Efficient synthesis method for phenyl silsesquioxane

Abstract

The present invention relates to an efficient synthesis method for phenyl silsesquioxane. In a catalyst prepared by the method, sodium mercaptoethoxide is used as a nucleophilic reagent and reacts with an electron-deficient double bond in triethanolamine maleate to form a stable addition product; 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide serves as a nucleophilic reagent and reacts with triethanolamine maleate; and an alkaline environment provided by [bmim]OH is beneficial for generating stable carbon anions, thereby accelerating the step of nucleophilic addition. In the present invention, phenyltrimethoxysilane is used as a raw material, the synthesis of phenyl silsesquioxane is achieved by means of a one-step method, the conversion rate reaches up to 99.21%, the reaction time is shortened by half, the reaction is simple and convenient, and the industrial production is facilitated.

Description

High-efficiency synthesis method of phenylsilsesquioxane TECHNICAL FIELD

[0001] The present application relates to the technical field of phenylsilsesquioxane, and particularly relates to a high-efficiency synthesis method of phenylsilsesquioxane. BACKGROUND

[0002] The synthesis method of octaphenylsilsesquioxane is mainly prepared by hydrolysis and condensation of phenyltrichlorosilane. The main method is to dissolve phenyltrichlorosilane into an organic solvent, add water under the condition of low temperature control, hydrolyze phenyltrichlorosilane into phenylsilanol, then add a catalyst after removing the water layer and heat to make it dehydrate and condense to form octaphenylsilsesquioxane.

[0003] Chinese patent CN100412077C: relates to a synthesis method of octaaminophenyl cage silsesquioxane, belonging to the technical field of nanomaterials. The existing preparation method still uses formic acid as a hydrogen donor and adopts a Pd / C catalytic system. The steps of the present application are as follows: stirring octanitrophenyl cage silsesquioxane, a solvent and Fe / C catalyst in an air or nitrogen atmosphere, heating to 50-100 DEG C; adding hydrazine hydrate or phenylhydrazine reducing agent according to the weight ratio of octanitrophenyl cage silsesquioxane to reducing agent 1:2-8, reacting for 2-12 hours; after the reaction, cooling to room temperature, filtering, adding ethyl acetate for extraction, and standing to separate layers; taking the organic phase after standing to separate layers, precipitating in petroleum ether, and after separation and drying, obtaining white precipitate.

[0004] Chinese patent CN104262385A: discloses a synthesis method of monofunctional seven phenylsilsesquioxane, which is prepared according to the following molar ratio of components: T7 sodium salt seven phenylsilsesquioxane sodium trisilanol 1.0: monofunctional trichlorosilane 1.2-2: second catalyst 0.01-0.05; T7 sodium salt is made of phenyltrimethoxysilane, deionized water and first catalyst, and the molar ratio is: phenyltrimethoxysilane 1.0: deionized water 1.1-5: first catalyst 0.5-2.

[0005] Chinese patent CN107778794A: a preparation method of octaphenylsilsesquioxane composite material, belonging to the field of material preparation, characterized in that: phenyltrichlorosilane is dissolved in benzene, stirred uniformly, deionized water is added dropwise, and reaction is carried out at room temperature; after standing to separate layers, the lower water phase is separated, and the organic phase is washed with deionized water until neutral; a benzyltrimethylammonium hydroxide methanol solution is added, heated to reflux, then stood, and after reflow cooling, white solid is obtained by filtering, washed with diethyl ether and dried to obtain white powder product; OPh-POSS, PACP and PET chips are dried in a vacuum oven; the additive is uniformly mixed with the PET chips, blended through a micro conical twin-screw extruder, extruded and granulated, and the material particles are vacuum dried and injection molded.

[0006] However, the phenylsilsesquioxane prepared by the above patent and prior art has a complex synthesis route, needs to control low temperature in the process, separates water phase, the product produces HCl, the reaction time is long, the yield is low and the like, which is very unfavorable for industrialization.

[0007] SUMMARY

[0008] The present application provides a high-efficiency synthesis method of phenylsilsesquioxane, selects phenyltrimethoxysilane as a raw material, completes the synthesis of phenylsilsesquioxane in one step, the conversion rate is as high as 99.21%, the reaction time is shortened by half, the reaction is simple and convenient, and is favorable for industrial production.

[0009] The technical scheme adopted by the present application to achieve the above object is as follows:

[0010] A high-efficiency synthesis method of phenylsilsesquioxane, the operation steps are:

[0011] S1: 30-40 parts of phenyltrimethoxysilane, 300-400 parts of a solvent are added to a three-necked flask, and after stirring and uniformly mixing, heating and temperature rising are carried out;

[0012] S2: stirring is started, a mixed solution of 10-20 parts of deionized water and 0.3-0.7 parts of a catalyst is slowly added by using a constant-pressure dropping funnel, after the addition is completed, stirring and reaction are continuously carried out;

[0013] S3: after the reaction is completed, filtration is carried out, the filter cake is washed with ethanol and deionized water until neutral, and after drying, phenylsilsesquioxane is obtained.

[0014] Preferably, the solvent is acetone or tetrahydrofuran.

[0015] Preferably, the heating temperature of S1 is 50-60 DEG C.

[0016] Preferably, the dropping time of S2 is 30-60 min.

[0017] Preferably, the reaction time of S2 is 24-48 h.

[0018] Preferably, the preparation mechanism of the catalyst is:

[0019] In the preparation of the catalyst, sodium mercaptoethanol acts as a nucleophile to react with the electron-deficient double bond in triethanolamine maleate ester, forming a stable addition product; in the preparation of the catalyst, 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt acts as a nucleophile to react with triethanolamine maleate ester; the basic environment provided by [bmim]OH promotes the above two addition reactions, and the basic conditions help to generate a stable carbanion, thereby accelerating the nucleophilic addition step.

[0020] Further, the preparation method of the catalyst is:

[0021] 11-22 parts of sodium mercaptoethanol, 20-40 parts of triethanolamine maleate ester, 0.001-0.1 parts of 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt, CAS: 1013932-26-7, 20-35 parts of [bmim]OH basic ionic liquid, are stirred at 60-70℃ for 30-70 minutes to obtain the catalyst.

[0022] Triethanolamine maleate ester is prepared according to the preparation method in section 2.2 of the study on the influence of modified triethanolamine polymer grinding aid on cement hydration.

[0023] The beneficial effects of the present application are as follows:

[0024] 1. When the catalyst prepared by the present application is applied to the hydrolysis and polycondensation process of phenyltrimethoxysilane, the technical effects include:

[0025] Increase yield: the catalyst can effectively promote the expected reaction of phenyltrimethoxysilane to phenylsilsesquioxane, increasing the yield of the target product;

[0026] Inhibit by-products: without the catalyst, the reaction can produce HCl as a by-product, and the use of the catalyst reduces such undesirable side reactions, reducing equipment corrosion and environmental impact;

[0027] Shorten reaction time: the catalyst accelerates the reaction rate, thereby reducing the time required to achieve the desired conversion rate and improving production efficiency;

[0028] 2. The present application selects phenyltrimethoxysilane as the raw material, and acetone or tetrahydrofuran as the solvent, and completes the synthesis of phenylsilsesquioxane in one step at 50-60℃, with a conversion rate of up to 99.21%, a reaction time reduced by half, and a simple and convenient reaction, which is conducive to industrial production. DETAILED DESCRIPTION

[0029] The present application will be further described below through specific examples, but the specific substances and amounts used in the examples of the present application should not be considered as limiting the present application.

[0030] Embodiment 1

[0031] A high-efficiency synthesis method of phenylsilsesquioxane, the operation steps of which are:

[0032] S1: 30g of phenyltrimethoxysilane, 300g of solvent were added to a three-necked flask, and after stirring and mixing uniformly, heating was performed to increase the temperature;

[0033] S2: stirring was started, and a mixed solution of 10g of deionized water and 0.3g of catalyst was slowly added dropwise using a constant-pressure dropping funnel, after the dropwise addition was completed, stirring was continued for reaction;

[0034] S3: after the reaction was completed, filtration was performed, and the filter cake was washed with ethanol and deionized water until neutral, and after drying, phenylsilsesquioxane was obtained.

[0035] The solvent is acetone.

[0036] The heating temperature of S1 is 50°C.

[0037] The dropwise addition time of S2 is 30min.

[0038] The reaction time of S2 is 24h.

[0039] The preparation method of the catalyst is:

[0040] 11g of sodium mercaptoethanol, 20g of maleic acid triethanolamine ester, 0.001g of 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt, CAS: 1013932-26-7, and 20g of [bmim]OH basic ionic liquid were stirred at 60°C for 30min to obtain the catalyst.

[0041] The maleic acid triethanolamine ester was prepared according to the preparation method in section 2.2 of the study on the influence of modified triethanolamine polymer grinding aid on cement hydration.

[0042] According to the analysis and calculation, the raw material conversion rate in this example is 98.57%, and the product yield is 95.81%.

[0043] Embodiment 2

[0044] A high-efficiency synthesis method of phenylsilsesquioxane, the operation steps of which are:

[0045] S1: 33g of phenyltrimethoxysilane, 340g of solvent were added to a three-necked flask, and after stirring and mixing uniformly, heating was performed to increase the temperature;

[0046] S2: stirring was started, and a mixed solution of 13g of deionized water and 0.4g of catalyst was slowly added dropwise using a constant-pressure dropping funnel, after the dropwise addition was completed, stirring was continued for reaction;

[0047] S3: After the reaction is completed, the filter cake is washed with ethanol and deionized water until neutral, and then dried to obtain the phenylsilsesquioxane.

[0048] The solvent is acetone.

[0049] The heating temperature of S1 is 55°C.

[0050] The dropwise addition time of S2 is 40 min.

[0051] The reaction time of S2 is 32 h.

[0052] The preparation method of the catalyst is:

[0053] 15 g of sodium mercaptoethanol, 25 g of maleic acid triethanolamine ester, 0.04 g of 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt, CAS: 1013932-26-7, and 25 g of [bmim]OH basic ionic liquid are stirred at 65°C for 40 min to obtain the catalyst.

[0054] The maleic acid triethanolamine ester is prepared according to the preparation method in section 2.2 of the study on the influence of modified triethanolamine polymer grinding aid on cement hydration.

[0055] According to the analysis and calculation, the raw material conversion rate in this example is 98.86%, and the product yield is 96.53%.

[0056] Example 3

[0057] An efficient synthesis method of phenylsilsesquioxane, the operation steps are:

[0058] S1: 38 g of phenyltrimethoxysilane, 380 g of solvent are added to a three-necked flask, and then stirred and mixed uniformly, and then heated and warmed up;

[0059] S2: Start stirring, slowly drop 18 g of deionized water and 0.6 g of catalyst mixture into the constant pressure dropping funnel, and continue stirring after the dropwise addition is completed.

[0060] S3: After the reaction is completed, the filter cake is washed with ethanol and deionized water until neutral, and then dried to obtain the phenylsilsesquioxane.

[0061] The solvent is tetrahydrofuran.

[0062] The heating temperature of S1 is 55°C.

[0063] The dropwise addition time of S2 is 50 min.

[0064] The reaction time of S2 is 45 h.

[0065] The preparation method of the catalyst is:

[0066] Stir 19g of sodium mercaptoethanol, 35g of triethanolamine maleate, 0.08g of 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt, CAS: 1013932-26-7, 30g of [bmim]OH basic ionic liquid at 65℃ for 60 minutes to obtain the catalyst.

[0067] The triethanolamine maleate is prepared according to the preparation method in section 2.2 of the study on the influence of modified triethanolamine polymer grinding aids on cement hydration.

[0068] According to the analysis and calculation, the raw material conversion rate in this example is 99.01%, and the product yield is 96.92%.

[0069] Example 4

[0070] A high-efficiency synthesis method of phenylsilsesquioxane, the operation steps are:

[0071] S1: Add 40g of phenyltrimethoxysilane and 400g of solvent to a three-necked flask, stir and mix uniformly, and then heat and warm up;

[0072] S2: Start stirring, slowly drop 20g of deionized water and 0.7g of catalyst mixture into a constant pressure dropping funnel, continue stirring after the dropping is completed, and then react;

[0073] S3: After the reaction is completed, perform suction filtration, wash the filter cake with ethanol and deionized water until it is neutral, dry, and then obtain phenylsilsesquioxane.

[0074] The solvent is tetrahydrofuran.

[0075] The heating temperature of S1 is 60℃.

[0076] The dropping time of S2 is 60min.

[0077] The reaction time of S2 is 48h.

[0078] The preparation method of the catalyst is:

[0079] Stir 22g of sodium mercaptoethanol, 40g of triethanolamine maleate, 0.1g of 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide salt, CAS: 1013932-26-7, 35g of [bmim]OH basic ionic liquid at 70℃ for 70 minutes to obtain the catalyst.

[0080] The triethanolamine maleate is prepared according to the preparation method in section 2.2 of the study on the influence of modified triethanolamine polymer grinding aids on cement hydration.

[0081] The conversion rate of raw materials and the product yield in this example are 99.21% and 97.35% respectively.

[0082] Comparative Example 1

[0083] The sodium mercaptoethanol is not added, and the other conditions are the same as in Example 1.

[0084] The conversion rate of raw materials and the product yield in this example are 77.23% and 67.51% respectively.

[0085] Comparative Example 2

[0086] The maleic acid triethanolamine ester is not added, and the other conditions are the same as in Example 1.

[0087] The conversion rate of raw materials and the product yield in this example are 85.87% and 82.67% respectively.

[0088] Comparative Example 3

[0089] The 1-aminopropyl-3-methyl imidazole bis(trifluoromethanesulfonyl) imide salt is not added, and the other conditions are the same as in Example 1.

[0090] The conversion rate of raw materials and the product yield in this example are 90.84% and 89.24% respectively.

[0091] According to the data analysis of the above examples and comparative examples, the catalyst prepared in the present application can effectively improve the conversion rate and the yield, and effectively inhibit the generation of by-products.

[0092] The above description is only the preferred embodiments of the present application, and does not limit the present application in any form. Although the present application has been disclosed as the above preferred embodiments, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content to obtain equivalent embodiments with equivalent changes, without departing from the technical solution of the present application. Any modification, change, equivalent change and modification of the above examples according to the technical essence of the present application are still within the scope of the technical solution of the present application.

Claims

1. A method for efficiently synthesizing phenylsilsesquioxane, comprising the following steps: S1: adding 30-40 parts of phenyltrimethoxysilane and 300-400 parts of a solvent into a three-necked flask, stirring and mixing until uniform, and then heating; S2: starting stirring, slowly adding a mixture of 10-20 parts of deionized water and 0.3-0.7 parts of a catalyst into the flask through a constant pressure dropping funnel, and continuing stirring after the dropping is completed; S3: after the reaction is completed, performing suction filtration, washing the filter cake with ethanol and deionized water until neutral, and drying to obtain phenylsilsesquioxane. The solvent is acetone or tetrahydrofuran. The heating temperature of S1 is 50-60℃. The dropping time of S2 is 30-60 min.

2. The process for the efficient synthesis of phenylsilsesquioxane according to claim 1, characterized in that: The reaction time of S2 is 24-48 h.

3. The process for the efficient synthesis of phenylsilsesquioxane as claimed in claim 1, wherein: The catalyst is prepared by the following method: mixing 11-22 parts of sodium mercaptoethanol, 20-40 parts of maleic acid triethanolamine ester, 0.001-0.1 parts of 1-aminopropyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and 20-35 parts of [bmim]OH basic ionic liquid, stirring at 60-70℃ for 30-70 min, and obtaining the catalyst.

4. The process for the efficient synthesis of phenylsilsesquioxane according to claim 1, characterized in that: ​ 5. The process for the efficient synthesis of phenylsilsesquioxane as claimed in claim 1, wherein: ​ 6. The process for the efficient synthesis of phenylsilsesquioxane as claimed in claim 1, wherein: ​ ​