Preparation method of heptaphenylmonohydridopolysilsesquioxane

Abstract

The invention discloses a preparation method of heptaphenylmonohydridopolysilsesquioxane, which relates to the technical field of POSS synthesis. Specifically, heptaphenyl T7 sodium salt is prepared by reflux reaction of deionized water, sodium hydroxide and phenyltrimethoxysilane in an organic solvent. The above sodium salt reacts with trichlorosilane and an iron organometallic stabilizer in an organic solvent, and after rotary evaporation and drying, heptaphenylmonohydridopolysilsesquioxane is obtained. This method has a simple process, strong operability, a high yield of the prepared heptaphenylmonohydridopolysilsesquioxane, and can be stably stored, having a broad market prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of POSS synthesis, and in particular to a preparation method of heptaphenylmonohydrosilicon polyhedral oligomeric silsesquioxane. Background Art

[0002] The full name of POSS is polyhedral oligomeric silsesquioxane, and its molecular formula is (RSiO3 / 2)n. When n is an even number, such compounds will form typical polyhedral oligomeric silsesquioxanes, also known as POSS. It is a new type of organic-inorganic hybrid material, and its special nanostructure, nano-size effect, cross-linking effect and effective modification of polymers have attracted great attention.

[0003] Patent Publication No. CN110511381A discloses a synthesis method of heptaisobutyltrisilanol POSS, belonging to the technical field of POSS preparation. The method is as follows: Add lithium hydroxide and ultrapure water to a mixed solution of methanol-ethanol or methanol-propanol, slowly dropwise add isobutyltrimethoxysilane, and carry out a condensation reflux reaction at 60-90°C for 18-24 hours; Take a 1mol / L dilute hydrochloric acid solution, pour it into the reaction solution, and filter it with a funnel or suction filter with a sintered glass funnel to obtain heptaisobutyltrisilanol POSS. The present invention improves the disadvantages of using highly toxic solvents such as acetone and THF to synthesize heptaisobutyltrisilanol POSS at home and abroad for a long time, uses alcohol reagents (ethanol, methanol, propanol) and other solvents with high polarity and low toxicity, changes the mixing ratio of alcohols, and synthesizes heptaisobutyltrisilanol POSS, which has the advantages of environmental friendliness, low toxicity to humans, high yield and simple post-treatment. The purity and yield of the synthesized product are both relatively high, with the purity above 70% and the yield about 60%.

[0004] Patent Publication No. US8044152B2 discloses an epoxy resin containing side-chain tethered cage-type POSS and a preparation method thereof, as well as an epoxy resin material containing POSS-epoxy resin and a preparation method thereof. The side-chain tethered cage-type POSS epoxy resin (POSS epoxy resin) is formed by tethering POSS groups on the side chains of bisphenol A diglycidyl ether (DGEBA) epoxy resin. The preparation method of POSS epoxy resin includes reacting epoxy resin with cage-type POSS to form side-chain tethered cage-type POSS epoxy resin (POSS-epoxy).

[0005] Patent Publication No. CN112143103A discloses a cage - type polyhedral oligomeric silsesquioxane - modified polypropylene composite material, which is made from the following components in parts by weight: 0.1 - 10 parts of cage - type polyhedral oligomeric silsesquioxane, 89 - 99.8 parts of polypropylene, and 0.1 - 1 part of antioxidant; the structural formula of the cage - type polyhedral oligomeric silsesquioxane is one of the following structural formulas: The cage - type polyhedral oligomeric silsesquioxane - modified polypropylene composite material of the invention greatly improves the crystallization temperature of polypropylene, promotes the crystallization of polypropylene, and improves its mechanical properties.

[0006] Patent Publication No. CN116041705A discloses a multifunctional cage - type oligomeric silsesquioxane and its preparation method and application. The method includes the following steps: (1) Preparation of cage - type oligomeric silsesquioxane salt; (2) Preparation of trifunctional polyhedral oligomeric silsesquioxane silanol; (3) Protection of trifunctional polyhedral oligomeric silsesquioxane silanol; (4) Vertex - capping reaction: In a solvent, after mixing phenylboronic acid - protected trifunctional polyhedral oligomeric silsesquioxane silanol with R1R2R3SiCl, a phenylboronic acid - protected trifunctional polyhedral oligomeric silsesquioxane is obtained by reaction; (5) Deprotection of trifunctional polyhedral oligomeric silsesquioxane silanol; (6) Vertex - capping reaction: In a solvent, after mixing monofunctional polyhedral oligomeric silsesquioxane disilanol with R4R5SiCl2, a multifunctional cage - type oligomeric silsesquioxane is obtained by reaction.

[0007] However, in the prior art, there are few disclosures of the preparation method of heptaphenylmonohydrosilane polyhedral oligomeric silsesquioxane, or the yield is not good, making it difficult to achieve large - scale production applications. Therefore, this method provides an efficient and simple method for preparing heptaphenylmonohydrosilane polyhedral oligomeric silsesquioxane.

[0008] Polyhedral oligomeric silsesquioxane needs to be maintained at ambient temperature for about three to six months for transportation and storage. These resins are not stable enough at ambient temperature, especially for resins with silanol and / or free - radical - curable functional groups. For silsesquioxane resins, these organic inhibitors are not always effective, possibly due to uneven distribution. Therefore, a stabilizer resin with efficacy is needed to improve the stability of heptaphenylmonohydrosilane polyhedral oligomeric silsesquioxane during storage at ambient temperature. Summary of the Invention

[0009] The purpose of the present invention is to solve the problems of poor yield in the preparation of existing heptaphenylmonohydrosilane polyhedral oligomeric silsesquioxane and insufficient stability at ambient temperature, and provides a preparation method of heptaphenylmonohydrosilane polyhedral oligomeric silsesquioxane, belonging to the technical field of POSS synthesis.

[0010] One of the purposes of the present invention: Discloses a preparation method of heptaphenylmonohydrosilane polyhedral oligomeric silsesquioxane, which is characterized by including the following steps:

[0011] A1: According to parts by mass, add 10 - 30 parts of deionized water and 2 - 5 parts of sodium hydroxide into a three-necked flask equipped with a reflux condenser and a magnetic stirrer. Keep the flask warm in a water bath, add 100 - 150 parts of an organic solvent, turn on the magnetic stirrer, add 16 - 22 parts of phenyltrimethoxysilane, and maintain the reflux reaction for 16 - 24 h. Filter the obtained white powder by suction filtration and dry it to obtain heptaphenyl T7 sodium salt;

[0012] A2: Add 2 - 5 parts of the heptaphenyl T7 sodium salt prepared in step A1 and 30 - 60 parts of an organic solvent into a three-necked flask equipped with a magnetic stirrer. Turn on the magnetic stirrer, add 3 - 8 parts of trichlorosilane and 0.03 - 0.8 part of an iron organometallic stabilizer, and react at room temperature to obtain a milky white solution;

[0013] A3: Filter the milky white solution through an organic membrane to obtain a clear solution, then rotary evaporate the clear solution to obtain a white powder. Wash and filter the white powder to obtain a precipitate, and dry it in an oven to obtain heptaphenylmonosilane hydrogen polyhedral oligomeric silsesquioxane.

[0014] As a supplement to the above technical solution, the organic solvent in A1 and A2 is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, carbon tetrachloride, and acetonitrile.

[0015] As a supplement to the above technical solution, the temperature of the water bath in A1 is set to 45 - 85 °C.

[0016] As a supplement to the above technical solution, it is dried in a vacuum oven in A1, the temperature is 65 - 85 °C, and the time is 2 - 6 h.

[0017] As a supplement to the above technical solution, the reaction time in A2 is 1 - 5 h.

[0018] As a supplement to the above technical solution, the white powder in A3 is washed with methanol or acetone, and the number of washing times is not less than 3 times.

[0019] As a supplement to the above technical solution, it is dried in a vacuum oven in A3, the temperature is 50 - 80 °C, and the time is 20 - 40 h.

[0020] The second object of the present invention: Disclosed is a preparation method of an iron organometallic stabilizer, which is obtained by a thiol addition reaction of the thiol group of tetramercapto porphyrin with vinyl ferrocene and a thiol addition reaction of the thiol group of tetramercapto porphyrin with diallyl bisphenol A to obtain the iron organometallic stabilizer.

[0021] As a supplement to the above technical solution, the preparation method of the iron organometallic stabilizer is characterized by including the following steps:

[0022] B1: Put 2 - 10 parts by weight of tetramercapto porphyrin into 100 - 200 parts of DMF, heat and stir for reaction for 20 - 60 minutes;

[0023] B2: Then add 0.02 - 0.5 parts of vinyl ferrocene and 0.5 - 2 parts of triethylamine, heat and stir for reaction for 20 - 40 minutes; then add 10 - 18 parts of diallyl bisphenol A, stir for reaction for 30 - 80 minutes, distill off DMF to obtain an iron organometallic stabilizer.

[0024] As a supplement to the above technical solution, the heating temperature in B1 and B2 is up to 70°C - 90°C.

[0025] A preparation method of heptaphenylmonohydridopolysilsesquioxane of the present invention has the following remarkable effects compared with the prior art:

[0026] 1. This method prepares a heptaphenylmonohydridopolysilsesquioxane, and the product yield can be stably controlled above 95%. The process is simple and has industrialization prospects;

[0027] 2. This method prepares an iron organometallic stabilizer, which can make the heptaphenylmonohydridopolysilsesquioxane be stably stored at room temperature, greatly improving its use performance and broadening its application scenarios. Description of the Drawings

[0028] Figure 1 It is an electron microscope image of the heptaphenylmonohydridopolysilsesquioxane prepared in Example 1 magnified 5000 times. Detailed Description of the Invention

[0029] The present invention will be described in detail through the following specific embodiments. Through these descriptions, the features and advantages of the present invention will become clearer and more definite.

[0030] Example 1

[0031] A preparation method of heptaphenylmonohydridopolysilsesquioxane, characterized by comprising the following steps:

[0032] A1: Add 10 g of deionized water and 2 g of sodium hydroxide into a three-necked flask equipped with a reflux condenser and a magnetic stirrer, keep the flask warm in a water bath, add 100 g of organic solvent, turn on the magnetic stirrer, add 16 g of phenyltrimethoxysilane, and keep the reflux reaction for 16 h. Filter the obtained white powder by suction, and obtain heptaphenyl T7 sodium salt after drying;

[0033] A2: Add 2 g of the heptaphenyl T7 sodium salt prepared in step A1 and 30 g of organic solvent into a three-necked flask equipped with a magnetic stirrer, turn on the magnetic stirrer, add 3 g of trichlorosilane and 0.2 g of iron organometallic stabilizer, and react at room temperature to obtain a milky white solution;

[0034] A3: The milky white solution is filtered through an organic membrane to obtain a clear solution, and then the clear solution is rotary evaporated to obtain a white powder. The white powder is washed and filtered to obtain a precipitate, which is dried in an oven to obtain heptaphenylmonohydridopolysilsesquioxane.

[0035] In A1 and A2, the organic solvent is selected from N,N-dimethylformamide.

[0036] In A1, the temperature of the water bath is set at 45 °C.

[0037] In A1, it is dried in a vacuum oven at a temperature of 65 °C for 6 h.

[0038] In A2, the reaction time is 1 h.

[0039] In A3, the white powder is washed with methanol, and the number of washing times is not less than 3 times.

[0040] In A3, it is dried in a vacuum oven at a temperature of 50 °C for 40 h.

[0041] The preparation method of the iron organometallic stabilizer:

[0042] B1: Put 2 g of tetrathiomaleoporphyrin into 100 g of DMF, heat to 70 °C, and stir and react for 20 minutes;

[0043] B2: Then add 0.1 g of vinylferrocene and 0.5 g of triethylamine, heat to 70 °C, and stir and react for 20 minutes; then add 10 g of diallylbisphenol A, stir and react for 30 minutes, and distill off DMF to obtain the iron organometallic stabilizer.

[0044] In this example, the prepared heptaphenylmonohydridopolysilsesquioxane is dissolved in a tetrahydrofuran solution to prepare a solution with a concentration of 10 wt%. 200 g of the solution is placed in an HDPE bottle and shaken evenly. The molecular weight of the filtered solution is measured by gel permeation chromatography (GPC), and the stability of the resin solution is monitored by molecular weight determination. The solution is kept in an air ventilated oven at 35 °C, and some samples are taken at 5 days, 10 days and 20 days for GPC analysis to monitor the molecular weight. The results are shown in the following table:

[0045]

[0046] Example 2

[0047] A preparation method of heptaphenylmonohydridopolysilsesquioxane, characterized by comprising the following steps:

[0048] A1: Add 20 g of deionized water and 3.5 g of sodium hydroxide into a three-necked flask equipped with a reflux condenser and a magnetic stirrer. Keep the flask warm in a water bath, add 125 g of an organic solvent, turn on the magnetic stirrer, add 19 g of phenyltrimethoxysilane, and maintain the reflux reaction for 20 h. Filter the obtained white powder by suction filtration and dry it to obtain the sodium salt of heptaphenyl T7.

[0049] A2: Add 3.5 g of the sodium salt of heptaphenyl T7 prepared in step A1 and 45 g of an organic solvent into a three-necked flask equipped with a magnetic stirrer. Turn on the magnetic stirrer, add 5.5 g of trichlorosilane and 0.4 g of an iron organometallic stabilizer, and react at room temperature to obtain a milky white solution.

[0050] A3: Filter the milky white solution through an organic membrane to obtain a clear solution, and then rotary evaporate the clear solution to obtain a white powder. Wash and filter the white powder, and dry the obtained precipitate in an oven to obtain heptaphenylmonosilane hydrogen polyhedral oligomeric silsesquioxane.

[0051] The organic solvent in A1 and A2 is selected from N,N-dimethylacetamide.

[0052] The temperature of the water bath in A1 is set at 65 °C.

[0053] In A1, it is dried in a vacuum oven at a temperature of 75 °C for 4 h.

[0054] The reaction time in A2 is 3 h.

[0055] In A3, the white powder is washed with methanol, and the number of washing times is not less than 3 times.

[0056] In A3, it is dried in a vacuum oven at a temperature of 65 °C for 30 h.

[0057] The preparation method of the iron organometallic stabilizer:

[0058] B1: Put 6 g of tetramercapto porphyrin into 150 g of DMF, heat to 80 °C, and stir and react for 40 minutes.

[0059] B2: Then add 0.25 g of vinyl ferrocene and 1.2 g of triethylamine, heat to 80 °C, stir and react for 30 minutes; then add 14 g of diallyl bisphenol A, stir and react for 55 minutes, and distill off DMF to obtain the iron organometallic stabilizer.

[0060] In this example, the prepared heptaphenylmonohydridopolysilsesquioxane was dissolved in a tetrahydrofuran solution to prepare a solution with a concentration of 10 wt%. 200 g of the solution was placed in an HDPE bottle and shaken evenly. The molecular weight of the filtered solution was measured by gel permeation chromatography (GPC), and the stability of the resin solution was monitored by measuring the molecular weight. The solution was kept in an air ventilated oven at 35 °C, and some samples were taken at 5 days, 10 days, and 20 days for GPC analysis to monitor the molecular weight. The results are shown in the following table:

[0061]

[0062] Example 3

[0063] A method for preparing heptaphenylmonohydridopolysilsesquioxane, characterized by comprising the following steps:

[0064] A1: Add 30 g of deionized water and 5 g of sodium hydroxide into a three-necked flask equipped with a reflux condenser and a magnetic stirrer. Keep the flask warm in a water bath, add 150 g of an organic solvent, turn on the magnetic stirrer, add 22 g of phenyltrimethoxysilane, and maintain the reflux reaction for 24 h. Filter the obtained white powder by suction filtration, and after drying, obtain heptaphenyl T7 sodium salt;

[0065] A2: Add 5 g of the heptaphenyl T7 sodium salt prepared in step A1 and 60 g of an organic solvent into a three-necked flask equipped with a magnetic stirrer. Turn on the magnetic stirrer, add 8 g of trichlorosilane and 0.8 g of an iron organometallic stabilizer, and react at room temperature to obtain a milky white solution;

[0066] A3: Filter the milky white solution through an organic membrane to obtain a clear solution, then rotary evaporate the clear solution to obtain a white powder. Wash and filter the white powder to obtain a precipitate, and dry it in an oven to obtain heptaphenylmonohydridopolysilsesquioxane.

[0067] The organic solvents in A1 and A2 are selected from tetrahydrofuran.

[0068] The temperature of the water bath in A1 is set to 85 °C.

[0069] In A1, it is dried in a vacuum oven at a temperature of 85 °C for 2 h.

[0070] The reaction time in A2 is 5 h.

[0071] In A3, the white powder is washed with methanol or acetone, and the number of washing times is not less than 3 times.

[0072] In A3, it is dried in a vacuum oven at a temperature of 80 °C for 20 h.

[0073] Preparation method of the iron organometallic stabilizer:

[0074] B1: Put 10 g of tetrathiomaleoporphyrin into 200 g of DMF, heat to 90 °C, and stir for reaction for 60 minutes;

[0075] B2: Then add 0.5 g of vinylferrocene and 2 g of triethylamine, heat to 90 °C, stir for reaction for 40 minutes; then add 18 g of diallylbisphenol A, stir for reaction for 80 minutes, distill off DMF to obtain the iron organometallic stabilizer.

[0076] In this example, the prepared heptaphenylmonohydridopolysilsesquioxane was dissolved in a tetrahydrofuran solution to prepare a concentration of 10 wt%, and 200 g of the solution was placed in an HDPE bottle and shaken evenly. The molecular weight of the filtered solution was measured by gel permeation chromatography (GPC), and the stability of the resin solution was monitored by measuring the molecular weight. The solution was kept in an air ventilated oven at 35 °C, and some samples were taken at 5 days, 10 days and 20 days for GPC analysis to monitor the molecular weight. The results are shown in the following table:

[0077]

[0078]

[0079] Comparative Example 1

[0080] A preparation method of heptaphenylmonohydridopolysilsesquioxane, characterized by comprising the following steps:

[0081] A1: Add 10 g of deionized water and 2 g of sodium hydroxide to a three-necked flask equipped with a reflux condenser and a magnetic stirrer, keep the flask warm in a water bath, add 100 g of an organic solvent, turn on the magnetic stirrer, add 16 g of phenyltrimethoxysilane, and keep the reflux reaction for 16 h to obtain a white powder, which is filtered by suction, and the heptaphenyl T7 sodium salt is obtained after drying;

[0082] A2: Add 2 g of the heptaphenyl T7 sodium salt prepared in step A1 and 30 g of an organic solvent to a three-necked flask equipped with a magnetic stirrer, turn on the magnetic stirrer, add 3 g of trichlorosilane, and react at room temperature to obtain a milky white solution;

[0083] A3: The milky white solution is filtered through an organic membrane to obtain a clear solution, and then the clear solution is rotary evaporated to obtain a white powder. The white powder is washed and filtered to obtain a precipitate, which is dried in an oven to obtain heptaphenylmonohydridopolysilsesquioxane.

[0084] The organic solvents in A1 and A2 are selected from N,N-dimethylformamide.

[0085] The water bath temperature in A1 is set at 45 °C.

[0086] In A1, it is dried in a vacuum oven at a temperature of 65 °C for 6 h.

[0087] The reaction time in A2 is 1 h.

[0088] In A3, the white powder is washed with methanol, and the number of washing times is not less than 3 times.

[0089] In A3, it is dried in a vacuum oven at a temperature of 50 °C for 40 h.

[0090] A method for preparing heptaphenylmonohydridopolysilsesquioxane, characterized by comprising the following steps:

[0091] A1: Add 10 g of deionized water and 2 g of sodium hydroxide to a three-necked flask equipped with a reflux condenser and a magnetic stirrer. Keep the flask warm in a water bath, add 100 g of organic solvent, turn on the magnetic stirrer, add 16 g of phenyltrimethoxysilane, and maintain reflux reaction for 16 h. Filter the obtained white powder by suction filtration, and obtain heptaphenyl T7 sodium salt after drying.

[0092] A2: Add 2 g of the heptaphenyl T7 sodium salt prepared in step A1 and 30 g of organic solvent to a three-necked flask equipped with a magnetic stirrer. Turn on the magnetic stirrer, add 3 g of trichlorosilane and 0.2 g of iron organometallic stabilizer, and react at room temperature to obtain a milky white solution.

[0093] A3: Filter the milky white solution through an organic membrane to obtain a clear solution, then rotary evaporate the clear solution to obtain a white powder. Wash and filter the white powder to obtain a precipitate, and dry it in an oven to obtain heptaphenylmonohydridopolysilsesquioxane.

[0094] The organic solvent in A1 and A2 is selected from N,N-dimethylformamide.

[0095] The water bath temperature in A1 is set at 45 °C.

[0096] In A1, it is dried in a vacuum oven at a temperature of 65 °C for 6 h.

[0097] The reaction time in A2 is 1 h.

[0098] In A3, the white powder is washed with methanol, and the number of washing times is not less than 3 times.

[0099] In A3, it is dried in a vacuum oven at a temperature of 50 °C for 40 h.

[0100] The preparation method of the iron organometallic stabilizer:

[0101] B1: Put 2 g of tetrathiomaleoporphyrin into 100 g of DMF, heat to 70 °C, and stir for reaction for 20 minutes;

[0102] B2: Then add 0.1 g of vinylferrocene and 0.5 g of triethylamine, heat to 70 °C, and stir for reaction for 20 minutes; then add 10 g of diallylbisphenol A, stir for reaction for 30 minutes, and distill off DMF to obtain an organoiron stabilizer.

[0103] In this example, the prepared heptaphenylmonohydridopolysilsesquioxane was dissolved in a tetrahydrofuran solution to prepare a concentration of 10 wt%, and 200 g of the solution was placed in an HDPE bottle and shaken evenly. The molecular weight of the filtered solution was measured by gel permeation chromatography (GPC), and the stability of the resin solution was monitored by molecular weight determination. The solution was kept in an air ventilated oven at 35 °C, and some samples were taken at 5 days, 10 days, and 20 days for GPC analysis to monitor the molecular weight. The results are shown in the following table:

[0104]

[0105] Comparative Example 2

[0106] A method for preparing heptaphenylmonohydridopolysilsesquioxane, characterized by comprising the following steps:

[0107] A1: Add 10 g of deionized water and 2 g of sodium hydroxide to a three-necked flask equipped with a reflux condenser and a magnetic stirrer, keep the flask warm in a water bath, add 100 g of an organic solvent, turn on the magnetic stirrer, add 16 g of phenyltrimethoxysilane, and keep the reflux reaction for 16 h. Filter the obtained white powder by suction filtration, and obtain heptaphenyl T7 sodium salt after drying;

[0108] A2: Add 2 g of the heptaphenyl T7 sodium salt prepared in step A1 and 30 g of an organic solvent to a three-necked flask equipped with a magnetic stirrer, turn on the magnetic stirrer, add 3 g of trichlorosilane and 0.2 g of an organoiron stabilizer, and react at room temperature to obtain a milky white solution;

[0109] A3: Filter the milky white solution through an organic membrane to obtain a clear solution, then rotary evaporate the clear solution to obtain a white powder. Wash and filter the white powder to obtain a precipitate, and dry it in an oven to obtain heptaphenylmonohydridopolysilsesquioxane.

[0110] The organic solvents in A1 and A2 are selected from N,N-dimethylformamide.

[0111] The temperature of the water bath in A1 is set to 45 °C.

[0112] In A1, it is dried in a vacuum oven at a temperature of 65 °C for 6 h.

[0113] The reaction time in A2 is 1 h.

[0114] The white powder in A3 is washed with methanol, and the number of washing times is not less than 3 times.

[0115] In A3, it is dried in a vacuum oven at a temperature of 50 °C for 40 h.

[0116] The preparation method of the iron organometallic stabilizer:

[0117] B1: Put 2 g of tetrathiomaleonitrile porphyrin into 100 g of DMF, heat to 70 °C, and stir and react for 20 minutes;

[0118] B2: Then add 0.5 g of triethylamine, heat to 70 °C, stir and react for 20 minutes; then add 10 g of diallylbisphenol A, stir and react for 30 minutes, and distill off DMF to obtain the organometallic stabilizer.

[0119] In this example, the prepared heptaphenylmonohydridopolysilsesquioxane was dissolved in a tetrahydrofuran solution to prepare a concentration of 10 wt%, and 200 g of the solution was placed in an HDPE bottle and shaken evenly. The molecular weight of the filtered solution was measured by gel permeation chromatography (GPC), and the stability of the resin solution was monitored by measuring the molecular weight. The solution was kept in an air ventilated oven at 35 °C, and some samples were taken at 5 days, 10 days, and 20 days for GPC analysis to monitor the molecular weight. The results are shown in the following table:

[0120]

[0121] Comparative Example 3

[0122] A preparation method of heptaphenylmonohydridopolysilsesquioxane, characterized by comprising the following steps:

[0123] A1: Add 10 g of deionized water and 2 g of sodium hydroxide to a three-necked flask equipped with a reflux condenser and a magnetic stirrer, keep the flask warm in a water bath, add 100 g of organic solvent, turn on the magnetic stirrer, add 16 g of phenyltrimethoxysilane, and keep the reflux reaction for 16 h. The white powder is filtered by suction, and after drying, heptaphenyl T7 sodium salt is obtained;

[0124] A2: Add 2 g of the heptaphenyl T7 sodium salt prepared in step A1 and 30 g of organic solvent to a three-necked flask equipped with a magnetic stirrer, turn on the magnetic stirrer, add 3 g of trichlorosilane and 0.2 g of the iron organometallic stabilizer, and react at room temperature to obtain a milky white solution;

[0125] A3: The milky white solution is filtered through an organic membrane to obtain a clear solution, and then the clear solution is rotary evaporated to obtain a white powder. The white powder is washed and filtered, and the obtained precipitate is dried in an oven to obtain heptaphenylmonohydropolysilsesquioxane.

[0126] In A1 and A2, the organic solvent is selected from N,N-dimethylformamide.

[0127] In A1, the temperature of the water bath is set at 45°C.

[0128] In A1, it is dried in a vacuum oven at a temperature of 65°C for 6 hours.

[0129] In A2, the reaction time is 1 hour.

[0130] In A3, the white powder is washed with methanol, and the number of washing times is not less than 3 times.

[0131] In A3, it is dried in a vacuum oven at a temperature of 50°C for 40 hours.

[0132] The preparation method of the iron organometallic stabilizer:

[0133] B1: Put 2 g of tetramercapto porphyrin into 100 g of DMF, heat to 70°C, and stir and react for 20 minutes;

[0134] B2: Then add 0.1 g of vinyl ferrocene and 0.5 g of triethylamine, heat to 70°C, stir and react for 50 minutes, and distill off DMF to obtain the iron organometallic stabilizer.

[0135] In this example, the prepared heptaphenylmonohydropolysilsesquioxane is dissolved in a tetrahydrofuran solution to prepare a concentration of 10 wt%, and 200 g of the solution is placed in an HDPE bottle and shaken evenly. The molecular weight of the filtered solution is measured by gel permeation chromatography (GPC), and the stability of the resin solution is monitored by molecular weight determination. The solution is kept in an air ventilated oven at 35°C, and some samples are taken at 5 days, 10 days and 20 days for GPC analysis to monitor the molecular weight. The results are shown in the following table:

[0136]

[0137] Thus, it can be seen that the heptaphenylmonohydropolysilsesquioxane product prepared by the method of this example has good stability and high yield, and has the prospect of industrialization.

[0138] The present invention has been described above through specific embodiments and examples. However, these descriptions are merely illustrative and should not be construed as limiting the scope of protection of the present invention. Without departing from the spirit and scope of protection of the present invention, those skilled in the art can make various improvements, modifications or equivalent substitutions to the technical solutions and their implementation manners of the present invention, and all of these should fall within the scope of protection of the present invention.

Claims

1. A preparation method of heptaphenylmonohydridopolysilsesquioxane, characterized in that, It includes the following steps: A1: According to mass parts, add 10 - 30 parts of deionized water and 2 - 5 parts of sodium hydroxide into a three-necked flask equipped with a reflux condenser and a magnetic stirrer. Keep the flask warm in a water bath, add 100 - 150 parts of organic solvent, turn on the magnetic stirrer, add 16 - 22 parts of phenyltrimethoxysilane, and maintain the reflux reaction for 16 - 24 h. Filter the obtained white powder by suction filtration, and after drying, obtain heptaphenyl T7 sodium salt; A2: Add 2 - 5 parts of the heptaphenyl T7 sodium salt prepared in step A1 and 30 - 60 parts of organic solvent into a three-necked flask equipped with a magnetic stirrer. Turn on the magnetic stirrer, add 3 - 8 parts of trichlorosilane and 0.03 - 0.8 part of an iron organometallic stabilizer, and react at room temperature to obtain a milky white solution; A3: Filter the milky white solution through an organic membrane to obtain a clear solution, then rotary evaporate the clear solution to obtain a white powder. Wash and filter the white powder to obtain a precipitate, and dry it in an oven to obtain heptaphenyl monosilane hydrogen polyhedral oligomeric silsesquioxane; The preparation method of the iron organometallic stabilizer in A2 is as follows; B1: By weight parts, put 2 - 10 parts of tetramercapto porphyrin into 100 - 200 parts of DMF, and heat and stir for reaction for 20 - 60 minutes; B2: Then add 0.02 - 0.5 part of vinyl ferrocene and 0.5 - 2 parts of triethylamine, heat and stir for reaction for 20 - 40 minutes; then add 10 - 18 parts of diallyl bisphenol A, stir for reaction for 30 - 80 minutes, and distill off DMF to obtain the iron organometallic stabilizer.

2. The preparation method of a heptaphenylmonohydridopolysilsesquioxane according to claim 1, wherein: The organic solvents in A1 and A2 are selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, carbon tetrachloride, and acetonitrile.

3. A preparation method of heptaphenylmonohydridopolysilsesquioxane according to claim 1, characterized in that: The temperature of the water bath in A1 is set at 45 - 85 °C.

4. A preparation method of heptaphenylmonohydridopolysilsesquioxane according to claim 1, characterized in that: The drying in A1 is drying in a vacuum oven at a temperature of 65 - 85 °C for 2 - 6 h.

5. A preparation method of heptaphenylmonohydridopolysilsesquioxane according to claim 1, characterized in that: The reaction time in A2 is 1 - 5 h.

6. A preparation method of heptaphenylmonohydrosilicon sesquisioxane according to claim 1, characterized in that: The heating temperature in B1 and B2 is up to 70 °C - 90 °C.

7. A method for preparing heptaphenylmonohydridopolysilsesquioxane according to claim 1, characterized in that: The white powder in A3 is washed with methanol or acetone, and the number of washing times is not less than 3 times.

8. A method for preparing heptaphenylmonohydridopolysilsesquioxane according to claim 1, characterized in that: The drying in A3 is drying in a vacuum oven at a temperature of 50 - 80 °C for 20 - 40 h.

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