A process for the preparation of a heptaphenyltrihydroxylsilsesquioxane

Abstract

The present application relates to the technical field of silsesquioxane preparation, in particular to a preparation method of heptaphenyl trihydroxysilsesquioxane; specifically, heptaphenyl trisodium silsesquioxane is prepared by reacting phenyl trimethoxysilane and sodium hydroxide in an organic solvent medium, then tin-doped solid acid catalyst and heptaphenyl trisodium silsesquioxane are added in a tetrahydrofuran medium, and heptaphenyl trihydroxysilsesquioxane is prepared in an ice water bath. The heptaphenyl trihydroxysilsesquioxane prepared by the method has high yield, and the service life of the solid acid catalyst is long, and the solid acid catalyst can be recycled.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silsesquioxane preparation, and particularly relates to a preparation method of heptaphenyltrihydroxysilsesquioxane. BACKGROUND

[0002] Silsesquioxane, also called POSS, refers to a kind of organic-inorganic hybrid molecules with Si-O bonds connected to each other and chemical composition conforming to the empirical formula (RSiO1.5)n, wherein R is various organic groups connected to silicon atoms. Silsesquioxane is a kind of molecular-level nanohybrid material with excellent performance. Silsesquioxane has been widely used in the preparation of organic-inorganic nanohybrid materials and functional materials such as optical, electrical and magnetic materials.

[0003] Patent document CN108034349A discloses a preparation method of an octanitro-silsesquioxane modified two-component waterborne polyurethane emulsion. In the method, the oligomer polyol and diisocyanate are mixed and reacted, then a chain extender is added to obtain a polyurethane polyol prepolymer, then a crosslinking agent and a neutralizing agent are added, and a waterborne polyurethane polyol dispersion is obtained by high-speed shearing emulsification and dispersion, then octanitro-silsesquioxane is added to obtain an octanitro-silsesquioxane modified waterborne polyurethane polyol dispersion, and finally the octanitro-silsesquioxane modified waterborne polyurethane polyol dispersion is mixed with a polyisocyanate curing agent to obtain an octanitro-silsesquioxane modified two-component waterborne polyurethane emulsion. The method is simple, the two-component waterborne polyurethane is modified by using octanitro-silsesquioxane, the water resistance, transparency and mechanical properties of the waterborne polyurethane are improved, and the waterborne polyurethane has good stability.

[0004] Patent document CN101723968A discloses a bismaleimide containing an aminopropyl cage-shaped silsesquioxane structure and a synthesis method thereof. 20 parts of bismaleimide are dissolved in 75-105 parts of a solvent at 60-90 ℃ to form a bismaleimide solution; 0.6-4.0 parts of aminopropyl cage-shaped silsesquioxane is dissolved in 12-60 parts of an organic alcohol to form an alcohol solution of aminopropyl cage-shaped silsesquioxane; under nitrogen protection, the alcohol solution of aminopropyl cage-shaped silsesquioxane is added dropwise into the bismaleimide solution, the temperature is raised to 100-160 ℃, and reflux reaction is performed for 1-3 hours; after solvent removal and vacuum drying, the bismaleimide containing the aminopropyl cage-shaped silsesquioxane structure is obtained. The synthesis method not only ensures that the structure of the cage-shaped silsesquioxane is not destroyed, so that the excellent heat resistance and dielectric properties of the POSS structure are fully utilized, but also endows the bismaleimide with good toughness due to the presence of the aminopropyl group.

[0005] Patent document FR 82018054 discloses the hydrolysis of alkoxysilanes with water in the presence of various hydrolysis catalysts. The hydrolysis catalysts include solid oxides of Group IIa metals and solid acid catalysts. The solid acid catalysts can be used in combination with neutralizing agents and also in combination with condensation catalysts. Generally, the process for hydrolyzing alkoxysilanes comprises mixing alkoxysilanes, a stoichiometric excess of water and an effective catalytic amount of a hydrolysis catalyst selected from solid oxides of Group IIa metals, solid acid catalysts and mixtures thereof; neutralizing the hydrolysis mixture with a sufficient amount of a neutralizing agent. The solid acid catalysts are clays activated with an acid, wherein the neutralizing agent is selected from magnesium silicate oxide and calcium oxide and mixtures thereof.

[0006] POSS is applied in catalysis, aerospace, porous materials and many other fields due to its regular internal silicon-oxygen three-dimensional skeleton, Si-O-Si inorganic main framework combined with organic external groups, easy functionalization and good thermal stability. In addition, as an organic-inorganic hybrid, it has the characteristics of organic materials and the advantages of inorganic materials, and can create unexpected new properties by synergizing the two. The solid catalysts in the prior art also have the shortcomings of short service life, greatly reduced catalytic activity and cannot be used for a long time. SUMMARY

[0007] In order to solve the shortcomings and deficiencies of the prior art, the primary purpose of the present application is to provide a preparation method of heptaphenyltrihydroxysilsesquioxane.

[0008] Another purpose of the present application is to provide heptaphenyltrihydroxysilsesquioxane obtained by the above preparation method.

[0009] The purpose of the present application is achieved by the following technical solutions:

[0010] A preparation method of heptaphenyltrihydroxysilsesquioxane, characterized in that it comprises the following steps:

[0011] A1: According to the mass fraction, 16-28 parts of phenyltrimethoxysilane and 100-150 parts of organic solvent are added to a three-necked flask equipped with a magnetic stirrer and a condenser device, the magnetic stirring is started, 1.6.-3.6 parts of deionized water and 1.2-2.6 parts of sodium hydroxide are added to adjust the pH value, and then the reaction is carried out in a water bath pot under reflux. After the reaction is completed, continue to stir at room temperature for 12-24 h, then remove the solvent by rotary evaporation, and vacuum dry the solid to obtain heptaphenyltrisodium salt silsesquioxane;

[0012] A2: In a three-necked flask, 3-9 parts of the seven phenyl trisodium salt of silsesquioxane prepared in step A1 and 45-80 parts of anhydrous tetrahydrofuran were dissolved, inert gas was introduced and stirred vigorously in an ice water bath, and 19-28 parts of tin-doped solid acid catalyst was added to the three-necked flask, and stirring was continued in an ice water bath for 1-3 h, then 50-80 parts of deionized water was added and the reaction was continued for 1-2 h, after the reaction was completed, the tetrahydrofuran was removed by rotary evaporation under reduced pressure, and then extracted with chloroform, the extract was washed and separated to obtain the supernatant, the chloroform was removed by rotary evaporation from the supernatant, and the solid was dried under vacuum to obtain seven phenyl trihydroxysilsesquioxane, and the tin-doped solid acid catalyst was recycled and used.

[0013] In some specific embodiments, the organic solvent in A1 is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, carbon tetrachloride, and acetonitrile.

[0014] In some specific embodiments, the pH value in A1 is adjusted to 7.5-9.

[0015] In some specific embodiments, the water bath temperature in A1 is 60-85°C, and the reflux reaction is carried out for 3-8 h.

[0016] In some specific embodiments, the inert gas in A2 is at least one of nitrogen, argon, or helium.

[0017] In some specific embodiments, when chloroform is added for extraction in A2, NaHCO3 solution and deionized water are used in sequence to wash to neutral.

[0018] In some specific embodiments, after extraction and washing and separation in A2, anhydrous MgSO4 is added to the supernatant to remove residual water in the solution.

[0019] In some specific embodiments, the temperature of the vacuum oven in A1 and A2 is 35-60°C, and the time is 12-24 h.

[0020] In some specific embodiments, the preparation method of the tin-doped solid acid catalyst is as follows:

[0021] B1: 100-130 parts of dry sodium type strong acid cation exchange resin (R-SO3Na), 20-40 parts of aminoacetyl chloride, 500-1000 parts of dichloroethane, and 10-18 parts of anhydrous aluminum chloride were weighed by weight parts and added to a stirred reaction kettle, stirred at -5 to 5°C for 10-15 hours, and filtered to obtain an amine sodium type strong acid cation exchange resin;

[0022] B2: 0.2-2 parts of dibutyl tin maleate, 2-5 parts of sodium ethoxide, 100-120 parts of vinyl acetate, are added to the stirred tank reactor in B1, stirred at 40-50℃ for 10-30 minutes, then 6-10 parts of magnesium acrylate are added, stirred for 1-4 hours, filtered to form a sodium type solid acid catalyst;

[0023] B3: The sodium type solid acid catalyst obtained in B2 is loaded into an exchange column, 1000-1300 parts of 10%-20% high-purity hydrochloric acid is introduced at a flow rate of 1-4 BV / h, then washed with deionized water to obtain a tin-doped solid acid catalyst.

[0024] In some specific embodiments, the dry base sodium type strong acid cation exchange resin is selected from macroporous styrene cation exchange resin in the form of sodium: such as D001, D006, A35, A15, etc. styrene cation exchange resin, dried to a moisture content of less than 0.5%.

[0025] Compared with the prior art, the beneficial effects of the present application are:

[0026] The method of the present application is characterized by the following steps: the amino group of the sodium type strong acid cation exchange resin is reacted with dibutyl tin maleate and magnesium acrylate respectively to form an amino addition reaction, and then ion exchange is performed to obtain a tin-doped solid acid catalyst. The solid acid catalyst effectively improves the selectivity of the seven phenyl trihydroxy silsesquioxane in the reaction process, and has a long service life and high catalytic activity, and can be used for a long time. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The seven phenyl trihydroxy silsesquioxane prepared in Example 1 is magnified 5000 times under an electron microscope. DETAILED DESCRIPTION

[0028] The present application will be described in detail below through specific embodiments, and through these descriptions, the characteristics and advantages of the present application will become clearer and more explicit.

[0029] Example 1

[0030] A method for preparing a seven phenyl trihydroxy silsesquioxane is characterized by the following steps:

[0031] A1: In a three-necked flask equipped with a magnetic stirrer and a condenser, 16 g of phenyl trimethoxysilane and 100 g of an organic solvent are added, the magnetic stirring is started, 1.6 g of deionized water and 1.2 g of sodium hydroxide are added to adjust the pH value, and then the reaction is carried out in a water bath kettle under reflux conditions. After the reaction is completed, continue to stir at room temperature for 12 h, then remove the solvent by rotary evaporation, and dry the solid under vacuum to obtain seven phenyl tri-sodium silsesquioxane;

[0032] A2: 3g of the seven phenyl trisodium salt silsesquioxane prepared in step A1 and 45g of anhydrous tetrahydrofuran were added into a three-necked flask, inert gas was bubbled in an ice water bath and stirred vigorously, while 19g of tin-doped solid acid catalyst was added into the three-necked flask, stirring was continued in the ice water bath for 1h, then 50g of deionized water was added to continue the reaction for 1h, after the reaction was completed, the tetrahydrofuran was removed by rotary evaporation under reduced pressure, then extracted with chloroform, the extract was washed and separated to obtain the supernatant, the chloroform in the supernatant was removed by rotary evaporation, and the solid was dried under vacuum to obtain seven phenyl trihydroxy silsesquioxane, and the tin-doped solid acid catalyst was recycled and used.

[0033] The organic solvent in A1 is selected from N,N-dimethylformamide.

[0034] The pH value in A1 is adjusted to 7.5.

[0035] The water bath temperature in A1 is 60°C, and the reflux reaction is 3h.

[0036] The inert gas in A2 is selected from nitrogen.

[0037] When chloroform is added for extraction in A2, NaHCO3 solution and deionized water are used in sequence to wash to neutral.

[0038] After the supernatant obtained after extraction and washing is separated, anhydrous MgSO4 is added to remove residual water in the solution.

[0039] The vacuum oven temperature in A1 and A2 is 35°C, and the time is 24h.

[0040] The preparation method of the tin-doped solid acid catalyst is:

[0041] B1: 100g of dry sodium type strong acid cation exchange resin (R-SO3Na), 20g of aminoacetyl chloride, 500g of dichloroethane, and 10g of anhydrous aluminum chloride were added into a stirring reaction kettle, stirred at -5°C for 10 hours, filtered, and the amine sodium type strong acid cation exchange resin was obtained;

[0042] B2: 0.2g of dibutyltin maleate, 2g of sodium ethoxide, and 100g of vinyl acetate were added into the stirring kettle reaction kettle in B1, stirred at 40°C for 10 minutes, then 6g of magnesium acrylate was added and stirred for 1 hour, filtered, and the sodium type solid acid catalyst was formed;

[0043] B3: The sodium type solid acid catalyst obtained in B2 was loaded into an exchange column, 1000g of 10% high-purity hydrochloric acid was bubbled in at a flow rate of 1 BV / h, then washed with deionized water to obtain a tin-doped solid acid catalyst.

[0044] The dry base sodium type strong acid cation exchange resin is selected from macroporous styrene cation exchange resin in the form of sodium at the factory: D001 styrene cation exchange resin is selected, and is dried to have a moisture content of less than 0.5%.

[0045] Evaluation: the tin-doped solid acid catalyst prepared in this example was recycled for 6 times, and the results are as follows:

[0046]

[0047] Example 2

[0048] A method for preparing a heptaphenyltrihydroxysilsesquioxane, characterized in that it comprises the following steps:

[0049] A1: a three-necked flask equipped with a magnetic stirrer and a condenser is charged with 22 g of phenyltrimethoxysilane and 125 g of an organic solvent, the magnetic stirring is started, 2.6 g of deionized water and 1.9 g of sodium hydroxide are added to adjust the pH value, and then the reaction is carried out in a water bath at reflux, after the reaction is completed, the stirring is continued at room temperature for 18 h, then the solvent is removed by rotary evaporation, and the solid is dried under vacuum to obtain heptaphenyltrisodium silsesquioxane;

[0050] A2: the three-necked flask is charged with 6 g of heptaphenyltrisodium silsesquioxane prepared in step A1 and 65 g of anhydrous tetrahydrofuran, an inert gas is bubbled in an ice-water bath and stirred vigorously, and 23 g of tin-doped solid acid catalyst is added to the three-necked flask, the stirring is continued in the ice-water bath for 2 h, then 65 g of deionized water is added for continuous reaction for 2 h, after the reaction is completed, the tetrahydrofuran is removed by rotary evaporation under reduced pressure, then extracted with chloroform, and the extract is washed and separated to obtain the supernatant, the chloroform is removed from the supernatant by rotary evaporation, and the solid is dried under vacuum to obtain heptaphenyltrihydroxysilsesquioxane, and the tin-doped solid acid catalyst is recycled.

[0051] The organic solvent in A1 is selected from N,N-dimethylacetamide.

[0052] The pH value in A1 is adjusted to 8.5.

[0053] The water bath temperature in A1 is 75℃, and the reflux reaction is carried out for 6 h.

[0054] The inert gas in A2 is selected from nitrogen.

[0055] When chloroform is added for extraction in A2, NaHCO3 solution and deionized water are used in sequence for washing until neutral.

[0056] After the supernatant obtained after extraction and washing in A2 is separated, anhydrous MgSO4 is added to remove residual water in the solution.

[0057] The vacuum oven temperature in A1 and A2 is 45℃, and the time is 16h.

[0058] The preparation method of the tin-doped solid acid catalyst is:

[0059] B1: Take 115g of dry base sodium type strong acid cation exchange resin (R-SO3Na), 30g of amino acetyl chloride, 750g of dichloroethane, and 14g of anhydrous aluminum chloride into a stirring reaction kettle, stir at 0℃ for 12.5h, filter, and obtain the amine sodium type strong acid cation exchange resin;

[0060] B2: Put 0.9g of dibutyltin maleate, 3.5g of sodium ethoxide, and 110g of vinyl acetate into the stirring kettle in B1, stir at 45℃ for 20min, then add 8g of magnesium acrylate, stir for 2.5h, filter, and form the sodium type solid acid catalyst;

[0061] B3: Put the sodium type solid acid catalyst obtained in B2 into an exchange column, pass 1150g of 15% high-purity hydrochloric acid at a flow rate of 2BV / h, and then wash with deionized water to obtain the tin-doped solid acid catalyst.

[0062] The dry base sodium type strong acid cation exchange resin is selected from macroporous styrene cation exchange resin, and the factory form is sodium type: D006 styrene cation exchange resin, which is dried to a moisture content of less than 0.5%.

[0063] Evaluation: The tin-doped solid acid catalyst prepared in this example is recycled for 6 times, and the results are as follows:

[0064]

[0065]

[0066] Example 3

[0067] A preparation method of a heptaphenyltrihydroxysilsesquioxane, characterized in that it comprises the following steps:

[0068] A1: In a three-necked flask equipped with a magnetic stirrer and a condenser, 28g of phenyltrimethoxysilane and 150g of an organic solvent are added, the magnetic stirring is started, 3.6g of deionized water and 2.6g of sodium hydroxide are added to adjust the pH value, and then the reaction is carried out in a water bath kettle under reflux. After the reaction is completed, continue to stir at room temperature for 24h, then remove the solvent by rotary evaporation, and vacuum dry the solid to obtain heptaphenyltrisodium salt silsesquioxane;

[0069] A2: 9g of the seven phenyl trisodium salt silsesquioxane prepared in step A1 and 80g of anhydrous tetrahydrofuran were added into a three-necked flask, inert gas was bubbled in and stirred vigorously in an ice water bath, 28g of tin-doped solid acid catalyst was added into the three-necked flask, stirring was continued in the ice water bath for 3h, then 80g of deionized water was added to continue the reaction for 2h, after the reaction was completed, tetrahydrofuran was removed by rotary evaporation under reduced pressure, then extracted with chloroform, the extract was washed and separated to obtain the supernatant, the chloroform in the supernatant was removed by rotary evaporation, and the solid was dried under vacuum to obtain seven phenyl trihydroxysilsesquioxane, and the tin-doped solid acid catalyst was recycled and used.

[0070] The organic solvent in A1 is selected from tetrahydrofuran.

[0071] The pH value in A1 is adjusted to 9.

[0072] The water bath temperature in A1 is 85°C, and the reflux reaction is 8h.

[0073] The inert gas in A2 is selected from argon.

[0074] When chloroform is added for extraction in A2, NaHCO3 solution and deionized water are used in sequence to wash to neutral.

[0075] After the supernatant obtained after extraction and washing is separated, anhydrous MgSO4 is added to remove residual water in the solution.

[0076] The temperature of the vacuum oven in A1 and A2 is 60°C, and the time is 12h.

[0077] The preparation method of the tin-doped solid acid catalyst is:

[0078] B1: 130g of dry sodium type strong acid cation exchange resin (R-SO3Na), 40g of aminoacetyl chloride, 1000g of dichloroethane, and 18g of anhydrous aluminum chloride were added into a stirring reaction kettle, stirred at 5°C for 15h, filtered, and an amine sodium type strong acid cation exchange resin was obtained.

[0079] B2: 2g of dibutyltin maleate, 5g of sodium ethoxide, and 120g of vinyl acetate were added into the stirring kettle reaction kettle in B1, stirred at 50°C for 30min, then 10g of magnesium acrylate was added, and stirred for 4h, filtered, and a sodium type solid acid catalyst was formed.

[0080] B3: The sodium type solid acid catalyst obtained in B2 was loaded into an exchange column, 1300g of 20% high-purity hydrochloric acid was bubbled in at a flow rate of 4BV / h, then washed with deionized water to obtain a tin-doped solid acid catalyst.

[0081] The dry base sodium form strong acid cation exchange resin is selected from macroporous styrene cation exchange resin in sodium form as delivered: A35 styrene cation exchange resin, dried to less than 0.5% moisture.

[0082] Evaluation: The tin-doped solid acid catalyst prepared in this example was recycled for 6 times, and the results are as follows:

[0083]

[0084] Comparative Example 1

[0085] A method for preparing a heptaphenyltrihydroxysilsesquioxane, characterized in that it comprises the following steps:

[0086] A1: In a three-necked flask equipped with a magnetic stirrer and a condenser, 16 g of phenyltrimethoxysilane and 100 g of an organic solvent were added, the magnetic stirring was started, 1.6 g of deionized water and 1.2 g of sodium hydroxide were added to adjust the pH value, and then the reaction was carried out in a water bath at reflux. After the reaction was completed, the stirring was continued at room temperature for 12 h, and then the solvent was removed by rotary evaporation, and the solid was dried in a vacuum oven to obtain heptaphenyltrisodium silyl silicate;

[0087] A2: In a three-necked flask, 3 g of heptaphenyltrisodium silyl silicate prepared in step A1 and 45 g of anhydrous tetrahydrofuran were dissolved, and inert gas was bubbled in an ice water bath and stirred vigorously for 1 h, then 50 g of deionized water was added and the reaction was continued for 1 h. After the reaction was completed, the tetrahydrofuran was removed by rotary evaporation under reduced pressure, and then extracted with chloroform, and the extract was washed and separated to obtain the supernatant, which was rotary evaporated to remove chloroform, and the solid was dried in a vacuum oven to obtain heptaphenyltrihydroxysilsesquioxane.

[0088] The organic solvent in A1 is selected from N,N-dimethylformamide.

[0089] The pH value in A1 is adjusted to 7.5.

[0090] The water bath temperature in A1 is 60°C, and the reflux reaction is carried out for 3 h.

[0091] The inert gas in A2 is selected from nitrogen.

[0092] When chloroform is added in A2 for extraction, NaHCO3 solution and deionized water are used in sequence to wash to neutral.

[0093] After the supernatant is separated after extraction and washing in A2, anhydrous MgSO4 is added to remove residual water in the solution.

[0094] The temperature of the vacuum oven in A1 and A2 is 35°C, and the time is 24 h.

[0095] Comparative Example 2

[0096] A process for preparing a heptaphenyltrihydroxysilsesquioxane, characterized in that it comprises the following steps:

[0097] A1: In a three-necked flask equipped with a magnetic stirrer and a condenser, 16 g of phenyltrimethoxysilane and 100 g of an organic solvent are added, the magnetic stirring is started, 1.6 g of deionized water and 1.2 g of sodium hydroxide are added to adjust the pH value, and then the reaction is carried out in a water bath at reflux. After the reaction is completed, the stirring is continued at room temperature for 12 h, and then the solvent is removed by rotary evaporation, and the solid is dried in a vacuum oven to obtain heptaphenyltrisodium silsesquioxane;

[0098] A2: In a three-necked flask, 3 g of heptaphenyltrisodium silsesquioxane prepared in step A1 and 45 g of anhydrous tetrahydrofuran are dissolved, inert gas is introduced in an ice water bath and stirred vigorously, 19 g of tin-doped solid acid catalyst is added to the three-necked flask, stirring is continued in the ice water bath for 1 h, then 50 g of deionized water is added and the reaction is continued for 1 h, after the reaction is completed, the tetrahydrofuran is removed by rotary evaporation under reduced pressure, then extracted with chloroform, the extract is washed and separated to obtain the supernatant, the chloroform in the supernatant is removed by rotary evaporation, and the solid is dried in a vacuum oven to obtain heptaphenyltrihydroxysilsesquioxane, and the tin-doped solid acid catalyst is recycled.

[0099] The organic solvent in A1 is selected from N,N-dimethylformamide.

[0100] The pH value in A1 is adjusted to 7.5.

[0101] The water bath temperature in A1 is 60℃, and the reflux reaction is carried out for 3 h.

[0102] The inert gas in A2 is selected from nitrogen.

[0103] When chloroform is added for extraction in A2, NaHCO3 solution and deionized water are used in sequence to wash to neutral.

[0104] After the supernatant is separated after extraction and washing, anhydrous MgSO4 is added to remove residual water in the solution.

[0105] The temperature of the vacuum oven in A1 and A2 is 35℃, and the time is 24 h.

[0106] The preparation method of the tin-doped solid acid catalyst is as follows:

[0107] B1: 100 g of dry sodium-type strong acid cation exchange resin (R-SO3Na), 20 g of aminoacetyl chloride, 500 g of dichloroethane, and 10 g of anhydrous aluminum chloride are weighed into a stirred reaction kettle, stirred at -5℃ for 10 hours, filtered, and the amine sodium-type strong acid cation exchange resin is obtained;

[0108] B2: 2g of sodium ethoxide, 100g of vinyl acetate, were added to the stirred tank reactor in B1, stirred for 10 minutes at 40℃, then 6g of magnesium acrylate was added, stirred for 1 hour, filtered to form a sodium type solid acid catalyst;

[0109] B3: The sodium type solid acid catalyst obtained in B2 was loaded into an exchange column, 1000g of 10% high-purity hydrochloric acid was introduced at a flow rate of 1 BV / h, then washed with deionized water to obtain a tin-doped solid acid catalyst.

[0110] The dry base sodium type strong acid cation exchange resin is selected from macroporous styrene cation exchange resin in the form of sodium at the factory: D001 styrene cation exchange resin is selected, and dried to a moisture content of less than 0.5%.

[0111] Evaluation: The tin-doped solid acid catalyst prepared in this example was recycled for 6 times, and the results are as follows:

[0112]

[0113]

[0114] Comparative Example 3

[0115] A method for preparing a heptaphenyltrihydroxylsilsesquioxane, characterized in that it comprises the following steps:

[0116] A1: In a three-necked flask equipped with a magnetic stirrer and a condenser, 16g of phenyltrimethoxysilane and 100g of organic solvent were added, the magnetic stirring was started, 1.6g of deionized water and 1.2g of sodium hydroxide were added to adjust the pH value, then the reaction was carried out in a water bath kettle under reflux, after the reaction was completed, the stirring was continued at room temperature for 12h, then the solvent was removed by rotary evaporation, and the solid was vacuum dried to obtain heptaphenyltrisodium silsesquioxane;

[0117] A2: In a three-necked flask, 3g of heptaphenyltrisodium silsesquioxane prepared in step A1 and 45g of anhydrous tetrahydrofuran were dissolved, inert gas was introduced in an ice water bath and stirred vigorously, 19g of tin-doped solid acid catalyst was added to the three-necked flask, stirring was continued in the ice water bath for 1h, then 50g of deionized water was added and the reaction was continued for 1h, after the reaction was completed, the tetrahydrofuran was removed by rotary evaporation under reduced pressure, then extracted with chloroform, the extract was washed and separated to obtain the upper clear liquid, the chloroform was removed from the upper clear liquid by rotary evaporation, and the solid was vacuum dried to obtain heptaphenyltrihydroxylsilsesquioxane, and the tin-doped solid acid catalyst was recycled and used.

[0118] The organic solvent in A1 is selected from N,N-dimethylformamide.

[0119] The pH value in A1 is adjusted to 7.5.

[0120] The water bath temperature in A1 is 60℃, and the reaction is refluxed for 3h.

[0121] The inert gas in A2 is selected from nitrogen.

[0122] When chloroform is added for extraction in A2, the solution is washed with NaHCO3 solution and deionized water in sequence until it is neutral.

[0123] After the supernatant is separated by extraction and washing in A2, anhydrous MgSO4 is added to remove residual water in the solution.

[0124] The temperature of the vacuum oven in A1 and A2 is 35℃, and the time is 24h.

[0125] The preparation method of the tin-doped solid acid catalyst is as follows:

[0126] B1: 100g of dry base sodium type strong acid cation exchange resin (R-SO3Na), 20g of aminoacetyl chloride, 500g of dichloroethane, and 10g of anhydrous aluminum chloride are weighed into a stirring reaction kettle, stirred for 10 hours at -5℃, filtered, and the amine sodium type strong acid cation exchange resin is obtained;

[0127] B2: 0.2g of dibutyltin maleate, 2g of sodium ethoxide, and 100g of vinyl acetate are added to the stirring kettle in B1, stirred for 1 hour at 40℃, filtered, and the sodium type solid acid catalyst is formed;

[0128] B3: The sodium type solid acid catalyst obtained in B2 is loaded into an exchange column, 1000g of 10% high-purity hydrochloric acid is introduced at a flow rate of 1BV / h, and then deionized water is used for washing to obtain the tin-doped solid acid catalyst.

[0129] The dry base sodium type strong acid cation exchange resin is selected from macroporous styrene cation exchange resin, and the factory form is sodium type: D001 styrene cation exchange resin is selected, and dried to less than 0.5% moisture.

[0130] Evaluation: The tin-doped solid acid catalyst prepared in this example is recycled for 6 times, and the results are as follows:

[0131]

[0132] The present application is described above through specific embodiments and examples, but these descriptions are only illustrative and should not be understood as limiting the protection scope of the present application. Those skilled in the art can make various improvements, modifications or equivalent replacements to the technical solutions and embodiments of the present application without departing from the spirit and protection scope of the present application, and these should all fall within the protection scope of the present application.

Claims

1. A method for preparing a heptaphenyltrihydroxysilsesquioxane, characterized in that, Includes the following steps: A1: According to the mass fraction, add 16-28 parts of phenyltrimethoxysilane and 100-150 parts of organic solvent to a three-necked flask equipped with a magnetic stirrer and a condenser. Turn on the magnetic stirrer, add 1.6-3.6 parts of deionized water and 1.2-2.6 parts of sodium hydroxide to adjust the pH value, and then keep the mixture under reflux in a water bath. After the reaction is completed, continue stirring at room temperature for 12-24 hours. Then remove the solvent by rotary evaporation and dry the solid under vacuum to obtain heptaphenyltrisodium silsesquioxane. A2: Dissolve 3-9 parts of heptaphenyltrisodium silsesquioxane and 45-80 parts of anhydrous tetrahydrofuran in a three-necked flask. Inert gas is introduced into an ice-water bath and the mixture is stirred vigorously. At the same time, 19-28 parts of tin-doped solid acid catalyst are added to the three-necked flask. Stirring is continued in an ice-water bath for 1-3 hours. Then, 50-80 parts of deionized water are added and the reaction is continued for 1-2 hours. After the reaction is completed, the tetrahydrofuran is removed by rotary evaporation under reduced pressure. The mixture is then extracted with chloroform. The extract is washed and separated to obtain the supernatant. The chloroform is removed by rotary evaporation of the supernatant. The solid is dried under vacuum to obtain heptaphenyltrihydroxysilsesquioxane. The tin-doped solid acid catalyst is recovered and recycled. The preparation method of the tin-doped solid acid catalyst is as follows: B1: Weigh 100-130 parts by weight of dry sodium-type strong acid cation exchange resin, 20-40 parts of aminoacetyl chloride, 500-1000 parts of dichloroethane, and 10-18 parts of anhydrous aluminum trichloride, add them to a stirred reactor, stir for 10-15 hours at -5 to 5°C, filter, and obtain amino-sodium-type strong acid cation exchange resin. B2: Add 0.2-2 parts of dibutyltin maleate, 2-5 parts of sodium ethoxide, and 100-120 parts of vinyl acetate to the stirred reactor in B1. Stir at 40-50°C for 10-30 minutes, then add 6-10 parts of magnesium acrylate and stir for 1-4 hours. Filter to form a sodium-type solid acid catalyst. B3: The sodium-type solid acid catalyst obtained in B2 is loaded into an exchange column, and 1000-1300 parts of 10%-20% high-purity hydrochloric acid are passed through at a flow rate of 1-4 BV / h. Then, it is washed with deionized water to obtain the tin-doped solid acid catalyst.

2. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to claim 1, characterized in that: The organic solvent in A1 is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, carbon tetrachloride, and acetonitrile.

3. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to claim 1, characterized in that: The pH value in A1 is adjusted to 7.5-9.

4. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to claim 1, characterized in that: The water bath temperature in A1 is 60-85℃, and the reflux reaction is carried out for 3-8 hours.

5. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to any one of claims 1-4, characterized in that: The inert gas in A2 is selected from at least one of nitrogen, argon, or helium.

6. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to claim 1, characterized in that: When adding chloroform to extract A2, it is washed sequentially with NaHCO3 solution and deionized water until neutral.

7. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to claim 1, characterized in that: Anhydrous MgSO4 is added to the supernatant after extraction, washing and separation in A2 to remove residual water from the solution.

8. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to claim 1, characterized in that: The vacuum drying temperature in A1 and A2 is 35-60℃, and the time is 12-24h.

9. The method for preparing a heptaphenyltrihydroxysilsesquioxane according to claim 1, characterized in that: The dry-based sodium-type strong acid cation exchange resin is selected from macroporous styrene-based cation exchange resins and is shipped in sodium form.

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