CN109021223A - 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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- CN109021223A CN109021223A CN201810984717.2A CN201810984717A CN109021223A CN 109021223 A CN109021223 A CN 109021223A CN 201810984717 A CN201810984717 A CN 201810984717A CN 109021223 A CN109021223 A CN 109021223A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/328—Polymers modified by chemical after-treatment with inorganic compounds containing other elements
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Abstract
The present invention provides a kind of preparation methods of silane coupler containing sulfur, in the presence of temperature of the preparation method at 0~10 DEG C and unformed FeOOH through vulcanizing treatment, diisopropylcarbodiimide is added, the probability for generating by-product can be reduced, thus it can greatly reduce the progress of side reaction, it to be also beneficial to improve reaction yield, is computed, yield of the present invention is 93~96%.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, the incipient scorch in advance of sizing material is avoided.
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 work
The trend of industry development, the preparation of green tire mainly pass through two methods, first, being made by the structure for changing rubber itself
Standby green tire, such as the exploitation and application of solution polymerized butadiene styrene rubber；Second, former using the rubber that inorganic substances filling prepares tire
Material-polymer material matrix, tire made from the method have good low-rolling-resistance and an anti-slippery, inorganic substances with
The combination of polymer material matrix need to be used in combination with silane coupling agent, and silane coupling agent can be poly- in inorganic substances and organic polymer height
" molecular bridge " is erected between the interface of object, so that the material of two kinds of property great disparities is linked together the property for improving composite material
It can and increase 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
Aqueous sodium polysulfide is cooled to 60~65 DEG C, PH regulator is added, organic solvent and halogenated alkoxy silicon are added after stirring
Alkane is warming up to 75~90 DEG C and is reacted, after reaction by filtration of crude product, liquid separation, organic phase removing organic solvent, system
Obtain silane coupler containing sulfur.The coupling agent that above-mentioned preparation method is prepared, can be used for surface modifying inorganic particle and grafting
In the association response of polymer.But the yield of the silane coupler containing sulfur in above-mentioned technology needs to be further improved.In view of
How this improves the preparation method of existing silane coupler containing sulfur to improve its reaction yield, this is for this field
It is a technical problem urgently to be resolved for technical staff.
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) sulphur powder and vulcanization sodium hydrate are subjected at 80~95 DEG C 2.5~3h of reaction, it is water-soluble that sodium polysulfide is made
Liquid；
(2) temperature of aqueous sodium polysulfide made from step (1) is down to 0~10 DEG C, the nothing through vulcanizing treatment is added
FeOOH, the diisopropylcarbodiimide of being formed form reaction system, and it is 7 that PH regulator, which is added, and adjusts the PH of reaction system
~8, γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane then is added and protonic solvent is reacted, is made
Silane coupler containing sulfur；
Wherein, the γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and the vulcanization sodium hydrate,
The unformed FeOOH through vulcanizing treatment, the diisopropylcarbodiimide molar ratio be (1.1~1.4): 1:
(0.1~0.2): (0.5~1.0).
Preferably, in the step (2), the temperature of the reaction is the reflux temperature of the protonic solvent, described anti-
The time answered is 2~3h, preferably 2.5h.
Preferably, in the step (2), the protonic solvent is dehydrated alcohol or acetic acid.
Preferably, in the step (1), the molar ratio of the sulphur powder and the vulcanization sodium hydrate is (1~5): 1, it is excellent
It selects (2~4): 1.
Preferably, in the step (2), the PH regulator is sodium bicarbonate or disodium hydrogen phosphate.
Preferably, in the step (2), the γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane rubs
The ratio between the parts by volume of that part and the protonic solvent (1.1~1.4): (300~400), preferably (1.2~1.3): (320~
350)；The molar part and the parts by volume relationship are mol/mL.
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 with dehydrated alcohol and is gone forward side by side
Row 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 preparation method of above-mentioned silane coupler containing sulfur further includes to described pure to reaction system progress after reaction
The step of changing processing: being down to room temperature for reaction system, and filtering retains filtrate and carries out liquid separation, and organic layer is concentrated, is dry, and
The volume ratio for being dissolved in acetone and water afterwards is (1~3): the in the mixed solvent of (1~2), cooling crystallization, and that filters to purify contains
Polysulfur silane coupling agent.
The second aspect of the present invention provides the sulfuric silane that the preparation method of above-mentioned silane coupler containing sulfur is prepared
Coupling 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 first by more vulcanizations obtained
The temperature of sodium water solution is controlled at 0~10 DEG C, and unformed FeOOH through vulcanizing treatment, two are added at this temperature
Diisopropylcarbodiimide and PH regulator, the PH for adjusting solution is 7~8, and γ-chloropropyl ethyoxyl two (poly- second two is then added
Alcohol list propyl ether base) silane and protonic solvent reacted, silane coupler containing sulfur is made.Temperature of the present invention at 0~10 DEG C
In the presence of the unformed FeOOH through vulcanizing treatment, diisopropylcarbodiimide is added, generation by-product can be reduced
Probability, thus can greatly reduce the progress of side reaction, thus be also beneficial to improve reaction yield, be computed, the present invention receive
Rate is 93~96%.In addition, silane coupler containing sulfur produced by the present invention is helped as rubber being modified to polymeric matrix
Agent in use, can less organic gas discharge, to reduce the porosity of rubber product obtained, simultaneously because sulfur-bearing
Glue is avoided so that rubber obtained has higher melting temperature containing long-chain polyether group in silane coupling agent molecular structure
The incipient scorch in advance of material.
2, the preparation method of silane coupler containing sulfur of the present invention further includes to described after reaction to reaction
System carries out the step of purification process: reaction system being down to room temperature, filtering retains filtrate and carries out liquid separation, and organic layer is dense
Contracting, drying, the volume ratio for being then dissolved in acetone and water is (1~3): the in the mixed solvent of (1~2), cooling crystallization, filtering
The purity of product silane coupler containing sulfur can be improved by purification step in the silane coupler containing sulfur that must be purified.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this
Invention 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
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.This
Outside, technical characteristic involved in invention described below different embodiments is as long as they do not conflict with each other
It can be combined with each other.
In following embodiment of the present invention, the preparation method of the unformed FeOOH through vulcanizing treatment is；It will be without fixed
1:2 is mixed in molar ratio for type FeOOH and sulphur, is stirred to get the unformed FeOOH through vulcanizing treatment.
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 is uniformly mixed with 58mL (1mol) dehydrated alcohol, 90 DEG C of reaction 4h is then heated to, through gas chromatographic detection γ-chloropropyl
Trichlorosilane 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
3,5g 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 silane coupler containing sulfur
168.04g (1mol) is vulcanized into sodium hydrate (Na2S·5H2O it) is mixed with 32g (1mol) sulphur powder, and in 140r/
95 DEG C are warming up under the revolving speed stirring of min, and reacts 2.5h at this temperature, obtains aqueous sodium polysulfide；
The temperature of above-mentioned aqueous sodium polysulfide is down to 0 DEG C, unformed hydroxyl oxygen of the 0.1mol through vulcanizing treatment is added
Change iron and 1.0mol diisopropylcarbodiimide forms reaction system, NaHCO is then added3The PH for adjusting reaction system is 7, most
γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane made from 1.4mol step (1) is added afterwards and 300mL is anhydrous
Ethyl alcohol is heated to alcohol reflux, and reacts 2h under this reflux temperature, and gas chromatographic detection reaction terminates, and reaction system is dropped
To room temperature, filtering retains filtrate and carries out liquid separation, by organic layer concentration, drying, is then dissolved in the volume ratio of acetone and water
For the in the mixed solvent of 1:2, cooling crystallization, the double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) silicon) for filtering to purify
Propyl]-tetrasulfide, it is computed, the yield of the product 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 is uniformly mixed with 58mL (1mol) dehydrated alcohol, 120 DEG C of reaction 2h is then heated to, through gas chromatographic detection γ-chloropropyl
Trichlorosilane 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
3,5g 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 silane coupler containing sulfur
168.04g (1mol) is vulcanized into sodium hydrate (Na2S·5H2O it) is mixed with 160g (5mol) sulphur powder, and in 150r/
80 DEG C are warming up under the revolving speed stirring of min, and reacts 3.0h at this temperature, obtains aqueous sodium polysulfide；
The temperature of above-mentioned aqueous sodium polysulfide is down to 10 DEG C, unformed hydroxyl of the 0.2mol through vulcanizing treatment is added
Iron oxide and 0.5mol diisopropylcarbodiimide form reaction system, and disodium hydrogen phosphate is then added and adjusts reaction system
PH is 7, be eventually adding γ made from 1.1mol step (1)-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and
400mL acetic acid is heated to acetic acid reflux, and reacts 3h under this reflux temperature, and gas chromatographic detection reaction terminates, and will react
System is down to room temperature, and filtering retains filtrate and carries out liquid separation, by organic layer concentration, drying, is then dissolved in the body of acetone and water
Product is than the in the mixed solvent for 3:1, cooling crystallization, the double-[3- (ethyoxyl two (polyethyleneglycol propyl ether base) for filtering to purify
Silicon) propyl]-tetrasulfide, it is computed, the yield of the product is 94%.
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 is uniformly mixed with 58mL (1mol) dehydrated alcohol, 100 DEG C of reaction 2.5h is then heated to, through gas chromatographic detection γ-chlorine third
Base 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
It is 3,5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-(poly- second of chloropropyl ethyoxyl two is made
Glycol monopropyl ether base) silane；
(2) preparation of silane coupler containing sulfur
168.04g (1mol) is vulcanized into sodium hydrate (Na2S·5H2O it) is mixed with 64g (2mol) sulphur powder, and in 150r/
85 DEG C are warming up under the revolving speed stirring of min, and reacts 2.8h at this temperature, obtains aqueous sodium polysulfide；
The temperature of above-mentioned aqueous sodium polysulfide is down to 5 DEG C, unformed hydroxyl of the 0.15mol through vulcanizing treatment is added
Iron oxide and 0.8mol diisopropylcarbodiimide form reaction system, and disodium hydrogen phosphate is then added and adjusts reaction system
PH is 8, be eventually adding γ made from 1.2mol step (1)-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and
350mL ethyl alcohol is heated to alcohol reflux, and reacts 2.5h under this reflux temperature, and gas chromatographic detection reaction terminates, will be anti-
System is answered to be down to room temperature, filtering retains filtrate and simultaneously carries out liquid separation, by organic layer concentration, dry, is then dissolved in acetone and water
Volume ratio is the in the mixed solvent of 1:1.5, cooling crystallization, double-[the 3- ((polyethyleneglycol third of ethyoxyl two for filtering to purify
Ether) silicon) propyl]-tetrasulfide, it is computed, the yield of the product is 93%.
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 is uniformly mixed with 58mL (1mol) dehydrated alcohol, 110 DEG C of reaction 3.5h is then heated to, through gas chromatographic detection γ-chlorine third
Base 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
It is 3,5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-(poly- second of chloropropyl ethyoxyl two is made
Glycol monopropyl 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 8 DEG C, unformed hydroxyl of the 0.18mol through vulcanizing treatment is added
Iron oxide and 0.9mol diisopropylcarbodiimide form reaction system, and disodium hydrogen phosphate is then added and adjusts reaction system
PH is 8, be eventually adding γ made from 1.3mol step (1)-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and
320mL ethyl alcohol is heated to alcohol reflux, and reacts 2.5h under this reflux temperature, and gas chromatographic detection reaction terminates, will be anti-
System is answered to be down to room temperature, filtering retains filtrate and simultaneously carries out liquid separation, by organic layer concentration, dry, is then dissolved in acetone and water
Volume ratio is the in the mixed solvent of 2:1, cooling crystallization, double-[3- ((the polyethyleneglycol propyl ether of ethyoxyl two for filtering to purify
Base) silicon) propyl]-tetrasulfide, it is computed, the yield of the product 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 5
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 is uniformly mixed with 58mL (1mol) dehydrated alcohol, 90 DEG C of reaction 3.0h is then heated to, through gas chromatographic detection γ-chlorine third
Base 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
It is 3,5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-(poly- second of chloropropyl ethyoxyl two is made
Glycol monopropyl 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, unformed hydroxyl of the 0.18mol through vulcanizing treatment is added
Iron oxide and 0.9mol diisopropylcarbodiimide form reaction system, and disodium hydrogen phosphate is then added and adjusts reaction system
PH is 8, be eventually adding γ made from 1.3mol step (1)-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and
320mL ethyl alcohol is heated to alcohol reflux, and reacts 3.0h under this reflux temperature, and gas chromatographic detection reaction terminates, will be anti-
System is answered to be down to room temperature, filtering retains filtrate and simultaneously carries out liquid separation, by organic layer concentration, dry, is then dissolved in acetone and water
Volume ratio is the in the mixed solvent of 3:2, cooling crystallization, double-[3- ((the polyethyleneglycol propyl ether of ethyoxyl two for filtering to purify
Base) silicon) propyl]-tetrasulfide, it is computed, the yield of the product is 95%.
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%.
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 is uniformly mixed with 58mL (1mol) dehydrated alcohol, 90 DEG C of reaction 3.0h is then heated to, through gas chromatographic detection γ-chlorine third
Base 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
It is 3,5g sodium ethoxide is added, after stirring 30min, filtering, filtrate is concentrated under reduced pressure, and γ-(poly- second of chloropropyl ethyoxyl two is made
Glycol monopropyl 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, is heated to ethyl alcohol
Reflux, and 3.0h is reacted under this reflux temperature, gas chromatographic detection reaction terminates, and reaction system is down to room temperature, filtering is protected
Reserved 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.
For those of ordinary skill in the art, other various forms of changes can also be made on the basis of the above description
Change or changes.There is no necessity and possibility to exhaust all the enbodiments.And obvious change extended from this
Change or 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) sulphur powder and vulcanization sodium hydrate are subjected at 80~95 DEG C 2.5~3h of reaction, aqueous sodium polysulfide is made；
(2) temperature of aqueous sodium polysulfide made from step (1) is down to 0~10 DEG C, be added through the unformed of vulcanizing treatment
FeOOH, diisopropylcarbodiimide form reaction system, and it is 7~8 that PH regulator, which is added, and adjusts the PH of reaction system, and
γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane is added afterwards and protonic solvent is reacted, sulfur-bearing silicon is made
Alkane coupling agent；
Wherein, the γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and the vulcanization sodium hydrate, the warp
The unformed FeOOH of vulcanizing treatment, the molar ratio of the diisopropylcarbodiimide are (1.1~1.4): 1:(0.1~
0.2): (0.5~1.0).
2. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that in the step (2), institute
The temperature for stating reaction is the reflux temperature of the protonic solvent, and the time of the reaction is 2~3h.
3. the preparation method of silane coupler containing sulfur according to claim 1 or 2, which is characterized in that the step (2)
In, the protonic solvent is dehydrated alcohol or acetic acid.
4. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that in the step (1), institute
The molar ratio for stating sulphur powder and the vulcanization sodium hydrate is (1~5): 1.
5. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that in the step (2), institute
Stating PH regulator is sodium bicarbonate or disodium hydrogen phosphate.
6. the preparation method of silane coupler containing sulfur according to claim 5, which is characterized in that in the step (2), institute
State the molar part of γ-chloropropyl ethyoxyl two (polyethyleneglycol propyl ether base) silane and the ratio between the parts by volume of the protonic solvent
(1.1~1.4): (300~400)；The molar part and the parts by volume relationship are mol/mL.
7. 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.
8. the preparation method of silane coupler containing sulfur according to claim 7, which is characterized in that the temperature of the reaction is
90~120 DEG C, the time of reaction is 2~4h.
9. the preparation method of silane coupler containing sulfur according to claim 1, which is characterized in that further include to the reaction
After to reaction system carry out purification process the step of:
Reaction system is down to room temperature, filtering retains filtrate and carries out liquid separation, by organic layer concentration, drying, is then dissolved in third
The volume ratio of ketone and water is (1~3): the in the mixed solvent of (1~2), cooling crystallization, the sulfuric silane coupling for filtering to purify
Agent.
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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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