CN110483776B - Synthesis method and synthesis device of high-purity silicone oil - Google Patents
Synthesis method and synthesis device of high-purity silicone oil Download PDFInfo
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- CN110483776B CN110483776B CN201910797498.1A CN201910797498A CN110483776B CN 110483776 B CN110483776 B CN 110483776B CN 201910797498 A CN201910797498 A CN 201910797498A CN 110483776 B CN110483776 B CN 110483776B
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract
The invention belongs to the technical field of chemical materials, and particularly relates to a synthetic method and a synthetic device of high-purity silicone oil. The invention provides a synthetic method of high-purity silicone oil, which comprises the following steps of 1, mixing a polysiloxane ring body, a blocking agent and a catalyst for reaction to obtain a reactant 1; step 2, removing the catalyst of the reactant 1 to obtain a product 1; and 3, mixing the product 1 with an azeotropic solvent, and performing azeotropic treatment to obtain the high-purity silicone oil. The invention provides a high-efficiency, simple and convenient silicone oil purification method and production process with low cost by introducing a low-boiling point organic alkane azeotropic solvent into a silicone oil synthesis reaction system and matching with azeotropic and condensation treatment, and the obtained silicone oil has high purity and can meet the special requirements of different industries on the quality of the silicone oil.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to a synthetic method and a synthetic device of high-purity silicone oil.
Background
The silicone oil is used as a basic raw material, has a large number of applications in various industries such as medical treatment, food, electric power, automobiles, industry and the like, and is also a basic polymer for preparing various organic silicon rubber products.
The silicone oil is mainly composed of polyorganosiloxane, and the synthesis of the silicone oil is that cyclic organosiloxane is used as a raw material, and linear polyorganosiloxane is prepared by ring-opening polymerization under the condition of taking acid or alkali as a catalyst. The ring-opening polymerization reaction of cyclic organosiloxane is an equilibrium reaction, and about 12 to 14% of cyclic siloxane, including D3-D20 small molecule rings such as hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and the like, and a small amount of small molecule linear polyorganosiloxanes are present in the synthesis reaction. Generally, after the equilibrium reaction of silicone oil is completed, the micromolecules are removed by heating and reducing pressure, in order to improve the purity of silicone oil, inert gases such as nitrogen and the like are blown into a reaction kettle to promote the removal of the micromolecules, or the micromolecule polysiloxane is removed by heating and reducing pressure of a reaction system by adopting methods such as a film evaporation container, a molecular distillation container, extraction and the like. However, the existing synthetic method for improving the purity of the silicone oil still has the technical defect that small molecules cannot be completely removed. For example, the synthetic reaction of the silicone oil is usually carried out in a vertical reaction kettle, the addition amount of liquid in the reaction kettle is not more than two thirds of the volume at most, the liquid level depth is higher, the content of low molecules in the silicone oil has higher boiling points, for example, the boiling point of D3 is 134 ℃, the boiling point of D4 is 175 ℃, the boiling point of D5 is 210 ℃, the boiling point is higher and higher along with the increase of the molecular weight, and the heating temperature of the materials in the reaction kettle is generally about 200 ℃ due to the temperature resistance limit of the silicone oil. When the pressure is reduced and the low-molecular-weight polysiloxane is removed, the temperature difference is easily formed due to the space of one third of the upper layer of the reaction kettle, so that the vaporized low-molecular-weight polysiloxane is continuously condensed and reflows and cannot be completely removed. And the method of blowing inert gases such as nitrogen and the like into the bottom of the reaction kettle is adopted to carry out vaporization of the low molecular weight polysiloxane, and the dispersion degree of bubbles blown out by the gases is insufficient, so that the low molecular weight polysiloxane is easy to gather, the amount of the low molecular weight polysiloxane which can be carried out is limited, the low molecular weight polysiloxane cannot be recycled, the cost is high, the time is long, and the tail gas is easy to cause environmental pollution. And the method of adopting film evaporation container or molecular distillation container, etc. has complex process, expensive equipment, high batch production cost, etc. The method of adding solvents such as methanol, ethanol, acetic acid and the like for extraction and then separating and distilling is adopted, because the extraction principle is that the selected extraction solvent is not compatible with the extracted main solution and is compatible with impurities in the main solution, but the low molecular weight polysiloxane ring body is the same as the silicone oil, the selected solvents such as methanol, ethanol, acetic acid and the like are not compatible with the silicone oil main body, the compatibility with the low molecular weight polysiloxane is limited, the extraction time is long, and the ideal effect cannot be achieved. Therefore, the content of the small molecule polysiloxane removed by the method is limited, so that the volatile matter index range of the standard of the conventional polysiloxane products on the market is generally 1% -3%.
The residual low molecular substances in the silicone oil can volatilize and exude in long-term use, so that contact faults in products such as electronic and electric appliances are easily caused, the surfaces of optical devices are blurred, the electrical insulating property is reduced, and the content of hazardous substances in the industries such as food, medical treatment and the like exceeds the standard. Therefore, the development of a synthetic method of high-purity silicone oil is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to develop a method for synthesizing high purity silicone oil with simple method and high efficiency.
The invention provides a synthetic method of high-purity silicone oil, which comprises the following steps:
and 3, mixing the product 1 with an azeotropic solvent, and performing azeotropic treatment to obtain the high-purity silicone oil.
Specifically, the polysiloxane ring body accounts for 100 parts by weight, the end-capping agent accounts for 0.1-5 parts by weight, the catalyst accounts for 0.01-3 parts by weight, and the azeotropic solvent accounts for 5-200 parts by weight.
Preferably, the polysiloxane ring body is selected from one or more of dimethylcyclosiloxane, methylvinylcyclosiloxane, methylphenylcyclosiloxane, diphenylcyclosiloxane, methyltrifluoropropylcyclosiloxane and methylhydrocyclosiloxane.
Preferably, the blocking agent is selected from one or more of hexamethyldisiloxane, methylvinyldisiloxane and methylhydrodisiloxane.
Preferably, the catalyst is selected from an acidic catalyst, a basic catalyst or a solid catalyst.
Preferably, the basic catalyst is selected from tetramethylammonium hydroxide or/and potassium hydroxide;
the solid catalyst is selected from cationic resin or/and linear polyphosphazene;
the acid catalyst is selected from phosphoric acid or/and hydrochloric acid.
Specifically, in step 1, after the polysiloxane ring body, the blocking agent and the catalyst are mixed, the mixture can be heated to react, and the heating temperature is 100-130 ℃. Preferably, the heating temperature is 105-.
Preferably, the azeotropic solvent is an organic alkane having a boiling point of 200 ℃ or lower.
Preferably, the azeotropic solvent is selected from one or more of pentane, hexane, heptane, octane and nonane.
Preferably, the weight ratio of the azeotropic solvent to the product 1 is (5-200): 100.
preferably, step 1 comprises:
step 1a, heating a polysiloxane ring body and then performing reduced pressure dehydration treatment to obtain a product I;
and step 1b, mixing and heating the first product, a blocking agent and a catalyst for reaction to obtain a reactant 1.
Specifically, in the step 1a, the heating temperature for heating the polysiloxane ring body is 60-80 ℃, and the decompression dehydration time is 10-60 min;
in the step 1b, the heating temperature for mixing and heating the first product, the blocking agent and the catalyst is 100-.
Specifically, in the step 1a, the heating temperature for heating the polysiloxane ring body is 60-80 ℃, wherein 60-80 ℃ is the early stage dehydration temperature, the early stage dehydration temperature is the early stage dehydration temperature without adding a blocking agent and a catalyst for reaction, the reaction temperature is not the reaction temperature, and the decompression dehydration time can be based on no condensate release.
The application also provides a synthesizer of high-purity silicone oil, including:
the device comprises a reaction kettle, a horizontal rotary evaporator, a condenser and a recovery tank;
the reaction kettle is connected with the horizontal rotary evaporator through a pipeline, a silicone oil outlet is formed in the bottom of the horizontal rotary evaporator, and a material inlet is formed in the top of the horizontal rotary evaporator;
the horizontal rotary evaporator is connected with the condenser through a pipeline;
the condenser is connected with the recovery tank through a pipeline.
Specifically, the reaction kettle is used for mixing the polysiloxane ring body, the end-capping reagent and the catalyst for reaction to obtain a reactant 1, and the catalyst used for removing the reactant 1 is used for obtaining a product 1.
Specifically, the horizontal rotary evaporator is used for mixing the product 1 with an azeotropic solvent to perform azeotropic treatment.
Specifically, the condenser is used to condense vapor generated by azeotropy in the horizontal rotary evaporator.
Specifically, the recovery tank is used for collecting the azeotropic solvent and the micromolecule substances condensed by the condenser.
Concretely, the recovery tank comprises a first sub-recovery tank and a second sub-recovery tank, the condenser is connected with the first sub-recovery tank and the second sub-recovery tank through a three-way valve, the first sub-recovery tank is used for recovering an azeotropic solvent, and the second sub-recovery tank is used for recovering D3-D20 micromolecule substances.
Specifically, when the synthesis device is used, the polysiloxane ring body, the end-capping agent and the catalyst can be independently fed into a reaction kettle, the reaction kettle can be a stirred temperature-adjustable reactor provided with a motor, and after the materials are independently fed, the polysiloxane ring body, the end-capping agent and the catalyst can be subjected to mixing reaction in the reaction kettle; the polysiloxane ring body, the end-capping reagent and the catalyst can also be premixed and then put into a reaction kettle for reaction, and the reaction kettle can also be a reactor with adjustable temperature; after the reaction is finished, the catalyst can be removed through high-temperature, neutralization or filtration treatment, then the product 1 is conveyed into a horizontal rotary evaporator, an azeotropic solvent is added from an inlet of the horizontal rotary evaporator, then azeotropic treatment is carried out to obtain high-purity silicone oil, meanwhile, steam generated by azeotropy is conveyed into a condenser, and the condensed azeotropic solvent with different boiling points and D3-D20 micromolecule substances enter a recovery tank through a pipeline for recycling.
The application still provides one high-purity silicon oil's synthesizer be equipped with reation kettle, horizontal rotary evaporator, condenser and recovery jar, through reacting the raw materials in reation kettle, carry out azeotropic treatment with result and azeotropic solvent in horizontal rotary evaporator, obtain high-purity silicon oil, and retrieve azeotropic solvent condensation through setting up condenser and recovery jar, recycle. The purity of the silicone oil product obtained by the synthesis method is tested by a Gas Chromatography (GC) method and volatilization, and the volatile micromolecule content of the silicone oil product is less than 0.5 percent by weight.
Preferably, the horizontal rotary evaporator is a rotary evaporator which is longer than high.
Preferably, step 2 specifically comprises: the product 1 is obtained after removing the catalyst of the reactant 1 by high temperature, neutralization or filtration treatment.
Preferably, step 3 specifically includes: and (3) carrying out azeotropic treatment on the product 1 and the azeotropic solvent in a horizontal rotary evaporator to obtain the high-purity silicone oil.
It should be noted that the horizontal rotary evaporator is a longer rotary evaporator than the high rotary evaporator.
Specifically, the step 3 specifically includes: and (3) vacuumizing the product 1 and the azeotropic solvent to be below-0.06 MPa in a horizontal rotary evaporator, and performing azeotropic treatment to obtain the high-purity silicone oil.
More preferably, in step 3, the azeotropic temperature is 25 to 200 ℃.
The azeotropic temperature range is 25-200 ℃. Since the temperature at which the azeotropic solution starts varies according to the boiling point of the selected azeotropic solvent, the azeotropic solvent may be one or more selected from pentane, hexane, heptane, octane and nonane, for example, n-hexane has a boiling point of about 60 ℃ at normal atmospheric pressure and evaporates at about 40 ℃ when the pressure is reduced to less than-0.06 MPa, the boiling point of the selected azeotropic solvent is lower, the liquid with different azeotropic points is evaporated continuously as the temperature gradually rises, and the low molecular substance is substantially removed at 200 ℃, the azeotropic temperature is preferably 25 to 200 ℃.
The method is characterized in that the azeotropic solvent removes polysiloxane micromolecules, the vaporized azeotropic solvent and the vaporized polysiloxane micromolecules are condensed by a tubular condenser, and condensed liquids at different temperatures are connected to different solvents through a three-way valve to realize separation and recovery of the azeotropic solvent and the polysiloxane micromolecules, so that a high-purity silicone oil product after evaporation is obtained in a horizontal rotary evaporator.
The invention aims to overcome the technical defect that the prior art can not prepare high-purity silicone oil, and provides a synthetic method and a production process of high-purity silicone oil, wherein the synthetic method comprises the following steps: by introducing organic alkane which is lower than low molecular polysiloxane in boiling point and has larger boiling point difference into the polyorganosiloxane mixture after equilibrium reaction, the boiling point and vaporization temperature of the azeotrope are reduced by utilizing the azeotropy of the organic alkane and the low molecular polysiloxane, and meanwhile, the volume of an upper layer space is reduced by adopting a horizontal rotary evaporator, so that the condensation reflux caused by the temperature difference of the upper layer space and the high boiling point of the polysiloxane is greatly reduced. The invention adopts a liquid azeotropic mode, the azeotropic solvent is more fully mixed with the polysiloxane mixture, and the low molecular polysiloxane can be fully carried out by continuously vaporizing organic alkane in large quantity. The vaporized organic alkane is condensed by a tubular condenser, and the organic alkane and the low molecular polysiloxane are directly separated and recovered by utilizing the different boiling points of the organic alkane and the low molecular polysiloxane for recycling. The method and the process greatly reduce the production flow of the silicone oil, improve the efficiency, simultaneously obtain the silicone oil with high purity and extremely low volatile content, and can meet the special requirements of different industries on the quality of the silicone oil. The purity of the silicone oil product obtained by the synthesis method is tested by a Gas Chromatography (GC) method and volatilization, and the volatile micromolecule content of the silicone oil product is less than 0.5 percent by weight. Compared with the traditional method, the technical scheme of the application introduces the azeotropic solvent, and in addition, the solvent is easier to recover and the production efficiency of the silicone oil is improved by matching with the synthesis device provided by the application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows a synthesis apparatus for high purity silicone oil provided by the present invention;
the device comprises a reaction kettle 1, a reaction kettle outlet 1-1, a horizontal rotary evaporator 2, a horizontal rotary evaporator inlet 2-1, a fourth raw material inlet 2-2, a horizontal rotary evaporator outlet 2-3, a high-purity silicone oil outlet 2-4, a condenser 3, a condenser inlet 3-1, a condenser outlet 3-2, a three-way valve 7, a second sub-recovery tank 4, a second sub-recovery tank inlet 4-1, a first sub-recovery tank 5, a first sub-recovery tank inlet 5-1, a motor 6, a first raw material inlet A, a second raw material inlet B, a third raw material inlet C, a fourth raw material D and a silicone oil finished product E.
Detailed Description
The invention provides a synthetic method and a synthetic device of high-purity silicone oil, which are used for solving the technical defects that the silicone oil synthesized by the prior art has low purity and can not completely remove low-molecular substances.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the following examples are all commercially available or self-made.
Example 1
The embodiment of the invention provides a first synthesis method of high-purity silicone oil, which comprises the following steps:
as shown in fig. 1, an embodiment of the present invention provides a synthesis apparatus for high-purity silicone oil, including: the system comprises a reaction kettle 1, a horizontal rotary evaporator 2, a condenser 3, a three-way valve 7, a second sub-recovery tank 4 and a first sub-recovery tank 5; an outlet 1-1 of the reaction kettle is connected with an inlet 2-1 of the horizontal rotary evaporator through a pipeline, the bottom of the horizontal rotary evaporator 2 is provided with a high-purity silicone oil outlet 2-4, and the top of the horizontal rotary evaporator 2 is provided with a fourth raw material inlet 2-2; an outlet 2-3 of the horizontal rotary evaporator is connected with an inlet 3-1 of the condenser through a pipeline; the outlet 3-2 of the condenser is respectively connected with the second sub-recovery tank 4 and the first sub-recovery tank 5 through pipelines by a three-way valve 7.
In the high-purity silicone oil synthesis device provided by the embodiment of the invention, 100 parts by weight of octamethylcyclotetrasiloxane is put into a reaction kettle 1 through a first raw material inlet A, the temperature is raised to 60 ℃, the vacuum is opened to be below-0.06 MPa, the dehydration is carried out for 30 minutes, 2 parts by weight of tetramethyldivinyl siloxane end-sealing agent and 0.02 part by weight of tetramethylammonium hydroxide alkali gel are respectively put into the reaction kettle 1 through a second raw material inlet B and a third raw material inlet C, the temperature is raised to 105 ℃ and 115 ℃ for equilibrium reaction for 4 hours, the reaction kettle 1 is heated to decompose the tetramethylammonium hydroxide alkali gel catalyst, the reacted materials are pumped into a horizontal rotary evaporator 2 through a conveying pipeline, 50 parts by weight of normal hexane is put into the horizontal rotary evaporator 2 through a fourth raw material inlet 2-2, the vacuum is opened to be below-0.06 MPa, the temperature is gradually raised to the azeotropic temperature of 180 ℃ in sections to carry out azeotropic reaction, and (3) removing low molecules to obtain a silicone oil finished product E, feeding steam generated by azeotropy into a condenser 3 through a steam pipeline, feeding the condensed azeotropic solvents with different boiling points and the D3-D20 micromolecule substances into a second sub-recovery tank 4 and a first sub-recovery tank 5 through a three-way valve 7 respectively, wherein the first sub-recovery tank is used for recovering the azeotropic solvents, and the second sub-recovery tank is used for recovering the D3-D20 micromolecule substances.
Example 2
The embodiment of the invention provides a second synthesis method of high-purity silicone oil, which comprises the following steps:
as shown in fig. 1, an embodiment of the present invention provides a synthesis apparatus for high-purity silicone oil, including: the system comprises a reaction kettle 1, a horizontal rotary evaporator 2, a condenser 3, a three-way valve 7, a second sub-recovery tank 4 and a first sub-recovery tank 5; an outlet 1-1 of the reaction kettle is connected with an inlet 2-1 of the horizontal rotary evaporator through a pipeline, the bottom of the horizontal rotary evaporator 2 is provided with a high-purity silicone oil outlet 2-4, and the top of the horizontal rotary evaporator 2 is provided with a fourth raw material inlet 2-2; an outlet 2-3 of the horizontal rotary evaporator is connected with an inlet 3-1 of the condenser through a pipeline; the outlet 3-2 of the condenser is respectively connected with the second sub-recovery tank 4 and the first sub-recovery tank 5 through pipelines by a three-way valve 7.
In the high-purity silicone oil synthesis device provided by the embodiment of the invention, 100 parts by weight of octamethylcyclotetrasiloxane is put into a reaction kettle 1 through a first raw material inlet A, the temperature is raised to 60 ℃, the vacuum is opened to be below-0.06 MPa, dehydration is carried out for 30 minutes, 5 parts by weight of hexamethyldisiloxane end-sealing agent and 0.02 part by weight of tetramethylammonium hydroxide alkali gel are respectively put into the reaction kettle 1 through a second raw material inlet B and a third raw material inlet C, the temperature is raised to 105 ℃ and 115 ℃ for equilibrium reaction for 4 hours, the reaction kettle 1 is heated to decompose the tetramethylammonium hydroxide alkali gel catalyst, the reacted materials are pumped into a horizontal rotary evaporator 2 through a conveying pipeline, 80 parts by weight of pentane is put into the horizontal rotary evaporator 2 through a fourth raw material inlet 2-2, the vacuum is opened to be below-0.06 MPa, the temperature is gradually raised to the azeotropic temperature of 180 ℃ in sections for azeotropic reaction, and (3) removing low molecules to obtain a silicone oil finished product E, feeding steam generated by azeotropy into a condenser 3 through a steam pipeline, feeding the condensed azeotropic solvents with different boiling points and the D3-D20 micromolecule substances into a second sub-recovery tank 4 and a first sub-recovery tank 5 through a three-way valve 7 respectively, wherein the first sub-recovery tank is used for recovering the azeotropic solvents, and the second sub-recovery tank is used for recovering the D3-D20 micromolecule substances.
Example 3
The embodiment of the invention provides a third synthesis method of high-purity silicone oil, which specifically comprises the following steps:
as shown in fig. 1, an embodiment of the present invention provides a synthesis apparatus for high-purity silicone oil, including: the system comprises a reaction kettle 1, a horizontal rotary evaporator 2, a condenser 3, a three-way valve 7, a second sub-recovery tank 4 and a first sub-recovery tank 5; an outlet 1-1 of the reaction kettle is connected with an inlet 2-1 of the horizontal rotary evaporator through a pipeline, the bottom of the horizontal rotary evaporator 2 is provided with a high-purity silicone oil outlet 2-4, and the top of the horizontal rotary evaporator 2 is provided with a fourth raw material inlet 2-2; an outlet 2-3 of the horizontal rotary evaporator is connected with an inlet 3-1 of the condenser through a pipeline; the outlet 3-2 of the condenser is respectively connected with the second sub-recovery tank 4 and the first sub-recovery tank 5 through pipelines by a three-way valve 7.
In the high-purity silicone oil synthesis device provided by the embodiment of the invention, 100 parts by weight of methyl hydrogen siloxane ring body (D4H) is put into a reaction kettle 1 through a first raw material inlet A, 5 parts by weight of hexamethyldisiloxane end-sealing agent and 5 parts by weight of cationic resin are respectively put into the reaction kettle 1 through a second raw material inlet B and a third raw material inlet C, the temperature is raised to 80 ℃ for equilibrium reaction for 4 hours, the reacted materials are filtered, the filtered materials are pumped into a horizontal rotary evaporator 2 through a conveying pipeline, 50 parts by weight of pentane is put into the horizontal rotary evaporator 2 through a fourth raw material inlet 2-2, the vacuum is opened to be below-0.06 MPa, the temperature is gradually raised in sections until the azeotropic temperature reaches 150 ℃ for azeotropic reaction, low molecules are removed, a silicone oil finished product E is obtained, steam generated by azeotropic reaction enters a condenser 3 through a steam pipeline, after condensation, the azeotropic solvent with different boiling points and the D3-D20 micromolecule substance enter a second sub-recovery tank 4 and a first sub-recovery tank 5 through a three-way valve 7 respectively, the first sub-recovery tank is used for recovering the azeotropic solvent, and the second sub-recovery tank is used for recovering the D3-D20 micromolecule substance.
Example 4
In this embodiment, the viscosity, volatile components and the content of D3-D20 small molecule ring bodies of the silicone oil finished product obtained in embodiments 1-3 are detected, and the specific steps are as follows:
the finished silicone oils of examples 1-3 were subjected to gas chromatography and 200 ℃/4 hour volatilization tests according to conventional methods, and the results are shown in the following table:
| test items | Conventional silicone oil | Example 1 | Example 2 | Example 3 |
| Viscosity (mPa.s) | 500 | 500 | 300 | 80 |
| Volatile matter | 1.8％ | 0.2％ | 0.13％ | 0.22％ |
| D3-D20 small molecule ring body content | 1.2％ | ＜0.1％ | ＜0.1％ | ＜0.1％ |
Note: the preparation method of the conventional silicone oil is similar to the preparation method of the finished silicone oil in example 1, and is different in that no azeotropic solvent is added, 100 parts by weight of octamethylcyclotetrasiloxane is put into a reaction kettle 1 through a first raw material inlet A, the temperature is raised to 60 ℃, the vacuum is opened to-0.06 MPa, the dehydration is carried out for 30 minutes, 2 parts by weight of tetramethyldivinyl siloxane end-sealing agent and 0.02 part by weight of tetramethylammonium hydroxide alkali gel are respectively put into the reaction kettle 1 through a second raw material inlet B and a third raw material inlet C, the temperature is raised to 180 ℃ and 200 ℃ for equilibrium reaction for 4 hours, the reaction kettle 1 is raised to decompose the tetramethylammonium hydroxide alkali gel catalyst, the product 1 is obtained after the synthesis reaction is completed, the product 1 is directly put into the reaction kettle, the vacuum is opened to-0.06 MPa or below, and the temperature is raised to 180 ℃ and 200 ℃ for removing small molecular substances to obtain the conventional silicone oil.
From the above table, it can be seen that the synthesis method of the present invention can synthesize high purity silicone oil with low volatile content and low D3-D20 small molecule ring body content.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for synthesizing high-purity silicone oil is characterized in that,
the high-purity silicone oil synthesizer comprises:
the device comprises a reaction kettle, a horizontal rotary evaporator, a condenser and a recovery tank;
the reaction kettle is connected with the horizontal rotary evaporator through a pipeline, a silicone oil outlet is formed in the bottom of the horizontal rotary evaporator, and a material inlet is formed in the top of the horizontal rotary evaporator;
the horizontal rotary evaporator is connected with the condenser through a pipeline;
the condenser is connected with the recovery tank through a pipeline;
the method comprises the following steps:
step 1, mixing a polysiloxane ring body, a blocking agent and a catalyst for reaction to obtain a reactant 1;
step 2, removing the catalyst of the reactant 1 to obtain a product 1;
step 3, conveying the product 1 into the horizontal rotary evaporator, adding an azeotropic solvent from an inlet of the horizontal rotary evaporator, performing azeotropic treatment to obtain high-purity silicone oil, conveying steam generated by azeotropic treatment into a condenser, and conveying the condensed azeotropic solvent with different boiling points and D3-D20 micromolecule substances into a recovery tank through a pipeline for recycling; the azeotropic solvent is an organic alkane having a boiling point of 200 ℃ or lower.
2. The method for synthesizing high-purity silicone oil according to claim 1, wherein the polysiloxane ring body is selected from one or more of dimethylcyclosiloxane, methylvinylcyclosiloxane, methylphenylcyclosiloxane, diphenylcyclosiloxane, methyltrifluoropropylcyclosiloxane and methylhydrogenocyclosiloxane.
3. The method for synthesizing high purity silicone oil according to claim 1, wherein the end-capping agent is one or more selected from hexamethyldisiloxane, methylvinyldisiloxane, and methylhydrodisiloxane.
4. The method for synthesizing high-purity silicone oil according to claim 1, wherein the catalyst is one selected from an acid catalyst, a basic catalyst, and a solid catalyst.
5. The method for synthesizing high-purity silicone oil according to claim 1, wherein the azeotropic solvent is one or more selected from pentane, hexane, heptane, octane and nonane.
6. The method for synthesizing a high-purity silicone oil according to claim 1, wherein the weight ratio of the azeotropic solvent to the product 1 is (5-200): 100.
7. the method for synthesizing high-purity silicone oil according to claim 1, wherein step 1 comprises:
step 1a, heating a polysiloxane ring body and then performing reduced pressure dehydration treatment to obtain a product I;
and step 1b, mixing and heating the first product, a blocking agent and a catalyst for reaction to obtain a reactant 1.
8. The synthesis process according to claim 1, characterized in that the horizontal rotary evaporator is a longer than tall rotary evaporator.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB788151A (en) * | 1953-10-19 | 1957-12-23 | Du Pont | Solid siliceous materials of high surface area, methods of making the same, and compositions containing them |
| CN201791386U (en) * | 2010-09-08 | 2011-04-13 | 郑州拓洋生物工程有限公司 | Horizontal evaporator |
| CN108102100A (en) * | 2017-12-27 | 2018-06-01 | 浙江福斯特新材料研究院有限公司 | A kind of production method and production system of low volatilization vinyl silicone oil |
| CN108610484A (en) * | 2018-05-25 | 2018-10-02 | 广州盛泰诺新材料科技有限公司 | A kind of thermostable transparent methyl-silicone oil and its synthetic method |
| CN108610483A (en) * | 2018-05-25 | 2018-10-02 | 广州盛泰诺新材料科技有限公司 | A kind of high-purity dimethicone of resistance to oxidation and its synthetic method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09150002A (en) * | 1995-11-29 | 1997-06-10 | Shin Etsu Chem Co Ltd | Refining method for silicone oil |
| JP3812661B2 (en) * | 2002-05-13 | 2006-08-23 | 信越化学工業株式会社 | Purification method of silicone oil |
| CN102079816B (en) * | 2009-11-27 | 2012-09-19 | 威海华康生物芯片有限公司 | Preparation method of high purity silicone oil |
| CN102898646B (en) * | 2012-09-06 | 2015-01-28 | 江苏梅兰化工有限公司 | Continuous production process for silicone oil |
| CN107778488B (en) * | 2017-11-16 | 2020-07-21 | 湖北兴瑞硅材料有限公司 | Low molecular remover and method for producing methyl silicone oil with viscosity of 30-1000000cs |
| CN108484913A (en) * | 2018-03-07 | 2018-09-04 | 江苏科幸新材料股份有限公司 | The preparation method of high-purity ethylene base silicone oil |
-
2019
- 2019-08-27 CN CN201910797498.1A patent/CN110483776B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB788151A (en) * | 1953-10-19 | 1957-12-23 | Du Pont | Solid siliceous materials of high surface area, methods of making the same, and compositions containing them |
| CN201791386U (en) * | 2010-09-08 | 2011-04-13 | 郑州拓洋生物工程有限公司 | Horizontal evaporator |
| CN108102100A (en) * | 2017-12-27 | 2018-06-01 | 浙江福斯特新材料研究院有限公司 | A kind of production method and production system of low volatilization vinyl silicone oil |
| CN108610484A (en) * | 2018-05-25 | 2018-10-02 | 广州盛泰诺新材料科技有限公司 | A kind of thermostable transparent methyl-silicone oil and its synthetic method |
| CN108610483A (en) * | 2018-05-25 | 2018-10-02 | 广州盛泰诺新材料科技有限公司 | A kind of high-purity dimethicone of resistance to oxidation and its synthetic method |
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