阅读说明：本技术 一种光致变色材料及其制备方法 (Photochromic material and preparation method thereof ) 是由 倪新龙 聂海根 宋建新 于 2021-09-09 设计创作，主要内容包括：本申请公开了一种光致变色材料,由主体物质和客体物质按照摩尔比1:1或1:2组成,其中,所述主体物质为八元瓜环或十元瓜环；所述客体物质为紫精化合物。本申请还提供一种光致变色材料的制备方法。本申请提供的光致变色材料,响应速度快、稳定性高,响应的波长范围350nm至1400nm,并且能够在液体、固体两种形态都具有快速、灵敏的光致可逆变色现象。本申请提供的制备方法,简单,操作简便。(The application discloses a photochromic material, which consists of a host substance and a guest substance according to a molar ratio of 1:1 or 1:2, wherein the host substance is an eight-element cucurbituril or a ten-element cucurbituril; the guest substance is a viologen compound. The application also provides a preparation method of the photochromic material. The photochromic material provided by the application has the advantages of high response speed, high stability, response wavelength range of 350nm to 1400nm, and capability of having a quick and sensitive photochromic reversible phenomenon in both liquid and solid forms. The preparation method provided by the application is simple and convenient to operate.)

1. The photochromic material is characterized by consisting of a host substance and a guest substance according to a molar ratio of 1:1 or 1:2, wherein the host substance is an eight-membered cucurbituril or a ten-membered cucurbituril; the guest substance is a viologen compound.

2. The photochromic material of claim 1 wherein the viologen compound is a conjugated substituent on one or both sides of 4,4' -bipyridine, the substituent being attached to N.

3. The photochromic material of claim 2, wherein the viologen compound is a counter anion compound of 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium), or a counter anion compound of 1-4-carboxyphenyl- (4,4' -bipyridinium).

4. The photochromic material of claim 3, wherein the viologen compound is 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride or 1-4-carboxyphenyl- (4,4' -bipyridinium) dichloride.

5. The photochromic material of claim 1, wherein the photochromic material is a liquid or a solid.

6. A method for preparing a photochromic material according to any one of claims 1 to 4, characterized in that it comprises the following steps:

dissolving a host substance and a guest substance in water according to a molar ratio of 1:1 or 1:2, and heating to enable the host substance and the guest substance in the solution to form a host-guest compound through self-assembly, thereby obtaining the photochromic material in a solution form.

7. The method for preparing a photochromic material according to claim 6, wherein the heating is specifically: heating and reacting for 1-2h at 40-100 ℃.

8. The method for preparing a photochromic material according to any one of claims 6 to 7, further comprising concentrating and drying the photochromic material in the form of a solution to obtain the photochromic material in the form of a solid.

9. The method for preparing photochromic material of claim 8 wherein the photochromic material in the form of solution is concentrated and dried by an evaporator.

Technical Field

The application relates to the technical field of material chemistry, in particular to a photochromic material and a preparation method thereof.

Background

Photochromic materials refer to materials that can change color when excited by a light source, and are generally realized by using the change of molecular structures of certain compounds under the action of light with certain wavelength and intensity, so that the absorption peak value of the photochromic materials to the light, namely the corresponding change of the color is caused. This change in color is generally reversible.

At present, the requirement that the absorption band is in a visible light region, the photoresponse speed is high, the sensitivity is high, the photochromic material with practical application value is very limited, and particularly, the material which has rapid and sensitive photochromic reversible phenomenon in both solution and solid states is very few, so the market requirement can not be met.

Disclosure of Invention

To solve the above technical problems, a first object of the present invention is to provide a photochromic material; the second purpose of the invention is to provide a preparation method of the photochromic material; the photochromic material provided by the application has the advantages of high response speed, high stability, response wavelength range of 350nm to 1400nm, and capability of having a quick and sensitive photochromic reversible phenomenon in both liquid and solid forms. The preparation method provided by the application is simple and convenient to operate.

The technical scheme provided by the invention is as follows:

a photochromic material consists of a host substance and a guest substance according to a molar ratio of 1:1 or 1:2, wherein the host substance is an eight-element cucurbituril or a ten-element cucurbituril; the guest substance is a viologen compound.

Preferably, the viologen compound is a conjugated substituent on one or both sides of 4,4' -bipyridine, the substituent being attached to N.

Preferably, the viologen compound is a counter anion compound of 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium), or a counter anion compound of 1-4-carboxyphenyl- (4,4' -bipyridinium).

Preferably, the viologen compound is 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride, or 1-4-carboxyphenyl- (4,4' -bipyridinium) dichloride.

Preferably, the photochromic material is a liquid or a solid.

A method for preparing the photochromic material of any one of the above items, comprising the following steps:

dissolving a host substance and a guest substance in water according to a molar ratio of 1:1 or 1:2, heating, and forming a host-guest compound by self-assembly of the host substance and the guest substance in the solution to obtain the photochromic material in a solution form.

Preferably, the heating is specifically: heating and reacting for 1-2h at 40-100 ℃.

Preferably, the method further comprises concentrating and drying the photochromic material in the form of solution to obtain the photochromic material in the form of solid.

Preferably, the photochromic material in the form of a solution is concentrated and dried by an evaporator.

The photochromic material provided by the application has the advantages of high response speed and high stability, the response wavelength range is 350nm to 1400nm, the radiation light source comprises visible light and ultraviolet light, the photochromic material can have quick and sensitive photochromic reversible phenomenon in liquid and solid forms, and the photochromic material is suitable for the fields of coating, decorative materials, information storage materials, energy-saving glass, anti-counterfeiting, confidentiality and the like. The preparation method provided by the application is simple and convenient to operate.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a graph of the UV absorption spectrum of the liquid photochromic material prepared in example 1 of the present invention under 365nm UV light;

FIG. 2 is a photograph showing the color change before and after irradiation of the liquid photochromic material prepared in example 1 under a 365nm ultraviolet lamp (A is before irradiation, B is after irradiation);

FIG. 3 is a photograph showing the color change of the solid photochromic material prepared in example 2 before and after irradiation under 365nm UV light (A is before irradiation and B is after irradiation).

FIG. 4 is an ultraviolet absorption spectrum of a solid photochromic material prepared in example 2 of the present invention obtained by irradiation under a 365nm ultraviolet lamp.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or be indirectly disposed on the other element; when an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.

It will be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like, refer to an orientation or positional relationship illustrated in the drawings for convenience in describing the present application and to simplify description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present application.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "plurality" or "a plurality" means two or more unless specifically limited otherwise.

It should be understood that the structures, ratios, sizes, and the like shown in the drawings are only used for matching the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the practical limit conditions of the present application, so that the modifications of the structures, the changes of the ratio relationships, or the adjustment of the sizes, do not have the technical essence, and the modifications, the changes of the ratio relationships, or the adjustment of the sizes, are all within the scope of the technical contents disclosed in the present application without affecting the efficacy and the achievable purpose of the present application.

The embodiments of the present application are written in a progressive manner.

As shown in the drawings, the embodiment of the present invention provides a photochromic material, which is composed of a host substance and a guest substance according to a molar ratio of 1:1 or 1:2, wherein the host substance is an eight-membered cucurbit uril or a ten-membered cucurbituril; the guest substance is a viologen compound.

The application provides a photochromic material, which consists of a host substance and a guest substance according to a molar ratio of 1:1 or 1:2, wherein the host substance is an eight-element cucurbituril or a ten-element cucurbituril; the guest substance is a viologen compound. Cucurbiturils (Cucurbit n uril abbreviated as Qn or CB n) are named as a novel macrocyclic compound, and the cucurbiturils are named as rings due to the structure of cucurbiturils which are seemingly pumpkin and are bridged by methylene. When n is 8, it is called eight-membered cucurbituril as Q [8], and when n is 10, it is called ten-membered cucurbituril as Q [10 ]. When the viologen compound and the eight-membered cucurbituril or the ten-membered cucurbituril form the host-guest compound, the cavity of the cucurbituril can effectively promote the electron transfer among guest molecules and stabilize viologen free radicals, so that the prepared photochromic material can be converted into another color when being illuminated, and the change of the color after being naturally placed at normal temperature is reversible.

The photochromic material provided by the application has the advantages of high response speed and high stability, the response wavelength range is 350nm to 1400nm, the radiation light source comprises visible light and ultraviolet light, the photochromic material can have quick and sensitive photochromic reversible phenomenon in liquid and solid forms, and the photochromic material is suitable for the fields of coating, decorative materials, information storage materials, energy-saving glass, anti-counterfeiting, confidentiality and the like.

Wherein the structural formula of the main substance is shown as the following formula:

when n is 3, the compound is an eight-membered cucurbituril; when n is 5, it is ten-membered cucurbituril.

The structural formula of the guest substance viologen compound is shown as the following formula:

wherein the radicals R are each present on both sides₁、R₂At the same time or at least one side of the aromatic ring substituent containing carboxyl, such as 4-carboxyl phenyl, hydroxyl benzoate and the like. X is a counter anion and may be Cl^-，Br^-，I^-，PF₆ ^-And (4) plasma.

When the viologen compound is 1,1 '-bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride, the host substance and the guest substance are assembled into a structural formula shown as the following formula:

two carboxyphenyls of 1,1 '-bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride are simultaneously wrapped in a cavity of an eight-membered cucurbituril to form a one-dimensional supramolecular polymer.

Preferably, the viologen compound is a conjugated substituent on one or both sides of 4,4' -bipyridine, the substituent being attached to N.

Preferably, the viologen compound is a counter anion compound of 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium), or a counter anion compound of 1-4-carboxyphenyl- (4,4' -bipyridinium).

Preferably, the viologen compound is 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride, or 1-4-carboxyphenyl- (4,4' -bipyridinium) dichloride.

Preferably, the viologen compound is a conjugated substituent on one or both sides of 4,4' -bipyridine, the substituent being attached to the N. Preferably 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium) or 1-4-carboxyphenyl- (4,4' -bipyridinium). More preferably, the viologen compound is 1,1' -bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride, or 1-4-carboxyphenyl- (4,4' -bipyridinium) dichloride. The applicant finds through experiments that the maximum ultraviolet visible absorption peaks of 1,1 '-bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride are respectively in light absorption of 350-420, 550-700, 900-1400nm, especially 900-1400nm, which cannot be achieved by the existing similar materials.

Preferably, the photochromic material is a liquid or a solid.

The photochromic material provided by the application can be in a liquid form or a solid form, can exert the photochromic characteristic and has wide application range.

A method for preparing the photochromic material of any one of the above items, comprising the following steps:

dissolving a host substance and a guest substance in water according to a molar ratio of 1:1 or 1:2, heating, and forming a host-guest compound by self-assembly of the host substance and the guest substance in the solution to obtain the photochromic material in a solution form.

Preferably, the heating is specifically: heating and reacting for 1-2h at 40-100 ℃.

Preferably, the method further comprises concentrating and drying the photochromic material in the form of solution to obtain the photochromic material in the form of solid.

Preferably, the photochromic material in the form of a solution is concentrated and dried by an evaporator.

The application also provides a preparation method of the photochromic material, which is to dissolve a host substance and a guest substance in water according to a molar ratio of 1:1 or 1:2 to obtain a host-guest compound solution, and the host substance and the guest substance in the solution form a host-guest compound through self-assembly to obtain the photochromic material in a solution form (namely a liquid form). Further, concentrating and drying the photochromic material in the form of solution to obtain the photochromic material in the form of solid powder.

The preparation method provided by the application is simple and convenient to operate.

Example 1

Respectively weighing eight-membered cucurbituril Q [8]]9mg (0.005mmol), 2.4mg (0) of 1,1 '-bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride005mmol) of the above-mentioned raw materials, adding them into 10mL of distilled water, heating at 60 deg.C and reacting for 1h, cooling to room temperature to obtain the liquid photochromic material whose concentration is 5.00X 10^-4mol/L。

The liquid photochromic material prepared in example 1 is irradiated under an ultraviolet lamp of 365nm, the ultraviolet absorption spectrum is shown in figure 1, and the color change before and after irradiation is shown in figure 2 (A is before irradiation, B is after irradiation).

Example 2

Respectively weighing 9mg (0.005mmol) of eight-membered cucurbituril Q8 and 2.4mg (0.005mmol) of 1,1 '-bis (4-carboxyphenyl) - (4,4' -bipyridinium) dichloride, adding into 10mL of distilled water, heating at 60 ℃ for reaction for 1h, and concentrating and drying by using a rotary evaporator to obtain the solid photochromic material.

The solid photochromic material prepared in example 2 was irradiated under a 365nm ultraviolet lamp, and the discoloration before and after irradiation was as shown in fig. 3 (a is before irradiation, B is after irradiation); the ultraviolet absorption spectrum of the obtained solid is shown in FIG. 4.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.