CN110484232B - Preparation method of thermoreversible color-changing composite material based on PDA and CoZn-ZIF - Google Patents
Preparation method of thermoreversible color-changing composite material based on PDA and CoZn-ZIF Download PDFInfo
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- CN110484232B CN110484232B CN201910823854.2A CN201910823854A CN110484232B CN 110484232 B CN110484232 B CN 110484232B CN 201910823854 A CN201910823854 A CN 201910823854A CN 110484232 B CN110484232 B CN 110484232B
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Abstract
The invention provides a thermoreversible color-changing composite material based on PDA and CoZn-ZIF, wherein a diacetylene monomer and a bimetallic zeolite imidazole ester framework structure compound are dissolved in a dimethyl sulfoxide-deionized water mixed solvent to form a mixed solution; and then carrying out ultrasonic treatment on the mixed solution at 50-80 ℃ for 30-60 min, cooling to room temperature, carrying out low-temperature self-assembly, and finally carrying out irradiation polymerization for 2-20 min under ultraviolet light with the wavelength of 254 nm to obtain the blue thermochromic composite material PDA/CoZn-ZIF, wherein the composite material is blue at room temperature. With the continuous rise of the temperature, the color of the composite material gradually changes from blue to purple and then to red; after the heating is stopped, the composite material returns to the original blue color within 1-2 min. The composite material has excellent heat sensitivity, can be subjected to repeated cycle thermoreversible color change, and can be used as a temperature sensor in various fields.
Description
Technical Field
The invention relates to a preparation method of a thermoreversible color-changing material, in particular to a preparation method of a thermoreversible color-changing composite material based on Polydiacetylene (PDA) and a bimetallic zeolite imidazolate framework structure compound (CoZn-ZIF), and belongs to the field of intelligent sensing.
Technical Field
The material is an essential part in the life process of human beings and is mainly divided into two parts: functional materials and structural materials. The intelligent material combines structural material and functional material, and has three basic elements of perception, response and feedback. The system can make judgment according to the change of the sensed external environment, and adjust the self condition in time to adapt to the change after sending an instruction. At present, intelligent materials are widely applied in numerous fields such as aerospace, industry, military, medical treatment and the like.
The Polydiacetylene (PDA) shows sensitive optical response characteristics when being stimulated by external environment, the color of the Polydiacetylene (PDA) shows the conversion from blue to red, and the Polydiacetylene (PDA) can be used as a temperature-sensitive sensor. But the PDA still appears red after the stimulus is removed, which limits the recycling of the PDA sensors. Research shows that in order to obtain a PDA sensor which can be recycled, DA monomers need to be chemically modified or prepared into a composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a thermoreversible color-changing composite material based on PDA and CoZn-ZIF.
Preparation of PDA/ZIF composite material
Dissolving a diacetylene monomer (DA) into a dimethyl sulfoxide-deionized water mixed solvent; dispersing a bimetallic zeolite imidazole ester framework structure compound (CoZn-ZIF) in deionized water; mixing the two solutions, performing ultrasonic treatment at 50-80 ℃ for 30-60 min, cooling to room temperature, and performing low-temperature self-assembly for 8-16 h to obtain a white suspension; and then placing the white suspension under ultraviolet light with the wavelength of 254 nm for irradiation polymerization for 2-20 min, wherein the obtained uniform blue suspension is a thermoreversible color-changing composite material and is marked as PDA/CoZn-ZIF.
The diacetylene monomer (DA) is 10, 12-pentacosadiynoic acid (PCDA) or 10, 12-tricosanedioic acid (TCDA);
the bimetallic zeolite imidazolate framework structure compound is CoZn-ZIF. The mass ratio of the diacetylene monomer to the bimetallic zeolite imidazole ester framework compound (CoZn-ZIF) is 1: 1-5: 1.
In the dimethyl sulfoxide-deionized water mixed solvent, the volume ratio of dimethyl sulfoxide to deionized water is 1: 5-1: 9.
In the mixed solution, the total amount of the diacetylene monomer and the bimetallic zeolite imidazole ester framework structure compound is 0.4-1.5 mg/mL.
Secondly, testing the thermoreversible color changing performance of the PDA/CoZn-ZIF composite material
And heating the PDA/CoZn-ZIF composite material in a water bath at the temperature of 30-95 ℃ to gradually increase the temperature, and respectively recording the ultraviolet absorption spectrum and the suspension color picture at different temperatures. The result shows that the PDA/CoZn-ZIF composite material presents blue color at room temperature; with the continuous rise of the temperature, the color of the composite material gradually changes from blue to purple and then to red; after the heating is stopped, the composite material returns to the original blue color within 1-2 min. Therefore, the PDA/CoZn-ZIF composite material has the performance of quick thermoreversible and reversible color change, has temperature sensitivity, can realize multiple reversible changes in color, and has good temperature sensor conditions.
In addition, researches also find that different mass ratios of Co and Zn in the CoZn-ZIF have certain influence on the thermochromism temperature of the PDA/CoZn-ZIF composite material.
The mechanism of the PDA/ZIF (polyhedral oligomeric silsesquioxane/ZIF) thermochromic property of the composite material is as follows: by introducing ZIF, the interaction between PDA and ZIF, the disordered PDA conformation can be restored to the original ordered conformation after being cooled after being heated, so that the composite material can be quickly restored to blue from red.
Drawings
FIG. 1 is a graph of the ultraviolet-visible absorption spectra of Poly (PCDA)/CoZn-ZIF composites at different temperatures.
FIG. 2 is a graph of the ultraviolet-visible absorption spectra of poly (TCDA)/CoZn-ZIF composites at different temperatures.
Detailed Description
The preparation and the thermoreversible coloring performance of the PDA/CoZn-ZIF composite material of the present invention are further described by the following specific examples.
Example 1 preparation of Poly (PCDA)/CoZn-ZIF composite and reversible thermochromic Properties
(1) Preparation of CoZn-ZIF: respectively adding 0.240 g of dimethyl imidazole, 5mL of triethylamine and 15mL of methanol into a beaker, and adding 0.365-0.610 g of Co (NO) after the dimethyl imidazole is completely dissolved by stirring 3 ) 2 ·6H 2 O and 0.041-0.368 g Zn (NO) 3 ) 2 · 6H 2 Continuously stirring for 12h after O, carrying out suction filtration on the obtained solid-liquid mixed solution, washing the solid for 3 times by using methanol, and carrying out vacuum drying for 24 h at the temperature of 30 ℃ to obtain 7 groups of CoZn-ZIF zeolite imidazole ester framework structure compounds with different Co-Zn mass ratios;
(2) preparing a Poly (PCDA)/CoZn-ZIF composite material: dissolving 12 mg of 10, 12-pentacosadiynoic acid (PCDA) in 1 mL of dimethyl sulfoxide, and adding 9 mL of deionized water to obtain a PCDA solution; respectively mixing the solution with 10 mL of 7 groups of deionized water solutions (different mass ratios of Co to Zn) dispersed with 6 mg of CoZn-ZIF, carrying out ultrasonic treatment at 50-80 ℃ for 30-60 min, cooling to room temperature, and standing at low temperature for 8-16 h to obtain a white suspension; placing the white suspension under ultraviolet light with the wavelength of 254 nm for irradiation polymerization for 5 min to obtain 7 groups of blue suspension-Poly (PCDA)/CoZn-ZIF;
(3) testing of reversible thermochromic behaviour of Poly (PCDA)/CoZn-ZIF: and (3) gradually heating 7 groups of Poly (PCDA)/CoZn-ZIF composite materials in a water bath at the temperature of 30-95 ℃ to increase the temperature, measuring the UV-vis absorption spectrum, and photographing and recording the color change. With the increase of the temperature of the system, the color of the Poly (PCDA)/CoZn-ZIF composite material is gradually changed into red, and after the color is completely changed into red, the composite material is naturally cooled, and 7 groups of the composite material are all immediately returned to the original blue color from the red.
FIG. 1 is a UV-VIS absorption spectrum of a Poly (PCDA)/CoZn-ZIF composite at different temperatures. As can be seen from FIG. 1, at room temperature, the Poly (PCDA)/CoZn-ZIF composite material is blue, and has a maximum absorption peak at 645 nm and a shoulder peak at 590 nm; with the continuous increase of the temperature, the color of the composite material gradually changes from blue to purple and then to red, meanwhile, the absorption peak undergoes blue shift along with the decrease of the light absorption intensity, the shoulder peak disappears, the whole absorption peak is widened, and the absorption peak shifts to 600 nm. After the heating is stopped, the composite material returns to the original blue color within 1-2 min.
Example 2 preparation of Poly (TCDA)/CoZn-ZIF composite and reversible thermochromic Properties
(1) Preparation of CoZn-ZIF: the same as example 1;
(2) preparing a poly (TCDA)/CoZn-ZIF composite material: 12 mg of purified 10, 12-tricosanoic acid (TCDA) is weighed and dissolved in 1 mL of dimethyl sulfoxide, and 9 mL of deionized water is added to obtain a TCDA solution. Respectively mixing the solution with 10 mL of 7 groups of deionized water solutions (different mass ratios of Co to Zn) dispersed with 6 mg of CoZn-ZIF, carrying out ultrasonic treatment at 50-80 ℃ for 30-60 min, cooling to room temperature, and standing at low temperature for 8-16 h to obtain a white suspension; placing the mixture under ultraviolet light with the wavelength of 254 nm for irradiation polymerization for 5 min to obtain 7 groups of blue suspension liquid-poly (TCDA)/CoZn-ZIF;
(3) testing of reversible thermochromic properties of poly (TCDA)/CoZn-ZIF: the 7 groups of poly (TCDA)/CoZn-ZIF have similar thermoreversible color properties to Poly (PCDA)/CoZn-ZIF.
FIG. 2 is a UV-VIS absorption spectrum of a poly (TCDA)/CoZn-ZIF composite at different temperatures. As can be seen from FIG. 2, at room temperature, the poly (TCDA)/CoZn-ZIF composite material exhibits a blue color, with a maximum absorption peak at 645 nm, accompanied by a shoulder peak at 590 nm; with the continuous increase of the temperature, the color of the composite material gradually changes from blue to purple and then to red, meanwhile, the absorption peak undergoes blue shift along with the decrease of the light absorption intensity, the shoulder peak disappears, the whole absorption peak is widened, and the absorption peak shifts to 600 nm. After the heating is stopped, the composite material returns to the original blue color within 1-2 min.
Claims (4)
1. The preparation method of the thermoreversible color-changing composite material based on PDA and CoZn-ZIF comprises the steps of dissolving a diacetylene monomer into a dimethyl sulfoxide-deionized water mixed solvent; dispersing a compound with a bimetallic zeolite imidazole ester framework structure in deionized water, and adding the mixture into a diacetylene monomer solution to form a mixed solution; then, carrying out ultrasonic treatment on the mixed solution at 50-80 ℃ for 30-60 min, cooling to room temperature, and then carrying out low-temperature self-assembly for 8-16 h to obtain a white suspension; finally, placing the white suspension under ultraviolet light with the wavelength of 254 nm for irradiation polymerization for 2-20 min to obtain a uniform blue thermochromism composite material PDA/CoZn-ZIF; the zeolite imidazole ester framework structure compound is CoZn-ZIF, and the diacetylene monomer is 10, 12-tricosanoic diacetylene acid or 10, 12-pentacosadiynoic acid.
2. The method for preparing a PDA and CoZn-ZIF based thermoreversible color composite material as claimed in claim 1, wherein: the mass ratio of the diacetylene monomer to the bimetallic zeolite imidazole ester framework structure compound is 1: 1-5: 1.
3. The method for preparing a PDA and CoZn-ZIF based thermoreversible colour composite material according to claim 1, wherein: in the dimethyl sulfoxide-deionized water mixed solution, the volume ratio of dimethyl sulfoxide to deionized water is 1: 5-1: 9.
4. The method for preparing a PDA and CoZn-ZIF based thermoreversible color composite material as claimed in claim 1, wherein: in the mixed solution, the total amount of the diacetylene monomer and the bimetallic zeolite imidazole ester framework structure compound is 0.4-1.5 mg/mL.
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| CN112280551B (en) * | 2020-10-28 | 2023-06-20 | 西北师范大学 | Preparation of a thermally reversible color-changing composite based on PDA and bis (6-formylphenoxy) -copper bipyridine |
| CN113253509A (en) * | 2021-05-08 | 2021-08-13 | Tcl华星光电技术有限公司 | Display panel, manufacturing method thereof and display device |
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