CN112169821A - Silica gel carrier catalyst for preparing acetoxy propyl alkoxy silane and preparation method thereof - Google Patents

Silica gel carrier catalyst for preparing acetoxy propyl alkoxy silane and preparation method thereof Download PDF

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CN112169821A
CN112169821A CN202011065433.7A CN202011065433A CN112169821A CN 112169821 A CN112169821 A CN 112169821A CN 202011065433 A CN202011065433 A CN 202011065433A CN 112169821 A CN112169821 A CN 112169821A
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catalyst
silica gel
acetoxypropyl
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alkoxy silane
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孙佳丽
邱小魁
杨琴
陈�峰
何加勇
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Anhui Gb Silicones New Material Co ltd
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Anhui Gb Silicones New Material Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • C—CHEMISTRY; METALLURGY
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    • 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 Table
    • C07F7/02—Silicon compounds
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    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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Abstract

The invention discloses a silica gel carrier catalyst for preparing acetoxy propyl alkoxy silane and a preparation method thereof, belonging to the technical field related to organic synthesis. The silica gel carrier catalyst takes silica gel as a carrier, the catalyst is loaded on the silica gel carrier catalyst, the loading capacity is 20-30%, and the catalyst is a salt catalyst, wherein the salt catalyst comprises tetrabutylammonium bromide, benzyltributylammonium chloride, 1-butylpyridinium bromide, tetrabutylphosphonium bromide or dodecyl triphenyl phosphonium bromide; 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 the silica gel carrier catalyst, uniformly stirring, and keeping the temperature at 100-110 ℃ for 60-70 min; and cooling the obtained product, 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.

Description

Silica gel carrier catalyst for preparing acetoxy propyl alkoxy silane and preparation method thereof
Technical Field
The invention belongs to the technical field related to organic synthesis, and particularly relates to a silica gel carrier catalyst for preparing acetoxy propyl alkoxy silane and a preparation method thereof.
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 has the advantages of complex process and long time consumption, the catalyst is chloroplatinic acid and is expensive, and the byproduct hydrogen chloride generated by the reaction is difficult to treat and pollutes the environment; in addition, the method firstly carries out hydrosilylation reaction on trichlorosilane and allyl acetate under a catalyst to obtain acetoxypropyl trichlorosilane, only products with the same silane substituent can be prepared, and if products with different substituents need to be prepared, for example, acetoxypropyl methoxy diethoxy silane and acetoxypropyl methoxy ethoxy diethoxy silane need to be obtained, methanol and ethanol are used for esterification, 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, it is necessary to develop a silica gel supported catalyst for preparing acetoxypropyl alkoxysilane and a preparation method thereof.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the existing catalyst for synthesizing acetoxypropyl alkoxysilane is expensive and difficult to recycle, the invention provides a silica gel carrier catalyst for preparing acetoxypropyl alkoxysilane, which can be recycled by the design that the catalyst is loaded on silica gel, so that the phenomenon that the powdery catalyst is dissolved in a product and is possibly separated out in the storage process to cause product turbidity is avoided, the cost is saved, and meanwhile, the phenomenon that the product turns yellow is avoided.
Aiming at the problems of complex process and more byproducts of the existing method for synthesizing acetoxypropyl alkoxysilane, the invention also provides a method for synthesizing acetoxypropyl alkoxysilane, which simplifies the process flow and reduces 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 silica gel carrier catalyst for preparing acetoxypropyl alkoxysilane takes silica gel as a carrier, the catalyst is loaded on the silica gel carrier, the loading amount is 20-30%, and the catalyst is a salt catalyst.
Furthermore, the silica gel carrier catalyst is a supported spherical catalyst, and the particle size of the supported spherical catalyst is 2-4 mm.
Further, the preparation method of the supported catalyst comprises the following steps: firstly, dissolving a catalyst in absolute ethyl alcohol, adding a silica gel carrier, stirring, heating at 70-80 ℃ to remove alcohol, drying at 110 ℃ for 12-18 h, and finally calcining at 300-400 ℃ for 3-4 h.
Further, the salt catalyst comprises tetrabutylammonium bromide, benzyltributylammonium chloride, 1-butylpyridinium bromide, tetrabutylphosphonium bromide or dodecyltriphenylphosphonium bromide.
Further, the concentration of the catalyst after being dissolved in absolute ethyl alcohol is 100-150 g/L.
Further, the mass ratio of the catalyst to the silica gel carrier is (0.2-0.3): 1.0.
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 silica gel carrier catalyst, uniformly stirring, and keeping the temperature at 100-110 ℃ for 60-70 min; and cooling the obtained product, filtering to obtain a crude product, and carrying out reduced pressure distillation on the crude product to collect a finished product of acetoxypropyl alkoxysilane, wherein the silica gel carrier catalyst is the silica gel carrier catalyst for preparing the acetoxypropyl alkoxysilane.
In particular, the reaction temperature and the reaction time in each step are within wide ranges, and values outside the ranges can also be used for preparing the acetoxypropylalkoxysilane, but the reaction period and the reaction yield are affected.
Further, the acetate is sodium acetate, potassium acetate, ammonium acetate, magnesium acetate, or zinc acetate.
Further, the acetoxypropyl alkoxysilane has a general structural formula:
Figure BDA0002713627220000031
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.
Further, 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 silica gel carrier catalyst is 1.0-2.0% 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, is a phase transfer catalyst, increases the liquid-solid contact area, accelerates the dissolution and reaction of solid salt, and promotes the reaction. Compared with the method without adding a catalyst, the yield can be improved by about 20 percent, wherein the 1-butyl pyridine bromide is alkalescent, so that the generation of haloalkane is prevented, and the forward reaction is promoted;
meanwhile, the common salt catalyst is in a powder state, has small particle size, can be uniformly dispersed in a product or a solvent, is still remained and difficult to separate by adopting the modes of filtration, rectification and the like, and is possibly separated out when the temperature changes, so that the product is suspended or turbid; the carrier catalyst is adopted, the catalyst can be removed by means of filtration and the like, the residue is reduced, the product stability is improved, the catalyst can be recycled for 2-3 times, the cost is saved, and the phenomenon that the product is turbid and the quality problem is caused due to the fact that the commonly adopted powdery salt catalyst is dissolved in the product and can be separated out in the storage process is avoided;
(5) the catalyst carrier is silica gel, the silica gel can be used as the catalyst carrier and can remove moisture in a reaction system, and an inventor finds that a reaction product using industrial-grade acetate can be yellowed in an experimental process, because the moisture content of most of the industrial-grade acetate reaches more than 1%, the water content of the acetate is required to be less than 0.2%, the acetate is poor in stability and extremely easy to absorb water, for enterprises in mass production, the acetate can absorb water in a storage process inevitably, so that the purity is not high, a subsequent dehydration process is difficult, the silica gel can remove the moisture in the reaction system, 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 acetoxypropyltrimethoxysilane obtained in example 2;
FIG. 3 is a GC spectrum of acetoxypropyltrimethoxysilane obtained in example 3;
FIG. 4 is a GC spectrum of acetoxypropyltrimethoxysilane obtained in example 4;
FIG. 5 is a GC spectrum of acetoxypropyltrimethoxysilane obtained in example 5;
FIG. 6 is a GC spectrum of acetoxypropyltriethoxysilane obtained in example 6;
FIG. 7 is a GC spectrum of acetoxypropyltriethoxysilane obtained in example 7;
FIG. 8 is a GC spectrum of acetoxypropylmethyldimethoxysilane obtained in example 8;
FIG. 9 is a GC spectrum of acetoxypropyl dimethoxymethoxyethoxysilane obtained in example 9;
FIG. 10 is a GC spectrum of acetoxypropyldimethylmethoxysilane obtained in example 10;
FIG. 11 is a GC spectrum of acetoxypropyltrimethoxysilane obtained in comparative example 1.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The catalyst for acetoxypropylalkoxysilane of this example is tetrabutylammonium bromide/silica gel catalyst, and the preparation method is as follows:
firstly, 0.2g of tetrabutylammonium bromide is dissolved in a proper amount of absolute ethyl alcohol to form 100g/L tetrabutylammonium bromide solution, then 1.0g of silica gel carrier is added for stirring, the mixture is heated at 70 ℃ to remove alcohol, the mixture is placed in a 110 ℃ drying oven for drying for 12 hours, and finally the mixture is placed in a muffle furnace for calcining at 300 ℃ for 4 hours to obtain the blue tetrabutylammonium bromide/silica gel catalyst.
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
Figure BDA0002713627220000051
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 and 4.5g of tetrabutylammonium bromide/silica gel 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 initial product is cooled to below 60 ℃ after heat preservation is finished, acetoxypropyltrimethoxysilane crude product 320g is obtained by filtering the initial product, finally the crude product is distilled under reduced pressure to obtain acetoxypropyltrimethoxysilane finished product 200g, the product yield is 90%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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: 1.4101(25 ℃), density: 1.018(20 ℃), free chlorine: 2.31ppm, water solubility: as shown in FIG. 1, the GC spectrum of the acetoxypropyltrimethoxysilane synthesized in this example is acceptable.
It is worth to be noted that the extraction process steps of the sodium chloride generated by the synthesis reaction in this example are:
(1) dissolving the filtered wet sodium chloride salt in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) drying the obtained sodium chloride salt in an oven at 60-70 ℃ until the water content is less than 1%.
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/silica gel 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 catalyst filtered out in the example 1 is put into an oven to be dried and reused, the synthesis steps are the same as the example 1, 300g of crude acetoxypropyl trimethoxy silane is obtained, and finally the crude product is subjected to reduced pressure distillation to obtain 178g of acetoxypropyl trimethoxy silane finished product, the product yield is 84%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
Through GC chromatographic detection, the content of the finished acetoxypropyl trimethoxy silane product obtained after rectification is 98.16 percent, the color number is 15, and the refractive index is as follows: 1.4156(25 ℃), density: 1.017(20 ℃), free chlorine: 2.66ppm, water solubility: and (4) passing.
As can be seen, DMF is taken as a solvent, p-hydroxyanisole is taken as a polymerization inhibitor, and under the action of once-recovered tetrabutylammonium bromide/silica gel catalyst, the sodium salt reaction is carried out completely, the yield of the obtained product reaches 84%, the product purity is higher than 98%, and all indexes are qualified.
Example 3
The catalyst filtered out in the example 2 is put into an oven to be dried and reused, the synthesis steps are the same as the example 1, 280g of crude acetoxypropyl trimethoxysilane is obtained, and finally the crude acetoxypropyl trimethoxysilane is subjected to reduced pressure distillation to obtain 148g of finished acetoxypropyl trimethoxysilane, the product yield is 71%, and the appearance of the finished product is colorless and transparent.
Through GC chromatographic detection, the content of the finished acetoxypropyl trimethoxy silane product obtained after rectification is 97.56%, the color number is 15, and the refractive index is as follows: 1.4148(25 ℃), density: 1.015(20 ℃), free chlorine: 2.93ppm, water solubility: and (4) passing.
As can be seen, DMF is taken as a solvent, p-hydroxyanisole is taken as a polymerization inhibitor, sodium salt reaction is incomplete under the action of secondary recovery of the catalyst, about 3% of raw materials remain, the yield of the obtained product is lower than 71%, and the catalyst can be recycled for about 2-3 times.
Example 4
The catalyst for acetoxypropylalkoxysilane of this example is tetrabutylammonium bromide/silica gel catalyst, and the preparation method is as follows:
firstly, 0.3g of tetrabutylammonium bromide is dissolved in a proper amount of absolute ethyl alcohol to form a tetrabutylammonium bromide solution with the concentration of 150g/L, then 1.0g of silica gel carrier is added for stirring, the mixture is heated at 80 ℃ to remove alcohol, the mixture is placed in a drying oven at 110 ℃ for drying for 18h, and finally the mixture is placed in a muffle furnace at 400 ℃ for calcining for 3h to obtain the blue tetrabutylammonium bromide/silica gel catalyst.
The reaction equation of the preparation method steps of the acetoxypropyl alkoxysilane in this example is:
Figure BDA0002713627220000061
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 hydroquinone polymerization inhibitor is put into the flask when the temperature is raised to 60 ℃, 103g of potassium acetate and 5.0g of tetrabutylammonium bromide/silica gel catalyst are put into the flask when the temperature is raised to 100 ℃, the mixture is uniformly stirred, the reaction time is controlled to be 60min when the reaction temperature is stabilized at 105 ℃, the initial acetoxypropyltrimethoxysilane is obtained by cooling to below 60 ℃ after heat preservation is finished, 312g of acetoxypropyltrimethoxysilane crude product is obtained by filtering the initial product, 193g of acetoxypropyltrimethoxysilane product is obtained by distilling the crude product under reduced pressure, the product yield is 87%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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 99.18%, the color number is 15, and the refractive index is as follows: 1.4157(25 ℃), density: 1.029(20 ℃), free chlorine: 2.55ppm, water solubility: and (4) passing.
It is worth to be noted that the extraction process steps of the potassium chloride generated by the synthesis reaction in this example are:
(1) dissolving the filtered wet salt in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) drying the obtained potassium chloride salt in an oven at 60-70 ℃ until the water content is less than 1%.
It can be seen that, under the condition that DMF is taken as a solvent, hydroquinone is taken as a polymerization inhibitor and tetrabutylammonium bromide/silica gel is taken as a catalyst, the potassium salt reaction is carried out completely, the yield of the obtained product reaches 87%, the purity of the product is more than 99%, and all indexes are qualified.
Example 5
The catalyst for acetoxypropylalkoxysilane of this example is tetrabutylammonium bromide/silica gel catalyst, and the preparation method is as follows:
firstly, dissolving 0.25g of tetrabutylammonium bromide in a proper amount of absolute ethyl alcohol to form a tetrabutylammonium bromide solution with the concentration of 120g/L, then adding 1.0g of silica gel carrier, stirring, heating at 85 ℃ to remove alcohol, drying in a 110 ℃ oven for 12h, and finally calcining in a muffle furnace at 300-400 ℃ for 4h to obtain the blue tetrabutylammonium bromide/silica gel catalyst.
The preparation method of acetoxypropyl alkoxysilane in this example is as follows:
198g of gamma-chloropropyltrimethoxysilane and 100g of toluene are put into a 500ml three-neck flask with a stirring device, stirring is started, 0.04g of hydroquinone polymerization inhibitor is put into the flask when the temperature is raised to 60 ℃, 86g of sodium acetate and 6.0g of tetrabutylammonium bromide/silica gel catalyst are put into the flask when the temperature is raised to 100 ℃, the mixture is uniformly stirred, the reaction time is controlled to be 60min when the reaction temperature is stabilized at 105 ℃, the initial acetoxypropyltrimethoxysilane is obtained by cooling to below 60 ℃ after the heat preservation is finished, 312g of acetoxypropyltrimethoxysilane crude product is obtained by filtering the initial product, 195g of acetoxypropyltrimethoxysilane product is obtained by distilling the crude product under reduced pressure, the product yield is 88%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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 99.27 percent, the color number is 15, and the refractive index is as follows: 1.4133(25 ℃), density: 1.019(20 ℃), free chlorine: 2.50ppm, water solubility: and (4) passing.
It is worth to be noted that the extraction process steps of the sodium chloride generated by the synthesis reaction in this example are:
(1) dissolving the filtered wet sodium chloride salt in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) drying the obtained sodium chloride salt in an oven at 60-70 ℃ until the water content is less than 1%.
It can be seen that, under the condition of taking toluene as a solvent, hydroquinone as a polymerization inhibitor and tetrabutylammonium bromide/silica gel as a catalyst, the sodium salt reaction is thorough, the yield of the obtained product reaches 88%, the purity of the product is more than 99%, and all indexes are qualified.
Example 6
The catalyst for acetoxypropyl alkoxysilane of this example is a tetrabutylphosphonium bromide/silica gel catalyst, and the preparation method is as follows:
firstly, dissolving 0.2g of tetrabutyl phosphonium bromide in a proper amount of absolute ethyl alcohol to form a tetrabutyl phosphonium bromide solution with the concentration of 130g/L, then adding 1.0g of silica gel carrier, stirring, heating at 85 ℃ to remove alcohol, drying in an oven at 110 ℃ for 12h, and finally calcining in a muffle furnace at 300 ℃ for 4h to obtain the blue tetrabutyl phosphonium bromide/silica gel catalyst.
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
Figure BDA0002713627220000081
the specific preparation method is as follows:
adding 240g of gamma-chloropropyltriethoxysilane and 120g of DMF (dimethyl formamide) 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 86g of sodium acetate and 4.0g of tetrabutyl phosphonium bromide/silica gel 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 is finished, obtaining an initial acetoxypropyl triethoxysilane product, filtering the initial product to obtain 370g of a crude acetoxypropyl triethoxysilane product, and finally carrying out reduced pressure distillation on the crude product to obtain 236g of an acetoxypropyl triethoxysilane product, wherein the product yield is 89%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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 99.51%, the color number is 15, and the refractive index is as follows: 1.4144(25 ℃), density: 1.022(20 ℃), free chlorine: 2.50ppm, water solubility: and (4) passing.
It is worth to be noted that the extraction process steps of the sodium chloride generated by the synthesis reaction in this example are:
(1) dissolving the filtered wet sodium chloride salt in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) drying the obtained sodium chloride salt in an oven at 60-70 ℃ until the water content is less than 1%.
It can be seen that, under the conditions of taking DMF as a solvent, 2, 6-di-tert-butyl-p-cresol as a polymerization inhibitor and tetrabutyl phosphonium bromide/silica gel, the sodium salt reaction is thorough, the yield of the obtained product reaches 89%, the product purity is higher than 99%, and all indexes are qualified.
Example 7
The catalyst for acetoxypropyl alkoxysilane of this example is a dodecyltriphenylphosphonium bromide/silica gel catalyst, and the preparation method is as follows:
firstly, 0.2g of dodecyl triphenyl phosphonium bromide is dissolved in a proper amount of absolute ethyl alcohol to form 140g/L dodecyl triphenyl phosphonium bromide, then 1.0g of silica gel carrier is added for stirring, the mixture is heated at 80 ℃ to remove alcohol, the mixture is placed in a drying oven at 110 ℃ for drying for 12h, and finally the mixture is placed in a muffle furnace at 300-400 ℃ for calcining for 4h, so that the blue dodecyl triphenyl phosphonium bromide/silica gel catalyst is obtained.
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
Figure BDA0002713627220000091
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 86g of sodium acetate and 4.5g of dodecyltriphenylphosphonium bromide/silica gel, uniformly stirring, controlling the reaction time to be 60min when the reaction temperature is stabilized at 105 ℃, cooling to below 60 ℃ after heat preservation is finished, obtaining an initial acetoxypropyltriethoxysilane product, filtering the initial product to obtain 380g of a crude acetoxypropyltriethoxysilane product, and finally carrying out reduced pressure distillation on the crude product to obtain 231g of an acetoxypropyltriethoxysilane product, wherein the product yield is 87%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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 99.33%, the color number is 15, and the refractive index is as follows: 1.4132(25 ℃), density: 1.014(20 ℃), free chlorine: 2.33ppm, water solubility: and (4) passing.
It is worth to be noted that the extraction process steps of the sodium chloride generated by the synthesis reaction in this example are:
(1) dissolving the filtered wet sodium chloride salt in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) drying the obtained sodium chloride salt in an oven at 60-70 ℃ until the water content is less than 1%.
It can be seen that under the condition of using toluene as solvent, 2, 6-di-tert-butyl-p-cresol as polymerization inhibitor and dodecyl triphenyl phosphonium bromide/silica gel as catalyst, the sodium salt reaction is thorough, the yield of the obtained product reaches 87%, the purity of the product is more than 99%, and all indexes are qualified.
Example 8
The catalyst for acetoxypropyl alkoxysilane in this example is a benzyltributylammonium chloride/silica gel catalyst, and the preparation method is as follows:
firstly, 0.2g of benzyl tributyl ammonium chloride is dissolved in a proper amount of absolute ethyl alcohol to form a 130g/L benzyl tributyl ammonium chloride solution, then 1.0g of silica gel carrier is added for stirring, the mixture is heated at 75 ℃ to remove alcohol, the mixture is placed in a 110 ℃ drying oven for drying for 12 hours, and finally the mixture is placed in a muffle furnace for calcining for 4 hours at 300-400 ℃ to obtain the benzyl tributyl ammonium chloride/silica gel catalyst.
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
Figure BDA0002713627220000101
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 p-hydroxyanisole polymerization inhibitor, heating to 90 ℃, adding 80g of ammonium acetate and 4.5g of benzyl tributyl ammonium chloride/silica gel 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 is finished, obtaining an acetoxypropyl dimethoxy methylsilane initial product, filtering the initial product to obtain 300g of acetoxypropyl dimethoxy methylsilane crude product, and finally carrying out reduced pressure distillation on the crude product to obtain 175g of acetoxypropyl dimethoxy methylsilane finished product, wherein the product yield is 85%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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 dimethoxymethylsilane after rectification is 98.87%, the color number is 15, and the refractive index is as follows: 1.4113(25 ℃), density: 1.013(20 ℃), free chlorine: 2.67ppm, water solubility: and (4) passing.
It should be noted that the extraction process steps of the ammonium chloride generated by the synthesis reaction in this example are as follows:
(1) dissolving the filtered wet salt in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) drying the obtained ammonium chloride salt in an oven at 60-70 ℃ until the water content is less than 1%.
It can be seen that under the conditions of using n-heptane as solvent, p-hydroxyanisole as polymerization inhibitor and benzyl tributyl ammonium chloride/silica gel as catalyst, the ammonium salt reaction is completely carried out, the yield of the obtained product reaches 85%, the product purity is greater than 99%, and all indexes are qualified.
Example 9
The catalyst for acetoxypropylalkoxysilane of this example is a 1-butylpyridyl bromide/silica gel catalyst, and the preparation method is as follows:
firstly, 0.2g of 1-butylpyridinium bromide is dissolved in a proper amount of absolute ethyl alcohol to form a 120 g/L1-butylpyridinium bromide solution, then 1.0g of silica gel carrier is added for stirring, the mixture is heated at 75 ℃ to remove alcohol, the mixture is dried in a 110 ℃ oven for 12 hours, and finally the mixture is placed in a muffle furnace for calcination at 300-400 ℃ for 4 hours to obtain the blue 1-butylpyridinium bromide/silica gel catalyst.
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
Figure BDA0002713627220000111
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 and 4.5g of 1-butyl pyridine bromide/silica gel 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 is finished, obtaining an initial product of acetoxypropyl dimethoxy methoxy ethoxy silane, filtering the initial product to obtain 420g of acetoxypropyl dimethoxy methoxy ethoxy silane crude product, and finally carrying out reduced pressure distillation on the crude product to obtain 251g of acetoxypropyl dimethoxy methoxy ethoxy silane finished product, wherein the product yield is higher than 95%, and the appearance of the finished product is colorless and transparent. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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 product obtained after rectification is 97.14 percent, the color number is 15, and the refractive index is as follows: 1.4203(25 ℃), density: 1.021(20 ℃), free chlorine: 2.88ppm, water solubility: and (4) passing.
It is worth to be noted that the extraction process steps of the magnesium chloride generated by the synthesis reaction in this example are:
(1) dissolving the filtered wet solution in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) putting the obtained magnesium chloride salt into an oven for drying at 60-70 ℃ until the moisture is less than 1%.
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/silica gel is used as a catalyst, wherein 1-butylpyridinium bromide is alkalescent, so that haloalkane is prevented from being generated, 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 10
The catalyst for acetoxypropyl alkoxysilane in this example is a benzyltributylammonium chloride/silica gel catalyst, and the preparation method is as follows:
firstly, 0.2g of benzyl tributyl ammonium chloride is dissolved in a proper amount of absolute ethyl alcohol to form a 130g/L benzyl tributyl ammonium chloride solution, then 1.0g of silica gel carrier is added for stirring, the mixture is heated at 75 ℃ to remove alcohol, the mixture is placed in a 110 ℃ drying oven for drying for 12 hours, and finally the mixture is placed in a muffle furnace for calcining at 400 ℃ for 4 hours to obtain the blue benzyl tributyl ammonium chloride/silica gel catalyst.
The reaction equation of the preparation method of acetoxypropyl alkoxysilane in this example is:
Figure BDA0002713627220000121
the specific preparation method is as follows:
166g of gamma-chloropropyl dimethyl methoxy silane 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 and 4.5g of benzyl tributyl ammonium chloride/silica gel 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 crude product is cooled to below 60 ℃ after heat preservation is finished, acetoxypropyl dimethyl methoxy silane crude product is obtained, the crude product is filtered to obtain 280g of acetoxypropyl dimethyl methoxy silane crude product, and finally the crude product is subjected to reduced pressure distillation to obtain 158g of acetoxypropyl dimethyl methoxy silane finished product, the product yield is 83%, and the appearance of the finished product is colorless. The catalyst obtained by filtering is red, and is blue after being dried, and can be reused.
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 97.11 percent, the color number is 15, and the refractive index is as follows: 1.4196(25 ℃), density: 1.018(20 ℃), free chlorine: 2.92ppm, water solubility: and (4) passing.
It is worth to be noted that the extraction process steps of the zinc chloride generated by the synthesis reaction in this embodiment are as follows:
(1) dissolving the filtered wet salt in water to form a saturated solution, and stirring for 0.5-1.0 h;
(2) filtering the solution to remove impurities;
(3) distilling the filtrate obtained in the step (2) at normal pressure, and removing water to separate out most of salt;
(4) and (3) putting the obtained magnesium chloride salt into an oven for drying at 60-70 ℃ until the moisture is less than 1%.
It can be seen that under the condition that n-heptane is used as a solvent, p-hydroxyanisole is used as a polymerization inhibitor and benzyltributylammonium chloride/silica gel is used as a catalyst, the zinc salt reaction is carried out completely, the yield of the obtained product reaches 83%, the product purity is higher than 97%, and all indexes are qualified.
Comparative example 1
The preparation method of acetoxypropyl alkoxysilane in this example is as follows:
198g of gamma-chloropropyltrimethoxysilane is added into a 500ml three-neck flask with a stirring device, stirring is started, 0.03g of p-hydroxyanisole polymerization inhibitor is added when the temperature is raised to 60 ℃, 86g of sodium acetate (industrial grade, opening and standing for one week) and 3.0g of tetrabutylammonium bromide/gamma-Al are added when the temperature is raised to 90 DEG2O3And uniformly stirring the catalyst, controlling the reaction time to be 70min when the reaction temperature is stabilized at 105 ℃, cooling to below 60 ℃ after the heat preservation is finished to obtain an acetoxypropyl alkoxysilane initial product, filtering the initial product to obtain 220g of acetoxypropyl alkoxysilane crude product, and finally carrying out reduced pressure distillation on the crude product to obtain 111g of acetoxypropyl alkoxysilane finished product with the product yield of 50%. The product yield is the amount of the product (actually) produced per the theoretical amount of the target product × 100%.
The product appearance is: a light yellow transparent liquid.
Through GC chromatographic detection, the content of the finished acetoxypropyl alkoxy silane after rectification is 97.24 percent, the color number is 30, the refractive index is as follows: 1.4153(25 ℃), density: 1.015(20 ℃), free chlorine: 5.68ppm, water solubility: as shown in FIG. 1, the GC spectrum of the acetoxypropylalkoxysilane synthesized in this example is acceptable.
As can be seen, in the absence of solvent, p-hydroxyanisole is used as polymerization inhibitor, tetrabutylammonium bromide/gamma-Al2O3Under the condition that the catalyst is the catalyst, the reaction is not completely carried out, the yield of the obtained product is only 50%, the value of free chlorine of the product is higher, the appearance is light yellow, and the index can 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 silica gel carrier catalyst for preparing acetoxypropyl alkoxy silane is characterized in that: the silica gel carrier catalyst takes silica gel as a carrier, the catalyst is loaded on the silica gel carrier catalyst, the loading capacity is 20-30%, and the catalyst is a salt catalyst, wherein the salt catalyst comprises tetrabutylammonium bromide, benzyltributylammonium chloride, 1-butylpyridinium bromide, tetrabutylphosphonium bromide or dodecyl triphenyl phosphonium bromide.
2. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 1, wherein: the silica gel carrier catalyst is a supported spherical catalyst, and the particle size of the supported spherical catalyst is 2-4 mm.
3. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 1, wherein: the preparation method comprises the following steps: firstly, dissolving a catalyst in absolute ethyl alcohol, adding a silica gel carrier, stirring, heating at 70-80 ℃ to remove alcohol, drying at 110 ℃ for 12-18 h, and finally calcining at 300-400 ℃ for 3-4 h.
4. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 1, wherein: the concentration of the catalyst after being dissolved in absolute ethyl alcohol is 100-150 g/L; the mass ratio of the catalyst to the silica gel carrier is (0.2-0.3): 1.0.
5. 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 silica gel carrier catalyst, uniformly stirring, and keeping the temperature at 100-110 ℃ for 60-70 min; and (3) cooling the obtained product, filtering to obtain a crude product, and carrying out reduced pressure distillation on the crude product to collect a finished product of acetoxypropyl alkoxysilane, wherein the silica gel carrier catalyst is the silica gel carrier catalyst for preparing acetoxypropyl alkoxysilane according to any one of claims 1-4.
6. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 5, wherein: the acetate is sodium acetate, potassium acetate, ammonium acetate, magnesium acetate or zinc acetate.
7. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 5, wherein: the acetoxypropyl alkoxy silane has a structural general formula as follows:
Figure FDA0002713627210000011
Figure FDA0002713627210000021
wherein: r represents an alkyl group having 1 to 8 carbon atoms, R1Represents methoxy or ethoxy or methoxyethoxy.
8. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 5, wherein: the mass ratio of the chloropropyl alkoxy silane to the solvent is 1 (0.5-1); the mass of the polymerization inhibitor is 0.01-0.02% of the total mass of the chloropropyl alkoxy silane and the solvent; the mass of the silica gel carrier catalyst is 1.0-2.0% of the total mass of the chloropropyl alkoxy silane and the solvent.
9. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 5, wherein: 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.
10. The supported silica gel catalyst for producing acetoxypropyl alkoxysilane according to claim 5, wherein: the solvent is N, N-dimethylformamide or toluene or xylene or N-heptane; the polymerization inhibitor is p-hydroxyanisole or 2, 6-di-tert-butyl-p-cresol or hydroquinone.
CN202011065433.7A 2020-09-30 2020-09-30 Silica gel carrier catalyst for preparing acetoxy propyl alkoxy silane and preparation method thereof Pending CN112169821A (en)

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