Azobenzene derivative and application thereof

Abstract

The invention belongs to the technical field of energy storage materials, and particularly relates to an azobenzene derivative and application thereof. Compared with common azobenzene, the azobenzene derivative provided by the invention has the advantages that the absorption peak moves towards the long wavelength direction, and red shift occurs; the half-life period and the energy storage density are excellent, so that absorption, conversion and storage of solar energy are facilitated; the azobenzene can be used in the field of energy storage fabrics or photoinduced drivers, so that the technical problem of poor performance of azobenzene in the prior art is solved.

Description

Technical Field

[0001] The present application belongs to the technical field of energy storage materials, and in particular relates to an azobenzene derivative and its application. Background Art

[0002] With the development of the global economy, the demand for energy continues to increase; natural gas, oil, coal and other resources are important sources of energy. However, the large-scale use of natural gas, oil and coal may cause environmental problems on the one hand, and on the other hand, these resources are gradually being depleted, which limits human health and safety and economic development; the development of new energy such as wind energy, solar energy and geothermal energy is an important way to solve the problems of resource shortages and environmental pollution.

[0003] Compared with new energy sources such as wind energy and geothermal energy, the amount of solar energy reaching the earth every day is extremely considerable, and it has huge potential for utilization. The development of solar energy storage materials has become a hot area of ​​global scientific and technological research; azobenzene is an organic compound with special optical and thermal properties. Its structure contains an azo group (-N=N-) connecting two benzene rings. Azobenzene molecules can undergo cis-trans isomer conversion under light conditions, that is, from its more stable trans (trans) isomer to the higher energy cis (cis) isomer under ultraviolet light irradiation. The energy difference between cis and trans isomers can be used for solar energy storage. The cis isomer can be reversibly isomerized to the trans isomer by external stimulation and release the stored energy in the form of heat; azobenzene has the potential to store solar energy when it transforms between cis and trans isomers.

[0004] However, the maximum absorption peak of conventional azobenzene is often at a shorter wavelength, which leads to poor performance of azobenzene and limits its practical application. Summary of the invention

[0005] In view of this, the present application provides an azobenzene derivative and application thereof, which is used to solve the technical problem of poor performance of azobenzene in the prior art.

[0006] In a first aspect, the present application provides an azobenzene derivative, the chemical structure of which is shown in Formula I;

[0007] Formula I;

[0008] In formula I, R is selected from any one of an ether group, an ester group, and an amide group;

[0009] n=1~6.

[0010] A second aspect of the present application provides an energy storage fabric, wherein the energy storage module in the energy storage fabric uses the azobenzene derivative described in the first aspect.

[0011] A third aspect of the present application provides an application of an azobenzene derivative in the preparation of an energy storage fabric.

[0012] A fourth aspect of the present application provides a wearable device that uses energy storage fabric for energy supply.

[0013] A fifth aspect of the present application provides an application of an azobenzene derivative in the preparation of a thermal management energy storage fabric.

[0014] Preferably, the thermal management energy storage fabric is a cooling energy storage fabric.

[0015] Preferably, the thermal management energy storage fabric is a thermal insulation energy storage fabric.

[0016] The sixth aspect of the present application provides a photoactuator, in which a light response module uses the azobenzene derivative described in the first aspect.

[0017] The seventh aspect of the present application provides an application of an azobenzene derivative in the preparation of a photoactuator.

[0018] The eighth aspect of the present application provides a product corresponding to the photoactuator, which is an azobenzene liquid crystal driver that uses the photoactuator for deformation driving.

[0019] In summary, the present application provides an azobenzene derivative and its application. The azobenzene derivative provided by the present application not only has a simple preparation process, but also has excellent energy storage density and half-life. Moreover, compared with ordinary azobenzene, the absorption spectrum of the azobenzene derivative provided by the present application is red-shifted, and the energy of the electronic transition of the substance is reduced, which is beneficial to the absorption, conversion and storage of solar energy. The azobenzene derivative has excellent performance. The azobenzene derivative can be used in fields such as energy storage fabrics or photoactuators, thereby solving the technical problem of poor performance of azobenzene in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0021] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the azobenzene derivative provided in Example 1 of the present application;

[0022] Figure 2 This is the ultraviolet-visible light absorption spectrum of the azobenzene derivative provided in Example 1 of the present application under 450nm light;

[0023] Figure 3This is the UV-visible absorption spectrum of a common azobenzene molecule (4-hydroxyazobenzene) under dark conditions;

[0024] Figure 4 The differential scanning calorimeter test result diagram of the azobenzene derivative provided in Example 1 of the present application;

[0025] Figure 5 UV-visible absorption spectra of the azobenzene derivatives and common azobenzene molecules (4-hydroxyazobenzene) provided in Example 1 of the present application. DETAILED DESCRIPTION

[0026] The present application provides an azobenzene derivative and application thereof, which are used to solve the technical problem of poor performance of azobenzene in the prior art.

[0027] The technical solution of the present application will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0028] In view of the current defect of poor performance of azobenzene, the present application provides an azobenzene derivative, the chemical structure of the azobenzene derivative is shown in Formula I;

[0029] Formula I;

[0030] In formula I, R is selected from any one of an ether group, an ester group, and an amide group;

[0031] n=1~6.

[0032] The azobenzene derivative with the chemical structure shown in Formula I is obtained by connecting two azobenzene molecules with an alkyl chain, and is an azobenzene derivative having two azobenzene molecules; by comparing the UV-visible absorption spectra of ordinary azobenzene molecules (4-hydroxyazobenzene) and the azobenzene derivative provided in the present application, it can be seen that compared with the ordinary azobenzene molecules (4-hydroxyazobenzene), the absorption peak in the UV-visible absorption spectrum of the azobenzene derivative provided in the present application moves toward the long wavelength direction and undergoes a red shift, indicating that the energy of the electronic transition of the azobenzene derivative provided in the present application is reduced, which is beneficial to the absorption and conversion of solar energy, thereby overcoming the defect that the conventional azobenzene absorption peak is often at a shorter wavelength position, resulting in poor performance of azobenzene.

[0033] At the same time, compared with ordinary azobenzene molecules (4-hydroxyazobenzene), the azobenzene derivatives provided in the present application having two azobenzene molecules can occupy more space, increase their steric hindrance, and have better half-life and energy storage density, which is beneficial to the storage stability of solar energy; and the preparation process of the azobenzene derivatives provided in the present application is simple and has a high yield.

[0034] The azobenzene derivatives provided in the present application will be specifically described below in combination with examples and experimental tests.

[0035] Example 1

[0036] Example 1 of the present application provides a method for preparing an azobenzene derivative, which comprises: a step of preparing a mixed solution, and a step of performing a substitution reaction.

[0037] The step of preparing the mixed solution includes: weighing 0.01 mol 4-hydroxyazobenzene, 0.015 mol potassium carbonate, 0.001 mol potassium iodide and 40 ml DMF, and mixing the four to form a mixed solution.

[0038] The step of performing the substitution reaction includes: dropping 0.0045 mol of 1,6-dibromohexane into the mixed solution, then slowly heating to 120° C. and stirring and refluxing for 24 hours to obtain a solution containing an azobenzene derivative.

[0039] In this embodiment, the 4-hydroxyazobenzene used can be purchased directly or prepared in-house. The preparation process is to diazotize aniline to generate a diazonium salt, which is then coupled with phenol, and filtered and recrystallized to obtain 4-hydroxyazobenzene.

[0040] In this embodiment, after the azobenzene derivative is prepared by the substitution reaction, a post-treatment purification step is also included. The post-treatment purification step includes: rotary evaporating the solution containing the azobenzene derivative to 10 ml, adding dichloromethane to precipitate, collecting the crude product by suction filtration, purifying it through a chromatography column, and drying it to obtain a purified azobenzene derivative, which is recorded as product 1, and the yield is 70%.

[0041] Experimental Example 1

[0042] In this Experimental Example 1, the purified azobenzene derivative (Product 1) provided in Example 1 and the common azobenzene molecule (4-hydroxyazobenzene) were tested. The performance test included a molecular structure test and a performance test.

[0043] The molecular structure of the purified azobenzene derivative (product 1) provided in Example 1 is tested as follows: Figure 1 As shown in the H NMR spectrum, Figure 1 It can be seen that the preparation method provided in the present application can prepare the azobenzene derivative with the chemical structure shown in Formula I.

[0044] The performance test results of the purified azobenzene derivative (product 1) and the ordinary azobenzene molecule (4-hydroxyazobenzene) provided in Example 1 are as follows: Figure 2-4 As shown in the UV absorption spectrum and the differential scanning calorimeter test results, Figure 2-3 It can be seen that the purified azobenzene derivative (product 1) provided in Example 1, under 450nm light irradiation, has a significantly enhanced trans characteristic absorption peak in the ultraviolet absorption spectrum as time goes by, indicating that the azobenzene derivative changes from cis to trans, and cis→trans isomerization occurs. The ordinary azobenzene molecule (4-hydroxyazobenzene) also undergoes cis→trans isomerization under dark conditions as time goes by, and it can be clearly seen that the ordinary azobenzene molecule (4-hydroxyazobenzene) requires a shorter time for cis→trans isomerization, and has a lower half-life and energy density. The azobenzene derivative (product 1) provided in Example 1 has two azobenzene molecules, which can occupy more space, increase its steric hindrance, and have a better half-life and energy storage density. At the same time, the differential scanning calorimeter test result diagram also shows that the purified azobenzene derivative (product 1) provided in Example 1 has better performance, thereby solving the defect of poor performance of azobenzene in the prior art.

[0045] The performance test results of the purified azobenzene derivative (product 1) and the ordinary azobenzene molecule (4-hydroxyazobenzene) provided in Example 1 are as follows: Figure 5 As shown, from Figure 5 It can be seen that the maximum absorption peak of 4-hydroxyazobenzene is around 340nm, while the maximum absorption peak of the purified azobenzene derivative (product 1) provided in Example 1 is around 349nm, which indicates that the ultraviolet-visible absorption spectrum of the azobenzene derivative provided in the present application has undergone a red shift, and the energy of the electronic transition of the azobenzene derivative has decreased, which is conducive to the product's ability to absorb long-wavelength light in sunlight, and is conducive to solar energy absorption, conversion and storage.

[0046] Example 2

[0047] This embodiment 2 provides an energy storage fabric, which includes a substrate of a conventional textile material and the azobenzene derivative described in embodiment 1, and the azobenzene derivative is coated on the surface of the energy storage fabric as an energy storage module.

[0048] Since the absorption peak of the azobenzene derivative provided in Example 1 is at a longer wavelength, it can have strong absorption and electronic transition when irradiated with lower energy light, and has excellent cis-trans isomer conversion properties, which improves the performance of the energy storage material in absorbing light radiation and converting it into thermal energy. At the same time, the azobenzene derivative provided in the present application has a better half-life and energy storage density, can store energy well, and has strong energy storage stability, thereby improving the performance of the energy storage material in storing light radiation. When coated on the surface of the energy storage fabric, it can better absorb, convert and store solar energy.

[0049] Correspondingly, this embodiment also provides a product corresponding to the energy storage fabric, which is a wearable device. After the azobenzene derivative provided in the present application is used as an energy storage module in the energy storage fabric, after the energy storage fabric is used to prepare the wearable device, energy can be supplied to the wearable device.

[0050] Example 3

[0051] This embodiment 3 provides a thermal management and energy storage fabric, which includes conventional clothing and the azobenzene derivative described in embodiment 1.

[0052] At present, some thermal management energy storage fabrics use photothermal conversion materials and low phase change temperature organic phase change materials, which can convert and store energy when exposed to sunlight, and then release it at low temperatures to achieve thermal management of the energy storage fabric. When the energy storage fabric is worn on the human body, the temperature difference on the human body surface can be reduced to meet the human body's comfort requirements. The azobenzene derivatives provided in the present application have an absorption peak at a longer wavelength, and can have strong absorption and electronic transition when irradiated with lower energy light. They have excellent cis-trans isomer conversion properties, can better absorb, convert and store light energy, and release energy in the form of heat under certain external conditions. That is, they have both photothermal conversion and energy storage properties. Therefore, the azobenzene derivatives provided in the present application can also be used as thermal management energy storage fabrics.

[0053] Correspondingly, the present embodiment also provides a thermal management energy storage fabric as a cooling energy storage fabric; when the energy storage fabric is used in a high temperature and high light environment, by accelerating the process of converting the azobenzene derivative provided in the present application from the trans isomer to the cis isomer, the heat input caused by light can be reduced to a certain extent. When the energy storage fabric is worn on the human body, the increase in human body temperature can be reduced, thereby being used as a cooling energy storage fabric.

[0054] Correspondingly, the present embodiment also provides a thermal management energy storage fabric as a thermal insulation energy storage fabric; when the energy storage fabric is used in a low temperature and low light environment, by accelerating the process of converting the azobenzene derivative provided in the present application from the cis isomer to the trans isomer, the heat input caused by light can be compensated to a certain extent, and when the energy storage fabric is worn on the human body surface, the human body temperature is increased, thereby being used as a thermal insulation energy storage fabric.

[0055] Example 4

[0056] This embodiment 4 provides a photoactuator, which uses the azobenzene derivative described in embodiment 1 as a photoresponsive group.

[0057] Many plants in nature can be driven by changes in the external environment. For example, when the external dry environment changes to a moist environment, the scales of pine cones will change from an open state to a closed state. The azobenzene derivative provided in Example 1 can be used as a photoresponsive group to drive the device, and can be used to prepare a photoactuator to perform deformation drive under light conditions.

[0058] Correspondingly, this embodiment also provides a product corresponding to the photoactuator, the azobenzene liquid crystal driver includes a polysiloxane liquid crystal elastomer and the azobenzene derivative described in Example 1, the azobenzene derivative is grafted into the polysiloxane liquid crystal elastomer, and the azobenzene derivative is grafted into the polysiloxane liquid crystal elastomer.

[0059] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some or all of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims

1. An azobenzene derivative, characterized in that: The chemical structure is shown in Formula I; Formula I; In formula I, R is selected from any one of an ether group, an ester group, and an amide group; n=1~6。 2. An energy storage fabric, characterized in that: It comprises an energy storage module, wherein the energy storage module comprises the azobenzene derivative according to claim 1.

3. A wearable device, characterized in that: The invention comprises an energy storage fabric as claimed in claim 2.

4. Use of an azobenzene derivative according to claim 1 in the preparation of energy storage fabrics.

5. Use of an azobenzene derivative as claimed in claim 1 in the preparation of thermal management energy storage fabrics.

6. Use of an azobenzene derivative as claimed in claim 1 in the preparation of cooling and energy storage fabrics.

7. Use of the azobenzene derivative according to claim 1 in the preparation of thermal insulation and energy storage fabrics.

8. A photoactuator, characterized in that: It comprises a light response module, wherein the light response module comprises an azobenzene derivative as claimed in claim 1.

9. An azobenzene liquid crystal driver, characterized in that: The invention comprises an azobenzene derivative as claimed in claim 1.

10. Use of an azobenzene derivative as claimed in claim 1 in the preparation of a photoactuator.

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