CN117024470A - Synthesis method of 4-triethoxy silicon-based butyronitrile - Google Patents
Synthesis method of 4-triethoxy silicon-based butyronitrile Download PDFInfo
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- CN117024470A CN117024470A CN202310998283.2A CN202310998283A CN117024470A CN 117024470 A CN117024470 A CN 117024470A CN 202310998283 A CN202310998283 A CN 202310998283A CN 117024470 A CN117024470 A CN 117024470A
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- butyronitrile
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- triethoxysilylbutyronitrile
- triethoxysilane
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 title abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- VGIURMCNTDVGJM-UHFFFAOYSA-N 4-triethoxysilylbutanenitrile Chemical compound CCO[Si](OCC)(OCC)CCCC#N VGIURMCNTDVGJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000009833 condensation Methods 0.000 claims abstract description 19
- 230000005494 condensation Effects 0.000 claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 150000008363 butyronitriles Chemical class 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 11
- ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 4-chlorobutanenitrile Chemical compound ClCCCC#N ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- CQPGDDAKTTWVDD-UHFFFAOYSA-N 4-bromobutanenitrile Chemical compound BrCCCC#N CQPGDDAKTTWVDD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005909 Kieselgur Substances 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000002253 acid Substances 0.000 description 13
- 238000001514 detection method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- -1 Alkoxy silane Chemical compound 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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 Table
- 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
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The application provides a method for synthesizing 4-triethoxy silicon-based butyronitrile. The synthesis method comprises the following steps: under inert atmosphere, triethoxysilane, halogenated butyronitrile, organic solvent and diatomite are mixed, and then condensation coupling reaction is carried out to obtain a crude product; secondly, purifying the crude product to obtain 4-triethoxy silicon-based butyronitrile; wherein the halogenated butyronitrile is at least one of 4-chlorobutyronitrile and 4-bromobutyronitrile. The application can solve the problems of low yield, need of noble metal catalyst and difficult removal of heavy metal residue in the synthesis method of 4-triethoxysilyl butyronitrile in the prior art.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a method for synthesizing 4-triethoxy silicon-based butyronitrile.
Background
Alkoxy silane is one of the basic raw materials of the organosilicon industry, and has importance next to organohalosilanes in the organosilicon industry, and is also an important intermediate in the organosilicon industry. Catalytic disproportionation based on alkoxy hydrosilanes gives monosilanes of very high purity, which are required by the semiconductor industry. Alkoxy hydrogen-containing silane mainly refers to trimethoxy hydrogen-containing silane, triethoxy hydrogen-containing silane, tripropoxy hydrogen-containing silane and the like, and the varieties have very important application values.
Triethoxysilane has both unstable siloxane bonds and active silicon hydrogen bonds. Various organosilicon compounds can be obtained through a series of reactions, such as condensation, addition, polymerization and the like, and are important organosilicon intermediates, and silane coupling agents produced by taking the organosilicon intermediates as raw materials are widely applied to industries of coatings, electronics and the like.
4-triethoxy silicon-based butyronitrile is a novel silane coupling agent variety applied to the industries of glass fiber reinforced plastics, casting and the like in recent years, and has been developed very much.
However, the synthesis method of 4-triethoxysilyl butyronitrile is few, V.M.Vdovin, R.Sultanov and the like report a preparation method, and target product 4-triethoxysilyl butyronitrile is obtained by catalytic reaction of chloroplatinic acid by taking triethoxysilane and allylnitrile as raw materials. The catalyst chloroplatinic acid in the route is noble metal and expensive, and the heavy metal residue of the product is difficult to completely remove, so that the product performance is affected, the yield is only 48%, and the synthetic route is as follows:
in view of this, it is necessary to provide a new synthetic route for 4-triethoxysilylbutyronitrile.
Disclosure of Invention
The application mainly aims to provide a method for synthesizing 4-triethoxysilyl butyronitrile, which aims to solve the problems that the yield of the method for synthesizing 4-triethoxysilyl butyronitrile in the prior art is low, a noble metal catalyst is required, and heavy metal residues are difficult to remove.
In order to achieve the above object, according to one aspect of the present application, there is provided a method for synthesizing 4-triethoxysilylbutyronitrile, comprising: under inert atmosphere, triethoxysilane, halogenated butyronitrile, organic solvent and diatomite are mixed, and then condensation coupling reaction is carried out to obtain a crude product; secondly, purifying the crude product to obtain 4-triethoxy silicon-based butyronitrile; wherein the halogenated butyronitrile is at least one of 4-chlorobutyronitrile and 4-bromobutyronitrile.
Further, the mol ratio of triethoxysilane to halobutyronitrile is 1 (0.9-2.1).
Further, the step of mixing includes: firstly, premixing triethoxysilane, an organic solvent and diatomite to obtain a premixed raw material; then gradually adding halogenated butyronitrile into the premixed raw material to finish the mixing step; preferably, the rate of addition of halobutyronitrile to the premix feed is from 5 to 50d/min.
Further, the temperature of the condensation coupling reaction is 40-70 ℃ and the reaction time is 2-6 h.
Further, the weight ratio of the diatomite to the triethoxysilane is 1:2 to 5; preferably, the specific surface area of the diatomite is 40-65 m 2 /g。
Further, the ratio of the organic solvent to triethoxysilane was 1g: 4-20 ml.
Further, the organic solvent comprises one or more of tetrahydrofuran, toluene, methylene dichloride and n-hexane; preferably, the organic solvent is tetrahydrofuran.
Further, the crude product is purified by distillation under reduced pressure, preferably at an operating pressure of 60 to 600Pa and a temperature of 80 to 100 ℃.
Further, the water content of the organic solvent is lower than 0.1% by weight; preferably, the diatomaceous earth has a water content of less than 0.1%.
Further, the inert atmosphere is one of an argon atmosphere, a nitrogen atmosphere and a mixed atmosphere of argon and nitrogen.
By applying the technical scheme of the application, a synthesis method of 4-triethoxysilyl butyronitrile is provided. The application adopts safe and easily available triethoxysilane and halogenated butyronitrile as raw materials, and prepares the 4-triethoxysilyl butyronitrile through condensation coupling reaction. Compared with the traditional synthetic route, the synthetic method does not need to use expensive chloroplatinic acid, thereby greatly reducing the cost and avoiding the problem of heavy metal residue in the product. In particular, diatomite is introduced into a reaction system and is used as a material with larger specific surface area, so that triethoxysilane can be effectively dispersed, and side reactions of raw materials in mutual polymerization are prevented; meanwhile, the diatomite can adsorb acid generated by the reaction, promote the reaction to further occur, and prevent the acid from negatively affecting the reaction system. In general, the synthetic process has the advantages of short route, high yield, easy operation of reaction, small environmental pollution, no corrosion to equipment and higher practical value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 shows the nuclear magnetic hydrogen spectrum of 4-triethoxysilylbutyronitrile prepared according to example 1 of the present application.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
In order to solve the problems in the prior art as described above, according to an aspect of the present application, there is provided a method for synthesizing 4-triethoxysilylbutyronitrile, comprising: under inert atmosphere, triethoxysilane, halogenated butyronitrile, organic solvent and diatomite are mixed, and then condensation coupling reaction is carried out to obtain a crude product; secondly, purifying the crude product to obtain 4-triethoxy silicon-based butyronitrile; wherein the halogenated butyronitrile is at least one of 4-chlorobutyronitrile and 4-bromobutyronitrile.
The application adopts safe and easily available triethoxysilane and halogenated butyronitrile as raw materials, and prepares the 4-triethoxysilyl butyronitrile through condensation coupling reaction. Compared with the traditional synthetic route, the synthetic method does not need to use expensive chloroplatinic acid, thereby greatly reducing the cost and avoiding the problem of heavy metal residue in the product. In particular, diatomite is introduced into a reaction system and is used as a material with larger specific surface area, so that triethoxysilane can be effectively dispersed, and side reactions of raw materials in mutual polymerization are prevented; meanwhile, the diatomite can adsorb acid generated by the reaction, promote the reaction to further occur, and prevent the acid from negatively affecting the reaction system. In general, the synthetic process has the advantages of short route, high yield, easy operation of reaction, small environmental pollution, no corrosion to equipment and higher practical value.
Taking 4-chlorobutyronitrile as an example, the specific synthetic route of the application is as follows:
compared with the traditional synthetic method, which adopts allyl nitrile as a raw material to obtain the 4-triethoxy silicon-based butyronitrile through chloroplatinic acid catalytic reaction, the synthetic method has different applied mechanisms. In the condensation coupling reaction, diatomite is used as a material with larger specific surface area, so that triethoxysilane can be effectively dispersed, and side reactions of raw materials in mutual polymerization are prevented; meanwhile, the diatomite can adsorb acid generated by the reaction, promote the reaction to further occur, and prevent the acid from negatively affecting the reaction system. Compared with the traditional addition method, the synthesis method has the advantages of mild reaction and slow heat release.
In the synthetic method of the present application, diatomaceous earth provides a larger reaction platform as a carrier, and the inventors found that diatomaceous earth can provide an effect particularly outstanding compared to other carriers in the art, probably because diatomaceous earth has a small density and is easily and uniformly dispersed into a reaction system, which is advantageous in ensuring uniformity of the reaction system.
To further save costs, in some embodiments of the application, after the reaction, the diatomaceous earth and the organic solvent may each be recovered and reused. After recycling for multiple times, or when the diatomaceous earth and the organic solvent are reused at the same time, the yield and purity of the product may be relatively lowered, but the product of high purity may be obtained by secondary purification. The diatomite can be recovered by rinsing with water and drying. The organic solvent may be recovered by distillation or reduced pressure distillation. The skilled person can select an appropriate operation mode according to common general knowledge, and will not be described in detail herein.
In order to further promote the condensation coupling reaction, in a preferred embodiment, the molar ratio of triethoxysilane to halobutyronitrile is 1 (0.9 to 2.1). The excessive or too small amount of the halobutyronitrile is unfavorable for the sufficient contact between the reaction raw materials, and further unfavorable for the sufficient occurrence of the reaction.
In order to better smooth and fully occur the condensation coupling reaction, in a preferred embodiment, the step of mixing comprises: firstly, premixing triethoxysilane, an organic solvent and diatomite to obtain a premixed raw material; then gradually adding halogenated butyronitrile into the premixed raw material to finish the mixing step; preferably, the rate of addition of halobutyronitrile to the premix feed is from 5 to 50d/min. The selection of the above-mentioned feeding sequence is more advantageous for improving the yield of the product. The halogenated butyronitrile is introduced at the feeding speed, so that the yield and purity of the product are improved.
In a preferred embodiment, the temperature of the condensation coupling reaction is from 40 to 70℃and the reaction time is from 2 to 6 hours. The above reaction conditions are advantageous in promoting the occurrence of the condensation coupling reaction while reducing the occurrence of side reactions.
In a preferred embodiment, the weight ratio of diatomaceous earth to triethoxysilane is 1:2 to 5; preferably, the specific surface area of the diatomite is 40-65 m 2 And/g. The diatomaceous earth preferable under the above conditions is more advantageous in that triethoxysilane is sufficiently dispersed thereon, the progress of the reaction is promoted, and the occurrence of side reactions is reduced. Diatomaceous earth having the above specific surface area is also more advantageous for absorbing the generated acid, which is also more advantageous for the reaction to occur, and also for protecting the reaction equipment. In actual practice, the optional types include, but are not limited to, diatomaceous earth 545, diatomaceous earth 325, diatomaceous earth N82.
To further promote the condensation coupling reaction, in a preferred embodiment, the ratio of organic solvent to triethoxysilane is 1g: 4-20 ml. According to the above preferred conditions, it is more advantageous to provide a reaction system in which the raw materials are sufficiently dispersed and the concentration is appropriate.
To further facilitate the occurrence of the condensation coupling reaction, in a preferred embodiment, the organic solvent comprises one or more of tetrahydrofuran, toluene, methylene chloride, n-hexane; preferably, the organic solvent is tetrahydrofuran. The preferable organic solvent is favorable for fully dispersing the reaction raw materials, and is further favorable for avoiding side reactions because of containing no active hydrogen. Tetrahydrofuran is more preferable as an organic solvent, and is more advantageous in avoiding the residue of impurities.
In a preferred embodiment, the crude product is purified by distillation under reduced pressure, preferably at a pressure of from 60 to 600Pa and a temperature of from 80 to 100 ℃. In some embodiments of the application, during reduced pressure distillation, the organic solvent in the system is distilled off first, and the distilled organic solvent can be recovered for reuse.
In some embodiments of the application, after the reaction is completed, the reaction system is cooled to room temperature (15-35 ℃) and then pressure filtration is performed using a three-in-one apparatus.
In a preferred embodiment, the organic solvent has a water content of less than 0.1% by weight; preferably, the diatomaceous earth has a water content of less than 0.1%. The organic solvent with low water content and diatomite are adopted, so that the condensation coupling reaction is promoted, and side reactions are avoided.
In order to better promote the condensation coupling reaction, the inert atmosphere is one of an argon atmosphere, a nitrogen atmosphere and a mixed atmosphere of argon and nitrogen.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
In the following examples and comparative examples, the organic solvent and diatomaceous earth were used in advance to be subjected to drying treatment, and if not otherwise specified, the water content (by weight) thereof after drying was lower than 0.1% and 0.1%, respectively.
In the following examplesIn the comparative example, if no other explanation is given, the specification model of the diatomaceous earth is diatomaceous earth 545, and the specific surface area of the diatomaceous earth is 40 to 65m 2 /g。
Example 1
Triethoxysilane (40.0 g,0.243 mol), dry tetrahydrofuran (200 ml) and dry diatomaceous earth (10.0 g) were added to the flask under argon atmosphere, stirred well at room temperature, then heated to 50℃and 4-chlorobutyronitrile (25.2 g, 0.248 mol) was added dropwise over about 10 minutes, and the reaction was allowed to proceed with stirring for 3 hours. And (3) completely reacting, cooling to room temperature, performing filter pressing in three-in-one equipment, leaching with a small amount of water, drying for reuse, distilling filtrate under reduced pressure to remove tetrahydrofuran for reuse, continuously heating for reduced pressure distillation, and collecting fractions at 80-100 ℃ to obtain 50.3g colorless liquid.
Detection result: GC purity was 99.3%, moisture was 50ppm, heavy metals were not detected, and yield was 89%. Bp 100-101 ℃ (6 mmHg). 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 3.82 (q, 6H) 2.40 (t, 2H) 1.80 (m, 2H) 1.23 (t, 9H) 0.77 (t, 2H). The nuclear magnetic hydrogen spectrum of the 4-triethoxysilylbutyronitrile prepared according to example 1 is shown in FIG. 1.
Example 2
The only difference from example 1 was that the diatomaceous earth was replaced with recovered diatomaceous earth (moisture 100 ppm).
After distillation under reduced pressure, 46.2g of a colorless liquid was obtained.
Detection result: GC purity was 99.1%, moisture was 100ppm, heavy metals were not detected, and yield was 82%.
Example 3
The only difference from example 1 was that diatomaceous earth was replaced with recovered diatomaceous earth (moisture 100 ppm), and tetrahydrofuran was replaced with recovered tetrahydrofuran (80 ppm).
After distillation under reduced pressure, 45.6g of a colorless liquid was obtained.
Detection result: GC purity 98.9%, moisture 100ppm, undetected heavy metals, yield 81%.
Example 4
The only difference from example 1 is that the amount of diatomaceous earth used is 5g.
After distillation under reduced pressure, 23.1g of a colorless liquid was obtained.
Detection result: GC purity was 97.6%, moisture was 60ppm, heavy metals were not detected, and yield was 41%.
Example 5
The difference from example 1 is only that the amount of 4-chlorobutyronitrile used is 52.8g, 0.51mol. Correspondingly, the time for dropping 4-chlorobutyronitrile was 21min.
After distillation under reduced pressure, 50.5g of a colorless liquid was obtained.
Detection result: GC purity was 99.2%, moisture content was 40ppm, heavy metals were not detected, and yield was 89%.
Example 6
The only difference from example 1 is that the condensation coupling reaction is carried out at a temperature of 66 ℃.
After distillation under reduced pressure, 18.5g of a yellow liquid was obtained.
Detection result: GC purity 95.8%, moisture 70ppm, heavy metals undetected, yield 33%.
Example 7
The only difference from example 1 is that an equal volume of toluene was chosen as solvent instead of tetrahydrofuran.
After distillation under reduced pressure, 49.6g of a colorless liquid was obtained.
Detection result: GC purity was 99.2%, moisture was 50ppm, heavy metals were undetected, yield 88%.
Example 8
The only difference from example 1 is that diatomaceous earth was used as diatomaceous earth 535.
After distillation under reduced pressure, 35.9g of a colorless liquid was obtained.
Detection result: GC purity 98.5%, moisture 50ppm, undetected heavy metals, yield 64%.
Example 9
The difference from example 1 is that 4-chlorobutyronitrile was mixed with other reaction materials and heated together to effect the reaction.
After distillation under reduced pressure, 33.6g of a colorless liquid was obtained.
Detection result: GC purity 95.3%, moisture 50ppm, heavy metals undetected, yield 59%.
Example 10
The difference from example 1 is that an equimolar amount of 4-bromobutyronitrile is used instead of 4-chlorobutyronitrile.
Detection result: the water content is 100ppm, heavy metals are not detected, and the yield is 80%.
Comparative example 1
The difference from example 1 is that the diatomaceous earth is replaced by glass fiber of equal weight. Other process conditions are the same as in the present application.
After distillation under reduced pressure, 31.9g of a colorless liquid was obtained.
Detection result: GC purity 94.2%, moisture 100ppm, undetected heavy metals, yield 56%.
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
according to the synthesis method, the yield of more than 89% can be realized, and compared with the traditional synthesis route of the 4-triethoxysilyl butyronitrile in the prior art, the synthesis method has remarkable improvement. In addition, the synthetic route of the application has few polymers, high product purity and no heavy metal residue. In addition, the method is easy to operate, free of acid gas overflow, small in equipment corrosion and small in environmental pollution.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The synthesis method of the 4-triethoxysilyl butyronitrile is characterized by comprising the following steps:
under inert atmosphere, triethoxysilane, halogenated butyronitrile, organic solvent and diatomite are mixed, and then condensation coupling reaction is carried out to obtain a crude product; secondly, purifying the crude product to obtain the 4-triethoxysilyl butyronitrile; wherein the halogenated butyronitrile is at least one of 4-chlorobutyronitrile and 4-bromobutyronitrile.
2. The method for synthesizing 4-triethoxysilylbutyronitrile according to claim 1, wherein the molar ratio of said triethoxysilane to said halobutyronitrile is 1 (0.9 to 2.1).
3. The method for synthesizing 4-triethoxysilylbutyronitrile according to claim 1 or 2, wherein said step of mixing comprises:
firstly, premixing the triethoxysilane, the organic solvent and the diatomite to obtain a premixed raw material; secondly, gradually adding the halogenated butyronitrile into the premixed raw material to finish the mixing step;
preferably, the rate of addition of the halobutyronitrile to the premix feedstock is from 5 to 50d/min.
4. A method of synthesizing 4-triethoxysilylbutyronitrile according to any one of claims 1 to 3, wherein the condensation coupling reaction is carried out at a temperature of 40 to 70 ℃ for a reaction time of 2 to 6 hours.
5. The method for synthesizing 4-triethoxysilylbutyronitrile according to any one of claims 1 to 4, wherein the weight ratio of diatomaceous earth to triethoxysilane is 1:2 to 5; preferably, the specific surface area of the diatomite is 40-65 m 2 /g。
6. The method for synthesizing 4-triethoxysilylbutyronitrile according to any one of claims 1 to 5, wherein the ratio of the organic solvent to the triethoxysilane is 1g: 4-20 ml.
7. The method for synthesizing 4-triethoxysilylbutyronitrile according to any one of claims 1 to 6, wherein the organic solvent comprises one or more of tetrahydrofuran, toluene, dichloromethane, n-hexane; preferably, the organic solvent is tetrahydrofuran.
8. The method for synthesizing 4-triethoxysilylbutyronitrile according to any one of claims 1 to 7, characterized in that the crude product is purified by distillation under reduced pressure, preferably at an operating pressure of 60 to 600Pa and at a temperature of 80 to 100 ℃.
9. The method for synthesizing 4-triethoxysilyl butyronitrile according to any one of claims 1 to 8, wherein the water content of the organic solvent is lower than 0.1% by weight; preferably, the diatomaceous earth has a water content of less than 0.1%.
10. The method for synthesizing 4-triethoxysilylbutyronitrile according to any one of claims 1 to 9, wherein the inert atmosphere is one of argon atmosphere, nitrogen atmosphere, argon and nitrogen mixed atmosphere.
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