阅读说明：本技术 一种聚合物压致变色材料及其制备方法与应用 (Polymer piezochromic material and preparation method and application thereof ) 是由 侯学清 何淑花 罗迎春 肖寒 刘恩弟 于 2021-01-21 设计创作，主要内容包括：本发明涉及一种聚合物压致变色材料及其制备方法与应用,属于荧光材料技术领域。本聚合物压致变色材料,所述聚合物压致变色材料的结构式如下：本发明还提供上述聚合物压致变色材料的制备方法及应用。本聚合物压致变色材料在压力作用下,由原来的晶态转变为无定型态,改变了其固态条件下的堆积方式,具有压致变色性能,能够广泛应用于压致变色技术领域。(The invention relates to a polymer piezochromic material and a preparation method and application thereof, belonging to the technical field of fluorescent materials. The structural formula of the polymer piezochromic material is as follows: the invention also provides a preparation method and application of the polymer piezochromic material. The polymer piezochromic material is changed from the original crystalline state to the amorphous state under the action of pressure, changes the accumulation mode under the solid state condition, has piezochromic performance, and can be widely applied to the field of piezochromic technology.)

1. A polymeric piezochromic material, wherein the polymeric piezochromic material has the following structural formula:

2. the polymeric piezochromic material of claim 1, wherein the polymeric piezochromic material exhibits a purple red solid state fluorescence in an initial state and exhibits a deep red solid state fluorescence after grinding, the solid state fluorescence emission wavelength is red-shifted from 644nm to 668nm, the solid state fluorescence wavelength is red-shifted to 24nm, and the purple red solid state fluorescence in the initial state is recovered after fumigation.

3. A process for the preparation of a polymeric piezochromic material according to any of claims 1 to 2 comprising the steps of:

s1, taking 1-3mmol of 1, 4-dibutyloxy terephthalaldehyde and 1-3mmol of terephthalonitrile, adding a solvent for dissolving, and heating and stirring until complete dissolution to obtain a mixed solution;

s2, adding 2-4mmol of potassium tert-butoxide solid into the mixed solution obtained in the step S1, heating and stirring for reaction, filtering after the reaction is finished, washing filter residues, and drying to obtain the polymer piezochromic material.

4. The method for preparing the polymeric piezochromic material according to claim 3, wherein in step S1, the solvent is one or a mixture of t-butanol, n-butanol and ethanol in any ratio.

5. The method for preparing a polymeric piezochromic material according to claim 3, wherein in step S1, the temperature of the heating and stirring is 50-70 ℃.

6. The method for preparing a piezochromic material according to claim 3, wherein in step S2, the temperature of the heating stirring reaction is 50-70 ℃, the rotation speed of the stirring is 1000-1500r/min, and the reaction time is 5-7 h.

7. The method for preparing the polymeric piezochromic material according to any one of claims 3 to 6, wherein in step S2, the filtration is performed by suction filtration under reduced pressure.

8. The method for preparing the polymeric piezochromic material according to any one of claims 3 to 6, wherein in step S2, the solvent used for washing is one or a mixture of two of methanol and ethanol in any ratio.

9. Use of the polymeric piezochromic material according to any one of claims 1 to 2 in any one of the fields of light emitting devices, microstress sensing, information storage and trademark anti-counterfeiting.

Technical Field

The invention belongs to the technical field of fluorescent materials, and particularly relates to a polymer piezochromic material as well as a preparation method and application thereof.

Background

The conjugated polymer material causes an obvious change in optical properties by external stimuli such as changes in solvent, temperature and pressure. Polymer materials whose fluorescence properties change as a result of a change in the ambient pressure are referred to as piezochromic polymer materials. Due to the stimulation of the external pressure, the accumulation mode in the polymer molecules is changed, so that the aim of controlling the fluorescence property of the polymer molecules is fulfilled.

However, there are not many materials that change the optical properties of a conjugated polymer by changing the pressure, as compared with a polymer whose optical properties are changed by changing the solvent and the temperature.

Therefore, the development of a polymer material with piezochromic performance has potential application value.

Disclosure of Invention

The invention provides a polymer piezochromic material, a preparation method and application thereof for solving the technical problems.

In order to solve the above technical problems, the present invention provides a piezochromic material.

The technical scheme for solving the technical problems is as follows: a polymeric piezochromic material, the structural formula of the polymeric piezochromic material being as follows:

the polymer piezochromic material has the beneficial effects that:

the polymer piezochromic material is changed from the original crystalline state to the amorphous state under the action of pressure, the accumulation mode under the solid state condition is changed, the maximum fluorescence emission wavelength moves to the long wavelength direction, and the color of the solid fluorescence is changed from purple red to deep red; after solvent fumigation, the maximum emission wavelength of solid fluorescence is restored to the initial state, and the solid fluorescence has piezochromic performance and can be widely applied to the technical field of piezochromic.

On the basis of the technical scheme, the invention can be further improved as follows.

Further, the polymer piezochromic material shows purple red solid fluorescence in the initial state, shows deep red solid fluorescence after being ground, red shifts the solid fluorescence emission wavelength from 644nm to 668nm, and red shifts the solid fluorescence wavelength to 24nm, and the purple red solid fluorescence in the initial state is recovered after fumigation.

The beneficial effect of adopting the further scheme is that: has excellent piezochromic performance.

Secondly, the invention provides a preparation method of the polymer piezochromic material for solving the technical problems.

The technical scheme for solving the technical problems is as follows: a preparation method of the polymer piezochromic material comprises the following steps:

s1, taking 1-3mmol of 1, 4-dibutyloxy terephthalaldehyde and 1-3mmol of terephthalonitrile, adding a solvent for dissolving, and heating and stirring until complete dissolution to obtain a mixed solution;

s2, adding 2-4mmol of potassium tert-butoxide solid into the mixed solution obtained in the step S1, heating and stirring for reaction, filtering after the reaction is finished, washing filter residues, and drying to obtain the polymer piezochromic material.

The preparation method of the polymer piezochromic material has the beneficial effects that:

(1) the preparation method has reasonable and feasible synthetic route, simple steps, mild conditions and higher yield;

(2) the polymer material prepared by the invention has piezochromic property, is changed from the original crystalline state to the amorphous state under the action of pressure, changes the accumulation mode under the solid state condition, realizes color change, and has potential application value in the aspect of functional materials.

On the basis of the technical scheme, the invention can be further improved as follows.

Further, in step S1, the solvent is one or more of tert-butanol, n-butanol and ethanol, and is a mixture in any proportion.

The beneficial effect of adopting the further scheme is that: the solvent is favorable for dissolving 1, 4-dibutoxy terephthalaldehyde and terephthalonitrile, and the smell of the tertiary butyl alcohol, the n-butyl alcohol and the ethanol is small, thereby being favorable for production operation.

Further, in step S1, the temperature of the heating and stirring is 50-70 ℃.

The beneficial effect of adopting the further scheme is that: is favorable for dissolution and improves the solubility.

Further, in step S2, the temperature of the heating and stirring reaction is 50-70 ℃, the rotation speed of the stirring is 1000-1500r/min, and the reaction time is 5-7 h.

The beneficial effect of adopting the further scheme is that: is beneficial to the polymerization reaction and improves the product yield.

Further, in step S2, the filtration method is suction filtration under reduced pressure.

The beneficial effect of adopting the further scheme is that: is beneficial to solid-liquid separation and improves the efficiency.

Further, in step S2, the solvent used for washing is one or a mixture of two of methanol and ethanol in any ratio.

The beneficial effect of adopting the further scheme is that: is favorable for washing away impurities.

Thirdly, the invention provides an application of the polymer piezochromic material for solving the technical problems.

The technical scheme for solving the technical problems is as follows: the polymer piezochromic material is applied to any one of the fields of luminescent devices, microstress sensing, information storage or trademark anti-counterfeiting.

Drawings

FIG. 1 is a fluorescence emission spectrum of a piezochromic material prepared in example 1 of the present invention;

FIG. 2 is a powder X-ray diffraction pattern of the polymeric piezochromic material prepared in example 1 of the present invention.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.

Example 1

This example provides a polymeric piezochromic material having the following structural formula:

the polymer piezochromic material shows purple red solid fluorescence in an initial state, shows deep red solid fluorescence after being ground, and recovers the purple red solid fluorescence in the initial state after being fumigated.

In addition, the embodiment also provides a preparation method of the polymer piezochromic material, which comprises the following steps:

s1, adding 1mmol of 1, 4-dibutyloxy terephthalaldehyde and 1mmol of terephthalonitrile into a two-neck flask, adding a solvent for dissolving, wherein the solvent is n-butyl alcohol, heating to 50 ℃, and stirring until the n-butyl alcohol and the terephthalonitrile are completely dissolved to obtain a mixed solution.

S2, adding 2mmol of potassium tert-butoxide solid into the mixed solution obtained in the step S1, heating to 50 ℃, stirring at the rotating speed of 1000r/min for reaction for 5 hours, carrying out vacuum filtration after the reaction is finished, taking filter residue, washing with ethanol, and drying to obtain the polymer piezochromic material.

The specific reaction formula is as follows:

example 2

This example provides a polymeric piezochromic material having the following structural formula:

the polymer piezochromic material shows purple red solid fluorescence in an initial state, shows deep red solid fluorescence after being ground, and recovers the purple red solid fluorescence in the initial state after being fumigated.

In addition, the embodiment also provides a preparation method of the polymer piezochromic material, which comprises the following steps:

s1, adding 2mmol of 1, 4-dibutyloxy terephthalaldehyde and 2mmol of terephthalonitrile into a two-neck flask, adding a solvent for dissolving, wherein the solvent is tert-butyl alcohol, heating to 60 ℃, and stirring until the solvent is completely dissolved to obtain a mixed solution;

s2, adding 3mmol of potassium tert-butoxide solid into the mixed solution obtained in the step S1, heating to 60 ℃, stirring at the rotating speed of 1300r/min for reaction for 6 hours, carrying out vacuum filtration after the reaction is finished, taking filter residue, washing with methanol, and drying to obtain the polymer piezochromic material.

The specific reaction formula is as follows:

example 3

This example provides a polymeric piezochromic material having the following structural formula:

the polymer piezochromic material shows purple red solid fluorescence in an initial state, shows deep red solid fluorescence after being ground, and recovers the purple red solid fluorescence in the initial state after being fumigated.

In addition, the embodiment also provides a preparation method of the polymer piezochromic material, which comprises the following steps:

s1, taking 3mmol of 1, 4-dibutoxy terephthalaldehyde and 3mmol of terephthalonitrile, adding a solvent to dissolve, wherein the solvent is ethanol, heating to 70 ℃, and stirring until the solvent is completely dissolved to obtain a mixed solution;

s2, adding 3mmol of potassium tert-butoxide solid into the mixed solution obtained in the step S1, heating to 70 ℃, stirring at a rotating speed of 1500r/min for reaction for 7 hours, carrying out vacuum filtration after the reaction is finished, taking filter residue, washing with ethanol, and drying to obtain the polymer piezochromic material.

The specific reaction formula is as follows:

example 4

This example provides a polymeric piezochromic material having the following structural formula:

the polymer piezochromic material shows purple red solid fluorescence in an initial state, shows deep red solid fluorescence after being ground, and recovers the purple red solid fluorescence in the initial state after being fumigated.

In addition, the embodiment also provides a preparation method of the polymer piezochromic material, which comprises the following steps:

s1, taking 2mmol of 1, 4-dibutoxy terephthalaldehyde and 1mmol of terephthalonitrile, adding a solvent for dissolving, wherein the solvent is a mixture of tert-butyl alcohol and n-butyl alcohol according to any proportion, heating to 65 ℃, and stirring until the tert-butyl alcohol and the n-butyl alcohol are completely dissolved to obtain a mixed solution;

s2, adding 4mmol of potassium tert-butoxide solid into the mixed solution obtained in the step S1, heating to 70 ℃, stirring at the rotating speed of 1500r/min for reaction for 7 hours, carrying out vacuum filtration after the reaction is finished, taking filter residue, washing the filter residue by using a mixture of methanol and ethanol according to any proportion, and then drying to obtain the polymer piezochromic material.

The specific reaction formula is as follows:

example 5

This example provides a polymeric piezochromic material having the following structural formula:

the polymer piezochromic material shows purple red solid fluorescence in an initial state, shows deep red solid fluorescence after being ground, and recovers the purple red solid fluorescence in the initial state after being fumigated.

In addition, the embodiment also provides a preparation method of the polymer piezochromic material, which comprises the following steps:

s1, taking 3mmol of 1, 4-dibutoxy terephthalaldehyde and 1mmol of terephthalonitrile, adding a solvent for dissolving, wherein the solvent is a mixture of tert-butyl alcohol, n-butyl alcohol and ethanol according to any proportion, heating to 70 ℃, and stirring until the mixture is completely dissolved to obtain a mixed solution;

s2, adding 2mmol of potassium tert-butoxide solid into the mixed solution obtained in the step S1, heating to 55 ℃, stirring at the rotation speed of 1200r/min for reaction for 6 hours, carrying out vacuum filtration after the reaction is finished, taking filter residue, washing the filter residue by using a mixture of methanol and ethanol according to any proportion, and then drying to obtain the polymer piezochromic material.

The specific reaction formula is as follows:

experimental example 1

The experimental example performs structural characterization on the piezochromic material prepared in example 1, including GPC and nuclear magnetic hydrogen spectroscopy, as follows:

the GPC measurement result of the target product is: the polymer is uniformly distributed, wherein the number average molecular weight is 3921, the weight average molecular weight is 4191, the Z average molecular weight is 4656, and the distribution coefficient is 1.0688;¹H NMR(400MHz,CDCl₃)δ7.99(s,2H),7.87(s,2H),7.61(d,J＝8.6Hz,4H),7.30(d,J＝8.6Hz,4H),6.67(s,2H),4.11(t,J＝6.3Hz,4H),1.89-1.78(m,4H),1.50-1.46(m,4H),0.90(t,J＝12.5Hz,6H)。

experimental example 2

In this experimental example, the piezochromic performance of the polymer piezochromic material prepared in example 1 is detected, specifically, a fluorescence emission spectrogram and a powder X-ray diffraction spectrogram are detected, and specifically, as shown in fig. 1 and fig. 2.

As can be seen from fig. 1, the polymeric piezochromic material exhibited a purple-red solid state fluorescence in the initial state and exhibited a deep-red solid state fluorescence after being ground with a mortar. FIG. 1 clearly shows that the solid state fluorescence emission wavelength of the polymeric piezochromic material red-shifted from 644nm to 668nm and the solid state fluorescence wavelength red-shifted to 24nm before and after grinding. The ground sample was fumigated with a solvent, and the solid state fluorescence returned to the original state, with an emission wavelength of 644 nm. Indicating that the polymer piezochromic material has typical piezochromic properties.

As can be seen from fig. 2, the polymeric piezochromic material exhibited a purple-red solid state fluorescence in the initial state and exhibited a deep-red solid state fluorescence after being ground with a mortar. FIG. 2 clearly shows the powder X-ray diffraction spectra of the piezochromic material before and after grinding, and the powder X-ray diffraction of the piezochromic material before grinding has obvious peak type, which shows that the piezochromic material is a crystal compound; the powder X-ray diffraction after grinding shows an envelope peak, and no clear peak type is shown, so that the powder is an amorphous compound. The ground sample is fumigated by a solvent, and the main peak position of the powder X-ray diffraction of the sample is basically restored to the initial state, which indicates that the polymer piezochromic material has typical piezochromic performance.

The polymer piezochromic material is changed from the original crystalline state to the amorphous state, the accumulation mode under the solid state condition is changed, the maximum fluorescence emission wavelength of the polymer piezochromic material is further caused to move to the long wavelength direction, and the color of the solid fluorescence is changed from purple red to deep red; after solvent fumigation, the polymer piezochromic material can also be converted into a crystalline state from an amorphous state, and the maximum emission wavelength of solid fluorescence is recovered to the initial state, so that the piezochromic material has piezochromic performance.

In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings, which are merely for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be construed as limiting the invention. Furthermore, the terms "first", "second", etc. 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," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the invention, the meaning of "a plurality" is two or more unless otherwise specified.

In the description of the invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted", "connected" and "connected" are to be construed broadly, e.g. as being fixed or detachable or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the creation of the present invention can be understood by those of ordinary skill in the art through specific situations.

It is to be noted that "comprising" in the present invention means that it may include other components in addition to the components described, and the "comprising" may be replaced with "being" or "consisting of … …" in a closed manner.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.