CN109111568A - A kind of preparation method of silane coupler containing sulfur - Google Patents
A kind of preparation method of silane coupler containing sulfur Download PDFInfo
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- CN109111568A CN109111568A CN201811042057.2A CN201811042057A CN109111568A CN 109111568 A CN109111568 A CN 109111568A CN 201811042057 A CN201811042057 A CN 201811042057A CN 109111568 A CN109111568 A CN 109111568A
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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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
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Abstract
The present invention provides a kind of preparation methods of silane coupler containing sulfur, the preparation method reacts anhydrous sodium polysulfide obtained with γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane in the presence of catalyst rare earth neodymium organic compound and catalyst chloride, and silane coupler containing sulfur is made.On the one hand, reaction of the invention is in the presence of catalyst rare earth neodymium organic compound and chloride, reduce the probability for generating by-product, improve the yield of target product silane coupler containing sulfur, it is computed, yield of the present invention is 95~98%, furthermore, silane coupler containing sulfur produced by the present invention polymeric matrix is modified used as rubber chemicals when, can less organic gas discharge, to reduce the porosity of rubber product obtained, simultaneously because containing long-chain polyether group in silane coupler containing sulfur molecular structure, so that rubber obtained has higher melting temperature, avoid the incipient scorch in advance of sizing material.
Description
Technical field
The invention belongs to silane coupling agent preparation technical fields, and in particular to a kind of preparation side of silane coupler containing sulfur
Method.
Background technique
Green tire also has stronger anti-slippery while reducing tire drag, thus becomes tire industry
The preparation of the trend of development, green tire mainly passes through two methods, first, green to prepare by the structure for changing rubber itself
Colour wheel tire, such as the exploitation and application of solution polymerized butadiene styrene rubber；Second, poly- using the rubber raw materials-that inorganic substances filling prepares tire
Object material matrix is closed, tire made from the method has good low-rolling-resistance and anti-slippery, inorganic substances and polymer
The combination of material matrix need to be used in combination with silane coupling agent, and silane coupling agent can be at the interface of inorganic substances and organic polymer high polymer
Between erect " molecular bridge ", to the material of two kinds of property great disparities is linked together the performance for improving composite material and increased viscous
Viscous intensity.
Silane coupler containing sulfur not only may be implemented inoganic particle modified and graft polymers use in conjunction and reach to poly-
The effect that object matrix is modified is closed, and its polysulfide bond can participate in the vulcanization of rubber, to improve the dynamic bending of rubber
Can, thus become the hot spot of research and development.
For example, prior art discloses a kind of method for preparing silane coupler containing sulfur, preparation method specifically include as
Lower step: sulphur powder and vulcanization sodium hydrate are stirred first and are warming up to 50~70 DEG C, when vulcanization sodium hydrate and sulphur powder solid
Mixture is continuously heating to 100~105 DEG C of 2~4h of reaction after becoming brown-red solution, obtains aqueous sodium polysulfide, then will
Aqueous sodium polysulfide is cooled to 60~65 DEG C, and PH regulator is added, and organic solvent and halogenoalkoxysilane are added after stirring,
It is warming up to 75~90 DEG C to be reacted, after reaction by filtration of crude product, liquid separation, organic phase removes organic solvent, obtained to contain
Polysulfur silane coupling agent.The coupling agent that above-mentioned preparation method is prepared, can be used for surface modifying inorganic particle and graft polymers
Association response in.But the yield of the silane coupler containing sulfur in above-mentioned technology needs to be further improved.In consideration of it, how right
The preparation method of existing silane coupler containing sulfur is improved to improve its reaction yield, this for those skilled in the art and
Speech is a technical problem urgently to be resolved.
Summary of the invention
Technical problem to be solved by the present invention lies in present in the preparation method for overcoming existing silane coupler containing sulfur
The low defect of yield, and then provide a kind of preparation method of silane coupler containing sulfur.
The present invention solves the technical solution that above-mentioned technical problem uses are as follows:
The first aspect of the present invention provides a kind of preparation method of silane coupler containing sulfur, includes the following steps:
(1) sodium hydroxide and sulphur are reacted obtained aqueous sodium polysulfide in water, by the sodium polysulfide water
Solution primary dewatering under the conditions of air-distillation then carries out second dehydration in vacuumizing, anhydrous more sulphur is made under distillation condition
Change sodium；
(2) anhydrous sodium polysulfide made from the step (1) is dissolved in protonic solvent, catalyst A and catalysis is added
Agent B is then added γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and forms reaction system and in the protic
4.5~7h is reacted under the reflux temperature of solvent, stops reaction；
(3) reaction system after reacting will be stopped in the step (2) and is down to room temperature, filtering retains filtrate, by the filter
Liquid concentration, drying, the volume ratio for being then dissolved in ethyl acetate and petroleum ether is (1~4): the in the mixed solvent of (1~2), cold
But crystallization, the silane coupler containing sulfur for filtering to purify；
Wherein, the catalyst A is rare earth neodymium organic compound, and the catalyst B is chloride.
Preferably, the rare earth neodymium organic compound is neodymium naphthenate or neodymium iso-octanate；The chloride is a chlorine diethyl
Base aluminium.
Preferably, in the step (1), the mass ratio of the sodium hydroxide and the sulphur is 1:(0.9~1.5), it is excellent
Select 1:(1.0~1.3).
In the step (1), the temperature of the reaction is 100~125 DEG C, and preferably 110~120 DEG C, the time of reaction is 3
~5h；The temperature of the air-distillation is 70~90 DEG C, and preferably 75~85 DEG C, the time is 3~5h；The temperature for vacuumizing distillation
Degree is 95~140 DEG C, and preferably 100~120 DEG C, the time is 6~9h, and vacuum degree is -0.01~-0.1MPa.
Preferably, in the step (2), the anhydrous sodium polysulfide and the γ-two (polyethylene glycol of chloropropyl ethyoxyl
Single propyl ether base) silane, the catalyst A, the catalyst B molar ratio be (1.2~1.5): 1:(0.2~0.3): (0.1
~0.2), preferably 1.3:1:0.25:0.15.The protonic solvent is dehydrated alcohol or acetic acid.
Preferably, in the step (3), the volume ratio of the ethyl acetate and the petroleum ether is (1~2): 1.It is described
The temperature of cooling crystallization is -15~-5 DEG C, and the time is 10~20h.
The preparation method of above-mentioned silane coupler containing sulfur, the γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base)
The preparation method of silane includes the following steps:
Under nitrogen protection, γ-chloropropyl trichloro-silane, polyethyleneglycol propyl ether are mixed and is carried out with dehydrated alcohol
Reaction, is made the γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane.
Preferably, the temperature of the reaction is 90~120 DEG C, preferably 100~110, time of reaction is 2~4h, preferably
2.5~3.5h.
The second aspect of the present invention provides the sulfuric silane idol that the preparation method of above-mentioned silane coupler containing sulfur is prepared
Join agent.
Above-mentioned technical proposal of the invention has the advantages that
1, the preparation method of silane coupler containing sulfur of the present invention, the preparation method is by anhydrous sodium polysulfide obtained
With γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane in catalyst rare earth neodymium organic compound and catalyst chlorination
It is reacted in the presence of object, silane coupler containing sulfur is made.On the one hand, reaction of the invention organises in catalyst rare earth neodymium
In the presence of closing object and chloride, reduces the probability for generating by-product, improve the receipts of target product silane coupler containing sulfur
Rate is computed, and yield of the present invention is 95~98%, in addition, silane coupler containing sulfur produced by the present invention is to polymeric matrix
Be modified as rubber chemicals in use, can less organic gas discharge, to reduce the gas of rubber product obtained
Porosity, simultaneously because in silane coupler containing sulfur molecular structure contain long-chain polyether group so that rubber obtained have it is higher
Melting temperature avoids the incipient scorch in advance of sizing material；On the other hand, by by target product silane coupler containing sulfur in ethyl acetate
Purification process is carried out with the in the mixed solvent of petroleum ether composition, improves the purity of product silane coupler containing sulfur.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.In addition, below
Technical characteristic involved in described different embodiments of the present invention as long as they do not conflict with each other can be mutual
In conjunction with.
Embodiment 1
The preparation method of silane coupler containing sulfur provided in this embodiment includes the following steps:
(1) preparation of γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane
Under nitrogen protection, by 212g (1mol) γ-chloropropyl trichloro-silane, 560g (2mol) polyethyleneglycol propyl ether
It is uniformly mixed with 58mL (1mol) dehydrated alcohol, 90 DEG C of reaction 4h is then heated to, through gas chromatographic detection γ-chloropropyl trichlorine
Silane and ethyl alcohol react completely, stop heating, after being cooled to 60 DEG C or less, through detecting, the pH value of reaction system is about 3, is added
Enter 5g sodium ethoxide, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-(polyethyleneglycol third of chloropropyl ethyoxyl two is made
Ether) silane；
(2) preparation of anhydrous sodium polysulfide
Weigh 10g sodium hydroxide and 15g sulphur, 200mL aqueous solvent be added, form reaction system, by this reaction system in
5h is reacted at a temperature of 100 DEG C, stops reaction, and near room temperature, and aqueous sodium polysulfide is made, the sodium polysulfide is water-soluble
Liquid air-distillation 5h at 70 DEG C carries out primary dewatering, then steams under conditions of vacuum degree is -0.01MPa, temperature is 140 DEG C
It evaporates 6h and carries out second dehydration, anhydrous sodium polysulfide is made；
(3) preparation of silane coupler containing sulfur
It takes anhydrous sodium polysulfide made from 1.3mol step (2) to be dissolved in stirring in 500mL acetic acid extremely to dissolve, and backward acetic acid
γ-chloropropyl ethyoxyl made from middle addition 0.25mol neodymium iso-octanate, 0.15mol aluminium diethyl monochloride and 1mol step (1)
Two (polyethyleneglycol propyl ether base) silane form reaction system, which are warming up to the reflux temperature of dehydrated alcohol simultaneously
It is maintained under the reflux temperature and reacts 5h, then stop reaction；
It will stop the reaction system after reacting and be down to room temperature, filtering retains filtrate, and the filtrate is concentrated, is dry, then
The volume ratio for being dissolved in ethyl acetate and petroleum ether is the in the mixed solvent of 1:1, and in -15 DEG C of cooling crystallization 20h, is filtered
Double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) propyl]-tetrasulfide of purifying, is computed, the yield of the product
It is 96%.
The H spectrum of the product is as follows: for1H-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 is detected through HPLC, double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) propyl]-made from the present embodiment
The purity of tetrasulfide is 95%.
Embodiment 2
The preparation method of silane coupler containing sulfur provided in this embodiment includes the following steps:
(1) preparation of γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane
Under nitrogen protection, by 212g (1mol) γ-chloropropyl trichloro-silane, 560g (2mol) polyethyleneglycol propyl ether
It is uniformly mixed with 58mL (1mol) dehydrated alcohol, 120 DEG C of reaction 2h is then heated to, through gas chromatographic detection γ-chloropropyl three
Chlorosilane and ethyl alcohol react completely, stop heating, and after being cooled to 60 DEG C or less, through detecting, the pH value of reaction system is about 3,
5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-two (polyethylene glycol of chloropropyl ethyoxyl is made
Single propyl ether base) silane；
(2) preparation of anhydrous sodium polysulfide
Weigh 10g sodium hydroxide and 9g sulphur, 200mL aqueous solvent be added, form reaction system, by this reaction system in
3h is reacted at a temperature of 125 DEG C, stops reaction, and near room temperature, and aqueous sodium polysulfide is made, the sodium polysulfide is water-soluble
Liquid air-distillation 3h at 70 DEG C carries out primary dewatering, then distills under conditions of vacuum degree is -0.1MPa, temperature is 95 DEG C
9h carries out second dehydration, and anhydrous sodium polysulfide is made；
(3) preparation of silane coupler containing sulfur
It takes anhydrous sodium polysulfide made from 1.4mol step (2) to be dissolved in stirring in 500mL acetic acid extremely to dissolve, and backward acetic acid
γ-chloropropyl ethyoxyl made from middle addition 0.25mol neodymium iso-octanate, 0.15mol aluminium diethyl monochloride and 1mol step (1)
Two (polyethyleneglycol propyl ether base) silane form reaction system, which are warming up to the reflux temperature of dehydrated alcohol simultaneously
It is maintained under the reflux temperature and reacts 6h, then stop reaction；
It will stop the reaction system after reacting and be down to room temperature, filtering retains filtrate, and the filtrate is concentrated, is dry, then
The volume ratio for being dissolved in ethyl acetate and petroleum ether is the in the mixed solvent of 2:1, and in -5 DEG C of cooling crystallization 10h, filters pure
Double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) the propyl]-tetrasulfide changed, is computed, the yield of the product is
98%.
The H spectrum of the product is as follows: for1H-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 is detected through HPLC, double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) propyl]-made from the present embodiment
The purity of tetrasulfide is 96%.
Embodiment 3
The preparation method of silane coupler containing sulfur provided in this embodiment includes the following steps:
(1) preparation of γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane
Under nitrogen protection, by 212g (1mol) γ-chloropropyl trichloro-silane, 560g (2mol) polyethyleneglycol propyl ether
It is uniformly mixed with 58mL (1mol) dehydrated alcohol, 100 DEG C of reaction 3.5h is then heated to, through gas chromatographic detection γ-chloropropyl
Trichlorosilane and ethyl alcohol react completely, stop heating, after being cooled to 50 DEG C or less, through detecting, the pH value of reaction system is about
3,5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-chloropropyl ethyoxyl two (poly- second two is made
Alcohol list propyl ether base) silane；
(2) preparation of anhydrous sodium polysulfide
Weigh 10g sodium hydroxide and 10g sulphur, 200mL aqueous solvent be added, form reaction system, by this reaction system in
4h is reacted at a temperature of 110 DEG C, stops reaction, and near room temperature, and aqueous sodium polysulfide is made, the sodium polysulfide is water-soluble
Liquid air-distillation 4h at 85 DEG C carries out primary dewatering, then steams under conditions of vacuum degree is -0.05MPa, temperature is 100 DEG C
It evaporates 8h and carries out second dehydration, anhydrous sodium polysulfide is made；
(3) preparation of silane coupler containing sulfur
It takes anhydrous sodium polysulfide made from 1.5mol step (2) to be dissolved in stirring in 500mL dehydrated alcohol extremely to dissolve, and it is backward
γ-chloropropyl made from addition 0.2mol neodymium naphthenate, 0.2mol aluminium diethyl monochloride and 1mol step (1) in dehydrated alcohol
Ethyoxyl two (polyethyleneglycol propyl ether base) silane forms reaction system, which is warming up to the reflux of dehydrated alcohol
Temperature is simultaneously maintained under the reflux temperature and reacts 7h, then stops reaction；
It will stop the reaction system after reacting and be down to room temperature, filtering retains filtrate, and the filtrate is concentrated, is dry, then
The volume ratio for being dissolved in ethyl acetate and petroleum ether is the in the mixed solvent of 1:2, and in -10 DEG C of cooling crystallization 17h, is filtered
Double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) propyl]-tetrasulfide of purifying, is computed, the yield of the product
It is 97%.
The H spectrum of the product is as follows: for1H-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 is detected through HPLC, double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) propyl]-made from the present embodiment
The purity of tetrasulfide is 97%.
Embodiment 4
The preparation method of silane coupler containing sulfur provided in this embodiment includes the following steps:
(1) preparation of γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane
Under nitrogen protection, by 212g (1mol) γ-chloropropyl trichloro-silane, 560g (2mol) polyethyleneglycol propyl ether
It is uniformly mixed with 58mL (1mol) dehydrated alcohol, 110 DEG C of reaction 2.5h is then heated to, through gas chromatographic detection γ-chloropropyl
Trichlorosilane and ethyl alcohol react completely, stop heating, after being cooled to 50 DEG C or less, through detecting, the pH value of reaction system is about
3,5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-chloropropyl ethyoxyl two (poly- second two is made
Alcohol list propyl ether base) silane；
(2) preparation of anhydrous sodium polysulfide
Weigh 10g sodium hydroxide and 13g sulphur, 200mL aqueous solvent be added, form reaction system, by this reaction system in
4.5h is reacted at a temperature of 120 DEG C, is stopped reaction, and near room temperature, aqueous sodium polysulfide is made, by the sodium polysulfide water
Solution air-distillation 5h at 75 DEG C carries out primary dewatering, then under conditions of vacuum degree is -0.04MPa, temperature is 120 DEG C
It distills 7h and carries out second dehydration, anhydrous sodium polysulfide is made；
(3) preparation of silane coupler containing sulfur
It takes anhydrous sodium polysulfide made from 1.2mol step (2) to be dissolved in stirring in 500mL dehydrated alcohol extremely to dissolve, and it is backward
γ-chloropropyl made from addition 0.3mol neodymium naphthenate, 0.1mol aluminium diethyl monochloride and 1mol step (1) in dehydrated alcohol
Ethyoxyl two (polyethyleneglycol propyl ether base) silane forms reaction system, which is warming up to the reflux of dehydrated alcohol
Temperature is simultaneously maintained under the reflux temperature and reacts 4.5h, then stops reaction；
It will stop the reaction system after reacting and be down to room temperature, filtering retains filtrate, and the filtrate is concentrated, is dry, then
The volume ratio for being dissolved in ethyl acetate and petroleum ether is the in the mixed solvent of 4:1, and in -12 DEG C of cooling crystallization 12h, is filtered
Double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) propyl]-tetrasulfide of purifying, is computed, the yield of the product
It is 96%.
The H spectrum of the product is as follows: for1H-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 is detected through HPLC, double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) propyl]-made from the present embodiment
The purity of tetrasulfide is 95%.
Comparative example 1
The preparation method for the silane coupler containing sulfur that this comparative example provides includes the following steps:
(1) preparation of γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane
Under nitrogen protection, by 212g (1mol) γ-chloropropyl trichloro-silane, 560g (2mol) polyethyleneglycol propyl ether
It is uniformly mixed with 58mL (1mol) dehydrated alcohol, 90 DEG C of reaction 3.0h is then heated to, through gas chromatographic detection γ-chloropropyl three
Chlorosilane and ethyl alcohol react completely, stop heating, and after being cooled to 50 DEG C or less, through detecting, the pH value of reaction system is about 3,
5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-two (polyethylene glycol of chloropropyl ethyoxyl is made
Single propyl ether base) silane；
(2) preparation of silane coupler containing sulfur
168.04g (1mol) is vulcanized into sodium hydrate (Na2S·5H2O it) is mixed with 128g (4mol) sulphur powder, and in 150r/
90 DEG C are warming up under the revolving speed stirring of min, and reacts 2.6h at this temperature, obtains aqueous sodium polysulfide；
The temperature of above-mentioned aqueous sodium polysulfide is down to 3 DEG C, it is 8 that disodium hydrogen phosphate, which is added, and adjusts the PH of reaction system,
It is eventually adding 1.3mol γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and 320mL ethyl alcohol, ethyl alcohol is heated to and returns
Stream, and 3.0h is reacted under this reflux temperature, gas chromatographic detection reaction terminates, and reaction system is down to room temperature, filtering retains
Filtrate simultaneously carries out liquid separation, by organic layer concentration, drying, obtains product pair-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon)
Propyl]-tetrasulfide, it is computed, the yield of the product is 65%.
The H spectrum of the product is as follows: for1H-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-)。
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of silane coupler containing sulfur, which comprises the steps of:
(1) sodium hydroxide and sulphur are reacted obtained aqueous sodium polysulfide in water, by the aqueous sodium polysulfide
Primary dewatering under the conditions of air-distillation then carries out second dehydration in vacuumizing, anhydrous sodium polysulfide is made under distillation condition；
(2) anhydrous sodium polysulfide made from the step (1) is dissolved in protonic solvent, catalyst A and catalyst B is added,
γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane is then added and forms reaction system and in the protonic solvent
Reflux temperature under react 4.5~7h, stop reaction；
(3) reaction system after reacting will be stopped in the step (2) and is down to room temperature, filtering retains filtrate, and the filtrate is dense
Contracting, drying, the volume ratio for being then dissolved in ethyl acetate and petroleum ether is (1~4): the in the mixed solvent of (1~2), cooling analysis
Crystalline substance, the silane coupler containing sulfur for filtering to purify；
Wherein, the catalyst A is rare earth neodymium organic compound, and the catalyst B is chloride.
2. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that
The rare earth neodymium organic compound is neodymium naphthenate or neodymium iso-octanate；
The chloride is aluminium diethyl monochloride.
3. the preparation method of silane coupler containing sulfur according to claim 1 or 2, which is characterized in that the step (1)
In, the mass ratio of the sodium hydroxide and the sulphur is 1:(0.9~1.5).
4. the preparation method of silane coupler containing sulfur according to claim 3, which is characterized in that in the step (1), institute
The temperature for stating reaction is 100~125 DEG C, and the time of reaction is 3~5h；The temperature of the air-distillation is 70~90 DEG C, the time
For 3~5h；The temperature for vacuumizing distillation is 95~140 DEG C, and the time is 6~9h, and vacuum degree is -0.01~-0.1MPa.
5. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that in the step (2), institute
State anhydrous sodium polysulfide and the γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane, the catalyst A, described
The molar ratio of catalyst B is (1.2~1.5): 1:(0.2~0.3): (0.1~0.2).
6. the preparation method of silane coupler containing sulfur according to claim 5, which is characterized in that the protonic solvent is
Dehydrated alcohol or acetic acid.
7. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that in the step (3), institute
The volume ratio for stating ethyl acetate and the petroleum ether is (1~2): 1.
8. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that in the step (3), institute
The temperature for stating cooling crystallization is -15~-5 DEG C, and the time is 10~20h.
9. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that the γ-chloropropyl second
The preparation method of oxygroup two (polyethyleneglycol propyl ether base) silane includes the following steps:
Under nitrogen protection, γ-chloropropyl trichloro-silane, polyethyleneglycol propyl ether are mixed with dehydrated alcohol and is carried out anti-
It answers, the γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane is made；
Wherein, the temperature of the reaction is 90~120 DEG C, and the time of reaction is 2~4h.
10. a kind of sulfur-bearing silicon that the preparation method by silane coupler containing sulfur according to any one of claims 1 to 9 is prepared
Alkane coupling agent.
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| CN111635428A (en) * | 2020-07-28 | 2020-09-08 | 荆州市江汉精细化工有限公司 | Preparation method of sulfur-containing silane coupling agent containing long-chain alkoxy |
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