the temperature is raised to 90 ℃, the mixture is uniformly stirred, the reaction time is controlled to be 60min when the reaction temperature is stabilized at 105 ℃, the temperature is cooled to be below 60 ℃ after heat preservation, a centrifuge is introduced for filtration to obtain a crude product, 310g of acetoxypropyltrimethoxysilane crude product, and finally the crude product is subjected to reduced pressure distillation to obtain 202g of acetoxypropyltrimethoxysilane finished product, wherein the.
The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
Through GC chromatographic detection, the content of the finished acetoxypropyl trimethoxy silane product obtained after rectification is 99.36 percent, the color number is 15, and the refractive index is as follows: 1.4142(25 ℃), density: 1.013(20 ℃), free chlorine: 2.40ppm, water solubility: as shown in FIG. 6, the GC spectrum of the acetoxypropyltrimethoxysilane synthesized in this example is acceptable.
It is worth to say that the filtrate after centrifugation is led into a fine distillation kettle for distillation, and the solvent is recovered according to different boiling points to obtain a product; the filter cake after centrifugation can be recrystallized to obtain sodium chloride with higher purity.
It can be seen that under the condition that DMF is taken as a solvent, p-hydroxyanisole is taken as a polymerization inhibitor, and dodecyl triphenyl phosphonium bromide and 1-butyl pyridine bromide are mixed and added in a molar ratio of 1.5:1 as a catalyst, the sodium salt reaction is thorough, the yield of the obtained product reaches 91%, the purity of the product is more than 99%, and all indexes are qualified.
Example 7
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
the specific preparation method is as follows:
198g of gamma-chloropropyltrimethoxysilane and 100g of DMF are put into a 500ml three-neck flask with a stirring device, stirring is started, 0.04g of p-hydroxyanisole polymerization inhibitor is put into the flask when the temperature is raised to 60 ℃, 86g of sodium acetate (reagent grade, water content is less than or equal to 0.2%), 0.31g of tetrabutylammonium bromide catalyst and 0.29g of benzyltributylammonium chloride catalyst are put into the flask when the temperature is raised to 90 ℃, the reaction is uniformly stirred, when the reaction temperature is stabilized at 105 ℃, the reaction time is controlled to be 60min, after the heat preservation is finished, the temperature is cooled to be below 60 ℃, a centrifuge is led into the flask for filtering to obtain 320g of crude acetoxypropyltrimethoxysilane, and finally the crude product is subjected to reduced pressure distillation to obtain 204g of acetoxypropyltrimethoxysilane finished product, wherein.
The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
Through GC chromatographic detection, the content of the finished acetoxypropyl trimethoxy silane product obtained after rectification is 99.58 percent, the color number is 15, and the refractive index is as follows: 1.4153(25 ℃), density: 1.016(20 ℃), free chlorine: 2.30ppm, water solubility: as shown in FIG. 7, the GC spectrum of the acetoxypropyltrimethoxysilane synthesized in this example is acceptable.
It is worth to say that the filtrate after centrifugation is led into a fine distillation kettle for distillation, and the solvent is recovered according to different boiling points to obtain a product; the filter cake after centrifugation can be recrystallized to obtain sodium chloride with higher purity.
It can be seen that under the condition that DMF is taken as a solvent, p-hydroxyanisole is taken as a polymerization inhibitor and tetrabutylammonium bromide and benzyltributylammonium chloride are taken as mixed catalysts according to the molar ratio of 1:1, the sodium salt reaction is thorough, the yield of the obtained product reaches 92%, the product purity is higher than 99.5%, and all indexes are qualified.
Comparative example 1
This comparative example is essentially the same as example 1, except that: technical grade sodium acetate (1% water content with one week open) was used.
The product obtained was a yellowish transparent liquid in appearance.
Through GC chromatographic detection, the content of the finished acetoxypropyl alkoxy silane after rectification is 92.6 percent, the color number is 30, the refractive index is as follows: 1.4253(25 ℃), density: 1.014(20 ℃), free chlorine: 5.2ppm, water solubility: and (4) passing.
It can be seen that the water content of the acetate is high, the value of free chlorine of the product is high, the appearance is light yellow, and the index does not meet the requirement.
The above examples are only one of the embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and any modifications or equivalent substitutions that can be made without departing from the spirit and principle of the present invention shall be included in the scope of the claims of the present invention, for example, the range values of the reaction temperature and the reaction time of each step of the present invention are reasonably preferred, and in fact, the reaction temperature and the reaction time are relatively wide range values, and values that are not within the range values described in the present invention are all embodiments that are not mentioned in the present invention, as long as the product of the present invention can be prepared.
Claims (10)
1. A preparation method of acetoxy propyl alkoxy silane is characterized in that: mixing and heating chloropropyl alkoxy silane and a solvent, adding a polymerization inhibitor when the temperature is raised to 60-70 ℃, continuously raising the temperature to 90-100 ℃, adding acetate and a catalyst, uniformly stirring, and keeping the temperature at 100-110 ℃ for 60-70 min; and cooling the obtained product, introducing the product into a centrifugal machine, filtering to obtain a crude product, and carrying out reduced pressure distillation on the crude product to collect a finished product of acetoxypropyl alkoxy silane, wherein the catalyst is one or more of tetrabutylammonium bromide, benzyltributylammonium chloride, 1-butylpyridinium bromide, tetrabutylphosphonium bromide and dodecyl triphenyl phosphonium bromide.
2. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the water content of the acetate is less than or equal to 0.2 percent.
3. The method for preparing acetoxypropyl alkoxysilane according to claim 2, wherein: the acetate is sodium acetate, potassium acetate, ammonium acetate, magnesium acetate or zinc acetate.
4. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the acetoxypropyl alkoxy silane has a structural general formula as follows:
wherein: r represents an alkyl group having 1 to 8 carbon atoms, R1Represents methoxy or ethoxy or methoxyethoxy.
5. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the mass ratio of the chloropropyl alkoxy silane to the solvent is 1 (0.5-1).
6. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the mass of the polymerization inhibitor is 0.01-0.02% of the total mass of the chloropropyl alkoxy silane and the solvent.
7. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the mass of the catalyst is 0.2-0.3% of the total mass of the chloropropyl alkoxy silane and the solvent.
8. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the molar ratio of the addition amount of the acetate to the addition amount of the chloropropyl alkoxy silane is (1.0-1.1): 1.
9. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the solvent is N, N-dimethylformamide or toluene or xylene or N-heptane.
10. The process according to claim 1, wherein the acetoxypropylalkoxysilane is prepared by: the polymerization inhibitor is p-hydroxyanisole or 2, 6-di-tert-butyl-p-cresol or hydroquinone.
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