CN109111568B - Preparation method of sulfur-containing silane coupling agent - Google Patents
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Abstract
The invention provides a preparation method of a sulfur-containing silane coupling agent, which comprises the step of reacting prepared anhydrous sodium polysulfide with gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane in the presence of a catalyst rare earth neodymium organic compound and a catalyst chloride to prepare the sulfur-containing silane coupling agent. On one hand, in the presence of a rare earth neodymium organic compound and a chloride catalyst, the reaction of the invention reduces the probability of generating byproducts, and improves the yield of the target product sulfur-containing silane coupling agent, and the yield is 95-98% by calculation.
Description
Technical Field
The invention belongs to the technical field of preparation of silane coupling agents, and particularly relates to a preparation method of a sulfur-containing silane coupling agent.
Background
The green tire has stronger wet skid resistance while reducing the rolling resistance of the tire, so the green tire becomes the development trend of the tire industry, and the green tire is prepared by two methods, one of which is to prepare the green tire by changing the structure of the rubber, such as the development and application of solution polymerized styrene-butadiene rubber; secondly, the rubber raw material-polymer material matrix of the tire is filled with inorganic substances, the tire prepared by the method has good low rolling resistance and wet skid resistance, the inorganic substances and the polymer material matrix are combined with a silane coupling agent, and the silane coupling agent can support a molecular bridge between the interfaces of the inorganic substances and the organic polymer, so that the two materials with different properties are linked together to improve the performance of the composite material and increase the adhesive strength.
The sulfur-containing silane coupling agent can realize the combined application of inorganic particle modification and graft polymer to achieve the effect of modifying a polymer matrix, and polysulfide bonds of the sulfur-containing silane coupling agent can participate in rubber vulcanization, so that the dynamic bending property of rubber is improved, and the sulfur-containing silane coupling agent becomes a hot point of research and development.
For example, the prior art discloses a method for preparing a sulfur-containing silane coupling agent, which comprises the following steps of firstly stirring sulfur powder and a sodium sulfide hydrate, heating to 50-70 ℃, continuing heating to 100-105 ℃ for reaction for 2-4 hours after a solid mixture of the sodium sulfide hydrate and the sulfur powder becomes a brownish red solution, obtaining a sodium polysulfide aqueous solution, then cooling the sodium polysulfide aqueous solution to 60-65 ℃, adding a pH regulator, stirring, adding an organic solvent and halogenated alkoxy silane, heating to 75-90 ℃ for reaction, filtering a crude product after the reaction is finished, separating liquid, and removing the organic solvent from an organic phase to obtain the sulfur-containing silane coupling agent. The coupling agent prepared by the preparation method can be used for the combined reaction of inorganic particle surface modification and graft polymer. However, the yield of the sulfur-containing silane coupling agent in the above-mentioned technique is still to be further improved. In view of this, it is an urgent technical problem for those skilled in the art to improve the existing preparation method of the sulfur-containing silane coupling agent to increase the reaction yield.
Disclosure of Invention
The invention aims to overcome the defect of low yield of the existing preparation method of the sulfur-containing silane coupling agent, and further provides a preparation method of the sulfur-containing silane coupling agent.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect of the present invention, there is provided a method for preparing a sulfur-containing silane coupling agent, comprising the steps of:
(1) reacting sodium hydroxide and sulfur in water to prepare sodium polysulfide aqueous solution, dehydrating the sodium polysulfide aqueous solution for the first time under the condition of atmospheric distillation, and dehydrating for the second time under the condition of vacuum distillation to prepare anhydrous sodium polysulfide;
(2) dissolving the anhydrous sodium polysulfide prepared in the step (1) in a protic solvent, adding a catalyst A and a catalyst B, then adding gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane to form a reaction system, reacting for 4.5-7 h at the reflux temperature of the protic solvent, and stopping the reaction;
(3) cooling the reaction system after the reaction in the step (2) to room temperature, filtering and retaining the filtrate, concentrating and drying the filtrate, dissolving the filtrate in a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of (1-4) to (1-2), cooling and crystallizing, and filtering to obtain a purified sulfur-containing silane coupling agent;
the catalyst A is a rare earth neodymium organic compound, and the catalyst B is a chloride.
Preferably, the rare earth neodymium organic compound is neodymium naphthenate or neodymium isooctanoate; the chloride is diethyl aluminum monochloride.
Preferably, in the step (1), the mass ratio of the sodium hydroxide to the sulfur is 1 (0.9-1.5), preferably 1: (1.0-1.3).
In the step (1), the reaction temperature is 100-125 ℃, preferably 110-120 ℃, and the reaction time is 3-5 h; the temperature of the atmospheric distillation is 70-90 ℃, preferably 75-85 ℃, and the time is 3-5 h; the temperature of the vacuum-pumping distillation is 95-140 ℃, preferably 100-120 ℃, the time is 6-9 h, and the vacuum degree is-0.01 to-0.1 MPa.
Preferably, in the step (2), the molar ratio of the anhydrous sodium polysulfide to the gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane to the catalyst A to the catalyst B is (1.2-1.5): 1, (0.2-0.3): 0.1-0.2, preferably 1.3:1:0.25: 0.15. The protic solvent is absolute ethyl alcohol or acetic acid.
Preferably, in the step (3), the volume ratio of the ethyl acetate to the petroleum ether is (1-2): 1. The cooling crystallization temperature is-15 to-5 ℃, and the time is 10 to 20 hours.
The preparation method of the gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane comprises the following steps:
under the protection of nitrogen, mixing gamma-chloropropyl trichlorosilane, polyethylene glycol monopropyl ether and absolute ethyl alcohol, and reacting to obtain the gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane.
Preferably, the reaction temperature is 90-120 ℃, preferably 100-110, and the reaction time is 2-4 hours, preferably 2.5-3.5 hours.
In a second aspect of the present invention, there is provided a sulfur-containing silane coupling agent prepared by the above method for preparing a sulfur-containing silane coupling agent.
The technical scheme of the invention has the following advantages:
1. the preparation method of the sulfur-containing silane coupling agent comprises the step of reacting the prepared anhydrous sodium polysulfide with gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane in the presence of a catalyst rare earth neodymium organic compound and a catalyst chloride to prepare the sulfur-containing silane coupling agent. On one hand, in the presence of a rare earth neodymium organic compound and a chloride catalyst, the reaction reduces the probability of generating byproducts, and improves the yield of a target product, namely the sulfur-containing silane coupling agent, and the yield is 95-98% by calculation, and in addition, when a polymer matrix is modified by the sulfur-containing silane coupling agent prepared by the invention to be used as a rubber auxiliary agent, less organic gas can be discharged, so that the porosity of the prepared rubber product is reduced, and meanwhile, as the molecular structure of the sulfur-containing silane coupling agent contains a long-chain polyether group, the prepared rubber has higher mixing temperature, and the rubber material is prevented from being burnt in advance; on the other hand, the purity of the sulfur-containing silane coupling agent is improved by purifying the target sulfur-containing silane coupling agent in a mixed solvent consisting of ethyl acetate and petroleum ether.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The preparation method of the sulfur-containing silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane
Under the protection of nitrogen, uniformly mixing 212g (1mol) of gamma-chloropropyl trichlorosilane, 560g (2mol) of polyethylene glycol monopropyl ether and 58mL (1mol) of absolute ethyl alcohol, heating to 90 ℃ for reaction for 4 hours, detecting that the gamma-chloropropyl trichlorosilane and the ethyl alcohol completely react by using a gas chromatography, stopping heating, cooling to below 60 ℃, detecting that the pH value of a reaction system is about 3, adding 5g of sodium ethoxide, stirring for 30 minutes, filtering, and concentrating the filtrate under reduced pressure to obtain gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane;
(2) preparation of anhydrous sodium polysulfide
Weighing 10g of sodium hydroxide and 15g of sulfur, adding 200mL of solvent water to form a reaction system, reacting the reaction system at 100 ℃ for 5h, stopping the reaction, cooling to room temperature to obtain a sodium polysulfide aqueous solution, distilling the sodium polysulfide aqueous solution at 70 ℃ under normal pressure for 5h for primary dehydration, and then distilling at 140 ℃ under the conditions of vacuum degree of-0.01 MPa for 6h for secondary dehydration to obtain anhydrous sodium polysulfide;
(3) preparation of sulfur-containing silane coupling agent
Dissolving 1.3mol of anhydrous sodium polysulfide prepared in the step (2) in 500mL of acetic acid, stirring until the anhydrous sodium polysulfide is dissolved, adding 0.25mol of neodymium isooctanoate, 0.15mol of diethyl aluminum chloride and 1mol of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane prepared in the step (1) into the acetic acid to form a reaction system, heating the reaction system to the reflux temperature of anhydrous ethanol, keeping the reflux temperature for reacting for 5 hours, and stopping the reaction;
cooling the reaction system after the reaction is stopped to room temperature, filtering and reserving filtrate, concentrating and drying the filtrate, dissolving the filtrate in a mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 1:1, cooling and crystallizing for 20h at the temperature of-15 ℃, filtering to obtain purified bis- [3- (ethoxy di (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, and calculating to obtain the product with the yield of 96%.
The product has a H spectrum of1H-NMR(CDCl3,δ,ppm):0.72(t,4H，Si-CH2-)， 1.30(t,6H,Si-O-C-CH3)，1.56～1.87(br,16H,C-CH2-C and-C-C-CH3)，2.99(t,4H， -S-CH2-)，3.48-3.90(br,92H,-O-CH2-)。
The purity of bis- [3- (ethoxybis (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide prepared in this example was 95% by HPLC.
Example 2
The preparation method of the sulfur-containing silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane
Under the protection of nitrogen, uniformly mixing 212g (1mol) of gamma-chloropropyl trichlorosilane, 560g (2mol) of polyethylene glycol monopropyl ether and 58mL (1mol) of absolute ethyl alcohol, heating to 120 ℃ for reaction for 2 hours, detecting that the gamma-chloropropyl trichlorosilane and the ethyl alcohol completely react by using a gas chromatography, stopping heating, cooling to below 60 ℃, detecting that the pH value of a reaction system is about 3, adding 5g of sodium ethoxide, stirring for 30 minutes, filtering, and concentrating the filtrate under reduced pressure to obtain gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane;
(2) preparation of anhydrous sodium polysulfide
Weighing 10g of sodium hydroxide and 9g of sulfur, adding 200mL of solvent water to form a reaction system, reacting the reaction system at 125 ℃ for 3h, stopping the reaction, cooling to room temperature to obtain a sodium polysulfide aqueous solution, distilling the sodium polysulfide aqueous solution at 70 ℃ under normal pressure for 3h for primary dehydration, and then distilling at 95 ℃ under the conditions of vacuum degree of-0.1 MPa for 9h for secondary dehydration to obtain anhydrous sodium polysulfide;
(3) preparation of sulfur-containing silane coupling agent
Dissolving 1.4mol of anhydrous sodium polysulfide prepared in the step (2) in 500mL of acetic acid, stirring until the anhydrous sodium polysulfide is dissolved, adding 0.25mol of neodymium isooctanoate, 0.15mol of diethyl aluminum chloride and 1mol of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane prepared in the step (1) into the acetic acid to form a reaction system, heating the reaction system to the reflux temperature of anhydrous ethanol, keeping the reflux temperature for reacting for 6 hours, and stopping the reaction;
cooling the reaction system after the reaction is stopped to room temperature, filtering and reserving filtrate, concentrating and drying the filtrate, dissolving the filtrate in a mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 2:1, cooling and crystallizing for 10h at the temperature of minus 5 ℃, filtering to obtain purified bis- [3- (ethoxy di (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, and calculating the yield of the product to be 98%.
The product has a H spectrum of1H-NMR(CDCl3,δ,ppm):0.72(t,4H，Si-CH2-)， 1.30(t,6H,Si-O-C-CH3)，1.56～1.87(br,16H,C-CH2-C and-C-C-CH3)，2.99(t,4H， -S-CH2-)，3.48-3.90(br,92H,-O-CH2-)。
The purity of bis- [3- (ethoxybis (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide prepared in this example was 96% by HPLC.
Example 3
The preparation method of the sulfur-containing silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane
Under the protection of nitrogen, uniformly mixing 212g (1mol) of gamma-chloropropyltrichlorosilane, 560g (2mol) of polyethylene glycol monopropyl ether and 58mL (1mol) of absolute ethyl alcohol, heating to 100 ℃ for reaction for 3.5h, detecting that the gamma-chloropropyltrichlorosilane and the ethyl alcohol completely react by using a gas chromatography, stopping heating, cooling to below 50 ℃, detecting that the pH value of a reaction system is about 3, adding 5g of sodium ethoxide, stirring for 30min, filtering, and concentrating the filtrate under reduced pressure to obtain gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane;
(2) preparation of anhydrous sodium polysulfide
Weighing 10g of sodium hydroxide and 10g of sulfur, adding 200mL of solvent water to form a reaction system, reacting the reaction system at 110 ℃ for 4h, stopping the reaction, cooling to room temperature to obtain a sodium polysulfide aqueous solution, distilling the sodium polysulfide aqueous solution at 85 ℃ under normal pressure for 4h for primary dehydration, and then distilling under the conditions of vacuum degree of-0.05 MPa and temperature of 100 ℃ for 8h for secondary dehydration to obtain anhydrous sodium polysulfide;
(3) preparation of sulfur-containing silane coupling agent
Dissolving 1.5mol of anhydrous sodium polysulfide prepared in the step (2) in 500mL of anhydrous ethanol, stirring until the anhydrous sodium polysulfide is dissolved, adding 0.2mol of neodymium naphthenate, 0.2mol of diethyl aluminum chloride and 1mol of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane prepared in the step (1) into the anhydrous ethanol to form a reaction system, heating the reaction system to the reflux temperature of the anhydrous ethanol, keeping the reflux temperature for reacting for 7 hours, and stopping the reaction;
cooling the reaction system after the reaction is stopped to room temperature, filtering and reserving filtrate, concentrating and drying the filtrate, dissolving the filtrate in a mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 1:2, cooling and crystallizing for 17h at the temperature of minus 10 ℃, filtering to obtain purified bis- [3- (ethoxy di (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, and calculating the yield of the product to be 97%.
The product has a H spectrum of1H-NMR(CDCl3,δ,ppm):0.72(t,4H，Si-CH2-)，1.30(t,6H,Si-O-C-CH3)，1.56～1.87(br,16H,C-CH2-C and-C-C-CH3)，2.99(t,4H， -S-CH2-)，3.48-3.90(br,92H,-O-CH2-)。
The purity of bis- [3- (ethoxybis (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide prepared in this example was 97% by HPLC.
Example 4
The preparation method of the sulfur-containing silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane
Under the protection of nitrogen, uniformly mixing 212g (1mol) of gamma-chloropropyltrichlorosilane, 560g (2mol) of polyethylene glycol monopropyl ether and 58mL (1mol) of absolute ethyl alcohol, heating to 110 ℃ for reaction for 2.5h, detecting that the gamma-chloropropyltrichlorosilane and the ethyl alcohol completely react by using a gas chromatography, stopping heating, cooling to below 50 ℃, detecting that the pH value of a reaction system is about 3, adding 5g of sodium ethoxide, stirring for 30min, filtering, and concentrating the filtrate under reduced pressure to obtain gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane;
(2) preparation of anhydrous sodium polysulfide
Weighing 10g of sodium hydroxide and 13g of sulfur, adding 200mL of solvent water to form a reaction system, reacting the reaction system at 120 ℃ for 4.5h, stopping the reaction, cooling to room temperature to obtain a sodium polysulfide aqueous solution, distilling the sodium polysulfide aqueous solution at 75 ℃ under normal pressure for 5h for primary dehydration, and then distilling at 120 ℃ under the conditions of vacuum degree of-0.04 MPa for 7h for secondary dehydration to obtain anhydrous sodium polysulfide;
(3) preparation of sulfur-containing silane coupling agent
Dissolving 1.2mol of anhydrous sodium polysulfide prepared in the step (2) in 500mL of anhydrous ethanol, stirring until the anhydrous sodium polysulfide is dissolved, then adding 0.3mol of neodymium naphthenate, 0.1mol of diethyl aluminum chloride and 1mol of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane prepared in the step (1) into the anhydrous ethanol to form a reaction system, heating the reaction system to the reflux temperature of the anhydrous ethanol, keeping the reflux temperature for reacting for 4.5 hours, and then stopping the reaction;
cooling the reaction system after the reaction is stopped to room temperature, filtering and reserving filtrate, concentrating and drying the filtrate, dissolving the filtrate in a mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 4:1, cooling and crystallizing at-12 ℃ for 12h, and filtering to obtain purified bis- [3- (ethoxy di (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, wherein the yield of the product is 96 percent by calculation.
The product has a H spectrum of1H-NMR(CDCl3,δ,ppm):0.72(t,4H，Si-CH2-)， 1.30(t,6H,Si-O-C-CH3)，1.56～1.87(br,16H,C-CH2-C and-C-C-CH3)，2.99(t,4H， -S-CH2-)，3.48-3.90(br,92H,-O-CH2-)。
The purity of bis- [3- (ethoxybis (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide prepared in this example was 95% by HPLC.
Comparative example 1
The preparation method of the sulfur-containing silane coupling agent provided by the comparative example comprises the following steps:
(1) preparation of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane
Under the protection of nitrogen, uniformly mixing 212g (1mol) of gamma-chloropropyltrichlorosilane, 560g (2mol) of polyethylene glycol monopropyl ether and 58mL (1mol) of absolute ethyl alcohol, heating to 90 ℃ to react for 3.0h, detecting that the gamma-chloropropyltrichlorosilane and the ethyl alcohol completely react by using a gas chromatography, stopping heating, cooling to below 50 ℃, detecting that the pH value of a reaction system is about 3, adding 5g of sodium ethoxide, stirring for 30min, filtering, and concentrating the filtrate under reduced pressure to obtain gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane;
(2) preparation of sulfur-containing silane coupling agent
168.04g (1mol) of sodium sulfide hydrate (Na)2S·5H2O) and 128g (4mol) of sulfur powder are mixed, the mixture is heated to 90 ℃ under the stirring of the rotating speed of 150r/min, and the mixture reacts for 2.6 hours at the temperature to obtain sodium polysulfide water solution;
and (2) reducing the temperature of the sodium polysulfide aqueous solution to 3 ℃, adding disodium hydrogen phosphate to adjust the pH value of the reaction system to 8, finally adding 1.3mol of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane and 320mL of ethanol, heating until the ethanol flows back, reacting for 3.0h at the reflux temperature, detecting the reaction completion by gas chromatography, reducing the temperature of the reaction system to room temperature, filtering to retain filtrate and separate liquid, concentrating and drying an organic layer to obtain a product bis- [3- (ethoxy di (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, wherein the yield of the product is 65% by calculation.
The product has a H spectrum of1H-NMR(CDCl3,δ,ppm):0.72(t,4H，Si-CH2-)， 1.30(t,6H,Si-O-C-CH3)，1.56～1.87(br,16H,C-CH2-C and-C-C-CH3)，2.99(t,4H， -S-CH2-)，3.48-3.90(br,92H,-O-CH2-)。
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The preparation method of the sulfur-containing silane coupling agent is characterized by comprising the following steps:
(1) reacting sodium hydroxide and sulfur in water to prepare sodium polysulfide aqueous solution, dehydrating the sodium polysulfide aqueous solution for the first time under the condition of atmospheric distillation, and dehydrating for the second time under the condition of vacuum distillation to prepare anhydrous sodium polysulfide;
(2) dissolving the anhydrous sodium polysulfide prepared in the step (1) in a protic solvent, adding a catalyst A and a catalyst B, then adding gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane to form a reaction system, reacting for 4.5-7 h at the reflux temperature of the protic solvent, and stopping the reaction;
(3) cooling the reaction system after the reaction in the step (2) to room temperature, filtering and retaining the filtrate, concentrating and drying the filtrate, dissolving the filtrate in a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of (1-4) to (1-2), cooling and crystallizing, and filtering to obtain a purified sulfur-containing silane coupling agent;
the catalyst A is a rare earth neodymium organic compound, and the catalyst B is a chloride;
the rare earth neodymium organic compound is neodymium naphthenate or neodymium isooctanoate; the chloride is diethyl aluminum monochloride.
2. The method for producing the sulfur-containing silane coupling agent according to claim 1, wherein the mass ratio of the sodium hydroxide to the sulfur in the step (1) is 1 (0.9 to 1.5).
3. The method for preparing the sulfur-containing silane coupling agent according to claim 2, wherein in the step (1), the reaction temperature is 100 to 125 ℃, and the reaction time is 3 to 5 hours; the temperature of the atmospheric distillation is 70-90 ℃, and the time is 3-5 h; the temperature of the vacuum-pumping distillation is 95-140 ℃, the time is 6-9 h, and the vacuum degree is-0.01 to-0.1 MPa.
4. The method of claim 1, wherein the molar ratio of the anhydrous sodium polysulfide to the gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane to the catalyst A to the catalyst B in step (2) is (1.2-1.5): 1, (0.2-0.3): (0.1-0.2).
5. The method for producing the sulfur-containing silane coupling agent according to claim 4, wherein the protic solvent is absolute ethanol or acetic acid.
6. The method for producing the sulfur-containing silane coupling agent according to claim 1, wherein in the step (3), the volume ratio of the ethyl acetate to the petroleum ether is (1-2): 1.
7. The method for preparing the sulfur-containing silane coupling agent according to claim 1, wherein the cooling crystallization temperature in the step (3) is-15 to-5 ℃ and the time is 10 to 20 hours.
8. The method for preparing a sulfur-containing silane coupling agent according to claim 1, wherein the method for preparing γ -chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane comprises the steps of:
under the protection of nitrogen, mixing gamma-chloropropyl trichlorosilane, polyethylene glycol monopropyl ether and absolute ethyl alcohol and carrying out reaction to prepare gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane;
wherein the reaction temperature is 90-120 ℃, and the reaction time is 2-4 h.
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