CN115304878B - Cu-BTC/high polymer composite film with thermal reversible color change property and preparation method and product thereof - Google Patents
Cu-BTC/high polymer composite film with thermal reversible color change property and preparation method and product thereof Download PDFInfo
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- CN115304878B CN115304878B CN202210956803.9A CN202210956803A CN115304878B CN 115304878 B CN115304878 B CN 115304878B CN 202210956803 A CN202210956803 A CN 202210956803A CN 115304878 B CN115304878 B CN 115304878B
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract
The invention discloses a Cu-BTC/high polymer composite film with a thermally reversible color-changing property, which comprises a metal organic framework and a high polymer; the metal organic framework is Cu-BTC and is generated by the reaction of copper nitrate trihydrate of metal salt and trimesic acid of an organic ligand; the high molecular polymer is polyvinyl butyral, polyvinylidene fluoride or polymethyl methacrylate; the mass fraction of the metal organic framework Cu-BTC in the composite film is 5.0-35 wt%. In addition, the preparation method of the metal organic framework/high polymer composite film with the thermal reversible color change property and the product prepared by the preparation method are also disclosed. According to the invention, copper nitrate trihydrate and trimesic acid are used as raw materials, cu-BTC powder of a metal organic framework is obtained at room temperature, and then the thermochromic composite film is obtained by compounding with a high-molecular polymer. The method has mild reaction conditions and simple process, is suitable for preparing the large-area thermochromic composite film, is favorable for popularization and application and industrialization realization, and has great application potential in the field of thermochromic materials.
Description
Technical Field
The invention relates to the technical field of intelligent color-changing materials, in particular to a metal organic framework Cu-BTC/high polymer composite film with a thermal reversible color-changing property, a preparation method thereof and a product thereof.
Background
With the rapid development of membrane science and technology, intelligent membranes are increasingly important in modern life and industrial production. The intelligent film belongs to a novel functional film material, and the physical and chemical properties of the film can be changed by the change of physical, chemical and other factors in the environment. Wherein, the color of the thermochromic intelligent film changes along with the change of temperature. To date, except VO 2 Besides thermochromic films, thermochromic films that can be practically used are very rare. However due to VO 2 Contains multiple crystal phases and prepares pure M-phase VO with thermochromic property 2 The membrane is difficult. In addition, in the conventional approach to pure M-phase VO preparation 2 In many cases, high vacuum equipment is required, which significantly increases the production cost, increases the complexity of the operation process, and is not suitable for mass production. Therefore, research and development of a novel thermochromic film and a preparation method thereof are urgently needed, and popularization and application are further carried out, so that industrialization value is realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Cu-BTC/high polymer composite film with a thermochromic property, and the thermochromic composite film is formed by compositing a metal organic framework Cu-BTC and a high polymer. Another object of the present invention is to provide a method for preparing the metal organic frame/high polymer composite film having the thermally reversible color-changing property and a product prepared thereby.
The aim of the invention is realized by the following technical scheme:
the Cu-BTC/high polymer composite film with the thermal reversible color-changing property comprises a metal organic framework and a high polymer; the metal organic framework is Cu-BTC and is generated by the reaction of copper nitrate trihydrate of metal salt and trimesic acid of an organic ligand; the high molecular polymer is polyvinyl butyral (PVB), polyvinylidene fluoride (PVDF) or polymethyl methacrylate (PMMA); the mass fraction of the metal organic framework Cu-BTC in the composite film is 5.0-35 wt%.
Further, the invention relates to copper nitrate trihydrate and trimesic acid=1-3:1 according to the mol ratio.
The other object of the invention is achieved by the following technical scheme:
the preparation method of the Cu-BTC/high polymer composite film with the thermal reversible color-changing property provided by the invention comprises the following steps:
(1) Method for preparing Cu-BTC powder of metal organic framework by adopting solution reaction method
Dissolving the copper nitrate trihydrate and the organic ligand trimesic acid into a dimethyl sulfoxide solvent to obtain a mixed solution with the trimesic acid molar concentration of 0.2-1.0 mol/L; adding the mixed solution into ethanol according to the volume ratio of the mixed solution to the ethanol=1:40-60, stirring for reaction, centrifuging, washing and drying to obtain metal organic framework Cu-BTC powder;
(2) Dispersing the metal organic framework Cu-BTC powder in acetone by ultrasonic according to the ratio of Cu-BTC powder to acetone=0.075-0.1 g:1.0-3.3 mL to obtain Cu-BTC/acetone dispersion;
(3) Dissolving the high molecular polymer in DMF to obtain a high molecular polymer DMF solution containing 4.0-10wt% of the high molecular polymer, and then adding the high molecular polymer DMF solution into the Cu-BTC/acetone dispersion liquid to obtain a casting film liquid;
(4) And (3) dropwise adding the casting film on the smooth substrate surface, and heating in an oven to evaporate the solvent to obtain the metal organic framework Cu-BTC/high polymer composite film with the thermal reversible color change property.
In the scheme, the stirring reaction time in the step (1) is 15-120 min; the particle size of the metal organic framework Cu-BTC powder is 50-400 nm. The ultrasonic dispersion time in the step (2) is 30-120 min. The heating temperature in the step (4) is 50-100 ℃.
The composite film product prepared by the preparation method has the thickness of 5-35 mu m, and is bluish green in color at 25 ℃, and the R.G.B value is R=22-66, G=144-162 and B=142-158; the color changes to blue-green at 60 ℃, and the R.G.B value is R=31 to 49, G=116 to 137 and B=144 to 153; as the temperature further increases, the color becomes blue at 80 ℃ and above, and the r.g.b. values thereof are r=46 to 64, g=76 to 97, and b=138 to 150.
The invention has the following beneficial effects:
(1) According to the invention, copper nitrate trihydrate and trimesic acid are used as raw materials, cu-BTC powder of a metal organic framework is obtained at room temperature, and then the Cu-BTC powder is compounded with a high polymer to obtain the thermochromic film, the reaction condition is mild, the color of the obtained thermochromic film changes along with the change of temperature, the color changes from turquoise to turquoise and blue along with the rise of temperature, and the color can be changed back to the color corresponding to the original temperature after the temperature is reduced.
(2) The invention has the characteristics of simple preparation process, controllable film thickness, adjustable powder diameter, low cost, capability of large-area film preparation and the like, has strong controllability and repeatability, is suitable for preparing large-area thermochromic films, is favorable for popularization and application and industrialization realization, and has great application potential in the field of thermochromic materials.
Drawings
The invention will be described in further detail with reference to examples and figures:
FIG. 1 is a graphical representation of the Cu-BTC/PVB composite film prepared in the examples of the present invention at various temperatures (a: 25 ℃ C.; b:60 ℃ C.; c:80 ℃ C.).
Detailed Description
Embodiment one:
the preparation method of the Cu-BTC/high polymer composite film with the thermal reversible color-changing property comprises the following steps:
(1) Method for preparing Cu-BTC powder of metal organic framework by adopting solution reaction method
1.27g of copper nitrate trihydrate and 0.53g of trimesic acid are dissolved in 5mL of dimethyl sulfoxide solvent to obtain a mixed solution, then the mixed solution is slowly dripped into 250mL of ethanol under the stirring state, the mixed solution is magnetically stirred at room temperature for reaction for 30min, and then is centrifuged by a centrifuge for 10min (centrifugation rate 7000 r/min), the supernatant is removed, and then the mixed solution is washed by ethanol, and the process is repeated for three times; drying the collected solid particles in an oven at 80 ℃ for 12 hours to obtain metal organic framework Cu-BTC powder;
(2) Adding 75mg of the Cu-BTC powder of the metal organic frame into 2.5mL of acetone, sealing by using a preservative film, and putting into an ultrasonic water bath for ultrasonic treatment for 30min to uniformly disperse the powder, so as to obtain Cu-BTC/acetone dispersion;
(3) 0.75g PVB is weighed to be dissolved in 9.25g DMF, and after being fully stirred to be completely dissolved, DMF solution containing 7.5wt% PVB is obtained; adding 2g of DMF solution containing PVB into the Cu-BTC/acetone dispersion liquid, and performing ultrasonic dispersion for 30min to obtain a casting solution;
(4) And (3) dripping the casting film on the surface of a glass sheet, and heating the glass sheet in a 60 ℃ oven for 6 hours to evaporate the solvent, thereby obtaining the Cu-BTC/PVB composite film with the thermal reversible color change property, wherein the thickness is 15 mu m.
Embodiment two:
the preparation method of the Cu-BTC/high polymer composite film with the thermal reversible color-changing property comprises the following steps:
(1) Method for preparing Cu-BTC powder of metal organic framework by adopting solution reaction method
Dissolving 0.92g of copper nitrate trihydrate and 0.53g of trimesic acid in 5mL of dimethyl sulfoxide solvent to obtain a mixed solution, slowly dripping the mixed solution into 200mL of ethanol under a stirring state, magnetically stirring at room temperature for reaction for 60min, centrifuging for 10min (centrifugation rate 7000 r/min) by using a centrifuge, removing supernatant, washing by using ethanol, and repeating the process for three times; drying the collected solid particles in an oven at 80 ℃ for 12 hours to obtain metal organic framework Cu-BTC powder;
(2) Adding 30mg of the Cu-BTC powder of the metal organic frame into 1.0mL of acetone, sealing by using a preservative film, and putting into an ultrasonic water bath for ultrasonic treatment for 30min to uniformly disperse the powder, so as to obtain Cu-BTC/acetone dispersion;
(3) 0.5g PVB is weighed to be dissolved in 9.5g DMF, and after being fully stirred to be completely dissolved, DMF solution containing 5.0wt% PVB is obtained; adding 2g of DMF solution containing PVB into the Cu-BTC/acetone dispersion liquid, and performing ultrasonic dispersion for 60min to obtain a casting solution;
(4) And (3) dripping the casting film on the surface of a glass sheet, and heating the glass sheet in an oven at 80 ℃ for 3 hours to evaporate the solvent, thereby obtaining the Cu-BTC/PVB composite film with the thermal reversible color change property, wherein the thickness is 9 mu m.
Embodiment III:
the preparation method of the Cu-BTC/high polymer composite film with the thermal reversible color-changing property comprises the following steps:
(1) Method for preparing Cu-BTC powder of metal organic framework by adopting solution reaction method
1.27g of copper nitrate trihydrate and 0.53g of trimesic acid are dissolved in 5mL of dimethyl sulfoxide solvent to obtain a mixed solution, then the mixed solution is slowly dripped into 280mL of ethanol under the stirring state, the mixed solution is magnetically stirred at room temperature for reaction for 120min, and then is centrifuged by a centrifuge for 10min (centrifugation rate 7000 r/min), the supernatant is removed, and then the mixed solution is washed by ethanol, and the process is repeated for three times; drying the collected solid particles in an oven at 80 ℃ for 12 hours to obtain metal organic framework Cu-BTC powder;
(2) Adding 50mg of the Cu-BTC powder of the metal organic frame into 1.25mL of acetone, sealing by using a preservative film, and putting into an ultrasonic water bath for ultrasonic treatment for 30min to uniformly disperse the powder, so as to obtain Cu-BTC/acetone dispersion;
(3) 0.8g PVB is weighed to be dissolved in 9.2g DMF, and after being fully stirred to be completely dissolved, DMF solution containing 8.0wt% PVB is obtained; adding 2g of DMF solution containing PVB into the Cu-BTC/acetone dispersion liquid, and performing ultrasonic dispersion for 90min to obtain a casting solution;
(4) And (3) dripping the casting film on the surface of a glass sheet, and heating in a 90 ℃ oven for 2 hours to evaporate the solvent, thereby obtaining the Cu-BTC/PVB composite film with the thermal reversible color change property, wherein the film thickness is 9.3 mu m.
The Cu-BTC/PVB composite film prepared by the embodiment of the invention has a bluish green color at 25 ℃ (see figure 1 a), and the R.G.B value is R=23, G=146 and B=143; at 60 ℃ the color turns blue-green (see fig. 1B), with r.g.b values of r=33, g=121, b=145; as the temperature further increases, the color changes to blue at 80 ℃ (see fig. 1 c), with r.g.b. values r=51, g=83, b=145.
Claims (6)
1. A Cu-BTC/high polymer composite film with thermally reversible color-changing property is characterized in that: comprises a metal organic framework and a high molecular polymer; the metal organic framework is Cu-BTC, and is generated by the reaction of copper nitrate trihydrate and organic ligand trimesic acid, wherein the molar ratio of copper nitrate trihydrate to trimesic acid=1-3:1; the high molecular polymer is polyvinyl butyral, polyvinylidene fluoride or polymethyl methacrylate; the mass fraction of the metal organic framework Cu-BTC in the composite film is 5.0-35 wt%.
2. The method for producing a Cu-BTC/high molecular polymer composite film having a thermally reversible color-changing property as set forth in claim 1, comprising the steps of:
(1) Dissolving the copper nitrate trihydrate and the organic ligand trimesic acid into a dimethyl sulfoxide solvent to obtain a mixed solution with the trimesic acid molar concentration of 0.2-1.0 mol/L; adding the mixed solution into ethanol according to the volume ratio of the mixed solution to the ethanol=1:40-60, stirring for reaction, centrifuging, washing and drying to obtain metal organic framework Cu-BTC powder;
(2) Dispersing the metal organic framework Cu-BTC powder in acetone by ultrasonic according to the ratio of Cu-BTC powder to acetone=0.075-0.1 g:1.0-3.3 mL, so as to obtain Cu-BTC/acetone dispersion;
(3) Dissolving the high molecular polymer in DMF to obtain a high molecular polymer DMF solution containing 4.0-10 and wt% of the high molecular polymer, and then adding the high molecular polymer DMF solution into the Cu-BTC/acetone dispersion liquid to obtain a casting film liquid;
(4) And (3) dropwise adding the casting film on the smooth substrate surface, and heating in an oven to evaporate the solvent to obtain the metal organic framework Cu-BTC/high polymer composite film with the thermal reversible color change property.
3. The method for producing a Cu-BTC/high molecular polymer composite film having a thermally reversible color-changing property according to claim 2, characterized by: the stirring reaction time in the step (1) is 15-120 min; the particle size of the metal organic framework Cu-BTC powder is 50-400 nm.
4. The method for producing a Cu-BTC/high molecular polymer composite film having a thermally reversible color-changing property according to claim 2, characterized by: the ultrasonic dispersion time in the step (2) is 30-120 min.
5. The method for producing a Cu-BTC/high molecular polymer composite film having a thermally reversible color-changing property according to claim 2, characterized by: the heating temperature in the step (4) is 50-100 ℃.
6. A product obtainable by the process according to any one of claims 2 to 5, characterized in that: the thickness of the prepared composite film is 5-35 mu m, the color of the composite film is bluish green at 25 ℃, and the R.G.B value of the composite film is R=22-66, G=144-162 and B=142-158; the color changes to blue-green at 60 ℃, and the R.G.B value is R=31 to 49, G=116 to 137 and B=144 to 153; as the temperature further increases, the color becomes blue at 80 ℃ and above, and the r.g.b. values thereof are r=46 to 64, g=76 to 97, and b=138 to 150.
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