CN113461726A - Preparation method of sulfur-containing silane coupling agent - Google Patents
Preparation method of sulfur-containing silane coupling agent Download PDFInfo
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- CN113461726A CN113461726A CN202110816090.1A CN202110816090A CN113461726A CN 113461726 A CN113461726 A CN 113461726A CN 202110816090 A CN202110816090 A CN 202110816090A CN 113461726 A CN113461726 A CN 113461726A
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- sulfur
- silane coupling
- coupling agent
- containing silane
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 59
- 239000011593 sulfur Substances 0.000 title claims abstract description 59
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 30
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 28
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims abstract description 11
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 claims description 12
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004042 decolorization Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 9
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 abstract description 7
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- -1 organic cation compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002602 strong irritant Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/34—Polysulfides of sodium or potassium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The application provides a preparation method of a sulfur-containing silane coupling agent, in particular to a preparation method of sulfur-containing silane coupling agents Si69 and Si75, which comprises the steps of carrying out chemical reaction on sodium polysulfide solution, crown ether phase transfer catalysts and gamma-chloropropyltriethoxysilane to generate the sulfur-containing silane coupling agent, wherein the crown ether phase transfer catalysts are 18-crown-6 or 15-crown-5; the application adopts the crown ether phase transfer catalyst to improve the reaction rate and reduce the reaction temperature; the product does not contain tri-n-butylamine, so that potential safety hazards in the use process are avoided; the problem of overhigh heating decrement of the product is solved; the problem that the color of the product gradually becomes heavier along with the prolonging of the storage time of the product is solved; the produced wastewater does not contain ammonia nitrogen and has little pollution to the environment; the yield of the product is more than or equal to 98 percent, the content of impurities is less than or equal to 2.0 weight percent, the heating decrement is less than or equal to 1.0 percent, and the chroma of the product is still 6 after the product is stored for 6 months.
Description
Technical Field
The invention relates to the technical field of preparation of silane coupling agents, in particular to a preparation method of a sulfur-containing silane coupling agent.
Background
The white carbon black is used as a reinforcing filler, the strength and the tearing property of the sizing material reinforced by the white carbon black are higher, the wet skid resistance is better, the rolling resistance is lower, and the white carbon black is an essential reinforcing filler for green tires. Because a large number of silicon hydroxyl groups exist on the surface of the white carbon black, the white carbon black is easy to agglomerate in nonpolar rubber (such as NR, styrene butadiene rubber and butadiene rubber), so that the viscosity of the rubber material is increased, the processing performance is poor, and the large number of silicon hydroxyl groups on the surface of the white carbon black have acidity and hygroscopicity, so that the vulcanization rate and the crosslinking density of the rubber material are influenced. In order to improve the dispersibility of the white carbon black in the rubber compound, a modifier (such as a coupling agent Si69 or Si75) is often used for modifying the surface of the white carbon black. The sulfur-containing silane coupling agent can react with hydroxyl on the surface of the white carbon black, so that the white carbon black is changed from hydrophilicity to hydrophobicity, the compatibility of the white carbon black and a rubber matrix is improved, the dispersity of the white carbon black in a sizing material is improved, and meanwhile, sulfur atoms in the sulfur-containing silane can also participate in a crosslinking reaction, so that the crosslinking density of the sizing material is improved.
With the development of green tires, white carbon black is applied more and more, and higher quality requirements are provided for silane coupling agents. Bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide (Si69) and bis- [3- (triethoxysilyl) -propyl ] -disulfide (Si75) are commonly used silane coupling agents, and because of their multifunctional action on rubber, they can be used as reinforcing agent, coupling agent and plasticizer in processing, and are widely used in various rubber industries. At present, the preparation method of Si69 or Si75 generally adopts chloropropyl triethoxysilane to react with sodium polysulfide under the condition of organic ammonium salt phase transfer catalyst to obtain Si69 or Si 75. In the synthesis process, tri-n-butylamine is introduced into Si69 or Si75, has high toxicity and has certain potential safety hazard in the use process; in addition, the heating loss of Si69 or Si75 is too high; the long-term storage causes the color of Si69 or Si75 to be increased, and the appearance of the product is affected.
Disclosure of Invention
The invention aims to provide a preparation method of a sulfur-containing silane coupling agent Si 69. The invention also aims to provide a preparation method of the sulfur-containing silane coupling agent Si 75.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a sulfur-containing silane coupling agent Si69 comprises the following steps in sequence:
1.1) preparing a disodium tetrasulfide solution;
1.2) carrying out chemical reaction on the disodium tetrasulfide solution prepared in the step 1.1), a crown ether phase transfer catalyst and gamma-chloropropyltriethoxysilane to obtain an intermediate liquid A after the reaction is finished;
1.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid A prepared in the step 1.2) to obtain the sulfur-containing silane coupling agent Si 69.
Preferably, step 1.1) is specifically: the aqueous solution of sodium hydroxide is mixed with sulfur powder to generate chemical reaction to generate disodium tetrasulfide solution.
Preferably, the reaction temperature of the chemical reaction after the aqueous solution of sodium hydroxide and the sulfur powder are mixed is 80-100 ℃, and the reaction time of the chemical reaction under the stirring state is 0.5-1.5 h.
Preferably, in step 1.2), the crown ether type phase transfer catalyst used is 18-crown-6 or 15-crown-5.
Preferably, in the step 1.2), the amount of the disodium tetrasulfide is equal to that of the crown ether phase transfer catalyst, and the amount of the gamma-chloropropyltriethoxysilane is equal to (4.0-4.5) and is equal to 1;
the reaction temperature of the chemical reaction in the step 1.2) is 60-80 ℃, and the reaction time of the chemical reaction under the stirring state is 1-3 h.
A preparation method of a sulfur-containing silane coupling agent Si75 comprises the following steps in sequence:
6.1) preparing a disodium disulfide solution;
6.2) carrying out chemical reaction on the disodium disulfide solution prepared in the step 6.1), the crown ether phase transfer catalyst and gamma-chloropropyltriethoxysilane to obtain an intermediate liquid B after the reaction is finished;
6.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid B prepared in the step 6.2) to obtain the sulfur-containing silane coupling agent Si 75.
Preferably, step 6.1) is specifically: the sodium hydrosulfide aqueous solution, the sulfur powder and the sodium bicarbonate are mixed and then undergo a chemical reaction to generate a disodium disulfide solution.
Preferably, the reaction temperature of the chemical reaction after the aqueous solution of sodium hydrosulfide, the sulfur powder and the sodium bicarbonate are mixed is 80-100 ℃, and the reaction time of the chemical reaction under the stirring state is 0.5-1.5 h.
Preferably, in step 6.2), the crown ether type phase transfer catalyst used is 18-crown-6 or 15-crown-5.
Preferably, in the step 6.2), the amount of the disodium disulfide substance, the amount of the crown ether phase transfer catalyst substance, and the amount of the gamma-chloropropyltriethoxysilane substance are (4.0-4.5): 1;
the reaction temperature of the chemical reaction in the step 6.2) is 60-80 ℃, and the reaction time of the chemical reaction under the stirring state is 1-3 h.
The application obtains the following beneficial technical effects:
1) in the application, one of the most important characteristics of crown ether is that the crown ether can form stable complex with various metal salts, ammonium salts, organic cation compounds and the like, and various salts can be dissolved in organic solvents by utilizing the property; crown ether can chelate cations in the ring, and can generate a complex due to the presence of an outward organic gene and can also be dissolved in a nonpolar organic solvent; in the invention, crown ether is complexed with sodium ions in sodium polysulfide to ensure that the sodium ions can be dissolved in an organic solvent, polysulfide negative ions also enter the organic solvent along with the sodium polysulfide negative ions, the crown ether is not complexed with the polysulfide negative ions, but the reaction activity of free or naked polysulfide negative ions is very high, so that the polysulfide negative ions can be rapidly contacted with gamma 2 and can rapidly participate in the reaction, and compared with an organic ammonium salt phase transfer catalyst, the crown ether phase transfer catalyst adopted in the invention has the advantages of higher substrate reaction activity, higher reaction rate, simpler reaction condition, more convenient operation, higher product quality and the like.
2) In the application, the crown ether phase transfer catalyst is combined with sodium ions in sodium polysulfide, so that high-activity polysulfide negative ions are released, can quickly contact with gamma 2 for reaction, and the reaction activation energy is reduced, so that the reaction temperature of the sodium polysulfide and gamma-chloropropyltriethoxysilane for chemical reaction to generate the sulfur-containing silane coupling agent is reduced.
3) Compared with the traditional process, the invention does not use the conventional quaternary ammonium salt phase transfer catalyst, so the obtained sulfur-containing silane coupling agent does not contain tri-n-butylamine, and the tri-n-butylamine is inflammable, corrosive, strong irritant, can cause burn to human bodies and has strong irritation to the human bodies.
4) In the application, repeated analysis and detection prove that the tri-n-butylamine is a main source of heating decrement, and a quaternary ammonium salt phase transfer catalyst is not introduced, so that the problem of overhigh heating decrement of the prepared sulfur-containing silane coupling agent in the prior art is solved.
5) It is found that in the prior art, because the tri-n-butylamine is colorless to yellowish liquid, oxidation easily occurs with the time, so that the color of the Si69 or the Si75 is gradually increased; therefore, as quaternary ammonium base phase transfer catalysis is not introduced, the sulfur-containing silane coupling agent obtained by the method does not contain tri-n-butylamine, so that the problem that the color of the product is gradually increased along with the prolonging of the storage time of the product in the prior art is solved.
6) In the application, because no quaternary ammonium base phase transfer catalyst is introduced, the produced wastewater does not contain ammonia nitrogen, has little pollution to the environment, can be subjected to concentration post-treatment, and has industrial production value.
7) In the application, the prepared sulfur-containing silane coupling agent Si69 is a light yellow transparent liquid, the yield is more than or equal to 98 percent, the impurity content is less than or equal to 2.0 weight percent, the heating loss is less than or equal to 1.0 percent, and the chroma of the product is still 6 after the product is stored for 6 months.
8) In the application, the prepared sulfur-containing silane coupling agent Si75 is colorless and transparent liquid, the yield is more than or equal to 98 percent, the impurity content is less than or equal to 2.0 percent, and the heating loss is less than or equal to 1.0 percent.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The application provides a preparation method of a sulfur-containing silane coupling agent Si69, which comprises the following steps in sequence:
1.1) preparing a disodium tetrasulfide solution;
1.2) carrying out chemical reaction on the disodium tetrasulfide solution prepared in the step 1.1), a crown ether phase transfer catalyst and gamma-chloropropyltriethoxysilane to obtain an intermediate liquid A after the reaction is finished;
1.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid A prepared in the step 1.2) to obtain the sulfur-containing silane coupling agent Si 69.
In one embodiment of the present application, step 1.1) is specifically: the aqueous solution of sodium hydroxide is mixed with sulfur powder to generate chemical reaction to generate disodium tetrasulfide solution.
In one embodiment of the present application, the reaction temperature of the chemical reaction after the aqueous solution of sodium hydroxide and the sulfur powder are mixed is 80 ℃ to 100 ℃, and the reaction time of the chemical reaction under stirring is 0.5h to 1.5 h.
In one example of the present application, in step 1.2), the crown ether type phase transfer catalyst used is 18-crown-6 or 15-crown-5.
In one embodiment of the application, in the step 1.2), the amount of the substance of the disodium tetrasulfide, the amount of the substance of the crown ether phase transfer catalyst, the amount of the substance of the gamma-chloropropyltriethoxysilane, is (4.0-4.5), and the amount of the substance of the gamma-chloropropyltriethoxysilane is (4.0-4.5), 1;
the reaction temperature of the chemical reaction in the step 1.2) is 60-80 ℃, and the reaction time of the chemical reaction under the stirring state is 1-3 h.
The application provides a preparation method of a sulfur-containing silane coupling agent Si75, which comprises the following steps in sequence:
6.1) preparing a disodium disulfide solution;
6.2) carrying out chemical reaction on the disodium disulfide solution prepared in the step 6.1), the crown ether phase transfer catalyst and gamma-chloropropyltriethoxysilane to obtain an intermediate liquid B after the reaction is finished;
6.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid B prepared in the step 6.2) to obtain the sulfur-containing silane coupling agent Si 75.
In one embodiment of the present application, step 6.1) is specifically: the sodium hydrosulfide aqueous solution, the sulfur powder and the sodium bicarbonate are mixed and then undergo a chemical reaction to generate a disodium disulfide solution.
In one embodiment of the present application, the reaction temperature of the chemical reaction after mixing the aqueous solution of sodium hydrosulfide, the sulfur powder and the sodium bicarbonate is 80 ℃ to 100 ℃, and the reaction time of the chemical reaction under stirring is 0.5h to 1.5 h.
In one example of the present application, in step 6.2), the crown ether type phase transfer catalyst used is 18-crown-6 or 15-crown-5.
In one embodiment of the application, in the step 6.2), the amount of the disodium disulfide substance, the amount of the crown ether phase transfer catalyst substance, the amount of the gamma-chloropropyltriethoxysilane substance, is (4.0-4.5): 1;
the reaction temperature of the chemical reaction in the step 6.2) is 60-80 ℃, and the reaction time of the chemical reaction under the stirring state is 1-3 h.
The sulfur powder in the application is sulfur powder.
Compounds, methods and devices, etc., not described in detail herein are prior art and are not described in detail.
For further understanding of the present invention, the following examples are provided to illustrate the preparation of a sulfur-containing silane coupling agent according to the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
A preparation method of a sulfur-containing silane coupling agent Si69 comprises the following steps in sequence:
1.1) adding 70g of aqueous solution containing 32.62g of sodium hydroxide into a 500mL flask, adding 44.3g of sulfur powder, controlling the reaction temperature to be 90 ℃ and the reaction time to be 1 h;
1.2) then adding 1.5g of 18-crown-6, then adding 137.5g of intermediate gamma-chloropropyltriethoxysilane (gamma 2), controlling the reaction temperature to be 70 ℃, reacting for 1.5h under a stirring state, and obtaining an intermediate liquid A after the reaction is finished;
1.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid A prepared in the step 1.2) to obtain 149.5g of light yellow Si69 transparent liquid.
In example 1, the yield calculated as γ 2 was 98.68%, the total sulfur content in the sulfur-containing silane coupling agent Si69 was 22.78 wt%, the chlorine content in the sulfur-containing silane coupling agent Si69 was 0.21 wt%, the impurity content in the sulfur-containing silane coupling agent Si69 was 1.19 wt%, and the heating loss was 0.75%, which satisfied the standard requirements.
Example 2
A preparation method of a sulfur-containing silane coupling agent Si69 comprises the following steps in sequence:
1.1) adding 60g of aqueous solution containing 28.54g of sodium hydroxide into a 500mL flask, adding 38.8g of sulfur powder, controlling the reaction temperature to be 90 ℃ and the reaction time to be 1 h;
1.2) then adding 1.5g of 15-crown-5, then adding 120.3g of intermediate gamma-chloropropyltriethoxysilane (gamma 2), controlling the reaction temperature to be 70 ℃, reacting for 1.5h under a stirring state, and obtaining an intermediate liquid A after the reaction is finished;
1.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid A prepared in the step 1.2) to obtain 133g of light yellow Si69 transparent liquid.
In example 2, the yield calculated as γ 2 was 98.81%, the total sulfur content in the sulfur-containing silane coupling agent Si69 was 22.75 wt%, the chlorine content in the sulfur-containing silane coupling agent Si69 was 0.19 wt%, the impurity content in the sulfur-containing silane coupling agent Si69 was 1.16 wt%, and the heating loss was 0.81%, and the standard requirements were satisfied.
Example 3
A preparation method of a sulfur-containing silane coupling agent Si75 comprises the following steps in sequence:
6.1) adding 70g of aqueous solution containing 25.6g of sodium hydrosulfide into a 500mL flask, adding 15g of sodium carbonate and 10.3g of sulfur powder, controlling the reaction temperature to be 100 ℃ and the reaction time to be 1 h;
6.2) then adding 1.5g of 18-crown-6, then adding 125g of intermediate gamma-chloropropyltriethoxysilane (gamma 2), controlling the reaction temperature to be 70 ℃, reacting for 3h under a stirring state, and obtaining an intermediate liquid B after the reaction is finished;
6.3) the intermediate liquid B obtained in step 6.2) is subjected to liquid separation, activated carbon decolorization and distillation in sequence, and 120.8g of colorless Si75 transparent liquid is obtained after the completion.
In example 3, the yield calculated as γ 2 was 98.00%, the total sulfur content in the sulfur-containing silane coupling agent Si75 was 14.84 wt%, the chlorine content in the sulfur-containing silane coupling agent Si75 was 0.25 wt%, the impurity content in the sulfur-containing silane coupling agent Si75 was 1.54 wt%, and the heating loss was 0.75%, which satisfied the standard requirements.
Example 4
A preparation method of a sulfur-containing silane coupling agent Si75 comprises the following steps in sequence:
6.1) adding 80g of aqueous solution containing 28g of sodium hydrosulfide into a 500mL flask, adding 18g of sodium carbonate and 11g of sulfur, controlling the reaction temperature to be 100 ℃ and the reaction time to be 1 h;
6.2) then adding 1.5g of 15-crown-5, then adding 128g of intermediate gamma-chloropropyltriethoxysilane (gamma 2), controlling the reaction temperature to be 70 ℃, reacting for 3h under a stirring state, and obtaining an intermediate liquid B after the reaction is finished;
6.3) the intermediate liquid B obtained in step 6.2) was subjected to liquid separation, activated carbon decolorization and distillation in this order to obtain 124.7g of colorless Si75 transparent liquid.
In example 4, the yield calculated as γ 2 was 98.83%, the total sulfur content in the sulfur-containing silane coupling agent Si75 was 14.72 wt%, the chlorine content in the sulfur-containing silane coupling agent Si75 was 0.28 wt%, the impurity content in the sulfur-containing silane coupling agent Si75 was 1.27 wt%, and the heating loss was 0.86%, which satisfied the standard requirements.
Comparative example 1
Bis- [3- (triethoxysilyl) -propyl ] -tetrasulfide (Si69) was synthesized according to the method of example 1, except that: replacing the phase transfer catalyst 18-crown-6 with tetrabutylammonium bromide; the product yield was 96.34% in terms of γ 2, the impurity content in the sulfur-containing silane coupling agent Si69 was 3.47 wt%, and the heating loss was 1.89%.
Comparative example 2
Bis- [3- (triethoxysilyl) -propyl ] -disulfide (Si75) was synthesized according to example 3, except that: replacing the phase transfer catalyst 18-crown-6 with tetrabutylammonium bromide; the product yield was 95.82% in terms of γ 2, the impurity content in the sulfur-containing silane coupling agent Si75 was 3.25 wt%, and the heating loss was 2.17%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a sulfur-containing silane coupling agent Si69 is characterized by comprising the following steps of:
1.1) preparing a disodium tetrasulfide solution;
1.2) carrying out chemical reaction on the disodium tetrasulfide solution prepared in the step 1.1), a crown ether phase transfer catalyst and gamma-chloropropyltriethoxysilane to obtain an intermediate liquid A after the reaction is finished;
1.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid A prepared in the step 1.2) to obtain the sulfur-containing silane coupling agent Si 69.
2. The method for preparing the sulfur-containing silane coupling agent Si69 according to claim 1, wherein the step 1.1) is specifically as follows: the aqueous solution of sodium hydroxide is mixed with sulfur powder to generate chemical reaction to generate disodium tetrasulfide solution.
3. The method for preparing the sulfur-containing silane coupling agent Si69 according to claim 2, wherein the reaction temperature of the chemical reaction after the aqueous solution of sodium hydroxide is mixed with the sulfur powder is 80-100 ℃, and the reaction time of the chemical reaction under stirring is 0.5-1.5 h.
4. The method for preparing Si69, which is a sulfur-containing silane coupling agent, according to claim 1, wherein the crown ether phase transfer catalyst used in step 1.2) is 18-crown-6 or 15-crown-5.
5. The method for preparing the sulfur-containing silane coupling agent Si69 according to claim 1, wherein in step 1.2), the amount of disodium tetrasulfide, the amount of crown ether phase transfer catalyst, the amount of gamma-chloropropyltriethoxysilane, is (4.0-4.5) and (4.0-4.5) is 1;
the reaction temperature of the chemical reaction in the step 1.2) is 60-80 ℃, and the reaction time of the chemical reaction under the stirring state is 1-3 h.
6. A preparation method of a sulfur-containing silane coupling agent Si75 is characterized by comprising the following steps of:
6.1) preparing a disodium disulfide solution;
6.2) carrying out chemical reaction on the disodium disulfide solution prepared in the step 6.1), the crown ether phase transfer catalyst and gamma-chloropropyltriethoxysilane to obtain an intermediate liquid B after the reaction is finished;
6.3) sequentially carrying out liquid separation, activated carbon decolorization and distillation on the intermediate liquid B prepared in the step 6.2) to obtain the sulfur-containing silane coupling agent Si 75.
7. The method for preparing the sulfur-containing silane coupling agent Si75 according to claim 6, wherein the step 6.1) is specifically as follows: the sodium hydrosulfide aqueous solution, the sulfur powder and the sodium bicarbonate are mixed and then undergo a chemical reaction to generate a disodium disulfide solution.
8. The method for preparing the sulfur-containing silane coupling agent Si75 according to claim 7, wherein the reaction temperature of the chemical reaction after mixing the aqueous solution of sodium hydrosulfide, the sulfur powder and the sodium bicarbonate is 80-100 ℃, and the reaction time of the chemical reaction under stirring is 0.5-1.5 h.
9. The method for preparing Si75 of claim 6, wherein the crown ether phase transfer catalyst used in step 6.2) is 18-crown-6 or 15-crown-5.
10. The method for preparing the sulfur-containing silane coupling agent Si75 according to claim 6, wherein in step 6.2), the amount of the disodium disulfide is equal to the amount of the crown ether phase transfer catalyst, the amount of the gamma-chloropropyltriethoxysilane is equal to (4.0-4.5) and (4.0-4.5) is equal to 1;
the reaction temperature of the chemical reaction in the step 6.2) is 60-80 ℃, and the reaction time of the chemical reaction under the stirring state is 1-3 h.
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| CN108250233A (en) * | 2018-01-26 | 2018-07-06 | 青岛科技大学 | The method that one kind prepares silane coupling agent-Si-69 in water phase |
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