CN112442175A

CN112442175A - Preparation method of octaaminopropyl cage-type octapolysilsesquioxane

Info

Publication number: CN112442175A
Application number: CN201910826617.1A
Authority: CN
Inventors: 王砥; 李明; 岳傲龙
Original assignee: Northeast Forestry University
Current assignee: Northeast Forestry University
Priority date: 2019-09-03
Filing date: 2019-09-03
Publication date: 2021-03-05

Abstract

The invention belongs to the technical field of organic-inorganic nano hybrid materials, and discloses a preparation method of octaaminopropyl cage-type octa-polysilsesquioxane. The preparation method comprises the following steps of adding a solvent, aminopropyltriethoxysilane and a catalyst into a reactor provided with a cooling reflux device, stirring, controlling the temperature of the system to be 70-90 ℃, stirring for 18-20 hours, adding tetrahydrofuran, performing rotary evaporation until a large amount of solids are separated out, cooling, and performing vacuum filtration on the obtained solution to obtain a white solid. Dissolving the white solid in deionized water, adding sodium bicarbonate to the solution until the solution is saturated, placing the solution in a dialysis bag, dialyzing the solution in the deionized water until the external solution does not contain impurity ions, and freeze-drying the dialysate to obtain the white solid. The method has short synthesis time, and the obtained product is relatively pure and is suitable for commercial production.

Description

Preparation method of octaaminopropyl cage-type octapolysilsesquioxane

Technical Field

The invention belongs to the technical field of organic-inorganic nano hybrid materials, and particularly relates to a preparation process of octaaminopropyl cage-type octa polysilsesquioxane

Background

The oligomeric polyhedral silsesquioxane is an organic-inorganic hybrid nano material taking Si-O-Si as a main framework, and is widely applied to the fields of materials, biology and the like due to the multi-selectivity and easy-modification property of organic groups on Si atoms. Oligomeric polyhedral silsesquioxanes have strong symmetry and have a variety of geometric structures, with cage structures being the most common. In view of the above, we propose a method for preparing cage-type octapolysilsesquioxane containing specific reactive groups (aminopropyl) by hydrolysis and condensation of aminopropylsilane coupling agent. The method can obtain the pure aminopropyl octa-poly cage-type silsesquioxane, and is convenient for later modification and doping application.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a synthetic method of octaaminopropyl cage-type octapolysilsesquioxane.

The invention provides a preparation method of octaaminopropyl cage-type octa-polysilsesquioxane, which comprises the following steps:

(1) in methanol solvent at a ratio of 1: (1.5-2) adding aminopropyltriethoxysilane (99 wt%, 0.946 g/cm)³)

And concentrated hydrochloric acid (36.5 wt%, 1.179 g/cm)³) And carrying out condensation reflux at 70-90 ℃ for 18-20 hours for reaction.

(2) And pouring the reacted solution into a tetrahydrofuran solution, carrying out rotary evaporation on the mixed solution at 40 ℃ until a large amount of solid is separated out, cooling the mixture, carrying out vacuum filtration, repeatedly washing with the tetrahydrofuran solution until the vacuum gauge number is not more than-0.95 MPa, and thus obtaining a white solid.

(3) The white solid was dissolved in an appropriate amount of deionized water and sodium bicarbonate was added thereto until the solution was saturated. And filtering the mixed substance to remove insoluble solid substances to obtain a clear mixed solution.

(4) And putting the mixed solution into a 500MW dialysis bag, and putting the bag into deionized water for dialysis until the external solution does not react with silver nitrate to generate white precipitate and does not react with dilute hydrochloric acid to generate bubbles. The dialysate was placed in a beaker and frozen at-19 ℃.

(5) And when the temperature of the cold trap is lower than-75 ℃, putting the frozen solid into a freeze dryer, wherein the pressure in the freeze dryer does not exceed 10Pa, and obtaining a white solid.

Compared with the prior art, the invention has the following advantages: the invention successfully synthesizes octaaminopropyl cage octapolysilsesquioxane by using aminopropyltriethoxysilane, and the obtained product has a clear structure and is very pure and suitable for commercial production.

Drawings

The invention is further illustrated with reference to the following figures and examples.

FIG. 1 is a matrix-assisted laser desorption ionization time-of-flight mass spectrum of octaaminopropyl cage octapolysilsesquioxane prepared in example 1.

FIG. 2 is an infrared spectrum of octaaminopropyl cage octapolysilsesquioxane prepared in example 1.

FIG. 3 is a matrix-assisted laser desorption ionization time-of-flight mass spectrum of octaaminopropyl cage octapolysilsesquioxane prepared in example 2.

FIG. 4 is an infrared spectrum of octaaminopropyl cage octapolysilsesquioxane prepared in example 2.

Detailed Description

The present invention is described in further detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

The preparation and purification method of octaaminopropyl cage type octapolysilsesquioxane comprises the following specific steps:

(1) to 36mL of methanol were added 2mL of aminopropyltriethoxysilane and 3mL of hydrochloric acid, and the mixture was condensed at 70 ℃ under reflux for 19 hours.

(2) And pouring the reacted solution into 45mL of tetrahydrofuran solution, carrying out rotary evaporation on the mixed solution at 40 ℃ until a large amount of solid is separated out, carrying out cooling treatment, carrying out vacuum filtration on the mixture, and repeatedly washing the mixture by using the tetrahydrofuran solution to obtain a white solid.

(3) The white solid was dissolved in an appropriate amount of deionized water, and sodium bicarbonate was added thereto to saturate. And filtering the mixed substance to remove insoluble solid substances to obtain a clear mixed solution.

(4) And putting the mixed solution into a 500MW dialysis bag, and putting the bag into deionized water for dialysis until the external solution does not react with silver nitrate to generate white precipitate and no bubble is generated when a dilute hydrochloric acid solution is dripped. The dialysate was placed in a beaker and frozen at-19 ℃.

(5) And when the temperature of the cold trap is lower than-75 ℃, putting the frozen solid into a freeze dryer, wherein the pressure in the freeze dryer does not exceed 10Pa, and obtaining a white solid. The matrix-assisted laser desorption ionization time-of-flight mass spectrum of the obtained octaaminopropyl cage octapolysilsesquioxane is shown in FIG. 1. The infrared spectrum of the obtained octaaminopropyl cage octapolysilsesquioxane is shown in FIG. 2.

Example 2

(1) to 180mL of methanol were added 7.5mL of aminopropyltriethoxysilane and 15mL of hydrochloric acid, and the mixture was condensed at reflux at 90 ℃ for 18 hours.

(2) And pouring the reacted solution into 250mL of tetrahydrofuran solution, carrying out rotary evaporation on the mixed solution at 40 ℃ until a large amount of solid is separated out, carrying out vacuum filtration on the mixture, and repeatedly washing the mixture by using the tetrahydrofuran solution to obtain a white solid.

(3) The white solid was dissolved in an appropriate amount of deionized water, sodium bicarbonate was added thereto to saturate, and the mixture was filtered to remove insoluble solid matter to obtain a clear mixture.

(5) And when the temperature of the cold trap is lower than-75 ℃, putting the frozen solid into a freeze dryer, wherein the pressure in the freeze dryer does not exceed 10Pa, and obtaining a white solid. The matrix-assisted laser desorption ionization time-of-flight mass spectrum of the obtained octaaminopropyl cage octapolysilsesquioxane is shown in fig. 3. The infrared spectrum of the obtained octaaminopropyl cage octapolysilsesquioxane is shown in FIG. 4.

Claims

1. The preparation method of the octaaminopropyl cage-type octapolysilsesquioxane is characterized by comprising the following operation steps.

(1) Mixing the components in a volume ratio of 1: (1.5-2) aminopropyltriethoxysilane (99 wt%, 0.946g/mL), concentrated hydrochloric acid (36.5 wt%, 1.179g/mL) and a solvent methanol, and pretreating a mixed solution after reacting for 18-20 hours to obtain octaaminopropyl cage-type octapolysilsesquioxane hydrochloride-containing solid.

(2) The white solid obtained in the above step was dissolved in a solvent, and a weak base was added thereto to saturate. And filtering the mixed substance to remove insoluble solid substances to obtain a clear mixed solution.

(3) And (3) putting the mixed solution into a 500MW dialysis bag for dialysis until the external solution does not contain sodium salt, and pretreating and drying the obtained dialysis internal solution to obtain a white solid substance.

2. The method of claim 1, wherein: the pretreatment in the step (1) is that the mixed solution is mixed with tetrahydrofuran and then is subjected to rotary evaporation at 40 ℃ until a large amount of solid is separated out, the temperature is reduced to 4 ℃, the treatment is carried out, and then the vacuum filtration is carried out, wherein the vacuum indicator does not exceed-0.95 MPa.

3. The method of claim 1, wherein: and (3) the solvent in the step (2) is deionized water, and the weak base is sodium bicarbonate.

4. The method of claim 1, wherein: and (3) titrating the dialysis solution through a silver nitrate solution until no white insoluble precipitate is generated in the external solution, and dropwise adding a proper amount of dilute hydrochloric acid solution until no bubble is generated, so that the next step of drying can be carried out.

5. The method of claim 1, wherein: and (3) the pretreatment is to freeze and compact the mixed solution at the temperature of minus 19 ℃, the drying is freeze drying, the temperature of a cold trap is lower than minus 75 ℃, the drying time is not lower than 48 hours, and the vacuum degree is not higher than 10 Pa.

6. A white solid obtained by the process according to claims 1 to 5, which is octaaminopropyl cage octapolysilsesquioxane.