CN1544438A - Double-[3-( triethoxy)silicon propyl]tetrasulfide preparation method - Google Patents
Double-[3-( triethoxy)silicon propyl]tetrasulfide preparation method Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims description 15
- 239000010703 silicon Substances 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 40
- 239000011593 sulfur Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 37
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 31
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 29
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 25
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 22
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013067 intermediate product Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- -1 alkoxy sodium Chemical compound 0.000 claims description 10
- 238000001308 synthesis method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 239000005077 polysulfide Substances 0.000 description 13
- 229920001021 polysulfide Polymers 0.000 description 12
- 150000008117 polysulfides Polymers 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
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- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
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- 125000004436 sodium atom Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Abstract
A process for preparing bis-(3-[triethoxy silyl propyl]-tetrasulfide by using waterless sodium sulfide, sulfur and chloropropyl triethoxysilane as raw material, sodium as catalyst, ethanol as reaction medium by the mole ratio of sodium sulfide : sulfur : chloropropyl triethoxysilane = 1:3:2:(0.10-0.30) through the steps of, synthesizing sodium polysulfide intermediate product from sodium sulfide and sulfur at the presence of sodium as catalyst and with anhydrous alcohol neutralization and nitrogen protection, dropping chloropropyl triethoxysilane into the reaction solution in the previous step, thus bis-(3-[triethoxy silyl propyl]-tetrasulfide is synthesized, and the finished product is obtained through post-treatment.
Description
Technical Field
The invention relates to a preparation method of a rubber additive, in particular to a preparation method of bis- [3- (triethoxy) silicon propyl]tetrasulfide, and the product belongs to fine chemical products.
Background
Bis- [3- (triethoxy) silylpropyl]tetrasulfide, commercial name Si-69, chemical structure:
(C2H5O)3Si(CH2)3-S4-(CH2)3Si(OH5C2)3
the multifunctional silane coupling agent can be used as a coupling agent, a softening agent and a reinforcing agent in rubber, and has the functions of improving the surface activity of white carbon black and carbon black, enhancing the combination of the rubber and an inorganic filler, and improving the strength, the tear resistance, the wear resistance, the tensile fatigue resistance and the elasticity of a rubber material. The Si-69-containing tyre additive is widely applied to rubber products, is an essential additive for automobile tyres in particular, and the automobile tyres added with Si-69 abroad are called environment-friendly green tyres.
There are three current methods for preparing bis- [3- (triethoxy) silylpropyl]tetrasulfide:
1) based on polysulfides, with alkoxysilanes to give
See U.S. Pat. Nos. 3,978,103(1976.8.31) and 3,842,111(1974.10.15) for descriptions of polysulfides Me2SxReacting with alkoxy silane to generate bis- [3- (triethoxy) silicon propyl group]Tetrasulfide, wherein X is 1-6, Me represents sodium, potassium, ammonium, barium or chlorine.
The common polysulfide is sodium polysulfide, which is an existing product, and the production method is that sodium sulfide reacts with sulfur in aqueous solution at 85-95 ℃ for 2.5 hours (see inorganic salt industry handbook, chemical industry publisher) and then is dehydrated into anhydrous sodium polysulfide product. Since sodium polysulfide is unstable and easily decomposed during dehydration, it is difficult to prepare anhydrous sodium polysulfide products.
2) Reacting anhydrous hydrosulfide as base material with alkoxy silane to produce
See US 4,507,490 (1985.5.26). As the current world has no anhydrous hydrosulfide industrial products (only reagents, price is 350 yuan to 375 yuan/g, 10 months in 2003), only the hydrous hydrosulfide can be used as a reaction base material, such as sodium hydrosulfide, potassium, ammonium, zinc and the like, the bound water in the molecule is removed by a physical method, and then the reaction with the alkoxy silane is carried out. Because the dehydration of the aqueous sodium hydrosulfide is very difficult, the quality and the conversion rate of the final product can not meet the requirements.
3) The anhydrous sodium sulfide is used as a reaction base material to react with gamma-chloropropyltriethoxysilane and the like to generate
See the report on pages 538-540 of "Synthesis and application of bis- [3- (triethoxy) silicopropyl tetrasulfide" on volume 18, 9 of "Fine chemistry" 2001. Synthesizing bis- [3- (triethoxy) silicon propyl]tetrasulfide by adopting gamma-chloropropyltriethoxysilane, sodium, sulfur and sodium sulfide, wherein the reaction ratio of the raw materials (unit; gram) is as follows:
sodium sulfide, sulfur, gamma-chloropropyltriethoxysilane, sodium 15 (15-18), 72 (2.5-3)
The reduced stoichiometric ratio (moles):
sodium sulfide, sulfur,gamma-chloropropyltriethoxysilane, sodium 1.28, (3.125-3.75) 2, (0.725-0.87)
The synthesis is completed by one step, no independent sodium polysulfide synthesis step is arranged in the middle, and the sulfur content in the finally synthesized bis- [3- (triethoxy) silicon propyl]tetrasulfide is 22.3 percent.
In summary, in both of the former two U.S. patents, polysulfide is used as a base material to react with alkoxysilane to synthesize bis- [3- (triethoxy) silylpropyl]tetrasulfide, and even though the latter U.S. patent uses anhydrous hydrosulfide as a base material to react with alkoxysilane, sodium hydrosulfide actually reacts with sulfur and metallic sodium in ethanol to generate sodium polysulfide, and then reacts with alkoxysilane to generate sodium polysulfide. This is because sodium hydrosulfide is readily soluble in ethanol and reacts very readily with sulfur in ethanol to form sodium polysulfide (see inorganic chemistry series, first volume). Therefore, it has been conventionally thought that sodium sulfide does not have a hydrogen atom in its molecular structure and is insoluble in ethanol (inorganic chemistry series, first volume), so that it is difficult to produce sodium polysulfide by addition reaction with sulfur in an alcohol solvent, and bis- [3- (triethoxy) silylpropyl]tetrasulfide cannot be synthesized by reaction of sodium sulfide with sulfur in ethanol and then with alkoxysilane.
The third preparation method uses sodium sulfide as a reaction base material to synthesize bis- [3- (triethoxy) silicon propyl]tetrasulfide, which has breakthrough in theory and practice, but the conversion rate and the quality stability of the product, especially the sulfur content, are still required to be further improved.
Due to the rapid development of industry, the requirements on rubber products are higher and higher, especially the requirements on automobile tires for mass construction and environment and use of highways are higher and higher, and a bis- [3- (triethoxy) silicon propyl]tetrasulfide product with higher sulfur content is needed to meet the development requirements of domestic and international markets, so the invention aims to provide a synthesis method of a bis- [3- (triethoxy) silicon propyl]tetrasulfide with high conversion rate, stable quality and over 23 percent of sulfur content.
Disclosure of Invention
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing bis- [3- (triethoxy) silicon propyl]tetrasulfide takes anhydrous sodium sulfide, sulfur and chloropropyl triethoxysilane as raw materials, sodium is used as a catalyst, and ethanol is used as a reaction medium;
the stoichiometric ratio (mole number) of each raw material and the catalyst is as follows:
sodium sulfide, sulfur, gamma-chloropropyltriethoxysilane, sodium 1: 3: 2 (0.10-0.30)
The synthesis method comprises the following steps:
(1) adding anhydrous sodium sulfide according to the mole ratio under the protection of anhydrous ethanol and nitrogen, stirring at normal temperature, gradually adding sodium metal, continuously stirring, removing heat generated by reaction and waste gas generated, heating to 45-85 ℃, adding dried sulfur, and reacting for 2-4 hours to generate a sodium polysulfide intermediate product;
the reaction formula is as follows:
(2) keeping the temperature of the solution generated in the last step at 45-70 ℃, dropwise adding gamma-chloropropyltriethoxysilane in a metering manner, raising thetemperature of the reaction solution to 70-75 ℃, and reacting for 3-6 hours;
the reaction formula is as follows:
(3) and then carrying out post-treatment to obtain a finished product.
The relevant contents and variations of the above technical solution are explained as follows:
1. in the second step, the dripped gamma-chloropropyltriethoxysilane is neutral or weakly alkaline, and the pH value is 6-9. Specifically, the pH value of the dropwise added gamma-chloropropyltriethoxysilane can be adjusted to 6-9 by adopting sodium alkoxide.
2. The dropping time of the gamma-chloropropyltriethoxysilane in the second step is 30-60 minutes.
3. In the above scheme, N is used for preparing sodium polysulfide2The protection is to prevent the sodium polysulfide from being oxidized by air. In addition, the raw materials, catalysts, apparatus and N used in the entire preparation2It is necessary to remove all water and the whole reaction is carried out under anhydrous conditions.
4. The post-treatment in the third step refers to conventional processes and means such as standing, cooling, filtering, distilling, refining and the like.
The mechanism of the invention is as follows: adopts a two-step synthesis scheme, wherein in the first step, sodium metal is used as a catalyst of the polysulfide reaction and an anti-crosslinking agent (the crosslinking and solidification of the whole reaction system are prevented during the second step of synthesis), so that sodium sulfide and sulfur can well perform the polysulfide reaction in ethanol to generate sodium polysulfide, and the reaction is carried out in N2Under protection. Secondly, the generated sodium polysulfide and the metallic sodium catalyst in the solution are reacted with gamma-chloropropyltriethoxysilane to synthesize the bis- [3- (triethoxy) silicopropyl group]Tetrasulfide.
The essential difference of the invention compared with the background art is that:
1. unlike the comparative materials and methods described in the background of the invention in U.S. Pat. Nos. 3,978,103(1976.8.31) and 3,842,111 (1974.10.15).
2. Unlike the comparative feedstock of US 4,507,490(1985.5.26) introduced in the background art, it is noteworthy that: the mechanism of participation of metallic sodium is also different.
The synthetic reaction formula of taking sodium sulfide as a base material is as follows:
the synthetic reaction formula of taking sodium hydrogen sulfide as a base material is as follows:
the two synthetic reactions are represented by formula (1) as formula Na2S +3S and the left NaHS +3S + Na of formula (2) both form sodium polysulfide (Na)2S4) The synthesis reaction is actually gamma-chloropropyltriethoxysilane and sodium polysulfide (Na)2S4) Reaction to produce bis- [3- (triethoxy) silicopropyl]Tetrasulfide. Na in reaction formula (1) based on sodium sulfide2S +3S to Na2S4Sodium is not required to participate in the synthesis reaction, and the added metal sodium is only a catalyst and is not a raw material. When sodium hydrosulfide is usedas the base material, NaHS +3S generates Na2S4One sodium atom is not available, so sodium is also used as a reaction raw material. When sodium sulfide is used as a base material, sodium is not a raw material required for reaction, but if sodium does not exist, the whole reaction system is easy to crosslink and solidify when sodium sulfide and sulfur are synthesized with alkoxy silane after polysulfide reaction, so that the synthesis failure is interrupted. And the metallic sodium is adopted as an additive to catalyze the sodium sulfide and the polysulfide reaction of sulfur, so that the crosslinking and solidification phenomena of the system can not occur.
According to the stoichiometric ratio of the reaction formula (1), the molar ratio of the reaction is as follows:
sodium sulfide, sulfur, gamma-chloropropyltriethoxysilane, sodium 1: 3: 2, (0.10-0.40) (3)
And the reaction mole number of the reaction formula (2) is:
sodium hydrosulfide, sulfur, gamma-chloropropyltriethoxysilane, sodium 1: 3: 2: 1 (4)
The above conclusion can also be drawn from a comparison of formula (3) and formula (4).
3. Compared with the third preparation method introduced in the background art, the method is characterized in that ① is prepared by the prior art not by a sodium polysulfide method and not recorded by a polysulfide reaction step, ② is different in stoichiometric ratio mole number among all compounds participating in the reaction, especially metal sodium is used as a catalyst for the polysulfide reaction in the first step, the proportioning dosage is much less than that in the third method and is only 13.8-46.0%, ③ is prepared by the prior art by a one-step synthesis method, the method is prepared by a two-step synthesis method, the process conditions are different, ④ is different in requirements on temperature control and time in the reaction process, and different temperature and time control measures are adopted in the two-step synthesis reaction according to different stages and different requirements, so that the reaction can be smoothly carried out according to the expected target.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention can obtain the bis- [3- (triethoxy) silicon propyl]tetrasulfide product with higher sulfur content, and the sulfur content is more than 23.6 percent. The third method in the background art introduces sodium sulfide as base material to produce bis- [3- (triethoxy) silicon propyl]tetrasulfide, and the sulfur content in the product is 22.3%. The sulfur content of the product produced with industrial sodium hydrosulfide (water content 30%) is below 22%. At present, the standard of the sulfur content of the product in the international market is more than 22 percent.
2. The invention can improve the product conversion rate to 97-99%, while the third method in the background art adopts sodium sulfide as base material to produce bis- [3- (triethoxy) silicon propyl]tetrasulfide, which can only reach 96%. The method has practical significance for industrial production.
3. If the mixing proportion of sulfur is increased, the high-sulfur bis- [3- (triethoxy) silicon propyl]sulfide with the sulfur content of more than 24 percent can be prepared, and compared with the prior art, the method is a new synthesis method.
4. The product of the invention has stable quality and meets the requirements of the international market.
Drawings
FIG. 1is a Mass spectrum of bis- [3- (triethoxy) silicopropyl]tetrasulfide, a testing instrument, High Resolution Mass Spectrometer GCT-TOF, Micromass Co. of U.K, Resolution>5000, according to a first embodiment of the present invention;
FIG. 2 is a mass spectrum of high-thio bis- [3- (triethoxy) silicopropyl]sulfide according to example III of the present invention. The instrument for testing, High Resolution Mass Spectrometry GCT-TOF, Micromass Co. of U.K, Resolution>5000. Molar mass of bis- [3- (triethoxy) silicopropyl]sulfide: dithio, 474.9; trithio, 507.0; tetrathio, 539.1; pentathio, 571.2; hexathio, 603.3.
Detailed Description
The invention is further described below with reference to the following examples:
the first embodiment is as follows:
the first step is the synthesis of sodium polysulfide. A2L four-mouth flask is adopted, one mouth is used for reflux condensation, one mouth is used for feeding, one mouth is used for stirring, and one mouth is used for N2A gas inlet or a waste gas outlet and a thermometer socket. The operation steps are as follows: 2L four-necked flask was charged with N2Adding 800ml of absolute ethyl alcohol into the mixture, and adding 85.9g of 92% Na at normal temperature2S (1.0moles), stirred for 30 minutes. Then 5.75g Na (0.25moles) was added and the reaction stirred for 30 minutes, cooling water was turned on to remove the heat of reaction and the temperature was kept below 30 ℃ to form a pale yellow emulsion. The temperature was raised to 55 ℃ and 96.4g (3.0moles) of dried sulfur was added to the reaction flask in one portion to give a reddish brown almost transparent liquid, which was allowed to react at a constant temperature for 3 hours to give a muddy liquid having an earthy yellow color.
And the second step of synthesizing bis- [3- (triethoxy) silicon propyl]tetrasulfide. Gradually raising the temperature of the system to 70-75 ℃, adjusting the pH value of 506g of 95% gamma-chloropropyltriethoxysilane (2.0moles) to be equal to 8 by adopting sodium alkoxide, metering and dropwise adding into the first-step reaction system for 45 minutes, wherein the liquid is reddish brown after the addition is finished, the liquid is lightened after the reaction is carried out for 30 minutes, the liquid is finally yellowish from reddish brown to orange, and the reaction is finished for 4 hours.
And thirdly, post-treatment. After the reaction, the mixture was cooled, precipitated, and vacuum-filtered, the clear solution was further distilled, and ethanol was recovered and reused, to obtain 531.9g of yellow to orange-red bis- [3- (triethoxy) silylpropyl]tetrasulfide, which was 98.5% of theoretical.
The product was analyzed by infrared and mass spectrometry as tetrathiobis triethoxysilylpropyl compound, and had a molecular weight of 540, a refractive index of 1.4918 at 21 ℃ as measured by a digital abbe refractometer, and a sulfur content of 23.6%, as shown in FIG. 1.
Example two:
400ml of ethanol was placed in a 1L four-necked flask, 43g (92%), 2.5g and 49.5g of sodium sulfide, metallic sodium and sulfur were added, respectively, to the solution, and after 2 hours of polysulfide reaction at 60 ℃, 243g (95%) of gamma-chloropropyltriethoxysilane having a pH of 6 was added to the solution, and the reaction was carried out at 75 ℃ for 3 hours to obtain 267g of bis- [3- (triethoxy) silylpropyl]tetrasulfide, with a yield of 98.9% and a sulfur content of the product of 24.4%.
Example three:
400ml of ethanol was placed in a 1L four-necked flask, 43g (92%), 4.0g and 50.8g of sodium sulfide, metallic sodium and sulfur were added, respectively, and after 3 hours of a polysulfide reaction at 50 ℃ was carried out, 243g (95%) of gamma-chloropropyltriethoxysilane having a pH of 10 was added to the solution and reacted at 70 ℃ for 5 hours to obtain 265g of bis- [3- (triethoxy) silylpropyl]tetrasulfide with a yield of 98.3% and a product of bis- [3- (triethoxy) silylpropyl]tetrasulfide with a sulfur content of 25.6%, as shown in FIG. 2.
Claims (4)
1. A method for preparing bis- [3- (triethoxy) silicon propyl]tetrasulfide is characterized in that: anhydrous sodium sulfide, sulfur and gamma-chloropropyl triethoxysilane are used as raw materials, sodium is used as a catalyst, and ethanol is used as a reaction medium;
the stoichiometric ratio mole number of each raw material and the catalyst is as follows:
sodium sulfide, sulfur, gamma-chloropropyltriethoxysilane, sodium 1: 3: 2 (0.10-0.40)
The synthesis method comprises the following steps:
(1) adding anhydrous sodium sulfide according to the mole ratio under the protection of anhydrous ethanol and nitrogen, stirring at normal temperature, adding metal sodium, continuously stirring, removing heat and waste gas generated by reaction, heating to 45-85 ℃, adding dried sulfur, and reacting for 2-4 hours to generate a sodium polysulfide intermediate product;
the reaction formula is as follows:
(2) controlling the temperature of the reaction solution synthesized in the last step at 70-75 ℃, simultaneously dropwise adding gamma-chloropropyltriethoxysilane in a metering manner, and then continuously reacting for 3-6 hours;
the reaction formula is as follows:
(3) and then carrying out post-treatment to obtain a finished product.
2. The process for producing bis- [3- (triethoxy) silylpropyl]tetrasulfide according to claim 1, characterized in that: in the second step, the dripped gamma-chloropropyltriethoxysilane is neutral or alkaline, and the pH value is 6-9.
3. The process for producing bis- [3- (triethoxy) silylpropyl]tetrasulfide according to claim 2, characterized in that: and (3) regulating the pH value of the dropwise added gamma-chloropropyltriethoxysilane to 6-9 by adopting alkoxy sodium.
4. The process for producing bis- [3- (triethoxy) silylpropyl]tetrasulfide according to claim 1, characterized in that: the dropping time of the gamma-chloropropyltriethoxysilane in the second step is 30-60 minutes.
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| CN 200310106304 Expired - Lifetime CN1275972C (en) | 2003-11-13 | 2003-11-13 | Double-[3-( triethoxy)silicon propyl]tetrasulfide preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304476C (en) * | 2005-04-21 | 2007-03-14 | 上海交通大学 | Method for preparing tribasic ethylene propylene rubber/polypropylene thermoplastic elastomer |
| CN104277066A (en) * | 2014-09-26 | 2015-01-14 | 山东大学 | Bis-(alpha-trialkoxysilylmethyl)tetrasulfide, and preparation method and application thereof |
| CN111234315A (en) * | 2020-02-25 | 2020-06-05 | 南京曙光精细化工有限公司 | Sulfur-containing silane coupling agent releasing low-level VOC in use and preparation method thereof |
| CN116478204A (en) * | 2023-04-27 | 2023-07-25 | 唐山三孚新材料有限公司 | Preparation method of bis- [ triethoxysilylpropyl ] -tetrasulfide |
-
2003
- 2003-11-13 CN CN 200310106304 patent/CN1275972C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304476C (en) * | 2005-04-21 | 2007-03-14 | 上海交通大学 | Method for preparing tribasic ethylene propylene rubber/polypropylene thermoplastic elastomer |
| CN104277066A (en) * | 2014-09-26 | 2015-01-14 | 山东大学 | Bis-(alpha-trialkoxysilylmethyl)tetrasulfide, and preparation method and application thereof |
| CN111234315A (en) * | 2020-02-25 | 2020-06-05 | 南京曙光精细化工有限公司 | Sulfur-containing silane coupling agent releasing low-level VOC in use and preparation method thereof |
| CN116478204A (en) * | 2023-04-27 | 2023-07-25 | 唐山三孚新材料有限公司 | Preparation method of bis- [ triethoxysilylpropyl ] -tetrasulfide |
| CN116478204B (en) * | 2023-04-27 | 2024-10-15 | 唐山三孚新材料有限公司 | Preparation method of bis- [ triethoxysilylpropyl ] -tetrasulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1275972C (en) | 2006-09-20 |
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