阅读说明：本技术 一种可跟踪助剂及其制备方法 (Trackable auxiliary agent and preparation method thereof ) 是由 姜彦� 陈玉瑛 张洪文 于 2020-05-19 设计创作，主要内容包括：本发明属于复合材料领域,具体涉及一种可跟踪助剂及其制备方法,所述制备方法为：先以乙烯基三甲氧基硅烷为原料,通过水解缩合得到乙烯基笼型聚倍半硅氧烷(OVi-POSS),再用水溶性淀粉通过超声法制备碳量子点乙醇溶液,加入γ-甲基丙烯酰氧丙基三甲氧基硅烷水解缩合即得改性碳量子点乙醇溶液；将乙烯基POSS,含氢硅油,碳量子点乙醇溶液在铂催化剂的作用下,通过硅氢加成得到荧光POSS。本发明自制乙烯基POSS和碳量子点乙醇溶液进行加成反应后得到了具有荧光的笼型聚倍半硅氧烷,从而拓宽了聚硅氧烷和碳量子点在复合材料方面的应用。(The invention belongs to the field of composite materials, and particularly relates to a trackable auxiliary agent and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, taking vinyl trimethoxy silane as a raw material, obtaining vinyl cage polysilsesquioxane (OVi-POSS) through hydrolytic condensation, preparing a carbon quantum dot ethanol solution by using water-soluble starch through an ultrasonic method, and adding gamma-methacryloxypropyl trimethoxy silane for hydrolytic condensation to obtain a modified carbon quantum dot ethanol solution; and carrying out hydrosilylation on vinyl POSS, hydrogen-containing silicone oil and a carbon quantum dot ethanol solution under the action of a platinum catalyst to obtain the fluorescent POSS. According to the invention, the fluorescent cage-type polysilsesquioxane is obtained after the self-made vinyl POSS and the carbon quantum dot ethanol solution are subjected to addition reaction, so that the application of polysiloxane and carbon quantum dots in the aspect of composite materials is widened.)

1. The traceable auxiliary is characterized by being vinyl POSS modified by modified carbon quantum dots connected through hydrogen-containing silicone oil, and having the following structural formula:

2. the preparation method of the trackable auxiliary agent is characterized by comprising the following steps:

(1) preparation of vinyl POSS: dissolving vinyl trimethoxy silane in an ethanol solution, adding deionized water, fully stirring, slowly dropwise adding hydrochloric acid to adjust the pH value, keeping the rotation speed at 300-60 ℃, fully stirring and reacting for 12 hours at 40-60 ℃, performing suction filtration after the reaction is finished, recrystallizing, and drying in a vacuum drying oven at 50 ℃ to obtain vinyl POSS;

(2) preparing a carbon quantum dot ethanol solution, namely respectively dissolving water-soluble starch and sodium hydroxide (NaOH) in deionized water, performing ultrasonic treatment to fully dissolve the water-soluble starch and the sodium hydroxide to obtain a water-soluble starch solution and a sodium hydroxide solution, pouring the water-soluble starch solution and the sodium hydroxide solution into a 100m L single-neck flask, performing ultrasonic treatment for 10-12 hours to obtain a carbon quantum dot aqueous solution, drying the carbon quantum dot aqueous solution in a 50 ℃ oven until the solution is 20m L, adjusting the pH of the solution to be neutral by hydrochloric acid while stirring, gradually adding anhydrous ethanol to the solution till the solution is 100m L, adding 20% anhydrous magnesium sulfate, standing for 3 days, taking supernatant, centrifuging and filtering to obtain the carbon quantum dot ethanol solution;

(3) preparing a modified carbon quantum dot ethanol solution: absorbing the carbon quantum dot ethanol solution prepared in the step (2), adding KH-570 and deionized water, reacting at 0 ℃ for 0.5h, and heating to 60 ℃ for 2-4h to obtain a modified carbon quantum dot ethanol solution;

(4) preparation of fluorescent POSS: and (2) adding the vinyl POSS prepared in the step (1), the modified carbon quantum dot ethanol solution prepared in the step (3) and hydrogen-containing silicone oil in a tetrahydrofuran solution, dropwise adding a drop of platinum catalyst to perform hydrosilylation reaction, precipitating a product with deionized water after the reaction is finished, centrifuging, washing with absolute ethyl alcohol for multiple times, and drying in a vacuum oven at 50 ℃ to obtain the fluorescent POSS.

3. The method of claim 2, wherein the volume ratio of vinyltrimethoxysilane to deionized water in step (1) is 1:1 to 1: 3; the volume ratio of the absolute ethyl alcohol to the vinyl trimethoxy silane is 10:1, and the pH is adjusted to 2-3.

4. The method for preparing the trackable aid according to claim 2, wherein the mass ratio of the water-soluble starch to the sodium hydroxide in the step (2) is 1:2, the mass concentration of the water-soluble starch solution is 4%, and the mass concentration of the sodium hydroxide solution is 8%.

5. The method for preparing the trackable aid according to claim 2, wherein the mass ratio of the KH-570 to the carbon quantum dot ethanol solution in the step (3) is as follows: 1: 37.5; the filtration was performed using a 0.22um membrane.

6. The method for preparing a trackable aid according to claim 2, wherein the centrifugation speed in step (4) is 1000r/min and the centrifugation time is 10 min.

7. The method for preparing the trackable aid according to claim 2, wherein the vinyl POSS in the step (4) is used in an amount of 1g, the hydrogen-containing silicone oil is used in an amount of 2g, the modified carbon quantum dot ethanol solution is used in an amount of 3-7m L, and the tetrahydrofuran is used in an amount of 15m L.

8. The process for preparing a traceable auxiliary according to claim 1, wherein the reaction temperature in the step (4) is 40 ℃ and the reaction time is 18 to 24 hours; the amount of platinum catalyst used was 1 drop.

Technical Field

The invention belongs to the field of composite materials, and particularly relates to a trackable auxiliary agent and a preparation method thereof.

Background

Polysiloxanes are a class of macromolecules with a backbone chain of-Si-O-and organic groups bonded to the Si atom. The popularization and application of the polysiloxane are beneficial to reducing the dependence of human beings on non-renewable resources, the application range of the polysiloxane can be further expanded by improving the performance of the polysiloxane, and the performance of the high polymer material is mainly determined by the main chain structure of the high polymer material. Therefore, it is of great importance to prepare polysiloxanes having a particular topology. Macrocyclic, closed polycyclic, hyperbranched, cage, semi-cage, double-deck and ladder types are several polysiloxanes with special topologies, of which the cage type isPolysilsesquioxanes have been more studied. The cage Polysilsesquioxane (POSS) is a nano-scale inorganic filler with an organic/inorganic hybrid structure and has a general formula of (RsiO)_1.5)_nWherein n can be 6, 8, 10 and 12, and is a central control cage type inorganic structure with silicon-oxygen alternately connected, and eight vertexes of Si atom are connected with an organic group R.

Carbon quantum dots are a carbon-based zero-dimensional material. The carbon quantum dots have the advantages of excellent optical properties, good water solubility, low toxicity, environmental friendliness, wide raw material source, low cost, good biocompatibility and the like. Since the first discovery of carbon quantum dots, many synthetic methods have been developed, including arc discharge methods, laser ablation methods, electrochemical synthesis methods, chemical oxidation methods, combustion methods, hydrothermal synthesis methods, microwave synthesis methods, template methods, and the like. The carbon quantum dots are widely applied and have good application prospects in a plurality of fields such as medical imaging technology, environmental monitoring, chemical analysis, catalyst preparation, energy development and the like.

The carbon quantum dot ethanol solution exists in a liquid state, and ethanol is volatile and difficult to store for a long time, so that the application range of the carbon quantum dot ethanol solution is limited. The carbon quantum dot ethanol solution is prepared into powder, so that the application range of the carbon quantum dot ethanol solution can be increased, but the preparation of the carbon quantum dot ethanol solution into powder can cause fluorescence quenching.

Disclosure of Invention

The invention discloses a preparation method of a trackable auxiliary agent, which is characterized in that vinyl POSS, hydrogen-containing silicone oil and a modified carbon quantum dot ethanol solution are subjected to hydrosilylation reaction under the action of a platinum catalyst to prepare cage-type polysilsesquioxane with fluorescence, and carbon quantum dots with fluorescence are introduced to the cage-type polysilsesquioxane, so that the research and application range of a polysiloxane composite material can be expanded, and meanwhile, the application range of the carbon quantum dots is expanded.

In order to achieve the purpose, the invention adopts the following technical scheme: the reaction equation for preparing the fluorescent POSS polymer is as follows:

a preparation method of a trackable auxiliary agent is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) preparation of vinyl POSS: dissolving vinyl trimethoxy silane in an ethanol solution, adding deionized water, fully stirring, slowly dropwise adding hydrochloric acid to adjust the pH value, keeping the rotation speed at 300-60 ℃, fully stirring and reacting for 12 hours at 40-60 ℃, performing suction filtration after the reaction is finished, recrystallizing, and drying in a vacuum drying oven at 50 ℃ to obtain vinyl POSS;

wherein the volume ratio of the vinyl trimethoxy silane to the water is 1:1-1:3, the volume ratio of the vinyl trimethoxy silane to the ethanol is 1:10, and hydrochloric acid is dripped to adjust the pH value to 2-3.

(2) Respectively dissolving water-soluble starch and sodium hydroxide (NaOH) in deionized water, performing ultrasonic treatment to fully dissolve the water-soluble starch and the sodium hydroxide, pouring the water-soluble starch and the sodium hydroxide into a 100m L single-neck flask, performing ultrasonic treatment for 12 hours (changing water every 1 hour) to obtain a carbon quantum dot aqueous solution, drying the carbon quantum dot aqueous solution in a 50 ℃ oven until the solution is 20m L, adjusting the pH of the solution to be neutral by hydrochloric acid while stirring, sequentially adding anhydrous ethanol to 100m L, adding 20% anhydrous magnesium sulfate, standing for 3 days, centrifuging supernatant, and filtering to obtain the carbon quantum dot ethanol solution;

the mass ratio of the water-soluble starch to the sodium hydroxide is 1:2, the mass concentration of the water-soluble starch solution is 4%, and the mass concentration of the sodium hydroxide solution is 8%.

(3) Absorbing the carbon quantum dot ethanol solution prepared in the step (2), adding 0.8g of KH-570 and 5m L deionized water, reacting at 0 ℃ for 0.5h, and heating to 60 ℃ for 4h to obtain a modified carbon quantum dot ethanol solution;

the mass ratio of the KH-570 to the carbon quantum dot ethanol solution is as follows: 1: 37.5; the filtration was performed using a 0.22um membrane.

(4) Preparation of fluorescent POSS: and (2) adding the vinyl POSS prepared in the step (1), the modified carbon quantum dot ethanol solution prepared in the step (3) and hydrogen-containing silicone oil in a tetrahydrofuran solution, dropwise adding a drop of platinum catalyst to perform hydrosilylation reaction, precipitating a product with deionized water after the reaction is finished, centrifuging, washing with absolute ethyl alcohol for multiple times, and drying in a vacuum oven at 50 ℃ to obtain the fluorescent POSS.

The centrifugation speed is 1000r/min, and the centrifugation time is 10 min.

The dosage of the vinyl POSS is 1g, the dosage of the hydrogen-containing silicone oil is 2g, the dosage of the modified carbon quantum dot ethanol solution is 3-7m L, and the dosage of the tetrahydrofuran is 15m L.

The reaction temperature is 40 ℃, and the reaction time is 18-24 h; the amount of platinum catalyst used was 1 drop.

Has the advantages that:

the preparation method comprises the steps of firstly preparing vinyl POSS with good dispersibility, then preparing carbon quantum dot ethanol solution and modified carbon quantum dot ethanol solution, then taking hydrogen-containing silicone oil as an intermediate bridge, and compounding the vinyl POSS and the carbon quantum dots through hydrosilylation reaction to obtain the fluorescent cage-type polysilsesquioxane, thereby providing a beneficial idea for the development of the polysiloxane composite material.

The distribution and stability can be observed by complexing it with other polymers and by fluorescence. And the complex with the vinyl POSS has small fluorescence quenching property due to the large vacancy resistance of the POSS.

Drawings

FIG. 1 is a Fourier transform infrared (ATR/FTIR) spectrum of vinyl polysilsesquioxane as in step (1) of example 1.

FIG. 2 is a graph of Fourier transform infrared (ATR/FTIR) spectra of carbon quantum dots, modified carbon quantum dots, and fluorescent POSS in steps (2) - (4) of example 1.

FIG. 3 is a fluorescence spectrum (P L) of an ethanol solution containing carbon quantum dots at different excitation wavelengths in step (2) of example 1.

FIG. 4 is a fluorescence spectrum of fluorescent POSS at different excitation wavelengths in step (4) of example 1.

FIG. 5 is a Thermogravimetric (TGA) plot of vinyl polysilsesquioxane, example 1, step (1).

FIG. 6 is a fluorescence spectrum of the fluorescent POSS/silicone rubber composite of example 1.

Detailed Description

The present invention will be described in further detail with reference to examples.