CN110818735A - Method for preparing 1,1,3, 3-tetramethyldisiloxane - Google Patents
Method for preparing 1,1,3, 3-tetramethyldisiloxane Download PDFInfo
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Abstract
The invention relates to a preparation method of high-purity 1,1,3, 3-tetramethyldisiloxane. The method adopts organochlorosilane low-boiling-point substances with the boiling point of less than 40 ℃ and alcohol compounds as raw materials, the low-boiling-point substances and the alcohol compounds are fed according to a specific ratio, subjected to alcoholysis and hydrolysis, kept stand to remove acid water, dried and filtered, the filtered hydrolysate is rectified, distillate at the temperature of 70-71 ℃ at the top of a tower is extracted, and the product 1,1,3, 3-tetramethyldisiloxane with the purity of more than or equal to 98.5 percent is obtained. The 1,1,3, 3-tetramethyl disiloxane can be used as raw materials for the production of addition type silicone rubber, silicone gel, methyl hydrogen silicone oil (SiH bond is more than 3) and other special additives.
Description
Technical Field
The invention relates to the technical field of chemical industry, belongs to the technical field of organic silicon materials, and particularly relates to a preparation method for synthesizing 1,1,3, 3-tetramethyldisiloxane from low-boiling-point organic chlorosilane.
Background
1,1,3, 3-tetramethyl disiloxane, also known as hydrogen-containing double-end socket, can introduce various organic groups on a polysiloxane molecular chain by utilizing SiH bonds on the end group of the 1,1,3, 3-tetramethyl disiloxane through hydrosilation reaction, so that the hydrogen-end polysiloxane has important application in synthesis of plastics, resin modification, silicone oil modification, cross-linking agents of liquid silicone rubber, special organic silicon surfactants and dendritic polymers.
At present, there are few reports on the synthesis of 1,1,3, 3-tetramethyldisiloxane at home and 3 major synthesis methods at abroad (1) direct method EP348902B (Cameron R A, Lewis K M, Kanner B, et al. direct Synthesis Process for Organohalohydrosilanes:1990-01-03.) discloses a direct synthesis method for producing Organohalohydrosilanes, in which a mixture of active silicon, organohalide and hydrogen is subjected to a catalytic reaction under the condition that the concentration of a selected metal atom is controlled, to produce Organohalohydrosilanes with high rate, high selectivity and high conversion rate selectively. (2) The Grignard method: JPH0656852(Kubota T, Endo M, Yamamoto A, et al.Production of dimethyl chlorosilane:1994-03-01) discloses a process for the production of dimethylsilane gas from dimethylsilane and dimethyldichlorosilane by injecting the dichlorosilane into a solution of methyl magnesium chloride prepared from methyl chloride and magnesium in a Grignard reactor. In a disproportionation reactor, continuously carrying out disproportionation reaction on dimethyl silane gas and dimethyl dichlorosilane to obtain a target compound. (3) Reduction method: EP0476597B (Takago T, Kishita H, Fujii H. Process for preparing 1,1,3, 3-tetramethyl 1,3 Disiloxanes: 1992-03-25.) discloses a process for preparing 1,1,3, 3-tetramethyl 1, 3-Disiloxane comprising the step of reducing 1,1,3, 3-tetramethyl, 3-dichloro, 3-Disiloxane by using a metal hydride such as lithium aluminum hydride, sodium aluminum hydride, etc.; the process described is very economically advantageous and in significantly high yields.
In the above synthesis method, the direct process reaction tail gas contains excessive hydrogen and chloromethane, which are difficult to compress and separate; the main raw material adopted by the Grignard method is dihydrodichlorosilane, so that the raw material is not easy to purchase and the synthesis cost is high; the reduction method adopts dimethyldichlorosilane and cyclic or linear polydimethylsiloxane as raw materials, and mainly obtains products of dimethyl siloxane tripolymer of chlorine end capping by means of Lewis acid telomerization or hydrolysis, while the yield of intermediate dichlorotetramethyldisiloxane is only 30%. In addition, the expensive lithium aluminum hydride is mainly selected as a reducing agent in the literature, so that the cost is too high, and the industrialization is not facilitated.
The by-product obtained by synthesizing methyl chlorosilane by a direct method contains 1-2% of a series of compounds with boiling points lower than 40 ℃. With the rapid increase in the production capacity and yield of methylchlorosilanes, the absolute amount of low boilers is also rapidly increasing. The organosilicon low-boiling mainly contains methyl-rich tetramethylsilane (the content is more than 30 percent) and dimethylchlorosilane (the content is about 20 percent), is not easy to store, and low-boiling residues can not be recycled, and the treatment method mainly comprises the step of treating the low-boiling residues by burning or selling at low price and subsiding to qualified units. At present, the incinerator has limited capacity, and more organosilicon low-boiling-point substances are produced, so that warehouse blockage is easy to occur and production stoppage is faced, and the low-boiling-point utilization is imperative.
In order to effectively solve the problem of low-cost sale of byproducts, remove the worries about expanding the production scale of monomers and simultaneously be the indispensable trend of sustainable development, the 1,1,3, 3-tetramethyldisiloxane is prepared by hydrolyzing low-boiling-point substances to generate new economic benefits, and the method has certain significance for the technical progress of organic silicon, leading industry, safe production and environmental protection.
In view of the above-mentioned disadvantages of the prior art, there is also a need for a better method for treating low boiling components in the production of organosilicon monomers, and a safer, environmentally friendly and low-cost method for producing 1,1,3, 3-tetramethyldisiloxane is desired.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing 1,1,3, 3-tetramethyldisiloxane, which has mild reaction conditions and simple reaction process, and the method synthesizes the 1,1,3, 3-tetramethyldisiloxane by using low-boiling-point substances generated in the production process of organosilicon monomers and through steps of alcoholysis, hydrolysis and rectification.
According to the invention, the low-boiling substances are a mixture of low-boiling substances removed during the production of the organosilicon monomers, the collected low-boiling substances have a boiling point range of < 40 ℃ and mainly contain SiM430-50％，HSiCl3Less than 2%, M215-45% of H, less than 10% of MH, less than 20% of hydrocarbon and the like.
The organosilicon monomer low-boiling-point substance can be obtained from any known organosilicon monomer production process, and the specific composition of the obtained organosilicon low-boiling-point substance can be changed due to the change of reaction conditions, raw materials and the like in different production processes, but the organosilicon low-boiling-point substance contains organosilicon chlorosilane low-boiling-point substances with higher proportion in general and can be used in the synthesis method of the invention. In contrast, the higher the content of dimethylhydrochlorosilane in the organosilicon chlorosilane low-boiling residue, the higher the yield of 1,1,3, 3-tetramethyldisiloxane produced by the method of the invention. In one embodiment of the invention, typical components and percentages of the low boilers of the organosilicon chlorosilanes can be as follows, for example:
in the above table: SiM4Is tetramethylsilicon, HSiCl3Is trichlorosilane, M2H is dimethyl hydrogen chlorosilane, and MH is methyl hydrogen dichlorosilane.
In the method for preparing 1,1,3, 3-tetramethyl disiloxane by using organosilicon monomer low-boiling residues, because the difference of the boiling points of all substances in the low-boiling residues is less than 10 ℃, the compounds are difficult to separate by direct normal-pressure rectification, in addition, the direct low-boiling residues contain more trifunctional group substances, more cross-linked substances are generated during hydrolysis, equipment is easy to block, and the yield is generally less than 50%; the inventor finds that impurities of trichlorosilane and methylhydrodichlorosilane which are trifunctional substances in low-boiling-point substances can be removed through alcoholysis, the purity of dimethylhydrochlorosilane is improved, the yield is more than 85 percent, and preparation is provided for preparing 1,1,3, 3-tetramethyldisiloxane.
Further, the invention provides a method for preparing 1,1,3, 3-tetramethyldisiloxane by taking organosilicon chlorosilane low-boiling-point substances as raw materials, which comprises the following steps:
(1) alcoholysis step: dropwise adding an alcohol compound into the organosilicon chlorosilane low-boiling-point substance to carry out alcoholysis reaction, rapidly heating, and rectifying to extract a fraction at the temperature of less than 40 ℃;
(2) a hydrolysis step: dropwise adding the fraction into water for hydrolysis, balancing after dropwise adding, layering oil and water after standing, collecting an upper oil phase, drying, neutralizing and filtering;
(3) a rectification step: rectifying the hydrolysate, and receiving distillate at the temperature of 70-71 ℃ at the top of the tower, namely 1,1,3, 3-tetramethyldisiloxane;
according to the invention, the preferable dropping flow rate in the step (1) is 250 g/h-300 g/h, and the alcoholysis reaction temperature is 10-20 ℃;
according to the invention, preferably, in the step (2), the dropping flow rate is 450-530 g/min, the hydrolysis reaction temperature is 6-8 ℃, the balance is 0.5h after the dropping, and the standing time is 5 min; drying with anhydrous sodium sulfate, and neutralizing and stirring with a neutralizing agent for 0.5-2 h;
according to the invention, the weight ratio of the raw materials is preferably as follows: low-boiling-point substances: the alcohol compound is (8-13: 1), preferably (8-12: 1); in a preferred embodiment of the invention, the low boilers: the weight ratio of the alcohol compounds is as follows: (9 to 12: 1)
According to the invention, the preferred weight ratio of alcoholysis overhead is: fraction (c): the water is (1: 1.3-2.2), preferably (1: 1.3-2.0); in a preferred embodiment of the invention, the fraction: the weight ratio of water is as follows: (1: 1.3 to 1.9)
The reaction kettle and the reaction tower used according to the invention can be reaction kettles and reaction towers commonly used in the field, and the materials and the specifications can be materials and specifications which are conventional in the field.
According to the invention, the purification and refining method comprises vacuum rectification and optional atmospheric rectification.
In one embodiment of the present invention, the purification and purification method is: rectifying under normal pressure, and separating 1,1,3, 3-tetramethyldisiloxane in a fraction at 70-71 ℃.
Preferably, when the distillation is carried out under normal pressure, the distillation top temperature is controlled to be 70-71 ℃. According to the invention, M is distilled off2H can be used as a method for synthesizing 1,1,3, 3-tetramethyldisiloxane used in the present invention; can also be used as raw materials in other processes for synthesizing 1,1,3, 3-tetramethyldisiloxane.
Preferably, in the above method for preparing 1,1,3, 3-tetramethyldisiloxane, the raw materials are organochlorosilane low-boiling components and alcohols with boiling points less than 40 ℃.
Preferably, in the preparation method of 1,1,3, 3-tetramethyldisiloxane, the alcoholysis reaction temperature is 10-25 ℃, and preferably 10-20 ℃.
Preferably, in the above method for preparing 1,1,3, 3-tetramethyldisiloxane, the alcohol compound used in the alcoholysis reaction is selected from aliphatic alcohols, aromatic alcohols and alicyclic alcohols, preferably from aliphatic alcohols, and more preferably from one or a mixture of two of methanol, ethanol, propanol, ethylene glycol, propylene glycol and glycerol.
Preferably, in the preparation method of the 1,1,3, 3-tetramethyldisiloxane, the hydrolysis reaction temperature is 5-12 ℃, and the most preferred temperature is 6-8 ℃.
Preferably, in the preparation method of the 1,1,3, 3-tetramethyldisiloxane, the alcoholysis dropping flow rate is 250-400 g/h, and preferably 250-350 g/h.
Preferably, in the preparation method of 1,1,3, 3-tetramethyldisiloxane, the reaction equilibrium time is 0.5-1 h, and the equilibrium time is 0.5 h.
Preferably, in the preparation method of the 1,1,3, 3-tetramethyldisiloxane, the neutralization time is 0.5-2 h, and more preferably 1-2 h.
Preferably, in the preparation method of the 1,1,3, 3-tetramethyldisiloxane, the purity range of the rectification extraction reaction product 1,1,3, 3-tetramethyldisiloxane can be controlled to be more than or equal to 98.5%.
Preferably, in the preparation method of the 1,1,3, 3-tetramethyldisiloxane, the viscosity of the reaction product 1,1,3, 3-tetramethyldisiloxane can be controlled within the range of 2-2.5 cs.
Preferably, in the above method for preparing 1,1,3, 3-tetramethyldisiloxane, the reaction product 1,1,3, 3-tetramethyldisiloxane has a storage temperature of less than 20 deg.C
The preparation process comprises the following steps: feeding materials according to a certain proportion, adding the weighed organosilicon chlorosilane low-boiling material into a four-neck flask with a stirring device, a thermometer, a rectifying tower and a condensing device, fixing the flask in a constant-temperature cooling device, adding the weighed alcohol compound into a dropping bottle when the temperature of an ice maker is reduced to 0 ℃, controlling the dropping speed to be 250-350 g/h, controlling the reaction temperature to be 10-20 ℃, discharging tail gas into an acid water tank for absorption, balancing for 30min after dropping, starting a heating device, and starting heating for rapid rectification and extraction of fractions less than 40 ℃.
Feeding a fraction extracted by rectification and less than 40 ℃ and water according to a certain ratio, firstly adding the water into a four-neck flask with a stirring device, a thermometer, a condensing device and a constant-pressure dropping funnel, fixing the flask in a constant-temperature cooling device, when the temperature of an ice maker is reduced to 3 ℃, beginning to drop the fraction, controlling the dropping flow rate to be 450-530 g/h, simultaneously controlling the reaction temperature to be 6-8 ℃, balancing for 0.5h after dropping, standing for 5min to remove lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying a filtered hydrolysate, extracting a distillate at the temperature of 70-71 ℃ at the top of the tower for chromatographic analysis, wherein the purity of 1,1,3, 3-tetramethyldisiloxane is more than or equal to 98.5%.
ADVANTAGEOUS EFFECTS OF INVENTION
The novel method for synthesizing 1,1,3, 3-tetramethyldisiloxane by using the organosilicon chlorosilane low-boiling-point substance has the following excellent effects:
(1) the invention uses organosilicon chlorosilane low-boiling residue as raw material, M2The conversion per pass of H is more than 85 percent, the synthesis cost of 1,1,3, 3-tetramethyldisiloxane is reduced in the actual production, the process is simple, the technical problem that the byproduct low-boiling-point substances produced by the organosilicon monomer are converted into products with high added values is solved, the method belongs to waste utilization, increases the high-value economic benefits of the byproduct, and is environment-friendly and low in comprehensive cost.
(2) In the preparation method of the invention, the useful substance in the low-boiling raw material is M2H, becomes 1,1,3, 3-tetramethyl disiloxane after reaction, and all M is contained in the rest low-boiling substances4And a CH compound, M4 can be used for disproportionation reaction, the rest CH material enters an incineration device, and the kettle liquid can be used for preparing hydrogen-containing silicone oil.
(3) The organosilicon chlorosilane low-boiling-point substance is fully utilized, and the danger of the organosilicon chlorosilane low-boiling-point substance as liquid waste is reduced; the low-boiling component contains relatively more chain hydrocarbon, has low flash point, is extremely easy to burn and is more dangerous. The low-boiling-point substances are converted into products with higher secondary value, and a new idea for treating the low-boiling-point waste is provided.
(4) The purity of the 1,1,3, 3-tetramethyldisiloxane prepared by the method is more than or equal to 98.5 percent, the viscosity range is 2-2.5cs, and the yield is more than 80 percent.
Drawings
FIG. 1: a process flow diagram for preparing 1,1,3, 3-tetramethyl disiloxane from organosilicon monomer low-boiling residues;
FIG. 2: the gas chromatogram of the low boiling substance as the raw material used in example 1 and the contents of the main components;
FIG. 3: example 1 gas chromatogram and main component content of 1,1,3, 3-tetramethyldisiloxane obtained after rectification.
Detailed Description
Hereinafter, a mode for carrying out the present invention will be described in detail.
The present invention is further described below with reference to examples. It should be noted that the examples are not intended to limit the scope of the present invention, and those skilled in the art will appreciate that any modifications and variations based on the present invention are within the scope of the present invention.
Conventional chemicals used in the following examples are commercially available.
The low-boiling-point substances used in the following examples are derived from the by-products of the synthesis of organosilicon monomers, and the typical components and percentages of the low-boiling-point substances are as follows:
boiling point of low-boiling component
The boiling points and compositions of the main components in the low-boiling components are shown in the above table.
Sources and purities of the raw materials used in the following examples:
organosilicon chlorosilane low-boiling-point substances: ekensin Silicones Ltd
Methanol, ethanol, propanol: analytical purity
Water: deionized water
Anhydrous sodium sulfate: analytical purity
Sodium bicarbonate: analytical purity
Diatomite: 60-80 mesh Guangzhou Yikang New Material science and technology Co., Ltd
Example 1:
adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 55g of methanol into a dropping bottle, dropping when the temperature in the flask is cooled to 10 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 300g/h, starting a heating device to heat up, performing fast rectification to extract fractions with the temperature of less than 40 ℃, and M2The H utilization was 92.3%. . Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 3 ℃, pouring 168g of fraction which is extracted by rectification and is less than 40 ℃ into a dropping bottle, starting dropping fraction, controlling the dropping flow rate at 472g/h, controlling the reaction temperature at 8 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate with the purity of 98.97% of a hydrogen-containing double-end enclosure at the top of a tower at 70-71 ℃. The viscosity is 2.1cs, and the yield of the hydrogen-containing double-end socket is 83.7%.
TABLE 1 gas chromatography measurement of the content of the main component of the raw Material Low boiling substance
TABLE 2 gas chromatography measurement of the content of the main component of the rectified product
Note: retention time min: the time from the introduction of the separated component to the time when the maximum concentration of the component appears after the column
The percentage content is as follows: mass fraction of a certain component
Example 2:
adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 55g of methanol into a dropping bottle, dropping when the temperature in the flask is cooled to 10 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 300g/h, starting a heating device to heat up, performing fast rectification to extract fractions with the temperature of less than 40 ℃, and M2The H utilization was 93.9%. . Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 3 ℃, pouring 168g of fraction which is extracted by rectification and is less than 40 ℃ into a dropping bottle, starting dropping fraction, controlling the dropping flow rate at 472g/h, controlling the reaction temperature at 8 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate with the purity of 98.97% of a hydrogen-containing double-end enclosure at the top of a tower at 70-71 ℃. The viscosity is 2.1cs, and the yield of the hydrogen-containing double-end socket is 86.5%.
Example 3:
adding 600g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 50g of ethanol into a dropping bottle, dropping when the temperature in the flask is cooled to 10 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 250g/h, starting a heating device to heat up, performing fast rectification to extract fractions with the temperature of less than 40 ℃, and M2The H utilization was 95.1%. . Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 3 ℃, pouring 150g of fraction with the temperature less than 40 ℃ obtained by rectification into a dropping bottle, starting dropping the fraction, controlling the dropping flow rate at 490g/h, controlling the reaction temperature at 8 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate with the purity of 98.57% containing hydrogen and double end enclosures at the top of the tower at 70-71 ℃. The viscosity is 2.0cs, and the yield of the hydrogen-containing double end enclosure is 89.4%.
Example 4:
adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 62.5g of ethanol into a dropping bottle, dropping when the temperature in the flask is cooled to 10 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 300g/h, starting a heating device to start heating up, performing fast rectification and extraction on fractions with the temperature of less than 40 ℃, and performing M-phase rectification on fractions with the temperature of less than 40 DEG C2The H utilization was 93.6%. . Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 3 ℃, pouring 187g of fraction obtained by rectification and extraction at the temperature of less than 40 ℃ into a dropping bottle, starting dropping the fraction, controlling the dropping flow rate at 472g/h, controlling the reaction temperature at 8 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate at the tower top at 70-71 ℃ with the purity of 98.97 percent of a hydrogen-containing double-end enclosure. The viscosity is 2.1cs, and the yield of the hydrogen-containing double-end socket is 84.9%.
Example 5:
adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 55g of propanol into a dropping bottle, dropping when the temperature in the flask is cooled to 10 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 300g/h, starting a heating device to heat up, performing fast rectification to extract fractions with the temperature of less than 40 ℃, and M2The H utilization was 93.6%. . Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 3 ℃, pouring 168g of fraction which is extracted by rectification and is less than 40 ℃ into a dropping bottle, starting dropping fraction, controlling the dropping flow rate at 472g/h, controlling the reaction temperature at 8 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate with the purity of 98.97% of a hydrogen-containing double-end enclosure at the top of a tower at 70-71 ℃. The viscosity is 2.1cs, and the yield of the hydrogen-containing double-end socket is 86.8%.
Example 6:
500g of organosilicon chlorosilane low-boiling residue is added into a dry 1000mL four-mouth bottle and controlledWhen the temperature of an ice maker is reduced to 0 ℃, adding 45g of propanol into a dropping bottle, dropping when the temperature in the flask is cooled to 10 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate at 350g/h, starting a heating device to heat up, performing rapid rectification, extracting fractions with the temperature of less than 40 ℃, and M2The H utilization was 95.1%. . Weighing 350g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 3 ℃, pouring 205g of fraction which is extracted by rectification and is less than 40 ℃ into a dropping bottle, starting dropping the fraction, controlling the dropping flow rate at 450g/h, controlling the reaction temperature at 6 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate at the tower top of 70-71 ℃ with the purity of a hydrogen-containing double-end enclosure of 99.04%. The viscosity is 2.12cs, and the yield of the hydrogen-containing double-end socket is 88.2%.
Example 7:
adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 52g of a mixture of methanol and ethanol into a dropping bottle, dropping when the temperature in the flask is cooled to 15 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 250g/h, starting a heating device to heat up, performing fast rectification and extracting fractions with the temperature of less than 40 ℃, and performing M2The H utilization was 94.1%. . Weighing 350g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 3-10 ℃, pouring 269g of fraction with the distillation extraction temperature being less than 40 ℃ into a dropping bottle, starting dropping the fraction, controlling the dropping flow rate at 530g/min, controlling the reaction temperature at 8 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and obtaining a distillate with the purity of 98.49 percent of a hydrogen-containing double-end enclosure at the top of a receiving tower, wherein the distillate at the temperature of 70-71 ℃ is hydrogen-containing. The viscosity is 2.2cs, and the yield of the hydrogen-containing double-end socket is 87.8%. .
Example 8:
adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 53g of methanol and propanol mixture, and dropwise addingIn a bottle, dropwise adding when the temperature in the flask is cooled to 12 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropwise adding flow rate at 320g/h, starting a heating device to heat up, performing rapid rectification, extracting fractions with the temperature of less than 40 ℃, and performing M2The H utilization was 92.5%. . Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 5 ℃, pouring 214g of fraction which is extracted by rectification and is less than 40 ℃ into a dropping bottle, beginning dropping the fraction, controlling the dropping flow rate at 450g/min, controlling the reaction temperature at 7 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate with the purity of 99.23% of a hydrogen-containing double-end enclosure at the top of the tower at 70-71 ℃. The viscosity is 2.07cs, and the yield of the hydrogen-containing double end socket is 85.3%. .
Comparative example 1
Adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 71g of a methanol and propanol mixture into a dropping bottle, dropping when the temperature in the flask is cooled to 12 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 320g/h, starting a heating device to start heating up, performing fast rectification and extraction on fractions with the temperature of less than 40 ℃, and causing part M to be partially due to excessive alcohol at the moment2H was alcoholyzed and M2H utilization was 72%. Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 5 ℃, pouring 250g of fraction with the temperature less than 40 ℃ obtained by rectification into a dropping bottle, starting dropping the fraction, controlling the dropping flow rate at 450g/min, controlling the reaction temperature at 7 ℃, balancing the dropping for 0.5h, standing for 5min, removing lower-layer acid water, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate for drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate with the purity of 98.13% of a hydrogen-containing double-end enclosure at the top of the tower at 70-71 ℃. The viscosity is 2.02cs, and the yield of the hydrogen-containing double end socket is 69%.
Comparative example 2
Adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 35.71g of methanol and propanol mixture into a dropwise adding bottle until the flask is readyCooling to 12 deg.C, dripping, discharging tail gas into acid water tank for absorption, controlling dripping flow rate at 320g/h, starting heating device to heat, rapidly rectifying to extract fraction less than 40 deg.C, and introducing part of substances MH, M not subjected to alcoholysis into distillate2The H utilization was 67%. Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 5 ℃, pouring 291g of fraction with the temperature less than 40 ℃ obtained by rectification into a dropping bottle, starting dropping the fraction, controlling the dropping flow rate at 450g/min, controlling the reaction temperature at 7 ℃, balancing for 0.5h after dropping, allowing part of MH hydrolyzed cross-linked substances in the reaction bottle to stand for 5min, removing acid water and cross-linked substances at the lower layer, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate, drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate at the top of the tower with the temperature of 70-71 ℃ and having the purity of 98.13% of a hydrogen-containing double-end enclosure. The viscosity is 2.02cs, and the yield of the hydrogen-containing double-end socket is 62%.
Comparative example 3
Adding 500g of organic chlorosilane low-boiling-point substances into a dry 1000mL four-mouth bottle, controlling the temperature of an ice maker to be reduced to 0 ℃, adding 35.71g of a mixture of methanol and propanol into a dropping bottle, dropping when the temperature in the flask is cooled to 12 ℃, discharging tail gas into an acid water tank for absorption, controlling the dropping flow rate to be 320g/h, starting a heating device to heat up, performing fast rectification to extract fractions with the temperature of less than 40 ℃, and carrying partial substances MH, M which do not finish alcoholysis into distillate2The H utilization was 68%. Weighing 300g of water, adding the water into a dry 1000mL four-mouth bottle, when the temperature of an ice maker is reduced to 5 ℃, pouring 130g of fraction with the temperature of less than 40 ℃ obtained by rectification into a dropping bottle, starting dropping the fraction, controlling the dropping flow rate at 450g/min, controlling the reaction temperature at 7 ℃, balancing for 0.5h after dropping, allowing part of MH hydrolyzed cross-linked substances in the reaction bottle to stand for 5min, removing acid water and cross-linked substances at the lower layer, collecting an oil phase by using a glass bottle, adding anhydrous sodium sulfate, drying, neutralizing and stirring by using sodium bicarbonate for 0.5-2 h, filtering, rectifying the filtered hydrolysate, and receiving distillate with the temperature of 70-71 ℃ at the top of a tower, wherein the purity of a hydrogen-containing double-end enclosure is 98.13. The viscosity is 2.02cs, and the yield of the hydrogen-containing double-end socket is 63%.
The above embodiments are merely illustrative of the present disclosure and do not represent a limitation of the present disclosure. Other variations of the specific structure of the invention will occur to those skilled in the art.
Claims (9)
1. A preparation method for synthesizing 1,1,3, 3-tetramethyl disiloxane by organosilicon chlorosilane low-boiling-point substances is characterized in that the 1,1,3, 3-tetramethyl disiloxane is synthesized by alcoholysis and hydrolysis of the organosilicon chlorosilane low-boiling-point substances; the low-boiling-point substance is a mixture consisting of low-boiling-point substances removed in the process of producing the organic silicon monomer, the boiling point range of the collected low-boiling-point substance is less than 40 ℃, and the low-boiling-point substance mainly contains SiM430-50wt％，HSiCl3Less than 2 wt%, M215-45 wt% of H, less than 10 wt% of MH and less than 20 wt% of hydrocarbons, wherein the sum of all the components is 100 wt%.
2. The method of preparing 1,1,3, 3-tetramethyldisiloxane in accordance with claim 1, comprising the steps of:
(1) alcoholysis: dropwise adding an alcohol compound into the organosilicon chlorosilane low-boiling residue for alcoholysis reaction, quickly heating and rectifying, and extracting a fraction with the temperature of less than 40 ℃ from a distillate at the top of an alcoholysis tower;
(2) hydrolysis: dropwise adding the fraction into water for hydrolysis, balancing after dropwise adding, layering oil and water after standing, collecting an upper oil phase, drying, neutralizing, and filtering to obtain a hydrolysate;
(3) and (3) rectification: rectifying the hydrolysate, and receiving distillate at the temperature of 70-71 ℃ at the top of the tower, namely 1,1,3, 3-tetramethyldisiloxane;
in the step (1), the dropping flow rate of the alcohol compound is 250-400 g/h, and the alcoholysis reaction temperature is 10-25 ℃; the weight ratio of the raw materials is as follows: low-boiling-point substances: the alcohol compound is (8-13: 1);
in the step (2), the dropping flow rate of the distillate is 450-530 g/min, the hydrolysis reaction temperature is 5-12 ℃, the dropping is balanced for 0.5-1 h, and the standing time is 5 min; drying with anhydrous sodium sulfate, and neutralizing and stirring with a neutralizing agent for 0.5-2 h; the weight ratio of the raw materials is as follows: fraction (c): the water is (1: 1.3-2.2).
3. The method of claim 2, wherein the neutralizing agent is anhydrous sodium bicarbonate.
4. The method for producing 1,1,3, 3-tetramethyldisiloxane in accordance with any one of claims 2 to 3, wherein the alcoholysis reaction temperature is 10 to 20 ℃ and the hydrolysis reaction temperature is 6 to 8 ℃.
5. The process for producing 1,1,3, 3-tetramethyldisiloxane in accordance with any one of claims 2 to 4, wherein the alcohol dropping flow rate in the step (1) is 250 to 350g/h, and the hydrolyzate dropping flow rate in the step (2) is 480 to 530 g/h.
6. The process for producing 1,1,3, 3-tetramethyldisiloxane in accordance with any one of claims 2 to 5, wherein the low-boiling hydrolyzate equilibration time is 0.5 to 1.0 hour and the low-boiling hydrolyzate neutralization time is 0.5 to 2 hours.
7. The method for preparing 1,1,3, 3-tetramethyldisiloxane in accordance with any one of claims 2 to 6, characterized in that the weight ratio of the raw materials is: low-boiling-point substances: the alcohol is (8-13: 1).
8. The process of any one of claims 2-7, wherein the alcoholysis overhead is in the following weight ratio: fraction (c): the water is (1: 1.3-2.2).
9. The method of producing 1,1,3, 3-tetramethyldisiloxane in accordance with any one of claims 2 to 8, wherein the viscosity of the reaction product 1,1,3, 3-tetramethyldisiloxane is 2 to 2.5 cs.
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| CN111909191A (en) * | 2020-07-01 | 2020-11-10 | 鲁西化工集团股份有限公司硅化工分公司 | Method and system for preparing tetramethyl dihydrodisiloxane by hydrolyzing organosilicon low-boiling-point substances and comprehensive utilization method |
| CN114262342A (en) * | 2021-12-28 | 2022-04-01 | 郑州原理生物科技有限公司 | Method for purifying phenylsilane |
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