CN113461944B - Solid acid and preparation method and application thereof - Google Patents
Solid acid and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of silicone oil production, and particularly provides a solid acid and a preparation method and application thereof, wherein the preparation method of the solid acid comprises the steps of mixing carboxylic acid and a silicon source to prepare sol gel; mixing the sol-gel with an acidic substance, aging and drying to prepare solid acid; the solid acid prepared by the method has high acid strength, the product synthesized by using the solid acid has high yield, the quality of the solid acid is stable and reliable, and the acid substances in the solid acid are not easy to lose after repeated recycling, so that the requirement of high product yield can be still met after repeated application.
Description
Technical Field
The invention relates to the technical field of silicone oil production, and particularly relates to a solid acid and a preparation method and application thereof.
Background
The dimethyl silicone oil is a dimethyl linear silicone polymer with chain structure of different polymerization degrees, and the viscosity is generally 0.65 multiplied by 10 6 mm 2 /s～1×10 6 mm 2 The dimethyl silicone oil is colorless and odorless transparent liquid at room temperature, and has the molecular characteristics of low glass transition temperature (-about 123 ℃), high molar volume (75.5 cm) 3 ·mol -1 Left and right) small, low cohesive energy density, low solubility parameter and dielectric constant, good lipophilicity and hydrophobicity, good thermodynamic stability and the like, and is widely applied to the fields of machinery, electricity, textile, coating, cosmetics, medicine and the like.
At present, the industrial production method of the dimethyl silicone oil mainly comprises the following two methods:
the first method comprises the following steps: the method comprises the steps of utilizing halogenated silane to carry out hydrolytic polycondensation to generate linear and cyclic oligosiloxane mixtures, wherein the most common monomer is dichlorodimethylsilane, adopting concentrated sulfuric acid to carry out telomerization, adding activated carbon to stir after the reaction is finished, then washing the mixture to be neutral, and then filtering and decoloring the mixture to obtain the finished product.
The second method comprises the following steps: the cyclic monomer is subjected to ring-opening polymerization under the condition of acid or base as a Catalyst to obtain polysiloxane, wherein the cyclic monomer is mostly researched and commonly adopted to be prepared from low-molecular-weight cyclosiloxane (such as octaalkylcyclotetrasiloxane D4 or dimethylcyclosiloxane DMC) and low-molecular-weight hexamethyldisiloxane as an end-capping agent through ring-opening polymerization and equilibration reaction under the action of a Catalyst (Catalyst), and the reaction can be carried out under very mild conditions without nitrogen charging protection.
The reaction equation is as follows:
for both of the above-mentioned production methods, the use of an acidic catalyst can be used to obtain a lower viscosity dimethylsilicone fluid. At present, the catalyst for industrially synthesizing the dimethyl silicone oil is mainly an acidic substance (such as H) 2 SO 4 、HClO 4 And CF 3 SO 3 H) The method not only can corrode equipment, but also is difficult to separate from the product, meanwhile, the product needs to be subjected to the processes of neutralization, water washing, filtration and the like, the treatment is complicated, and the acidic substances cannot be reused, so that the cost of the product is increased, and the method does not accord with green development, so that the development of a high-efficiency recyclable solid acid catalyst has important theoretical research value and practical application significance for the industrial production of the dimethyl silicone oil.
However, the existing solid acid mostly adopts a supported or mesoporous catalyst, so that the production cost is high, the preparation operation is complicated, the catalysts have the problem of poor stability when being used for synthesizing the dimethyl silicone oil, and the yield of the dimethyl silicone oil product is obviously reduced after the dimethyl silicone oil is recycled for many times. For example, chinese patent document CN101733142a reports a method for preparing a solid acid for silicone oil production, according to which a lewis acid salt is reflux-impregnated on a carrier, the impregnation takes 4-24 hours, and then the impregnation is performed by filtering, drying and roasting, so as to obtain the solid acid supported by the solid acid.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that active substances in the solid acid prepared by the prior art are easy to lose, and the catalytic activity is reduced after repeated use to cause low product yield, so that the solid acid and the preparation method and application thereof are provided.
The invention provides a preparation method of solid acid, which comprises the following steps:
mixing carboxylic acid and a silicon source to prepare sol-gel;
mixing the sol-gel with an acidic substance, aging and drying to obtain the solid acid.
After aging, the sol-gel transforms from a porridge-like to a jelly-like.
The acidic substance is a protic acid and/or an aprotic acid.
In certain preferred embodiments, the protic acid is selected from at least one of sulfuric acid, benzenesulfonic acid, phosphoric acid, and methanesulfonic acid, and the aprotic acid is selected from at least one of aluminum methylsulfonate, zinc methylsulfonate, and aluminum chloride.
Optionally, the carboxylic acid is selected from monocarboxylic acids and/or dicarboxylic acids.
In certain preferred embodiments, the monocarboxylic acid is selected from at least one of formic acid, acetic acid, and propionic acid, and the dicarboxylic acid is selected from at least one of oxalic acid and malonic acid.
Wherein the silicon-containing raw material is a silicon source. Optionally, the silicon source is selected from silicate ester and/or silicate salt.
In certain preferred embodiments, the silicate is selected from at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate.
In certain preferred embodiments, the silicate is selected from sodium silicate and/or potassium silicate.
In certain preferred embodiments, the molar ratio of the silicon source, carboxylic acid, and acidic species is from 0.5 to 2.0:3-20:0.01-0.2.
In certain preferred embodiments, the sol gel is prepared under stirring at a temperature of 25 to 80 ℃ for 20 to 40min.
In certain preferred embodiments, aging is carried out at a temperature of from 25 to 80 ℃ for from 1 to 4 hours.
In certain preferred embodiments, the drying temperature is from 100 ℃ to 130 ℃ and the time is from 4 to 6 hours.
More preferably, it is dried in a vacuum drying oven.
The invention also provides a solid acid prepared by the preparation method.
In the invention, the solid acid recovered in the preparation process of the dimethyl silicone oil is specifically as follows: the filtered filter cake was washed twice with water, the solid collected and dried.
In certain preferred embodiments, the solid acid has a surface area of not less than 100m 2 Per g, preferably 105 to 339m 2 (ii) in terms of/g. The research finds that the specific surface area is controlled to be 105-339m 2 The stability of solid acid is better, the product yield is higher, and the conversion rate of DM used for a plurality of times is higher.
In certain preferred embodiments, the acid strength is from 0.8 to 2.5mmol/g.
The invention also provides an application of the solid acid as a catalyst.
In certain preferred embodiments, the solid acid is used to prepare a dimethicone.
The invention also provides a preparation method of the dimethyl silicone oil, and the dimethyl silicone oil is prepared in the presence of the solid acid.
In certain preferred embodiments, the cyclosiloxane is octamethylcyclotetrasiloxane and/or dimethylcyclosiloxane.
In certain preferred embodiments, the reaction is carried out by contacting the cyclic siloxane with hexamethyldisiloxane in the presence of a solid acid.
In certain preferred embodiments, the mass of solid acid is 0.5 to 10% of the total mass of cyclosiloxane and hexamethyldisiloxane.
In certain preferred embodiments, the mass ratio of cyclosiloxane to hexamethyldisiloxane and solid acid is from 1 to 10:1-5.
In certain preferred embodiments, the reaction temperature in the preparation of dimethylsilicone oil is 30-40 ℃.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the solid acid, carboxylic acid and a silicon source are mixed to prepare sol-gel, and then the sol-gel is mixed with an acidic substance, aged and dried to prepare the solid acid; the solid acid prepared by the method has high acid strength, the yield of the product synthesized by using the solid acid is high, the quality of the solid acid is stable and reliable, and the acidic substances in the solid acid are not easy to lose after repeated cyclic use, so that the dimethyl silicone oil product produced repeatedly can still meet the requirement of high yield, and the method is suitable for the requirement of industrial production.
2. The invention provides a preparation method of solid acid, wherein the acidic substance is selected from protonic acid and/or non-protonic acid, wherein the protonic acid is selected from at least one of sulfuric acid, benzenesulfonic acid, phosphoric acid and methanesulfonic acid; the aprotic acid is at least one selected from the group consisting of aluminum methanesulfonate, zinc methanesulfonate and aluminum chloride. For protonic acid and aprotic acid, protonic acid such as sulfuric acid and phosphoric acid is preferably used, the prepared solid acid has higher strength and smaller specific surface area, the product yield can be improved while the reaction time is shortened, and for aprotic acid, the higher dosage and longer reaction time are needed to obtain high yield. Among protonic acids, sulfuric acid is most preferred, and the solid acid prepared has the highest strength and the smallest specific surface area, can reach catalytic equilibrium in the shortest time, and has the highest product yield.
4. The preparation method of the solid acid provided by the invention has the advantages that through optimization of preparation conditions, for example, the aging temperature is controlled to be 25-80 ℃, and the time is 1-4h; or the drying temperature is 100-130 ℃, the drying time is 4-6h, the stability of the solid acid can be further improved, and the product yield after repeated use is improved.
5. The preparation method of the solid acid provided by the invention is different from the treatment procedures of neutralization, washing, filtering and the like which are needed after the reaction balance of an acidic substance used as a catalyst, the preparation method is simple, the raw materials are easy to obtain, the production cost is low, the prepared solid acid is environment-friendly and pollution-free, and the solid acid is obtained by simple filtering and separation after the synthesis of the dimethyl silicone oil, so that the cyclic utilization and the continuous production are facilitated; compared with a supported or mesoporous catalyst, the preparation method provided by the invention has the advantages of simplicity in operation, easiness in obtaining raw materials and low production cost.
6. According to the preparation method of the dimethyl silicone oil, the solid acid prepared by the specific method is used as the catalyst to prepare the dimethyl silicone oil, the dimethyl silicone oil product with high yield can be obtained after the catalyst is recycled for multiple times, the product quality is good, the distribution state of each component in the product is stable through gas chromatography detection before and after 30 times of mechanical application or continuous production for 7 hours, no obvious change occurs, and the yield is high. Especially, the reaction time is controlled to be 30-40 ℃, the forward reaction can be accelerated, the reaction time is shortened, and the reaction yield is further improved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The gas chromatography conditions of MM content and D4 content in the dimethyl silicone oil prepared by the invention are as follows:
shimadzu InertCap-5 capillary column 30m × 0.25 μm × 0.32mm, sample amount 1 μ l, vaporizer 280 ℃, column temperature: keeping at 50 deg.C for 3min, heating at 10 deg.C/min to 300 deg.C, keeping at 10min, and detecting at 300 deg.C.
D4 represents octamethylcyclotetrasiloxane and MM represents hexamethyldisiloxane.
Example 1
The embodiment provides a preparation method of solid acid, which comprises the following steps:
(1) Methyl orthosilicate (1 mol, 152 g) and acetic acid (5 mol, 300 g) are put into a three-neck flask, the temperature is raised to 75 ℃, and the sol-gel is prepared by stirring for 20 min.
(2) 98% by mass of sulfuric acid (0.1 mol, 9.8 g) was added dropwise to the sol-gel, aged at 75 ℃ for 4h, transferred to a vacuum oven and dried at 120 ℃ for 5h to give 102g of a solid acid designated A-1.
The embodiment also provides a preparation method of the simethicone, which can be used for only carrying out a single experiment or continuing to carry out an application experiment after the single experiment, wherein the solid acid is recycled, and the preparation method comprises the following steps:
single experiment: 1483g of D4 and 162g of MM are put into a flask, 16.5g of solid acid A-1 is put into the flask, the temperature is heated to 35 ℃, the mixture is kept at 35 ℃ and stirred for 2 hours, and suction filtration is carried out to obtain dimethyl silicone oil, solid acid is recovered, namely, a filter cake is washed twice by water, and the solid is collected and dried.
The application experiment is as follows: putting 1483g of D4 and 162g of MM into a flask, putting the recovered solid acid into the flask, heating to 35 ℃, keeping the temperature and stirring for 2 hours at 35 ℃, performing suction filtration to obtain dimethyl silicone oil, recovering the solid acid, completing the first application, and repeating the application steps for 20 times to finish the application.
Example 2
The embodiment provides a preparation method of a solid acid, which comprises the following steps:
(1) Adding tetraethoxysilane (1 mol, 208 g) and acetic acid (3 mol, 180 g) into a three-neck flask, heating to 60 ℃, and stirring for 20min; and (4) preparing sol gel.
(2) Methanesulfonic acid (0.1 mol, 9.6 g) was added dropwise to the sol gel, and the mixture was aged at 60 ℃ for 4 hours to obtain a gel. The gel was transferred to a vacuum oven and dried at 120 ℃ for 5h to give 116g of solid acid, noted A-2.
The embodiment also provides a preparation method of the simethicone, which comprises the following steps:
single experiment: 1483g of D4 and 162g of MM are put into a flask, 16.5g of solid acid A-2 is put into the flask, the temperature is raised to 35 ℃, the mixture is kept at 35 ℃ and stirred for 3 hours, and suction filtration is carried out to obtain dimethyl silicone oil and recover the solid acid, namely, a filter cake is washed twice with water, and the solid is collected and dried.
The application experiment is as follows: putting 1483g of D4 and 162g of MM into a flask, putting the recovered solid acid into the flask, heating to 35 ℃, keeping the temperature and stirring for 3 hours at 35 ℃, performing suction filtration to obtain dimethyl silicone oil, recovering the solid acid, completing the first application, and repeating the application steps for 30 times to finish the application.
Example 3
The embodiment provides a preparation method of simethicone, which comprises the following steps:
30g of solid acid A-2 is loaded into an existing conventional solid bed packed column, the outer diameter of the packed column is 1 inch, the length of the packed column is 15cm, the volume of the packed column is 50mL, two feed inlets are arranged at two ends of the packed column, and a discharge outlet is arranged at the top end of the side wall.
Keeping the column temperature at 35 ℃, pumping D4 and MM into the packed column from the feed inlet of the packed column by using two plunger pumps respectively, enabling the flow rate of D4 to be 0.83mL/min and the flow rate of MM to be 0.17mL/min, collecting reaction liquid from the discharge outlet, pumping the collected reaction liquid into the packed column at the speed of 1mL/min by using a third plunger pump, starting timing reaction for 2 hours from the feeding of D4 and MM, and collecting the reaction liquid from the discharge outlet after the reaction is finished, thus obtaining the simethicone.
Example 4
The embodiment provides a preparation method of solid acid, which comprises the following steps:
(1) Methyl orthosilicate (1 mol, 152 g) and acetic acid (5 mol, 300 g) are put into a three-neck flask, the temperature is raised to 75 ℃, and the sol-gel is prepared after stirring for 20 min.
(2) Anhydrous aluminum trichloride (0.3 mol, 40 g) was added to the sol gel, aged at 75 deg.C for 4h, transferred to a vacuum oven and dried at 120 deg.C for 5h to give 132g of solid acid, noted A-3.
The embodiment also provides a preparation method of the simethicone, which comprises the following steps:
single experiment: 1483g of D4 and 162g of MM are put into a flask, solid acid A-3 (16.5 g) is put into the flask, the temperature is increased to 35 ℃, the mixture is kept at 35 ℃ and stirred for 8 hours, and the mixture is filtered by suction to obtain dimethyl silicone oil and recover the solid acid, namely, a filter cake is washed twice by water, and the solid is collected and dried.
The application experiment is as follows: putting 1483g of D4 and 162g of MM into a flask, putting the recovered solid acid into the flask, heating to 35 ℃, keeping the temperature at 35 ℃, stirring for 8 hours, performing suction filtration to obtain dimethyl silicone oil, recovering the solid acid, completing the first application, and repeating the application steps for 20 times to finish the application.
Example 5
The embodiment provides a preparation method of a solid acid, which comprises the following steps:
(1) Methyl orthosilicate (1 mol, 152 g) and acetic acid (5 mol, 300 g) are put into a three-neck flask, the temperature is raised to 75 ℃, and the sol-gel is prepared after stirring for 20 min.
(2) Zinc methanesulfonate (0.3 mol, 77 g) was added to the sol gel, aged at 75 ℃ for 4h, and transferred to a vacuum oven for drying at 120 ℃ for 5h to give 144g of a solid acid, designated A-4.
The embodiment also provides a preparation method of the simethicone, which comprises the following steps:
single experiment: 1483g of D4 and 162g of MM were put into a flask, solid acid A-4 (16.5 g) was put into the flask, heated to 35 ℃, kept at 35 ℃ and stirred for 12 hours, suction-filtered to obtain dimethylsilicone oil and recover the solid acid, that is, the filter cake was washed twice with water, the solid was collected and dried.
The application experiment is as follows: putting 1483g of D4 and 162g of MM into a flask, putting the recovered solid acid into the flask, heating to 35 ℃, keeping the temperature at 35 ℃, stirring for 12 hours, carrying out suction filtration to obtain dimethyl silicone oil, recovering the solid acid, completing the first application, and repeating the application steps for 20 times to finish the application.
Example 6
The embodiment provides a preparation method of solid acid, which comprises the following steps:
(1) Methyl orthosilicate (0.5 mol, 76 g) and acetic acid (20 mol, 1200 g) are put into a three-neck flask, the temperature is raised to 25 ℃, and the sol-gel is prepared by stirring for 40min.
(2) 98% by mass of sulfuric acid (0.01 mol, 0.98 g) was added dropwise to the sol-gel, and the mixture was aged at 25 ℃ for 4 hours, and then transferred to a vacuum oven and dried at 100 ℃ for 5 hours to obtain 53g of a solid acid, designated as A-5.
The embodiment also provides a preparation method of the simethicone, which comprises the following steps:
single experiment: putting 148.3g of dimethylcyclosiloxane and 741.5g of MM into a flask, putting 88.9g of solid acid A-5 into the flask, heating to 35 ℃, keeping the temperature and stirring for 8 hours at 35 ℃, performing suction filtration to obtain dimethyl silicone oil, recovering the solid acid, namely washing a filter cake twice by using water, collecting the solid, and drying.
The application experiment is as follows: putting 148.3g of dimethylcyclosiloxane and 741.5g of MM into a flask, putting the recovered solid acid into the flask, heating to 35 ℃, keeping the temperature and stirring for 8 hours at 35 ℃, performing suction filtration to obtain dimethyl silicone oil, recovering the solid acid, completing the first application, and repeating the application steps for 20 times.
Comparative example 1
The comparative example provides a method of preparing a solid acid comprising the steps of:
(1) Methyl orthosilicate (1 mol, 152 g) and acetic acid (5 mol, 300 g) are put into a three-neck flask, the temperature is raised to 75 ℃, and the sol-gel is prepared after stirring for 20 min.
(2) Sodium sulfate (0.1 mol, 14.2 g) was added dropwise to the sol gel, aged at 75 ℃ for 4h, transferred to a vacuum oven and dried at 120 ℃ for 5h to give 130g of solid acid, noted B-1.
The embodiment also provides a preparation method of the simethicone, which comprises the following steps:
1483g of D4 and 162g of MM are put into a flask, 16.5g of solid acid B-1 is put into the flask, the temperature is heated to 35 ℃, the mixture is kept at 35 ℃ and stirred for 12 hours, and suction filtration is carried out to obtain a reaction product, obtain a reaction solution and recover solid acid, namely a filter cake is washed twice by water, and the solid is collected and dried.
The application experiment is as follows: putting 1483g of D4 and 162g of MM into a flask, putting the recovered solid acid into the flask, heating to 35 ℃, keeping the temperature and stirring for 12 hours at 35 ℃, carrying out suction filtration to obtain dimethyl silicone oil, detecting by GC that the conversion rate is low and the silicone oil is unqualified, recovering the solid acid, washing a filter cake twice by using water, collecting the solid, drying, completing the first application, and repeating the application steps for 20 times to finish the application.
Comparative example 2
This comparative example also provides a process for the preparation of dimethylsilicone fluids using ion exchange resin solid acid (available from merck, model Amberlite IR-120, noted as solid acid B-2) in place of solid acid a-1 of example 1, and the remaining steps and conditions were the same as in example 1.
Experimental example 1 Properties of solid acid
The properties of the solid acids prepared in the above examples and comparative examples were measured, the specific surface area of the solid acids was measured using a physical adsorption apparatus, and the acid strength of the solid acids was measured using a Hammett indicator method, and the results are shown in table 1.
TABLE 1 specific surface area and acid Strength of solid acids
As can be seen from the above table, the specific surface area of the solid acid was significantly reduced and the acid strength was significantly improved for examples 1-5 as compared to comparative examples 1 and 2. In addition, the solid acid obtained in example 1 had the highest acid strength and the smallest specific surface area as compared with examples 2 to 5.
Experimental example 2 yield of target product
The yields of dimethylsilicone fluids prepared in examples 1-2, 4-6 and 1-2 in a single experiment using the respective solid acids initially prior to the application experiment and dimethylsilicone fluids prepared in example 3 with 2 hours of continuous operation were tested, and the DM content and MM content of the dimethylsilicone fluids obtained were calculated and the results are shown in Table 2.
TABLE 2 Synthesis results of Dimethylsilicone oils (Single experiment)
The 10 th application of experiments of examples 1-2, 4-6 and comparative examples 1-2, and example 3, which was continuously operated for 20 hours, were tested to calculate the conversion rate, and the results are shown in tables 3 and 4.
TABLE 2 Synthesis results of dimethylsilicone fluids (10 th application test)
The conversion rates were calculated by testing 20 th application experiments of examples 1-2, 4-6 and comparative examples 1-2, and the yield of dimethylsilicone oil obtained by continuously operating example 3 for 40 hours, and the DM content and MM content of the dimethylsilicone oil obtained, and the results are shown in tables 3 and 4.
TABLE 4 reaction results of Dimethylsilicone oil (20 th application test)
As can be seen from tables 2-4 above, comparative example 1 shows no dimethylsilicone oil production due to no addition of strongly acidic active material, and no polymerization occurred. Compared with the comparative example 2, the yield of the dimethyl silicone oil prepared by the embodiments 1 to 5 of the invention is obviously improved, particularly the yield of 10 times and 20 times of mechanical application is improved, and compared with aprotic acids such as aluminum chloride, zinc methylsulfonate and the like, the invention has higher yield by adopting protonic acids such as sulfuric acid, methanesulfonic acid and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. The preparation method of the solid acid is characterized by comprising the following steps:
mixing acetic acid and methyl orthosilicate, preparing sol-gel under the condition of stirring at the temperature of 60-75 ℃, stirring for 20min to prepare sol-gel,
mixing sol gel with sulfuric acid, aging, and drying to obtain solid acid, wherein the molar ratio of methyl orthosilicate to acetic acid to sulfuric acid is 1: 5:0.1, aging at 60-75 deg.C for 1-4h; the drying temperature is 120 ℃, and the drying time is 4-6h.
2. A solid acid produced by the production method according to claim 1.
3. Use of the solid acid of claim 2 as a catalyst in the preparation of simethicone.
4. A method for preparing dimethyl silicone oil, which is characterized in that the dimethyl silicone oil is prepared by taking cyclosiloxane and hexamethyldisiloxane as raw materials and reacting the cyclosiloxane and the hexamethyldisiloxane in the presence of the solid acid as claimed in claim 2.
5. The method according to claim 4, wherein the cyclosiloxane is octamethylcyclotetrasiloxane and/or dimethylcyclosiloxane; and/or the mass ratio of the cyclosiloxane to the hexamethyldisiloxane is 1-10:1-5.
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