CN112047975A - Synthesis method of silane coupling agent Si69 and intermediate thereof - Google Patents
Synthesis method of silane coupling agent Si69 and intermediate thereof Download PDFInfo
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- CN112047975A CN112047975A CN202010907176.0A CN202010907176A CN112047975A CN 112047975 A CN112047975 A CN 112047975A CN 202010907176 A CN202010907176 A CN 202010907176A CN 112047975 A CN112047975 A CN 112047975A
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- gamma
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- chloropropyltrichlorosilane
- silane coupling
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 35
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 30
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims abstract description 22
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960003750 ethyl chloride Drugs 0.000 claims abstract description 19
- 239000011592 zinc chloride Substances 0.000 claims abstract description 15
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 26
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 239000011593 sulfur Substances 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 16
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 claims description 13
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- IZPZQHISQHRLFP-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Na+].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Cl-].[Cl-].[Cl-].[Cl-] IZPZQHISQHRLFP-UHFFFAOYSA-J 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 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
-
- 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
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O 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
- C07F7/18—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a method for synthesizing a silane coupling agent Si69 and an intermediate thereof, wherein during the synthesis of the intermediate, ether is used as an alcoholysis substrate to attack gamma-chloropropyltrichlorosilane, and zinc chloride is used as a catalyst to promote the forward progress of the reaction in order to improve the reaction efficiency. Compared with the common synthesis process, the byproduct chloroethane has a low boiling point, is directly escaped in a gas form in a reaction system, and is collected by condensation, so that the reaction is favorably carried out in the forward direction, the chloroethane has a certain economic value, the intermediate does not need alkali washing, the post-treatment is simple, and the method is green and environment-friendly.
Description
Technical Field
The invention relates to a synthesis method of a silane coupling agent Si69 intermediate, in particular to a synthesis method of a silane coupling agent Si69 and an intermediate thereof, which has the advantages of short reaction time, simple post-treatment process, high economic benefit and environmental protection, and belongs to the technical field of organosilicon synthesis.
Background
Silane coupling agents are widely used as molecular bridges for connecting inorganic materials and organic materials in various fields such as automobiles, aviation, medical treatment, buildings, electronics and the like. For example, in the field of automobile tires, white carbon black can be used as a reinforcing agent and a filler of rubber, but the white carbon black has poor dispersibility in the rubber due to large difference of physicochemical properties of the white carbon black and the filler, and the introduction of the silane coupling agent well solves the problem of poor dispersibility of the white carbon black, and obviously improves the processing and use performances of the tires.
In addition, the silane coupling agent is used as a bridge for building inorganic matters and organic matters, and is also widely applied to surface modification of various materials. In recent years, the role of the silane coupling agent in the pretreatment of the metal surface is gradually concerned by scholars at home and abroad, and compared with the traditional phosphating process, the method has the advantages of no pollution of heavy metal ions, no phosphorus, less consumption, excellent anticorrosion effect, simple treatment process and the like.
The silane coupling agent Si69 is a bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, is a silane coupling agent commonly used in the rubber industry, and has the following conventional synthesis mode: ethanol is used as an alcoholysis substrate and reacts with gamma-chloropropyltrichlorosilane (with the trade name of gamma 1) to obtain an intermediate gamma-chloropropyltriethoxysilane (with the trade name of gamma 2), and then the gamma-chloropropyltriethoxysilane reacts with disodium tetrasulfide to obtain a silane coupling agent Si 69. In the synthesis method, ethanol is used as an alcoholysis substrate for synthesizing the intermediate gamma 2, the reaction time is long, a byproduct hydrogen chloride is generated, an organic solvent of insoluble hydrogen chloride is generally adopted for heating reflux, or nitrogen is introduced, vacuum is pumped and an alkaline compound is added as a hydrogen chloride absorbent during the synthesis reaction to remove the hydrogen chloride so as to promote the forward reaction, but the operations have the defects of complex operation, high production cost, high post-treatment difficulty and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a synthesis method of a silane coupling agent Si69 intermediate, ether is used as an alcoholysis substrate in the method, and compared with the traditional method using ethanol as the alcoholysis substrate, the method has the advantages of simple process operation, simple post-treatment process and environmental protection.
The synthesis method of the silane coupling agent Si69 intermediate provided by the invention comprises the step of reacting gamma-chloropropyltrichlorosilane with diethyl ether to form gamma-chloropropyltriethoxysilane. In the reaction, ethyl ether is used as an alcoholysis substrate instead of ethanol, the ethyl ether attacks gamma-chloropropyltrichlorosilane to obtain an intermediate gamma-chloropropyltriethoxysilane, and a byproduct chloroethane is formed in the reaction. The boiling point of the chloroethane is only 12.3 ℃, the boiling point is very low, the chloroethane can directly exist in a gas form in a reaction system, the chloroethane continuously overflows in a gas form in the reaction process and can be collected in a condensation mode, on one hand, the forward proceeding of the reaction is promoted, on the other hand, the chloroethane is also an organic chemical raw material, and has certain economic value and cost reduction. Compared with the byproduct hydrogen chloride generated by using ethanol as an alcoholysis substrate, the method has the advantages of simpler and more efficient recovery of chloroethane, no need of adding alkali for neutralization, simple post-treatment and low cost.
Furthermore, although the gamma-chloropropyltrichlorosilane and the diethyl ether can directly react, researches show that the reaction efficiency can be greatly improved and the reaction time can be shortened under the intervention of a catalyst. Thus, preferably, the reaction of gamma-chloropropyltrichlorosilane with diethyl ether is carried out in the presence of a catalyst which is zinc chloride. Under the action of a catalyst, the ethyl ether has higher reaction activity, the reason is that the essence of the first step of reaction is nucleophilic substitution reaction, zinc chloride can promote oxygen on the ethyl ether to attack electron-deficient silicon, the removed chlorine is combined with ethyl free radicals to generate ethyl chloride, the ethyl chloride escapes as gas under the condition of reaction temperature to promote the forward progress of the reaction, in addition, the escaped ethyl chloride is collected in a condensation mode, and the post-treatment process is simple. The reaction formula for preparing the intermediate gamma-chloropropyltriethoxysilane under the catalysis of zinc chloride is as follows:
furthermore, the dosage of the catalyst can be screened according to the experiment according to the molar ratio of the raw materials, and the molar ratio of the zinc chloride and the gamma-chloropropyltrichlorosilane as the catalyst is verified to be 0.1-0.3: 1, preferably 0.2 to 0.3: 1. the molar ratio of the diethyl ether to the gamma-chloropropyltrichlorosilane is 3.0-3.2: 1, preferably 3.0 to 3.1: 1.
further, the reaction temperature of the gamma-chloropropyltrichlorosilane and the diethyl ether is 30-70 ℃, and preferably 40-60 ℃. The reaction time is generally 2 to 4 hours, preferably 2 to 3 hours.
Further, a byproduct chloroethane formed by the reaction of the gamma-chloropropyltrichlorosilane and diethyl ether is discharged in the form of gas in the reaction process and is condensed and collected. After the reaction is finished, the catalyst is removed by filtration, the remainder is the intermediate gamma-chloropropyltriethoxysilane, the intermediate can directly enter the next reaction, alkali washing is not needed, the post-treatment is simple and efficient, the operation is easy, the catalyst obtained by filtration can be reused, and the cost is low.
The invention also provides a method for synthesizing a silane coupling agent Si69, namely bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, which comprises the step of synthesizing an intermediate gamma-chloropropyltriethoxysilane, wherein the gamma-chloropropyltriethoxysilane is synthesized by the method.
Further, the synthesis method of the silane coupling agent Si69 further comprises the step of reacting the gamma-chloropropyltriethoxysilane intermediate with sodium tetrasulfide to form the silane coupling agent Si 69. Sodium tetrasulfide can be synthesized by any method disclosed in the prior art, for example, sodium ethoxide is prepared by adding metal sodium into absolute ethyl alcohol, and sodium tetrasulfide is prepared by adding metal sodium and elemental sulfur into sodium ethoxide solution; or, under the protection of nitrogen, preparing sodium tetrachloride from anhydrous sodium sulfide and sulfur in anhydrous ethanol; or, under the protection of nitrogen, sodium hydroxide and sulfur powder are used for preparing sodium tetrasulfide; or, under the protection of nitrogen, reacting sodium hydrosulfide with sulfur powder in absolute ethyl alcohol to generate sodium polysulfide.
In one embodiment of the present invention, the silane coupling agent Si69 was prepared in the following manner: and reacting sodium hydroxide with sulfur to prepare disodium tetrasulfide, and then reacting the disodium tetrasulfide, gamma-chloropropyl triethoxysilane and tetrabutylammonium bromide to prepare a silane coupling agent Si 69. The reaction formula is as follows:
further, the molar ratio of the sodium hydroxide, the sulfur, the tetrabutylammonium bromide and the gamma-chloropropyltriethoxysilane is 1.5-1.7: 2.37-2.48:0.008-0.012:1, preferably 1.6:2.45:0.01: 1. The reaction temperature of the sodium hydroxide and the sulfur is 100-110 ℃, the reaction time is generally 2-3h, the reaction temperature of the disodium tetrasulfide, the gamma-chloropropyltriethoxysilane and the tetrabutylammonium bromide is 80-120 ℃, the reaction time is generally 2-5h, and the reaction time is preferably 3-4 h. By adopting the process, the obtained product is a light yellow transparent liquid, the yield is more than 92 percent based on gamma-chloropropyltrichlorosilane, the total sulfur content is 21.7 to 23.3 percent, and the impurity content is less than or equal to 4.0 percent.
In one embodiment of the present invention, a specific synthesis method of a silane coupling agent Si69 is provided, which comprises the following steps:
(1) reacting diethyl ether with gamma-chloropropyltrichlorosilane under the catalysis of zinc chloride, escaping chloroethane as a reaction byproduct at the reaction temperature, collecting by condensation, and filtering to remove a catalyst of zinc chloride to obtain gamma-chloropropyltriethoxysilane;
(2) reacting sodium hydroxide solution with sulfur to prepare disodium tetrasulfide, adding tetrabutyl ammonium bromide into the prepared disodium tetrasulfide solution, and then adding gamma-chloropropyl triethoxysilane for reaction;
(3) after the reaction is finished, the sulfur-containing silane coupling agent Si69 is obtained through water washing, liquid separation, drying and activated carbon decoloration post-treatment.
The invention has the following advantages:
1. according to the method, ethyl ether is used as an alcoholysis substrate, and a byproduct chloroethane generated in the formation process of the intermediate gamma-chloropropyltriethoxysilane can be directly condensed and collected, so that the method has certain economic benefit, and the post-treatment does not need alkali washing, is simple and efficient, and is green and environment-friendly.
2. The reaction of the ether and the gamma-chloropropyltrichlorosilane introduces the catalyst, the catalytic action of the catalyst can greatly shorten the reaction time, and the method has the advantages of short reaction time, simple production process, strong operability, high production efficiency, high industrial application value and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to be limiting.
In the following examples, the yield was calculated as: quality of the obtained product/theoretical quality of the product. The contents of impurities and sulfur are detected by a GB/T30309-2013 method.
Example 1
86.52g of gamma 1 (gamma-chloropropyltrichlorosilane, the same below) is added into a 500mL flask, 93.78g of diethyl ether and 11.13g of zinc chloride are then added, the temperature is slowly raised to 60 ℃, the mixture is reacted for 3 hours under a stirring state, formed chloroethane is collected by a condensing device in the reaction process, and after the reaction is finished, the zinc chloride is removed by suction filtration, so that 96.27g of intermediate gamma 2 (gamma-chloropropyltriethoxysilane, the same below) is obtained. The yield was 97.9% based on γ 1.
Example 2
83.57g of gamma 1 is added into a 500mL flask, 87.66g of diethyl ether and 8.06g of zinc chloride are added, the temperature is slowly increased to 30 ℃, the reaction is carried out for 4 hours under a stirring state, formed chloroethane is collected by a condensing device in the reaction process, and after the reaction is finished, the zinc chloride is removed by suction filtration to obtain 90.14g of intermediate gamma 2. The yield was 94.9% based on γ 1.
Example 3
Adding 90.24g of gamma 1 into a 500mL flask, then adding 100.97g of diethyl ether and 14.75g of zinc chloride, slowly heating to the system temperature of 70 ℃, reacting for 4 hours under a stirring state, collecting formed chloroethane through a condensing device in the reaction process, and performing suction filtration to remove the zinc chloride after the reaction is finished to obtain 98.46g of intermediate gamma 2. The yield was 96.0% based on γ 1.
Example 4
86.52g of gamma 1 is added into a 500mL flask, then 93.78g of diethyl ether is added, the temperature is slowly raised to 60 ℃, the mixture reacts for 10 hours under the stirring state, formed chloroethane is collected by a condensing device in the reaction process, and 95.21g of intermediate gamma 2 (gamma-chloropropyltriethoxysilane, the same is carried out below) is obtained after the reaction is finished. The yield was 96.8% based on γ 1.
Example 5
60g of 25.59g of sodium hydroxide aqueous solution is added into a 500mL flask, 31.34g of sulfur is added, the system temperature is controlled to be 100 ℃, the reaction time is 2 hours, then 1.29g of tetrabutylammonium bromide is added, 96.27g of intermediate gamma 2 prepared in the example 1 is added, the system temperature is controlled to be 110 ℃, the reaction is carried out for 3 hours under a stirring state, after the reaction is finished, water washing, liquid separation, drying and activated carbon decoloration post-treatment are carried out, 104.52g of light yellow transparent liquid is finally obtained, the yield is 97.0 percent by using gamma 2, the total sulfur content is 22.53 percent, and the impurity content is 2.36 percent.
Example 6
60g of aqueous solution containing 23.96g of sodium hydroxide is added into a 500mL flask, 29.35g of sulfur is added, the system temperature is controlled to be 100 ℃, the reaction time is 2 hours, then 1.41g of tetrabutylammonium bromide is added, 90.14g of intermediate gamma 2 prepared in the example 2 is added, the system temperature is controlled to be 110 ℃, the reaction is carried out for 3 hours under a stirring state, after the reaction is finished, water washing, liquid separation, drying and activated carbon decoloration post-treatment are carried out, 97.36g of light yellow transparent liquid is finally obtained, the yield is 96.5% by calculation of gamma 2, the total sulfur content is 22.48%, and the impurity content is 3.57%.
Example 7
60g of aqueous solution containing 26.17g of sodium hydroxide is added into a 500mL flask, 32.06g of sulfur is added, the system temperature is controlled to be 100 ℃, the reaction time is 2 hours, then 1.32g of tetrabutylammonium bromide is added, 98.46g of intermediate gamma 2 prepared in the example 3 is added, the system temperature is controlled to be 110 ℃, the reaction is carried out for 3 hours under a stirring state, after the reaction is finished, water washing, liquid separation, drying and activated carbon decoloration post-treatment are carried out, 106.57g of light yellow transparent liquid is finally obtained, the yield is 96.7% by taking gamma 2 as a calculation, the total sulfur content is 22.19%, and the impurity content is 2.83%.
Example 8
60g of aqueous solution containing 25.3g of sodium hydroxide is added into a 500mL flask, 31g of sulfur is added, the system temperature is controlled to be 100 ℃, the reaction time is 2 hours, then 1.28g of tetrabutylammonium bromide is added, 95.21g of intermediate gamma 2 prepared in example 4 is added, the system temperature is controlled to be 110 ℃, the reaction is carried out for 3 hours under the stirring state, after the reaction is finished, water washing, liquid separation, drying and activated carbon decoloration post-treatment are carried out, 102.36g of light yellow transparent liquid is finally obtained, the yield is 96.1% by calculation of gamma 2, the total sulfur content is 22.53%, and the impurity content is 2.36%.
Comparative example 1
The sulfur-containing silane coupling agent, Si69, was synthesized according to the method of example 6, except that: the reaction temperature in the synthesis process of the intermediate gamma 2 is 130 ℃, and the reaction time is 2 h. The yield of the obtained silane coupling agent Si69 calculated by gamma 2 was 81.53%, the total sulfur content was 20.73%, and the impurity content was 6.79%.
Comparative example 2
The sulfur-containing silane coupling agent, Si69, was synthesized according to the method of example 6, except that: the reaction temperature in the synthesis process of the intermediate gamma 2 is 20 ℃, and the reaction time is 4 h. The yield of the obtained silane coupling agent Si69 calculated by gamma 2 was 76.31%, the total sulfur content was 19.75%, and the impurity content was 8.23%.
Claims (10)
1. A synthetic method of a silane coupling agent Si69 intermediate is characterized by comprising the following steps: comprises the step of reacting gamma-chloropropyltrichlorosilane with diethyl ether to form gamma-chloropropyltriethoxysilane.
2. The method of synthesis according to claim 1, wherein: the reaction of gamma-chloropropyltrichlorosilane and diethyl ether is carried out in the presence of a catalyst, wherein the catalyst is zinc chloride.
3. The synthesis method according to claim 1 or 2, wherein: the molar ratio of the diethyl ether to the gamma-chloropropyltrichlorosilane is 3.0-3.2: 1, preferably 3.0 to 3.1: 1.
4. the method of synthesis according to claim 2, wherein: the mol ratio of the zinc chloride to the gamma-chloropropyltrichlorosilane is 0.1-0.3: 1, preferably 0.2 to 0.3: 1.
5. the synthesis process according to any one of claims 1 to 4, characterized in that: the chloroethane which is a byproduct formed by the reaction of the gamma-chloropropyltrichlorosilane and the diethyl ether is discharged in the form of gas in the reaction process and is condensed and collected.
6. The method of synthesis according to claim 1, wherein: the reaction temperature of the gamma-chloropropyltrichlorosilane and the diethyl ether is 30-70 ℃, and preferably 40-60 ℃; the reaction time of gamma-chloropropyltrichlorosilane with diethyl ether is 2 to 4 hours, preferably 2 to 3 hours.
7. The method of synthesis according to claim 2, wherein: after the gamma-chloropropyltrichlorosilane and the ether react, filtering to remove the catalyst, and obtaining the gamma-chloropropyltriethoxysilane.
8. A method for synthesizing a silane coupling agent Si69 is characterized by comprising the following steps: comprising the step of synthesizing gamma-chloropropyltriethoxysilane according to the synthesis method of the intermediate of silane coupling agent Si69 as set forth in any one of claims 1 to 7.
9. The method of synthesis according to claim 8, wherein: the method also comprises the steps of reacting sodium hydroxide with sulfur to prepare disodium tetrasulfide, and then reacting the disodium tetrasulfide, gamma-chloropropyltriethoxysilane and tetrabutylammonium bromide to prepare a silane coupling agent Si 69.
10. The method of synthesis according to claim 9, wherein: the mol ratio of the sodium hydroxide, the sulfur, the tetrabutylammonium bromide and the gamma-chloropropyltriethoxysilane is 1.5-1.7: 2.37-2.48:0.008-0.012:1, preferably 1.6:2.45:0.01: 1; the reaction temperature of the sodium hydroxide and the sulfur is 100-110 ℃; the reaction temperature of disodium tetrasulfide, gamma-chloropropyltriethoxysilane and tetrabutylammonium bromide is 80-120 ℃, preferably 90-110 ℃.
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