CN112047975B - 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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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 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 21
- 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
- 238000000034 method Methods 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
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 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 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 238000009835 boiling Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 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
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 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
- 239000000945 filler Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 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
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ethyl free radical Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment 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
- 239000000203 mixture 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
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a synthesis method of a silane coupling agent Si69 and an intermediate thereof, wherein diethyl ether is used as an alcoholysis substrate to attack gamma-chloropropyl trichlorosilane during the synthesis of the intermediate, 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 low boiling point, directly escapes in a reaction system in a gas form, is collected by condensation, is favorable for forward reaction, has certain economic value, does not need alkaline washing, and is simple in post-treatment and environment-friendly.
Description
Technical Field
The invention relates to a method for synthesizing a silane coupling agent Si69 intermediate, in particular to a method for synthesizing 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
The silane coupling agent is used as a molecular bridge for connecting inorganic materials and organic materials, and has wide application in various fields such as automobiles, aviation, medical treatment, construction, 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 a large physical and chemical property difference between the reinforcing agent and the filler, and the problem of poor dispersibility of the white carbon black is well solved by introducing a silane coupling agent, so that the processing and the service performance of the tire are remarkably improved.
In addition, the silane coupling agent is widely used for surface modification of various materials as a bridge for taking up inorganic matters and organic matters. In recent years, the effect of the silane coupling agent in the pretreatment of the metal surface is gradually focused by students at home and abroad, and compared with the traditional phosphating process, the silane coupling agent has the advantages of no pollution of heavy metal ions, no phosphorus, low consumption, excellent anti-corrosion effect, simple treatment process and the like.
The chemical name of the silane coupling agent Si69 is bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, which is a common silane coupling agent in the rubber industry, and the conventional synthesis mode is as follows: ethanol is taken as an alcoholysis substrate, reacts with gamma-chloropropyl trichlorosilane (with the commodity name of gamma 1) to obtain an intermediate gamma-chloropropyl triethoxysilane (with the commodity name of gamma 2), and then the gamma-chloropropyl triethoxysilane reacts with disodium tetrasulfide to obtain the silane coupling agent Si69. In the synthesis method, ethanol is adopted as an alcoholysis substrate for synthesis of the intermediate gamma 2, reaction time is long, hydrogen chloride is generated as a byproduct, and an organic solvent which is added with insoluble hydrogen chloride is generally adopted for heating reflux, or nitrogen is introduced, vacuumizing is carried out during synthesis reaction, an alkaline compound is added as a hydrogen chloride absorbent and other modes to remove the hydrogen chloride so as to promote forward progress of the reaction, but the operations have the defects of complicated operation, high production cost, high post-treatment difficulty and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a synthesis method of a silane coupling agent Si69 intermediate, which uses diethyl ether as an alcoholysis substrate.
The synthesis method of the silane coupling agent Si69 intermediate provided by the invention comprises the step of reacting gamma-chloropropyl trichlorosilane with diethyl ether to form gamma-chloropropyl triethoxysilane. In the reaction, diethyl ether is used as an alcoholysis substrate instead of ethanol, and the diethyl ether attacks the gamma-chloropropyl trichlorosilane to obtain an intermediate gamma-chloropropyl triethoxysilane, and simultaneously the reaction is carried out to form a byproduct chloroethane. 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 the gas form in the reaction process, and the chloroethane can be collected in a condensation mode, so that the forward reaction is promoted, and the chloroethane is an organic chemical raw material, has a certain economic value and reduces the cost. Compared with the byproduct hydrogen chloride generated by ethanol as an alcoholysis substrate, the method has the advantages of simpler and more efficient recovery of the chloroethane, no need of adding alkali for neutralization, simple post-treatment and low cost.
Furthermore, although the gamma-chloropropyl trichlorosilane and 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, it is preferred that the reaction of gamma-chloropropyl trichlorosilane with diethyl ether is carried out in the presence of a catalyst which is zinc chloride. Under the action of the catalyst, the diethyl ether has higher reactivity, the essence of the first reaction is nucleophilic substitution reaction, zinc chloride can promote oxygen on diethyl ether to attack silicon with electron deficiency, the removed chlorine combines with ethyl free radical to generate chloroethane, the chloroethane escapes as gas under the condition of reaction temperature to promote the forward progress of the reaction, and the escaped chloroethane is collected in a condensation mode, so that the post-treatment process is simple. The reaction formula for preparing the intermediate gamma-chloropropyl triethoxysilane under the catalysis of zinc chloride is as follows:
further, the catalyst can be screened according to experiments according to the mole ratio of raw materials, and the mole ratio of the catalyst zinc chloride to gamma-chloropropyl trichlorosilane is verified to be 0.1-0.3:1, preferably 0.2 to 0.3:1. the mol ratio of the diethyl ether to the gamma-chloropropyl trichlorosilane is 3.0-3.2:1, preferably 3.0-3.1:1.
further, the reaction temperature of gamma-chloropropyl trichlorosilane and diethyl ether is 30-70 ℃, preferably 40-60 ℃. The reaction time is generally 2 to 4 hours, preferably 2 to 3 hours.
Further, the byproduct chloroethane formed by the reaction of the gamma-chloropropyl trichlorosilane and diethyl ether is discharged in a gas form 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-chloropropyl triethoxysilane, 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 the silane coupling agent Si69, namely bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, which comprises the step of synthesizing an intermediate gamma-chloropropyl triethoxysilane, wherein the gamma-chloropropyl triethoxysilane is synthesized by adopting the method.
Further, the synthetic method of the silane coupling agent Si69 further comprises the step of reacting the gamma-chloropropyl triethoxysilane intermediate with sodium tetrasulfide to form the silane coupling agent Si69. Sodium tetrasulfide can be synthesized by any method disclosed in the prior art, for example, metal sodium is added into absolute ethyl alcohol to prepare sodium ethoxide, and then the metal sodium and elemental sulfur are added into sodium ethoxide solution to prepare sodium tetrasulfide; or under the protection of nitrogen, anhydrous sodium sulfide and sulfur are prepared into sodium tetrachloride in absolute ethyl alcohol; or preparing sodium tetrasulfide from sodium hydroxide and sulfur powder under the protection of nitrogen; or, under the protection of nitrogen, sodium hydrosulfide and sulfur powder react in absolute ethyl alcohol to generate sodium polysulfide.
In one embodiment of the invention, the silane coupling agent Si69 is prepared in the following manner: and (3) reacting sodium hydroxide with sulfur to obtain disodium tetrasulfide, and then reacting the disodium tetrasulfide, gamma-chloropropyl triethoxysilane and tetrabutylammonium bromide to obtain the silane coupling agent Si69. The reaction formula is as follows:
further, the molar ratio of sodium hydroxide, sulfur, tetrabutylammonium bromide and gamma-chloropropyl triethoxysilane is 1.5 to 1.7:2.37-2.48:0.008-0.012:1, preferably 1.6:2.45:0.01:1. The reaction temperature of sodium hydroxide and sulfur is 100-110 ℃, the reaction time is generally 2-3h, the reaction temperature of disodium tetrasulfide, gamma-chloropropyl triethoxysilane and tetrabutylammonium bromide is 80-120 ℃, preferably 90-110 ℃, and the reaction time is generally 2-5h, preferably 3-4h. By adopting the process, the appearance of the obtained product is light yellow transparent liquid, the yield is more than 92 percent based on gamma-chloropropyl trichlorosilane, the total sulfur content is 21.7-23.3 percent, and the impurity content is less than or equal to 4.0 percent.
In a specific embodiment of the invention, a specific synthesis method of a silane coupling agent Si69 is provided, and the steps are as follows:
(1) Diethyl ether and gamma-chloropropyl trichlorosilane react under the catalysis of zinc chloride, a reaction byproduct chloroethane escapes at the reaction temperature, and the gamma-chloropropyl triethoxysilane is obtained by condensing and collecting and then filtering and removing a catalyst zinc chloride;
(2) Sodium hydroxide solution reacts with sulfur to prepare disodium tetrasulfide, tetrabutylammonium bromide is added into the prepared disodium tetrasulfide solution, and then gamma-chloropropyl triethoxysilane is added for reaction;
(3) After the reaction is finished, the sulfur-containing silane coupling agent Si69 is obtained through water washing, liquid separation, drying and active carbon decoloration post-treatment.
The invention has the following advantages:
1. the invention uses diethyl ether as alcoholysis substrate, and the byproduct chloroethane generated in the formation process of the intermediate gamma-chloropropyl triethoxysilane can be directly condensed and collected, so that the invention has certain economic benefit, and the aftertreatment does not need alkaline washing, and the aftertreatment is simple and efficient and environment-friendly.
2. The reaction of diethyl ether and gamma-chloropropyl trichlorosilane 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 invention is further illustrated below with reference to the following examples, which are only illustrative and not limiting in any way.
In the following examples, the yield was calculated as: the obtained product quality/theoretical product quality. The impurity and sulfur content are detected by the GB/T30309-2013 method.
Example 1
86.52g of gamma 1 (gamma-chloropropyl trichlorosilane, the same applies hereinafter) 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 ℃ for reaction for 3 hours under stirring, the formed chloroethane is collected through a condensing device during the reaction, and after the reaction is finished, the zinc chloride is removed through suction filtration, so that 96.27g of intermediate gamma 2 (gamma-chloropropyl triethoxysilane, the same applies hereinafter) is obtained. The yield was 97.9% based on γ1.
Example 2
83.57g gamma 1 is added into a 500mL flask, then 87.66g diethyl ether and 8.06g zinc chloride are added, the temperature of the system is slowly raised to 30 ℃, the reaction is carried out for 4 hours under the stirring state, the 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, thus 90.14g intermediate gamma 2 is obtained. The yield was 94.9% based on γ1.
Example 3
90.24g of gamma 1 is added into a 500mL flask, 100.97g of diethyl ether and 14.75g of zinc chloride are then added, the temperature of the system is slowly raised to 70 ℃, the reaction is carried out for 4 hours under stirring, the 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 98.46g of intermediate gamma 2 is obtained. The yield was 96.0% based on γ1.
Example 4
86.52g of gamma 1 was added to a 500mL flask, followed by 93.78g of diethyl ether, and the mixture was slowly warmed to 60℃and allowed to react for 10 hours under stirring, and ethyl chloride formed was collected by a condensing device during the reaction, and then 95.21g of intermediate gamma 2 (gamma-chloropropyltriethoxysilane, the same applies hereinafter) was obtained after the reaction. The yield was 96.8% based on γ1.
Example 5
60g of an aqueous solution containing 25.59g of sodium hydroxide is added into a 500mL flask, 31.34g of sulfur is added, the temperature of the system 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 temperature of the system is controlled to be 110 ℃, the reaction is carried out for 3 hours under stirring, washing, liquid separation, drying and active carbon decoloration post-treatment are carried out after the reaction is finished, and 104.52g of light yellow transparent liquid is finally obtained, the calculated yield of gamma 2 is 97.0%, the total sulfur content is 22.53%, and the impurity content is 2.36%.
Example 6
60g of an 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 embodiment 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 active carbon decoloration post-treatment are carried out, and finally 97.36g of light yellow transparent liquid is obtained, the calculated yield of gamma 2 is 96.5%, the total sulfur content is 22.48%, and the impurity content is 3.57%.
Example 7
60g of an aqueous solution containing 26.17g of sodium hydroxide is added into a 500mL flask, 32.06g of sulfur is added, the temperature of the system 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 temperature of the system is controlled to be 110 ℃, the reaction is carried out for 3 hours under stirring, washing, liquid separation, drying and active carbon decoloration post-treatment are carried out after the reaction is finished, and 106.57g of light yellow transparent liquid is finally obtained, the calculated yield of gamma 2 is 96.7%, the total sulfur content is 22.19%, and the impurity content is 2.83%.
Example 8
60g of an 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 the example 4 is added, the system temperature is controlled to be 110 ℃, the reaction is carried out for 3 hours under a stirring state, water washing, liquid separation, drying and active carbon decoloration post treatment are carried out after the reaction is finished, 102.36g of light yellow transparent liquid is finally obtained, the calculated yield of gamma 2 is 96.1%, the total sulfur content is 22.53%, and the impurity content is 2.36%.
Comparative example 1
A sulfur-containing silane coupling agent Si69 was synthesized in the same manner as in example 6 except that: the reaction temperature in the synthesis process of the intermediate gamma 2 is 130 ℃, and the reaction time is 2 hours. The obtained silane coupling agent Si69 has a yield of 81.53% by gamma 2, a total sulfur content of 20.73% and an impurity content of 6.79%.
Comparative example 2
A sulfur-containing silane coupling agent Si69 was synthesized in the same manner as in example 6 except that: the reaction temperature in the synthesis process of the intermediate gamma 2 is 20 ℃ and the reaction time is 4 hours. The obtained silane coupling agent Si69 has a yield of 76.31% by gamma 2, a total sulfur content of 19.75% and an impurity content of 8.23%.
Claims (8)
1. A synthetic method of a silane coupling agent Si69 intermediate is characterized in that: the method comprises the step of reacting gamma-chloropropyl trichlorosilane with diethyl ether to form gamma-chloropropyl triethoxysilane, wherein the reaction is carried out in the presence of a catalyst, and the catalyst is zinc chloride; the mol ratio of the diethyl ether to the gamma-chloropropyl trichlorosilane is 3.0-3.1:1, the mol ratio of zinc chloride to gamma-chloropropyl trichlorosilane is 0.2-0.3:1, the reaction temperature is 30-70 ℃ and the reaction time is 2-4 hours.
2. The synthesis method according to claim 1, characterized in that: the byproduct chloroethane formed by the reaction of gamma-chloropropyl trichlorosilane and diethyl ether is discharged in the form of gas in the reaction process and is condensed and collected.
3. The synthesis method according to claim 1, characterized in that: the reaction temperature of the gamma-chloropropyl trichlorosilane and the diethyl ether is 40-60 ℃; the reaction time of the gamma-chloropropyl trichlorosilane and the diethyl ether is 2-3 hours.
4. The synthesis method according to claim 1, characterized in that: and after the gamma-chloropropyl trichlorosilane reacts with diethyl ether, filtering to remove the catalyst, thus obtaining the gamma-chloropropyl triethoxysilane.
5. A synthetic method of a silane coupling agent Si69 is characterized in that: comprising the step of synthesizing gamma-chloropropyl triethoxysilane according to the synthesis method of the silane coupling agent Si69 intermediate of any one of claims 1 to 4.
6. The synthesis method according to claim 5, wherein: and the method also comprises the steps of reacting sodium hydroxide with sulfur to obtain disodium tetrasulfide, and then reacting the disodium tetrasulfide, gamma-chloropropyl triethoxysilane and tetrabutylammonium bromide to obtain the silane coupling agent Si69.
7. The synthesis method according to claim 6, wherein: the molar ratio of sodium hydroxide, sulfur, tetrabutylammonium bromide and gamma-chloropropyl triethoxysilane is 1.5-1.7:2.37-2.48:0.008-0.012:1; the reaction temperature of sodium hydroxide and sulfur is 100-110 ℃; the reaction temperature of the disodium tetrasulfide, the gamma-chloropropyl triethoxysilane and the tetrabutylammonium bromide is 80-120 ℃.
8. The synthesis method according to claim 7, characterized in that: the molar ratio of sodium hydroxide to sulfur to tetrabutylammonium bromide to gamma-chloropropyl triethoxysilane is 1.6:2.45:0.01:1; the reaction temperature of the disodium tetrasulfide, the gamma-chloropropyl triethoxysilane and the tetrabutylammonium bromide is 90-110 ℃.
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