CN109021223B - Preparation method of sulfur-containing silane coupling agent - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
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Abstract
The invention provides a preparation method of a sulfur-containing silane coupling agent, which is characterized in that diisopropylcarbodiimide is added at the temperature of 0-10 ℃ in the presence of vulcanized amorphous iron oxyhydroxide, so that the probability of generating byproducts can be reduced, the occurrence of side reactions can be greatly reduced, the reaction yield can be improved, and the yield is 93-96% by calculation. In addition, when the sulfur-containing silane coupling agent prepared by the invention is used as a rubber auxiliary agent for modifying a polymer matrix, 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.
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 is changed into 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 alkoxysilane, 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 sulfur powder and a sodium sulfide hydrate at 80-95 ℃ for 2.5-3 h to prepare a sodium polysulfide aqueous solution;
(2) reducing the temperature of the sodium polysulfide aqueous solution prepared in the step (1) to 0-10 ℃, adding the amorphous FeOOH subjected to the sulfurization treatment and diisopropylcarbodiimide to form a reaction system, adding a pH regulator to regulate the pH of the reaction system to 7-8, and then adding gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane and a protic solvent to react to prepare a sulfur-containing silane coupling agent;
wherein the molar ratio of the gamma-chloropropylethoxy di (polyethylene glycol monopropyl ether) silane to the sodium sulfide hydrate to the vulcanized amorphous iron oxyhydroxide to the diisopropylcarbodiimide is (1.1-1.4): 1, (0.1-0.2): 0.5-1.0.
Preferably, in the step (2), the reaction temperature is the reflux temperature of the protic solvent, and the reaction time is 2-3 h, preferably 2.5 h.
Preferably, in the step (2), the protic solvent is absolute ethanol or acetic acid.
Preferably, in the step (1), the molar ratio of the sulfur powder to the sodium sulfide hydrate is (1-5): 1, preferably (2-4): 1.
preferably, in the step (2), the PH regulator is sodium bicarbonate or disodium hydrogen phosphate.
Preferably, in the step (2), the ratio of the molar parts of the gamma-chloropropylethoxy di (polyethylene glycol monopropyl ether) silane to the volume parts of the protic solvent is (1.1-1.4): (300-400), preferably (1.2-1.3): 320-350); the relation between the molar parts and the volume parts is mol/mL.
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.
The preparation method of the sulfur-containing silane coupling agent further comprises the step of purifying the reaction system after the reaction is finished, namely cooling the reaction system to room temperature, filtering and retaining filtrate, separating liquid, concentrating and drying an organic layer, dissolving the organic layer in a mixed solvent with the volume ratio of acetone to water being (1-3) to (1-2), cooling and crystallizing, and filtering to obtain the purified sulfur-containing silane coupling agent.
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 steps of firstly controlling the temperature of a prepared sodium polysulfide aqueous solution to be 0-10 ℃, adding vulcanized amorphous iron oxyhydroxide, diisopropylcarbodiimide and a pH regulator at the temperature, regulating the pH of the solution to be 7-8, and then adding gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane and a protic solvent for reaction to prepare the sulfur-containing silane coupling agent. In the invention, diisopropylcarbodiimide is added at the temperature of 0-10 ℃ in the presence of vulcanized amorphous hydroxyl ferric oxide, so that the probability of generating byproducts can be reduced, the occurrence of side reactions can be greatly reduced, the reaction yield is improved, and the yield is 93-96% by calculation. In addition, when the sulfur-containing silane coupling agent prepared by the invention is used as a rubber auxiliary agent for modifying a polymer matrix, 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.
2. The preparation method of the sulfur-containing silane coupling agent further comprises the step of purifying the reaction system after the reaction is finished, namely cooling the reaction system to room temperature, filtering and retaining filtrate and separating liquid, concentrating and drying an organic layer, dissolving the organic layer in a mixed solvent with the volume ratio of acetone to water being (1-3) to (1-2), cooling and crystallizing, filtering to obtain the purified sulfur-containing silane coupling agent, and improving the purity of the sulfur-containing silane coupling agent product through a purification step.
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 obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention. Furthermore, the technical features mentioned in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.
In the following examples of the present invention, the preparation method of the amorphous iron oxyhydroxide subjected to the vulcanization treatment is all; mixing amorphous iron oxyhydroxide and sulfur according to the molar ratio of 1:2, and stirring to obtain the vulcanized amorphous iron oxyhydroxide.
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-chloropropyltrichlorosilane, 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-chloropropyltrichlorosilane 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 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 32g (1mol) of sulfur powder are mixed, the mixture is heated to 95 ℃ under the stirring of the rotating speed of 140r/min, and the mixture reacts for 2.5 hours at the temperature to obtain sodium polysulfide aqueous solution;
cooling the aqueous solution of sodium polysulfide to 0 deg.C, adding 0.1mol sulfurized amorphous iron oxyhydroxide and 1.0mol diisopropylcarbodiimide to form a reaction system, and adding NaHCO3Adjusting the pH value of a reaction system to 7, finally adding 1.4mol of gamma-chloropropylethoxy di (polyethylene glycol monopropyl ether) silane prepared in the step (1) and 300mL of absolute ethanol, heating to ethanol reflux, reacting for 2h at the reflux temperature, detecting the reaction by gas chromatography, cooling the reaction system to room temperature, filtering to retain filtrate and separate liquid, concentrating and drying an organic layer, dissolving the organic layer in a mixed solvent with the volume ratio of acetone to water of 1:2, cooling and crystallizing, and filtering to obtain purified bis- [3- (ethoxy di (polyethylene glycol monopropyl ether) silicon) propyl ] bis]Tetrasulfide, calculated, the productThe yield of the product was 96%.
The product has a H spectrum of1H-NMR(CDCl3,,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 sulfur-containing silane coupling agent
168.04g (1mol) of sodium sulfide hydrate (Na)2S·5H2O) and 160g (5mol) of sulfur powder are mixed, the mixture is heated to 80 ℃ under the stirring of the rotating speed of 150r/min, and the mixture reacts for 3.0h at the temperature to obtain sodium polysulfide aqueous solution;
cooling the sodium polysulfide aqueous solution to 10 ℃, adding 0.2mol of vulcanized amorphous ferric hydroxide and 0.5mol of diisopropylcarbodiimide to form a reaction system, then adding disodium hydrogen phosphate to adjust the pH value of the reaction system to 7, finally adding 1.1mol of gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane prepared in the step (1) and 400mL of acetic acid, heating until the acetic acid is refluxed, reacting for 3h at the reflux temperature, detecting the reaction end by gas chromatography, cooling the reaction system to room temperature, filtering and retaining filtrate, separating liquid, concentrating and drying an organic layer, dissolving the organic layer in a mixed solvent with the volume ratio of acetone to water being 3:1, cooling and crystallizing, filtering to obtain purified bis- [3- (ethoxy di (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, the yield of this product was calculated to be 94%.
The product has a H spectrum of1H-NMR(CDCl3,,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 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 sulfur-containing silane coupling agent
168.04g (1mol) of sodium sulfide hydrate (Na)2S·5H2O) and 64g (2mol) of sulfur powder are mixed, the mixture is stirred at the rotating speed of 150r/min and heated to 85 ℃, and the mixture reacts for 2.8 hours at the temperature to obtain sodium polysulfide water solution;
cooling the sodium polysulfide aqueous solution to 5 ℃, adding 0.15mol of vulcanized amorphous ferric hydroxide and 0.8mol of diisopropylcarbodiimide to form a reaction system, then adding disodium hydrogen phosphate to adjust the pH of the reaction system to 8, finally adding 1.2mol of gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane prepared in the step (1) and 350mL of ethanol, heating until ethanol refluxes, reacting for 2.5h at the refluxes temperature, detecting the reaction by gas chromatography, cooling the reaction system to room temperature, filtering, retaining filtrate, separating liquid, concentrating and drying an organic layer, dissolving the organic layer in a mixed solvent with the volume ratio of acetone to water of 1:1.5, cooling for crystallization, filtering to obtain purified bis- [3- (ethoxy bis (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, the yield of this product was calculated to be 93%.
The product has a H spectrum of1H-NMR(CDCl3,,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 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 sulfur-containing silane coupling agent
168.04g (1mol) of sodium sulfide hydrate (Na)2S·5H2O) and 128g (4mol) of sulfur powder are mixed, and the temperature is increased under the stirring of the rotating speed of 150r/minThe temperature is increased to 90 ℃, and the reaction is carried out for 2.6 hours at the temperature, so as to obtain sodium polysulfide water solution;
cooling the sodium polysulfide aqueous solution to 8 ℃, adding 0.18mol of vulcanized amorphous ferric hydroxide and 0.9mol of diisopropylcarbodiimide to form a reaction system, then adding disodium hydrogen phosphate to adjust the pH of the reaction system to 8, finally adding 1.3mol of gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane prepared in the step (1) and 320mL of ethanol, heating until ethanol refluxes, reacting for 2.5h at the refluxes temperature, detecting the reaction by gas chromatography, cooling the reaction system to room temperature, filtering, retaining filtrate, separating liquid, concentrating and drying an organic layer, dissolving the organic layer in a mixed solvent with the volume ratio of acetone to water of 2:1, cooling, crystallizing, filtering to obtain purified bis- [3- (ethoxy bis (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, the yield of this product was calculated to be 96%.
The product has a H spectrum of1H-NMR(CDCl3,,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 5
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 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;
cooling the sodium polysulfide aqueous solution to 3 ℃, adding 0.18mol of vulcanized amorphous ferric hydroxide and 0.9mol of diisopropylcarbodiimide to form a reaction system, then adding disodium hydrogen phosphate to adjust the pH value of the reaction system to 8, finally adding 1.3mol of gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane prepared in the step (1) and 320mL of ethanol, heating until ethanol refluxes, reacting for 3.0h at the refluxes temperature, detecting the reaction end by gas chromatography, cooling the reaction system to room temperature, filtering to retain filtrate and separate liquid, concentrating and drying an organic layer, dissolving the organic layer in a mixed solvent with the volume ratio of acetone to water of 3:2, cooling and crystallizing, filtering to obtain purified bis- [3- (ethoxy bis (polyethylene glycol monopropyl ether) silicon) propyl ] -tetrasulfide, the yield of this product was calculated to be 95%.
The product has a H spectrum of1H-NMR(CDCl3,,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.
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;
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 end by gas chromatography, reducing the temperature of the reaction system to room temperature, filtering to retain filtrate and carry out liquid separation, 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,,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. All embodiments need not be, and cannot be, given poor exemplification here. 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 sulfur powder and a sodium sulfide hydrate at 80-95 ℃ for 2.5-3 h to prepare a sodium polysulfide aqueous solution;
(2) reducing the temperature of the sodium polysulfide aqueous solution prepared in the step (1) to 0-10 ℃, adding vulcanized amorphous iron oxyhydroxide and diisopropylcarbodiimide to form a reaction system, adding a pH regulator to regulate the pH of the reaction system to 7-8, and then adding gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane and a protic solvent to react to prepare a sulfur-containing silane coupling agent;
the preparation method of the amorphous FeOOH subjected to the vulcanization treatment comprises the following steps: mixing amorphous iron oxyhydroxide and sulfur according to the molar ratio of 1:2, and stirring to obtain the amorphous iron oxyhydroxide subjected to vulcanization treatment;
wherein the molar ratio of the gamma-chloropropyl ethoxy di (polyethylene glycol monopropyl ether) silane to the sodium sulfide hydrate to the vulcanized amorphous iron oxyhydroxide to the diisopropylcarbodiimide is (1.1-1.4): 1, (0.1-0.2): 0.5-1.0.
2. The method for preparing the sulfur-containing silane coupling agent according to claim 1, wherein in the step (2), the reaction temperature is the reflux temperature of the protic solvent, and the reaction time is 2 to 3 hours.
3. The method for producing the sulfur-containing silane coupling agent according to claim 1 or 2, wherein in the step (2), the protic solvent is absolute ethanol or acetic acid.
4. The method for producing the sulfur-containing silane coupling agent according to claim 1, wherein in the step (1), the molar ratio of the sulfur powder to the sodium sulfide hydrate is (1 to 5): 1.
5. the method for producing the sulfur-containing silane coupling agent according to claim 1, wherein in the step (2), the pH adjusting agent is sodium hydrogencarbonate or disodium hydrogenphosphate.
6. The method for preparing a sulfur-containing silane coupling agent according to claim 5, wherein in the step (2), the ratio of the molar parts of the gamma-chloropropylethoxy bis (polyethylene glycol monopropyl ether) silane to the volume parts of the protic solvent is (1.1 to 1.4): (300-400); the relation between the molar parts and the volume parts is mol/mL.
7. 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-chloropropyltrichlorosilane, polyethylene glycol monopropyl ether and absolute ethyl alcohol, and reacting at the temperature of 90-120 ℃ for 2-4 hours to obtain the gamma-chloropropylethoxy di (polyethylene glycol monopropyl ether) silane.
8. The method for producing a sulfur-containing silane coupling agent according to claim 1, further comprising a step of purifying the reaction system after the completion of the reaction:
and cooling the reaction system to room temperature, filtering and retaining the filtrate, separating the filtrate, concentrating and drying the organic layer, dissolving the organic layer in a mixed solvent of acetone and water in a volume ratio of (1-3) to (1-2), cooling and crystallizing, and filtering to obtain the purified sulfur-containing silane coupling agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405985A (en) * | 1994-07-08 | 1995-04-11 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| CN103351401A (en) * | 2013-07-16 | 2013-10-16 | 武汉大学 | Sulfur-containing silane coupling agent and preparation method thereof |
| CN105713032A (en) * | 2016-01-21 | 2016-06-29 | 杭州硅畅科技有限公司 | Method using one-pot method to prepare sulfur-bearing silane coupling agent |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405985A (en) * | 1994-07-08 | 1995-04-11 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| CN103351401A (en) * | 2013-07-16 | 2013-10-16 | 武汉大学 | Sulfur-containing silane coupling agent and preparation method thereof |
| CN105713032A (en) * | 2016-01-21 | 2016-06-29 | 杭州硅畅科技有限公司 | Method using one-pot method to prepare sulfur-bearing silane coupling agent |
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