阅读说明：本技术 一种前端聚合制备磁响应光子晶体凝胶的方法 (Method for preparing magnetic response photonic crystal gel through front-end polymerization ) 是由 刘思思 陈苏 汪晓巧 李晴 于 2019-10-09 设计创作，主要内容包括：本发明公开了一种前端聚合制备磁响应光子晶体凝胶的方法。将磁性四氧化三铁纳米粒子、乙烯基单体、β-环糊精、引发剂和交联剂溶于有机溶剂中,配成均匀溶液转移至试管中,同时将磁铁垂直或平行固定在试管底部或周围,通过一个电烙铁加热试管中溶液的液面,引发聚合反应,前端聚合完成后,最终得到将磁性的光子晶体结构固定在凝胶网络里面的光子晶体凝胶。本发明在聚合反应过程中不需要外加热源来维持整个体系的聚合,具有可控性,且聚合反应时间较短,节能,无污染；通过磁铁控制和热聚合结合,实现了光子晶体凝胶的一步快速制备,为磁性光子晶体的快速制备提供了方法,在工业化生产中具有很高的应用价值。(The invention discloses a method for preparing magnetic response photonic crystal gel by front-end polymerization, which is characterized in that magnetic ferroferric oxide nano particles, vinyl monomers, β -cyclodextrin, an initiator and a cross-linking agent are dissolved in an organic solvent to prepare a uniform solution, the uniform solution is transferred into a test tube, a magnet is vertically or parallelly fixed at the bottom or the periphery of the test tube, the liquid level of the solution in the test tube is heated by an electric iron to initiate polymerization reaction, and after the front-end polymerization is finished, the photonic crystal gel with a magnetic photonic crystal structure fixed in a gel network is finally obtained.)

1. A method for preparing magnetic response photonic crystal gel by front-end polymerization comprises the following specific steps:

(1) dissolving ferrocene in acetone, dropwise adding hydrogen peroxide after ultrasonic dispersion, transferring the solution into a reaction kettle after magnetic stirring, heating for reaction, naturally cooling the reaction kettle, and carrying out magnetic separation, drying and collection to obtain magnetic ferroferric oxide nano particles with the particle size of 135-215 nm;

(2) adding vinyl monomer, β -cyclodextrin, initiator and cross-linking agent into the solution, and continuing to perform ultrasonic treatment to obtain uniform mixed solution;

(3) transferring the mixed solution into a test tube, and fixing a magnet at the bottom or the periphery of the test tube;

(4) heating the liquid level of the solution in the test tube by a heat source to initiate polymerization reaction, removing the heat source, and diffusing the heat released by the polymerization reaction to an unreacted area until all raw materials in the whole reactor are converted into gel, thereby finally obtaining the magnetic-response photonic crystal gel with the magnetic photonic crystal structure fixed in the gel network.

2. The process according to claim 1, characterized in that the molar ratio of ferrocene to hydrogen peroxide in step (1) is 1: (13-20); the heating temperature in the reaction kettle is 200 ℃ and 230 ℃, and the reaction time is 60-80 h.

3. The method of claim 1, wherein: the mass ratio of the magnetic ferroferric oxide nano particles in the mixed solution is 0.2-0.5%, the mass ratio of the vinyl monomer is 39-60%, the mass ratio of the organic solvent is 30-50%, the mass ratio of the cyclodextrin is 7-10%, the mass ratio of the cross-linking agent is 0.5-5%, and the mass ratio of the initiator is 0.5-3%.

4. The method of claim 1, wherein: the vinyl monomer is at least one of acrylamide, N-dimethylacrylamide, N-vinyl caprolactam, N-isopropyl acrylamide or hydroxymethyl acrylamide.

5. The method of claim 1, wherein: the organic solvent is dimethyl sulfoxide, N'

-one of dimethylformamide or 1-methyl-2-pyrrolidone.

6. The method of claim 1, wherein the crosslinking agent is one of N, N' -methylenebisacrylamide, divinylbenzene, or ethylene glycol dimethacrylate; the initiator is one of benzoyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile.

7. The method according to claim 1, wherein the mixed solution is transferred to a test tube having a diameter of 10 to 20mm in the step (3); the magnets are vertically or parallelly fixed at the bottom or the periphery of the test tube.

8. The method of claim 1, wherein: the time of initiating polymerization reaction is 15-40s, the initiating temperature is 100-120 ℃, and the initiating distance is 0.8-1.2mm above the liquid level.

Technical Field

The invention relates to the technical field of functional polymer material preparation, in particular to a method for preparing magnetic response photonic crystal gel by front-end polymerization.

Background

The magnetic response photonic crystal gel material is popular with researchers because of the rapid response to the magnetic field, and has the advantages of remote control, convenient external field application and the like. The magnetic response photonic crystal gel formed by the magnetic induction self-assembly can quickly respond to the change of a magnetic field, realizes the great change of diffraction color, and provides a new platform for the application of the stimulus response color-changing material. At present, magnetic response photonic crystal gel is generally prepared by a traditional free radical polymerization or photocuring method, and the methods have the problems of long time consumption, high energy consumption, complicated steps and the like, so that the research on finding a method for rapidly preparing the magnetic response photonic crystal gel is widely focused by researchers. Front-end polymerization is a novel free radical reaction mode for converting hydrogel monomers into gels by the movement of localized reaction zones in the gel monomers. After the heat source is removed, the heat generated by the polymerization reaction is diffused to the unreacted area, and the polymerization is continuously initiated until the monomer in the container is completely polymerized. The method is simple to operate, does not need stirring in polymerization, saves energy and time, and is an ideal polymerization mode. Therefore, the magnetic field control and thermal polymerization are combined, and the magnetic response photonic crystal gel is prepared in one step by adopting the front-end polymerization method, so that the method has innovative significance and great popularization and application values.

Disclosure of Invention

The invention aims to provide a method for preparing magnetic response photonic crystal gel by front-end polymerization; the method has the advantages of high speed, high efficiency, low cost, high forming speed and the like, provides a path for realizing the rapid preparation of the magnetic photonic crystal, and has higher application value in industrial production.

The technical scheme of the invention is as follows: a method for preparing magnetic response photonic crystal gel by front-end polymerization comprises the following specific steps:

(1) dissolving ferrocene in acetone, dropwise adding hydrogen peroxide after ultrasonic dispersion, transferring the solution into a reaction kettle after magnetic stirring, heating for reaction, naturally cooling the reaction kettle, and carrying out magnetic separation, drying and collection to obtain magnetic ferroferric oxide nano particles with the particle size of 135-215 nm;

(2) adding vinyl monomer, β -cyclodextrin, initiator and cross-linking agent into the solution, and continuing to perform ultrasonic treatment to obtain uniform mixed solution;

(3) transferring the mixed solution into a test tube, fixing a magnet at the bottom or around the test tube, and immediately seeing a bright structural color;

(4) heating the liquid level of the solution in the test tube by a heat source to initiate polymerization reaction, removing the heat source, and diffusing the heat released by the polymerization reaction to an unreacted area until all raw materials in the whole reactor are converted into gel, thereby finally obtaining the magnetic-response photonic crystal gel with the magnetic photonic crystal structure fixed in the gel network.

The invention combines magnetic field control and thermal polymerization to realize one-step preparation of the magnetic response photonic crystal gel.

Preferably, the mole ratio of ferrocene to hydrogen peroxide in step (1) is 1: (13-20); the heating temperature in the reaction kettle is 200 ℃ and 230 ℃, and the reaction time is 60-80 h.

Preferably, the mass ratio of the magnetic ferroferric oxide nanoparticles in the mixed solution is 0.2-0.5%, the mass ratio of the vinyl monomer is 39-60%, the mass ratio of the organic solvent is 30-50%, the mass ratio of the cyclodextrin is 7-10%, the mass ratio of the crosslinking agent is 0.5-5%, and the mass ratio of the initiator is 0.5-3%.

Preferably, the vinyl monomer is at least one of acrylamide, N-dimethylacrylamide, N-vinylcaprolactam, N-isopropylacrylamide or methylolacrylamide.

Preferably, the organic solvent is one of dimethyl sulfoxide, N' -dimethylformamide or 1-methyl-2-pyrrolidone.

Preferably, the crosslinking agent is one of N, N' -methylene bisacrylamide, divinylbenzene or ethylene glycol dimethacrylate; the initiator is one of benzoyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile.

Preferably, the mixed solution in the step (3) is transferred to a test tube with the diameter of 10-20 mm; preferably, the magnets are fixed vertically or parallel to the bottom or periphery of the test tube.

Preferably, the polymerization is a front end polymerization process. The time of initiating polymerization reaction is 15-40s, the initiating temperature is 100-120 ℃, and the initiating distance is 0.8-1.2mm above the liquid level.

Before initiating polymerization, magnets are vertically or parallelly placed at the bottom or the side of a test tube, the arrangement direction of magnetic chains is changed, and the original sheet-shaped and cylindrical photonic crystal structure color gel can be obtained, and the magnetic response photonic crystal gel can be obtained after polymerization is completed within 5-10min by utilizing front end polymerization.

Has the advantages that:

the invention adopts a solvothermal method to prepare 135-plus 215nm magnetic ferroferric oxide nano particles, and prepares the magnetic response photonic crystal gel rapidly through front-end polymerization, the method is simple, the energy consumption is low, and the preparation of the magnetic response photonic crystal gel can be completed within 5-10 min; the direction of the magnet is simply controlled, so that the diffraction direction of the photonic crystal gel can be changed, and the disc-shaped and cylindrical magnetic response photonic crystal gel is finally obtained. The method combines magnetic field assembly and thermal polymerization simultaneously, completes the preparation of the magnetic response photonic crystal gel in one step in a short time, solves the problems of complicated preparation process, time consumption, energy consumption and the like of the traditional magnetic photonic crystal gel, and has higher popularization and application values.

Drawings

FIG. 1 is a schematic diagram of a disk-shaped magnetically responsive photonic crystal gel prepared by front-end polymerization in example 1;

FIG. 2 is a graph showing the response of the magnetic photonic crystal gel of example 1 under different compressive strains;

FIG. 3 is a schematic diagram of a cylindrical magnetic response photonic crystal gel prepared by front-end polymerization in example 2;

FIG. 4 is a graph showing the response of the magnetic photonic crystal gel of example 2 under different compressive strains.

Detailed Description

The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.