CN103952716A - Method for electrolytic synthesis of siloxane - Google Patents
Method for electrolytic synthesis of siloxane Download PDFInfo
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- CN103952716A CN103952716A CN201410207377.4A CN201410207377A CN103952716A CN 103952716 A CN103952716 A CN 103952716A CN 201410207377 A CN201410207377 A CN 201410207377A CN 103952716 A CN103952716 A CN 103952716A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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- C25B3/29—Coupling reactions
Abstract
The invention relates to a method for electrolytic synthesis of siloxane, belonging to the technical field of organosilicon chemistry. The method disclosed by the invention comprises the following steps of carrying out an electrolysis reaction on minerals containing SiO2 and an alkylating agent as raw materials at room temperature and normal pressure in an electrolyte solution comprising an aprotic polar organic solvent and an electrolyte by an electrolytic cell or an electrolytic bath with a cathode and an anode and synthesizing to obtain the silicone-containing materials, and finally the separating siloxane in the silicone-containing materials to obtain siloxane products. According to the method for electrolytic synthesis of siloxane, production costs and energy consumptions are greatly reduced, the production efficiency is improved; no pollution to the environment is generated and the synthesis process is environment friendly; a plurality of silicone products are obtained by flexibly choosing alkylating agents. The method disclosed by the invention has the advantages of high converted rate and product quality.
Description
Technical field
The present invention relates to a kind of synthetic method of siloxanes, more particularly, the present invention relates to a kind of method of electrolytic synthesis siloxanes, belong to organosilicon technical field of chemistry.
Background technology
Organosilicon, be silicoorganic compound, refer to and contain Si-O key, and to have an organic group at least be the compound being directly connected with Siliciumatom, also often make the compound that organic group is connected with Siliciumatom also be used as silicoorganic compound by oxygen, sulphur, nitrogen etc. those traditionally.Wherein, the polysiloxane of composition taking siloxane bond (Si-0-Si-) as skeleton, is maximum for counting in silicoorganic compound, studies dark, a most most widely used class, accounts for the more than 90% of total consumption.
The basic structural unit of organosilicon product is made up of Si-O chain link, and side chain is connected by the various organic groups of Siliciumatom and other.Therefore, both contained " organic group " in the structure of organosilicon product, and contained again " inorganic structure ", this special composition and molecular structure make it integrate the function of organic characteristic and inorganics.Compared with other macromolecular materials, the outstanding properties of organosilicon product is:
1, heatproof characteristic
Organosilicon product is taking Si-O key as backbone structure, the bond energy of C-C key is 82.6 kilocalories/mol, the bond energy of Si-O key is 121 kilocalories/mol in organosilicon, so the thermostability of organosilicon product is high, under high temperature, the chemical bond of (or radiation irradiation) molecule does not rupture, does not decompose.Organosilicon not only can be high temperature resistant, and low temperature resistant, can in a very wide temperature range, use.No matter be chemical property or physical and mechanical properties, variation with temperature is all very little.
2, weathering resistance
The main chain of organosilicon product is-Si-O-that unparalleled key exists, and is therefore difficult for being decomposed by UV-light and ozone.Organosilicon has than the better thermostability of other macromolecular materials and resistance to irradiation and weather-proof ability.Can reach decades the work-ing life in organosilicon under physical environment.
3, electrical insulation properties
Organosilicon product all has good electrical insulation capability, its dielectric loss, proof voltage, resistance to electric arc, resistance to corona, volume resistivity and surface resistivity etc. all come out at the top in insulating material, and their electric property is subject to the impact of temperature and frequency very little.Therefore, they are a kind of stable electrically insulating materials, are widely used in electronics, electrical industry.Organosilicon, except having good thermotolerance, also has excellent water repellency, and this is that electric installation uses the guarantee with high reliability under hygrometric state condition.
4, biological nature
Biological active organic silicon is a kind of nutrient substance of needed by human.Organosilicon is form tissue and participate in metabolic important element, is stored in the middle of each cell of human body, as the support of cell construction, helps other important substance as magnesium, phosphorus, the absorptions such as calcium simultaneously.Human body can only constantly obtain organosilicon by food.
5, low surface tension and low surface energy
Organosilyl main chain is very submissive, its intermolecular reactive force a little less than than hydrocarbon polymer many, therefore, low than the hydrocarbon polymer viscosity of same molecular weight, a little less than surface tension, surface can be little, film forming ability is strong.This low surface tension and low surface energy are the major causes that its obtains many-sided application: every excellent properties such as hydrophobic, froth breaking, foam stabilization, antiseized, lubricated, glazing.
Because organosilicon has above-mentioned these excellent performances, therefore its range of application is very extensive.It not only uses as the special material of aviation, sophisticated technology, military technique department, and for each department of national economy, its range of application diffuses into: building, electric, weaving, automobile, machinery, leather papermaking, chemical industry light industry, metal and paint, medicine medical treatment etc.
The production of current silicoorganic compound, all taking Pure Silicon Metal as raw material, is then oxidized to methyl chlorosilane at 200-400 DEG C of high temperature, catalyzer under existing, and these methyl chlorosilanes obtain the organosilane monomer such as methyl polysiloxane and organoalkoxysilane through condensation.And Pure Silicon Metal (Si) is with silica (SiO
2) for raw material high temperature (1500-3000 DEG C) reduction in electric furnace forms, this process not only consumes mass energy, and produces a large amount of greenhouse gases (as CO and CO
2deng) and dust, environment is had to very large harm.According to statistics, producing 1 ton of Pure Silicon Metal needs the about 12000KWh of power consumption, consumes approximately 1.5 tons, carbon, approximately 3.2 tons of discharge CO.So urgent need finds the method for the production organosilane monomer of a kind of less energy-consumption, low emission.
Summary document (the electrochemical synthesis of polysilane of delivering at Gao Mengjiao etc., polymer circular, the 8th phase in 2011,91-95), and other pertinent literature and patent also have Chem.Letters (1985:463-466), J.Organomet.Chem.321 (1987:C27), J.Organomet.Chem.358 (1988:31), EP2446578, DE14024600 to disclose some organosilyl electrochemical method for synthesizing.
It is CN1098724 that State Intellectual Property Office discloses a publication number in 1995.2.15, name is called the patent of invention of " electrochemical method for synthesizing of silicoorganic compound and equipment ", this patent has been described a kind of electrochemical preparation method of the silicoorganic compound that contain at least one SiC key organic group, comprising a kind of solution that contains at least one halogenated silanes that offers electrochemical reaction, a kind of anode that contains a kind of precious metal or a kind of alloy that contains one or more precious metal and the halogen scavenger that flowing around it.
In addition, it is CN1656252 that State Intellectual Property Office discloses a publication number in 2005.8.17, and name is called the patent of invention of " electrochemical method of manufacturing organofunctional silane ", and this patent relates to the method for preparing general formula (1) organofunctional silane.Wherein, utilize undivided electrolyzer, make silane and the general formula R of general formula (2)
1the compound of-Y carries out electrochemical reaction, and condition is mostly to be 0.1 mole most with respect to every mole of X complexing agent.The implication of R1, R2, R3, R4, X and Y as defined in claim 1.
But above-mentioned these documents and patent all make organosilane monomer taking chlorosilane as raw material by electrochemical method, and product is not siloxanes yet.As everyone knows, in traditional organosilicon synthetic method of aforementioned introduction, chlorosilane is also synthetic taking the Pure Silicon Metal of simple substance as raw material, and these metallic silicon raw materials need to consume a large amount of coal, electric power equally, discharge CO gas, this for solve highly energy-consuming of existing organosilicon industry and greenhouse gas emission be do not have helpful.
To sum up, the existing method that is prepared with organic silicon compound all have that energy consumption is high, price, the wasting of resources, heavy-polluted problem.
Summary of the invention
The object of the invention is to, for the deficiency in prior art, provides a kind of method of electrolytic synthesis siloxanes, reaches and reduces production energy consumption and cost, the object of production process environmental protection.
In order to realize foregoing invention object, concrete technical scheme is as follows:
A method for electrolytic synthesis siloxanes, is characterized in that: under room temperature and normal pressure, to contain SiO
2mineral substance and alkylating agent be raw material, in the electrolytic solution of non-proton polar organic solvent and electrolyte ingredient, carry out electrolytic reaction by the electrolyzer with negative electrode and anode or electrolyzer, the synthetic material that contains siloxanes of obtaining, finally the siloxanes in this material is separated, obtained silicone products.
Room temperature of the present invention and normal pressure refer to the heating and pressurizing not needing by artificial, or decrease temperature and pressure can complete whole building-up process.If but carry out artificial heating and pressurizing, or decrease temperature and pressure, also can complete building-up process of the present invention, just cannot reach best energy-saving effect.
Of the present inventionly siloxanes in material is separated to the filtration, rotary evaporation and the extracting and separating that refer to by this area routine go out siloxanes.
Raw material of the present invention needs SiO
2, therefore any described containing SiO
2mineral substance can serve as raw material of the present invention, as silica, silica sand, sand or quartz sand.
Another raw material alkylating agent of the present invention be utilized alkylating agent can electrochemical reduction general character, therefore alkylating agent of the present invention refers to all alkylating agents of this area, and described can refer to by electrochemical reduction: can obtain electronics and form negative ion or radical anion.Alkylating agent of the present invention can be selected conventional methyl alcohol, ethanol, methyl iodide or methylcarbonate.Wherein be preferably methyl alcohol.Select different alkylating agents can synthesize different silicone products.
Aprotic polar solvent of the present invention refers to all non-proton polar organic solvent of this area, conventional as tetrahydrofuran (THF), N, dinethylformamide, N, one in N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dioxane, acetonitrile, Nitromethane 99Min., glycol dimethyl ether and diethylene glycol dimethyl ether, or several arbitrary proportion mixture in these solvents.Wherein be preferably tetrahydrofuran (THF) or acetonitrile, or the arbitrary proportion mixture of two kinds.Non-proton polar organic solvent of the present invention should not react with raw material and product and in reaction process, be liquid state.
The present invention, in order to make reaction system have enough specific conductivity, need to add ionogen.Ionogen used should not react with reactive component, is indifferent salt.Ionogen is as chemical general formula M
+y
-shown in, wherein for example Mg, Li, Na, NMe of M
4, NEt
4, NBu
4, PMMIm, EOMIm, and such as ClO of Y
4, Cl, Br, NO
3, BF
4, AsF
6, BPh
4, PF
6, AlCl
4, CF
3sO
3, SCN; Me, Et, Bu, PMMIm, EOMIm, Ph are respectively methyl, ethyl, butyl, 1-butyl-2,3-methylimidazole, 1-ethyl-methyl ether-3-Methylimidazole, phenyl.Wherein be preferably tetraethyl-ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetraethyl-trifluoromethane sulfonic acid ammonium or tetrabutyl trifluoromethane sulfonic acid ammonium.Particularly preferred is tetrabutyl trifluoromethane sulfonic acid ammonium.
Electrolyzer of the present invention and electrolyzer are cellular-type or non-cellular-type.Wherein preferred, described electrolyzer is cellular-type electrolyzer, and described electrolyzer is separated electrolysis bath.
Electrolyzer of the present invention or electrolyzer are equipped with current stabilizer and potentiostat.
Negative electrode of the present invention and anode adopt to be had enough electroconductibility and under this reaction conditions, is chemically inert all material, and inertia refers to that chemical transformation does not occur this electrode under reaction conditions herein.Wherein preferred material is graphite cake, carbon plate, magnesium, aluminium, copper, nickel, chromium, platinum or stainless steel.Above-mentioned negative electrode and anode material can identical also can be different.
The process of electrolytic synthesis siloxanes of the present invention is carried out under the protection of nitrogen, argon gas or helium.Wherein preferred nitrogen.
Non-proton polar organic solvent in electrolytic solution of the present invention and electrolytical mass ratio are 5～20:1; Described containing SiO
2mineral substance and the mass ratio 4～50:1 of alkylating agent; Described electrolytic solution (non-proton polar organic solvent and electrolytical quality summation) and raw material are (containing SiO
2mineral substance and the quality summation of alkylating agent) mass ratio 5～15:1.Wherein containing SiO
2the specification of mineral substance stable, i.e. SiO
2stable content, aborning, add the amount of above-mentioned scope according to concrete specification, therefore only need to limit containing SiO
2the add-on of mineral substance.
The electrolysis voltage of electrolytic reaction of the present invention is 2.5～3.5V.
The reaction times of electrolytic reaction of the present invention is 10～200 minutes.
Above-mentioned electrolysis voltage and electrolytic reaction time be chosen as preferred version, the combination of the add-on ratios such as above-mentioned parameter scope and electrolytic solution, raw material, can reach the optimum balance of production cost, production efficiency and transformation efficiency, certainly select above-mentioned scope parameter in addition also can implement building-up process of the present invention.
Synthesis mechanism of the present invention:
The present invention is a kind of transfer transport/chemical reaction (EC) mechanism.Taking methyl alcohol as example, first produce Methanol radical negatively charged ion at electrode surface because of reduction potential
, Methanol radical negatively charged ion can resolve into methyl free radicals
and hydroxide radical anion (OH
-), Methanol radical negatively charged ion also may resolve into methoxyl group negatively charged ion (MeO
-) and hydroperoxyl radical
such 1 part of methyl alcohol generation reduction reaction, will produce 1 part of methyl group and 1 part of methoxyl group, the stoichiometric ratio of the two is 1:1, and react to each other with silica sphere, produce dimethyldimethoxysil,ne (DMDMS), then DMDMS just can utilize the water hydrolysis that reduction reaction produces at first to generate polydimethylsiloxane.If selecting methyl iodide or methylcarbonate is raw material, can only generate DMDMS, because there is no the generation of water, DMDMS can not continue hydrolysis and generate polydimethylsiloxane.
The useful technique effect that the present invention brings:
In prior art, although electrochemical method for synthesizing has been applied to the synthetic of silicoorganic compound, but the raw material of prior art is chlorosilane, and the synthetic product obtaining not is the siloxanes that we want, and siloxanes silicone intermediate is only the most widely used product of field of organic silicon.What adopt due to the raw material of prior art is chlorosilane, so this raw material still will be prepared by silicon (200～400 DEG C, under catalyzer, silicon reacts with methyl chloride), obtaining silicon needs the heat of a large amount of coal and 1500～3000 DEG C, and also can give off the CO gas of a large amount of contaminate environment.No matter so be the method that tradition is prepared siloxanes, or the existing method of preparing other organosilane monomers by electrochemical synthesis, all exist processing step many, production efficiency is low, and production cost is high, and energy consumption is huge, the problem of contaminate environment.And the synthetic method of a kind of siloxanes provided by the invention, raw material uses the very common SiO that contains
2mineral substance and alkylating agent, adopt electrolyzer, prepare specific electrolytic solution, carry out one-step electrolysis, just can obtain siloxanes.First raw material is easy to get, low price, electrolyzer is simple in structure, price is low, only need under room temperature normal pressure, apply very low voltage can carry out electrolytic synthesis, greatly reduces like this production cost and production energy consumption, and only needs single step reaction, more traditional three-step reaction has shortened the reaction times, has improved production efficiency; Secondly, can not give off gas or the liquid of any contaminate environment in electrolytic reaction, raw material, reagent etc. also can recycle, so just can not be to environment, and building-up process environmental protection; Finally, alkylating agent is selected wide, so just can, with same equipment, Same Way, obtain multiple silicone products, and method transformation efficiency of the present invention be high by flexible selection alkylating agent, and quality product is high.
The preferred alkylating agent of the present invention is methyl alcohol, and compared with methyl iodide, methylcarbonate, methyl alcohol is simple in structure, raw material is cheap; With ethanol ratio, react the hexamethyl cyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and the decamethylcyclopentaandoxane (D5) that obtain with methyl alcohol, market consumption maximum, value of the product is the highest.The preferred tetraethyl-ammonium tetrafluoroborate of ionogen of the present invention, tetrabutyl ammonium tetrafluoroborate, tetraethyl-trifluoromethane sulfonic acid ammonium or tetrabutyl trifluoromethane sulfonic acid ammonium have high conductivity, low volatility, wide, the high chemistry of electrochemical stability window and thermostability, there is good intermiscibility with reactant, catalyzer etc., because tetrabutyl trifluoromethane sulfonic acid ammonium specific conductivity is the highest, particularly preferably tetrabutyl trifluoromethane sulfonic acid ammonium.Electrolyzer of the present invention or the preferred cellular-type of electrolyzer, because separation negative electrode and anode can be avoided the mixing of product that the two poles of the earth generate, thereby prevent that side reaction and secondary reaction from purity, the yield of product occurring to affect.The preferred electrode materials of the present invention is cheap, and chemical stability is good, has good electro catalytic activity and selectivity, and electroconductibility is good, easily machine-shaping, and physical strength is good.
Embodiment
embodiment 1
A kind of method of electrolytic synthesis siloxanes:
Under room temperature and normal pressure, to contain SiO
2mineral substance and alkylating agent be raw material, in the electrolyte system of non-proton polar organic solvent and electrolyte ingredient, carry out electrolytic reaction by the electrolyzer with negative electrode and anode or electrolyzer, the synthetic material that contains siloxanes of obtaining, finally the siloxanes in this material is separated, obtained silicone products.
embodiment 2
Use cellular-type electrolyzer for electrolysis, its Anodic material is high purity nickel, and negative electrode material is graphite cake, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 500g tetrabutyl trifluoromethane sulfonic acid ammonium and 5000g tetrahydrofuran (THF).Under nitrogen protection, add respectively 32g methyl alcohol and 600g quartz sand from charging opening.Output voltage being set constant is 3V, starts current stabilization/potentiostat, electrolytic reaction 120min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted quartz sand (residual quartz sand can reuse) completely, filtrate is transferred in rotatory evaporator, under room temperature, tetrahydrofuran (THF) (recyclable) is removed in decompression suction, steam gradation in raffinate and add Skellysolve A extraction revolving, Skellysolve A is removed in last combining extraction liquid at room temperature decompression suction, obtain silicone products 24.6g altogether, Gc-ms product is mainly hexamethyl cyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentaandoxane (D5) and a small amount of dimethyldimethoxysil,ne (DMDMS), its composition is respectively 22.43%, 72.18%, 5.24%, 0.15%(weight ratio).
embodiment 3
Use cellular-type electrolyzer for electrolysis, its Anodic material is high purity nickel, and negative electrode material is carbon plate, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 460g tetraethyl-trifluoromethane sulfonic acid ammonium and 5200g acetonitrile.Under nitrogen protection, add respectively 35g methyl alcohol and 540g quartz sand from charging opening.Output voltage being set constant is 2.9V, starts current stabilization/potentiostat, electrolytic reaction 120min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted quartz sand (residual quartz sand can reuse) completely, filtrate is transferred in rotatory evaporator, under room temperature, acetonitrile (recyclable) is removed in decompression suction, steam gradation in raffinate and add petroleum ether extraction revolving, sherwood oil is removed in last combining extraction liquid at room temperature decompression suction, obtain altogether 26.4g of silicone products, composition D3, D4, D5, DMDMS are respectively 19.28%, 75.34%, 5.33%, 0.05%(weight ratio).
embodiment 4
Use cellular-type electrolyzer for electrolysis, its Anodic material is stainless steel, and negative electrode material is nickel plate, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 510g tetrabutyl ammonium tetrafluoroborate and 4200g glycol dimethyl ether.Under nitrogen protection, add respectively 60g methyl alcohol and 340g silica from charging opening.Output voltage being set constant is 3.4V, starts current stabilization/potentiostat, electrolytic reaction 140min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted silica (residual silica can reuse) completely, filtrate is transferred in rotatory evaporator, under room temperature, glycol dimethyl ether (recyclable) is removed in decompression suction, steam gradation in raffinate and add petroleum ether extraction revolving, sherwood oil is removed in last combining extraction liquid at room temperature decompression suction, obtain silicone products 41.5g altogether, Gc-ms product is mainly hexamethyl cyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentaandoxane (D5), without dimethyldimethoxysil,ne (DMDMS), composition D3, D4, D5 is respectively 24.42%, 69.21%, 6.37%(weight ratio).
embodiment 5
Use cellular-type electrolyzer for electrolysis, its Anodic material is high purity nickel, and negative electrode material is nickel plate, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 510g tetrabutyl trifluoromethane sulfonic acid ammonium, 2000g tetrahydrofuran (THF) and 3000g acetonitrile.Under nitrogen protection, add respectively 50g ethanol and 600g quartz sand from charging opening.Output voltage being set constant is 2.7V, starts current stabilization/potentiostat, electrolytic reaction 180min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted quartz sand (residual quartz sand can reuse) completely, filtrate is transferred in rotatory evaporator, under room temperature, solvents tetrahydrofurane and acetonitrile (recyclable) are removed in decompression suction, steam gradation in raffinate and add petroleum ether extraction revolving, sherwood oil is removed in last combining extraction liquid at room temperature decompression suction, obtain silicone products 38.4g altogether, Gc-ms product is mainly hexaetcycletrisiloxane (ethyl D3), octaethyl cyclotetrasiloxane (ethyl D4), diethyl diethoxy silane, its composition is respectively 62.24%, 27.3%, 10.46%(weight ratio).
embodiment 6
Use cellular-type electrolyzer for electrolysis, its Anodic material is high purity nickel, and negative electrode material is graphite cake, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 2500g tetrabutyl trifluoromethane sulfonic acid ammonium, 16000g tetrahydrofuran (THF).Under nitrogen protection, add respectively 700g ethanol and 3000g quartz sand from charging opening.Output voltage being set constant is 2.9V, starts current stabilization/potentiostat, electrolytic reaction 200min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted quartz sand (residual quartz sand can reuse) completely, filtrate is transferred in rotatory evaporator, under room temperature, solvents tetrahydrofurane (recyclable) is removed in decompression suction, steam gradation in raffinate and add petroleum ether extraction revolving, sherwood oil is removed in last combining extraction liquid at room temperature decompression suction, obtain silicone products 431.7g altogether, Gc-ms product is mainly hexaetcycletrisiloxane (ethyl D3), octaethyl cyclotetrasiloxane (ethyl D4), diethyl diethoxy silane, its composition is respectively 54.21%, 34.12%, 11.67%(weight ratio).
embodiment 7
Use non-cellular-type electrolyzer for electrolysis, its Anodic material is stainless steel, and negative electrode material is graphite cake, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 627g tetraethyl-ammonium tetrafluoroborate, 5200g dimethyl sulfoxide (DMSO).Under nitrogen protection, add respectively 54g methylcarbonate and 540g sand from charging opening.Output voltage being set constant is 3V, starts current stabilization/potentiostat, electrolytic reaction 100min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted sand (residual sand can reuse) completely, by filtrate stratification, by after supernatant liquid washed several times with water with calcium chloride dried overnight then suction filtration obtain product 42.1g, Gc-ms product is mainly dimethyldimethoxysil,ne (DMDMS), trimethoxymethylsila,e and a small amount of methoxytrimethylsilane, its composition is respectively 64.83%, 34.15%, 1.02%(weight ratio).
embodiment 8
Use separated electrolysis bath for electrolysis, wherein cathode and anode is magnesium plate, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient under helium protection.Electrolytic solution is made up of 210g lithium hexafluoro phosphate and 1050g DMF.Under nitrogen protection, add respectively 50.4g methyl iodide and 201.6g silica sand from charging opening.Output voltage being set constant is 2.5V, starts current stabilization/potentiostat, electrolytic reaction 10min under room temperature, helium protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted silica sand (residual silica sand can reuse) completely, by filtrate stratification, by after supernatant liquid washed several times with water with calcium chloride dried overnight then suction filtration obtain product 39.7g, its composition dimethyldimethoxysil,ne, trimethoxymethylsila,e, methoxytrimethylsilane are respectively 73.18%, 21.7%, 5.12%(weight ratio).
embodiment 9
Use separated electrolysis bath for electrolysis, its Anodic material is aluminium, and negative electrode material is magnesium, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under argon shield, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 550g sodium tetrafluoroborate and 11000g N,N-dimethylacetamide.Under argon shield, add respectively 120g methylcarbonate and 650g silica from charging opening.Output voltage being set constant is 3.5V, starts current stabilization/potentiostat, electrolytic reaction 195min under room temperature, argon shield.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted silica (residual silica can reuse) completely, by filtrate stratification, by after supernatant liquid washed several times with water with calcium chloride dried overnight then suction filtration obtain product 93g, its composition dimethyldimethoxysil,ne, trimethoxymethylsila,e, methoxytrimethylsilane are respectively 67.32%, 31.55%, 1.13%(weight ratio).
embodiment 10
Use cellular-type electrolyzer for electrolysis, its Anodic material is magnesium, and negative electrode material is copper, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under argon shield, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 1275g tetrabutylammonium perchlorate and 14025g dioxane.Under argon shield, add respectively 30g methyl iodide and 1500g silica sand from charging opening.Output voltage being set constant is 2.7V, starts current stabilization/potentiostat, electrolytic reaction 105min under room temperature, argon shield.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted silica sand (residual silica sand can reuse) completely, by filtrate stratification, by after supernatant liquid washed several times with water with calcium chloride dried overnight then suction filtration obtain product 21.5g, its composition dimethyldimethoxysil,ne (DMDMS), trimethoxymethylsila,e, methoxytrimethylsilane are respectively 69.17%, 24.9%, 5.93%(weight ratio).
embodiment 11
Use non-cellular-type electrolyzer for electrolysis, its Anodic material is platinum, and negative electrode material is graphite cake, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 800g lithium perchlorate and 4800g Nitromethane 99Min..Under nitrogen protection, add respectively 40g methyl alcohol and 760g sand from charging opening.Output voltage being set constant is 3.1V, starts current stabilization/potentiostat, electrolytic reaction 150min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted sand (residual sand can reuse) completely, filtrate is transferred in rotatory evaporator, under room temperature, Nitromethane 99Min. (recyclable) is removed in decompression suction, steam gradation in raffinate and add petroleum ether extraction revolving, sherwood oil is removed in last combining extraction liquid at room temperature decompression suction, obtain altogether 31.1g of silicone products, composition D3, D4, D5, DMDMS are respectively 14.4%, 77.18%, 7.25%, 1.17%(weight ratio).
embodiment 12
Use non-separated electrolysis bath for electrolysis, its Anodic material is stainless steel, and negative electrode material is carbon plate, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is by 668g 1-butyl-2, and 3-methylimidazole hexafluorophosphate [(PMMIm) PF6] and 6772g diethylene glycol dimethyl ether form.Under nitrogen protection, add respectively 20g ethanol and 600g silica sand from charging opening.Output voltage being set constant is 3V, starts current stabilization/potentiostat, electrolytic reaction 80min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted silica sand (residual silica sand can reuse) completely, filtrate is transferred in rotatory evaporator, under room temperature, solvent diethylene glycol dimethyl ether (recyclable) is removed in decompression suction, steam gradation in raffinate and add hexanaphthene extraction revolving, hexanaphthene is removed in last combining extraction liquid at room temperature decompression suction, obtain silicone products 13.3g altogether, its composition hexaetcycletrisiloxane (ethyl D3), octaethyl cyclotetrasiloxane (ethyl D4), diethyl diethoxy silane is respectively 47.89%, 45.91%, 6.2%(weight ratio).
embodiment 13
Use cellular-type electrolyzer for electrolysis, its Anodic material is stainless steel, and negative electrode material is copper, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.Electrolytic solution is made up of 250g magnesium chloride, 7500g tetrahydrofuran (THF), 2000g dioxane and 2500g Nitromethane 99Min..Under nitrogen protection, add respectively 72g methyl iodide and 953g silica from charging opening.Output voltage being set constant is 2.8V, starts current stabilization/potentiostat, electrolytic reaction 170min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted silica (residual silica can reuse) completely, by filtrate stratification, by after supernatant liquid washed several times with water with calcium chloride dried overnight then suction filtration obtain product 52.3g, its composition dimethyldimethoxysil,ne (DMDMS), trimethoxymethylsila,e, methoxytrimethylsilane are respectively 75.15%, 18.34%, 6.51%(weight ratio).
embodiment 14
Use cellular-type electrolyzer for electrolysis, its Anodic material is platinum, and negative electrode material is magnesium, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer under nitrogen protection, adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient.By 120g 1-ethyl-methyl ether-3-methyl imidazolium tetrafluoroborate, [(EOMIm) BF4,500g dimethyl sulfoxide (DMSO), 800g acetonitrile and 155g diethylene glycol dimethyl ether form electrolytic solution.Under nitrogen protection, add respectively 15g methylcarbonate and 90g quartz sand from charging opening.Output voltage being set constant is 2.6V, starts current stabilization/potentiostat, electrolytic reaction 120min under room temperature, nitrogen protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted quartz sand (residual quartz sand can reuse) completely, by filtrate stratification, by after supernatant liquid washed several times with water with calcium chloride dried overnight then suction filtration obtain product 10.5g, its composition dimethyldimethoxysil,ne (DMDMS), trimethoxymethylsila,e and a small amount of methoxytrimethylsilane are respectively 70.75%, 26.92%, 2.33%(weight ratio).
embodiment 15
Use cellular-type electrolyzer for electrolysis, wherein cathode and anode material is copper, and electrolyzer is equipped with current stabilization/potentiostat.After being cleaned totally, electrolyzer adds the electrolytic solution by non-proton polar organic solvent and electrolyte ingredient under helium protection.Electrolytic solution is made up of 195g tetraethyl-fluorine bromic acid ammonium, 2850g N,N-dimethylacetamide and 855g glycol dimethyl ether.Under helium protection, add respectively 45g methyl alcohol and 442.5g sand from charging opening.Output voltage being set constant is 3.3V, starts current stabilization/potentiostat, electrolytic reaction 60min under room temperature, helium protection.After reaction finishes, material in electrolyzer is emitted by filter screen, filter residue is unreacted sand (residual sand can reuse) completely, filtrate is transferred in rotatory evaporator, at 50 DEG C, solvent (recyclable) is removed in decompression suction, steam gradation in raffinate and add hexanaphthene extraction revolving, hexanaphthene is removed in last combining extraction liquid at room temperature decompression suction, obtains silicone products 32.4g altogether, composition D3, D4, D5 are respectively 16.43%, 75.44%, 8.13%(weight ratio).
Claims (16)
1. a method for electrolytic synthesis siloxanes, is characterized in that: under room temperature and normal pressure, to contain SiO
2mineral substance and alkylating agent be raw material, in the electrolytic solution of non-proton polar organic solvent and electrolyte ingredient, carry out electrolytic reaction by the electrolyzer with negative electrode and anode or electrolyzer, the synthetic material that contains siloxanes of obtaining, finally the siloxanes in this material is separated, obtained silicone products.
2. the method for a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: described containing SiO
2mineral substance be silica, silica sand, sand or quartz sand.
3. the method for a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: described alkylating agent is methyl alcohol, ethanol, methyl iodide or methylcarbonate.
4. according to the method for a kind of electrolytic synthesis siloxanes described in claim 1 or 3, it is characterized in that: described alkylating agent is methyl alcohol.
5. the method for a kind of electrolytic synthesis siloxanes according to claim 1, it is characterized in that: described aprotic polar solvent is tetrahydrofuran (THF), N, dinethylformamide, N, one in N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dioxane, acetonitrile, Nitromethane 99Min., glycol dimethyl ether and diethylene glycol dimethyl ether, or several arbitrary proportion mixture in these solvents.
6. a kind of method of electrolytic synthesis siloxanes according to claim 1 or 5, is characterized in that: described aprotic polar solvent is tetrahydrofuran (THF) or acetonitrile, or the arbitrary proportion mixture of two kinds.
7. the method for a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: described electrolytical chemical general formula is M
+y
-, wherein M is Mg, Li, Na, NMe
4, NEt
4, NBu
4, PMMIm or EOMIm, and Y is ClO
4, Cl, Br, NO
3, BF
4, AsF
6, BPh
4, PF
6, AlCl
4, CF
3sO
3or SCN.
8. according to the method for a kind of electrolytic synthesis siloxanes described in claim 1 or 7, it is characterized in that: described ionogen is tetraethyl-ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetraethyl-trifluoromethane sulfonic acid ammonium or tetrabutyl trifluoromethane sulfonic acid ammonium.
9. the method for a kind of electrolytic synthesis siloxanes according to claim 8, is characterized in that: described ionogen is tetrabutyl trifluoromethane sulfonic acid ammonium.
10. the method for a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: described electrolyzer is cellular-type electrolyzer, and described electrolyzer is separated electrolysis bath.
11. according to the method for a kind of electrolytic synthesis siloxanes described in claim 1 or 10, it is characterized in that: described electrolyzer or electrolyzer are equipped with current stabilizer and potentiostat.
The method of 12. a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: described negative electrode and anode are graphite cake, carbon plate, magnesium, aluminium, copper, nickel, chromium, platinum or stainless steel.
The method of 13. a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: the process of described electrolytic synthesis siloxanes is carried out under nitrogen protection.
The method of 14. a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: the non-proton polar organic solvent in described electrolytic solution and electrolytical mass ratio are 5～20:1; Described containing SiO
2mineral substance and the mass ratio 4～50:1 of alkylating agent; Mass ratio 5～the 15:1 of described electrolytic solution and raw material.
The method of 15. a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: the electrolysis voltage of described electrolytic reaction is 2.5～3.5V.
The method of 16. a kind of electrolytic synthesis siloxanes according to claim 1, is characterized in that: the reaction times of described electrolytic reaction is 10～200 minutes.
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| CN109265036A (en) * | 2018-10-26 | 2019-01-25 | 田丰 | A kind of preparation method of ventilative sand for building |
| CN112195481A (en) * | 2020-11-02 | 2021-01-08 | 上海漫关越水处理有限公司 | Method for large-scale clean synthesis of tetramethoxyethane by membrane electrolysis |
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