CN115260688A - Co-BTC/high molecular polymer composite membrane with thermoreversible color changing property and preparation method and product thereof - Google Patents
Co-BTC/high molecular polymer composite membrane with thermoreversible color changing property and preparation method and product thereof Download PDFInfo
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- C08J2327/00—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 a halogen; Derivatives of such polymers
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Abstract
The invention discloses a Co-BTC/high molecular polymer composite membrane with a thermoreversible color change property, which comprises a metal organic framework and a high molecular polymer; the metal organic framework is Co-BTC and is generated by the reaction of metal salt cobalt acetate tetrahydrate and organic ligand trimesic acid; the high molecular polymer is polyvinyl butyral and polyvinylidene fluoride; the mass fraction of the metal organic framework Co-BTC in the composite membrane is 5.0-40 wt%. In addition, the preparation method of the metal organic framework/high polymer composite membrane with the thermoreversible color change property and the product prepared by the preparation method are also disclosed. The invention takes cobalt acetate tetrahydrate and trimesic acid as raw materials to obtain metal organic framework Co-BTC powder at room temperature, and then the metal organic framework Co-BTC powder is compounded with a high molecular polymer to obtain the thermochromic composite film. The invention has mild reaction conditions and simple process, is suitable for preparing large-area thermochromic composite films, is beneficial to popularization and application and realization of industrialization, 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 Co-BTC/high molecular polymer composite film with a thermoreversible color-changing property, a preparation method thereof and a product thereof.
Background
With the rapid development of membrane science and technology, intelligent membranes play an increasingly important role in modern life and industrial production. The intelligent membrane belongs to a novel functional membrane material, and the physical and chemical properties of the membrane can be changed by the change of physical, chemical and other factors in the environment. Wherein, the color of the thermochromism intelligent film changes along with the change of temperature. So far, except VO 2 Besides thermochromic films, thermochromic films that can be practically used are very rare. However, due to VO 2 Contains a plurality of crystal phases and prepares pure M-phase VO with thermochromic property 2 The membrane is difficult. In addition, pure M-phase VO is prepared by adopting a conventional way 2 In most cases, high vacuum equipment is required, which significantly increases production costs, 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, so that popularization and application are realized, and an industrial value is realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Co-BTC/high molecular polymer composite membrane with a thermo-reversible color change property. The invention also aims to provide a preparation method of the metal organic framework/high molecular polymer composite membrane with the thermoreversible color change property and a product prepared by the preparation method.
The purpose of the invention is realized by the following technical scheme:
the invention provides a Co-BTC/high molecular polymer composite membrane with thermoreversible color changing property, which comprises a metal organic framework and a high molecular polymer; the metal organic framework is Co-BTC and is generated by the reaction of metal salt cobalt acetate tetrahydrate and organic ligand trimesic acid; the high molecular polymer is polyvinyl butyral (PVB) or polyvinylidene fluoride (PVDF); the mass fraction of the metal organic framework Co-BTC in the composite membrane is 5.0-40 wt%.
Further, the invention adopts the molar ratio of the tetrahydrate cobalt acetate to the trimesic acid = 1.5-2: 1.
The other purpose of the invention is realized by the following technical scheme:
the preparation method of the metal organic framework/high molecular polymer composite membrane with the thermoreversible color change property provided by the invention comprises the following steps:
(1) Co-BTC powder of metal organic frame prepared by solution reaction method
Respectively dissolving the metal salt cobalt acetate tetrahydrate and the organic ligand trimesic acid into deionized water and absolute ethyl alcohol to obtain a trimesic acid ethyl alcohol solution with the molar concentration of 0.02-0.05 mol/L and a cobalt acetate tetrahydrate aqueous solution with the molar concentration of 0.27-0.90 mol/L; then dropwise adding the cobalt acetate tetrahydrate aqueous solution into a trimesic acid ethanol solution, performing ultrasonic reaction, centrifuging, washing and drying to obtain metal organic framework Co-BTC powder;
(2) Dispersing Co-BTC powder of the metal organic framework in acetone through ultrasound according to the ratio of Co-BTC powder to acetone = 0.06-0.1 g: 2.0-3.3 mL to obtain Co-BTC/acetone dispersion liquid;
(3) Dissolving the high molecular polymer in DMF to obtain a high molecular polymer DMF solution containing 4.0-10 wt% of the high molecular polymer, and then adding the high molecular polymer DMF solution into the Co-BTC/acetone dispersion solution to obtain a membrane casting solution;
(4) And dropwise adding the casting solution on the smooth surface of the substrate, and heating in an oven to evaporate the solvent to obtain the Co-BTC/high-molecular polymer composite film with the thermo-reversible color change property.
In the scheme, the ultrasonic reaction time in the step (1) of the preparation method is 10 s-20 min; the grain diameter of the metal organic framework Co-BTC powder is 30-350 nm. The ultrasonic dispersion time in the step (2) is 30-90 min. The heating temperature in the step (4) is 50-100 ℃.
The composite film product prepared by the preparation method has the thickness of 5-40 mu m, the color is pink at 25 ℃, and the R.G.B value is R = 162-177, G = 137-158 and B = 151-173; a color of purple at 55 ℃, wherein R.G.B values are R = 137-167, G = 112-155, and B = 152-175; as the temperature further increases, the color changes to dark purple at 70 ℃ and above, with r.g.b values of R =117 to 138, G =96 to 127, B =153 to 168.
The invention has the following beneficial effects:
(1) The preparation method takes cobaltous acetate tetrahydrate and trimesic acid as raw materials, obtains Co-BTC powder of a metal organic framework at room temperature, further obtains the thermochromic membrane by compounding with a high polymer, has mild reaction conditions, changes the color of the obtained thermochromic membrane along with the change of temperature, changes the color from pink to purple along with the rise of the temperature, and can reversibly change the color back to the color corresponding to the original temperature after the temperature is reduced for a plurality of hours.
(2) The invention has the characteristics of simple preparation process, controllable film thickness, adjustable powder diameter, low cost, large-area film preparation and the like, has strong controllability and repeatability, is suitable for preparing large-area thermochromic films, is beneficial to popularization and application and realization of industrialization, and has great application potential in the field of thermochromic materials.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
FIG. 1 is a schematic representation of Co-BTC/PVB composite films prepared according to the present invention at different temperatures (a: 25 ℃; b:55 ℃; c:70 ℃).
Detailed Description
The first embodiment is as follows:
the embodiment of the invention relates to a preparation method of a Co-BTC/high molecular polymer composite membrane with a thermoreversible color change property, which comprises the following steps:
(1) Co-BTC powder for preparing metal organic frame by solution reaction method
Respectively dissolving 1.41g of cobalt acetate tetrahydrate and 0.66g of trimesic acid in 10mL of deionized water and 90mL of absolute ethanol solvent to obtain 0.57mol/L cobalt acetate tetrahydrate aqueous solution and 0.035mol/L trimesic acid ethanol solution; slowly dripping cobalt acetate tetrahydrate aqueous solution into the trimesic acid ethanol solution under the stirring state, carrying out ultrasonic reaction at room temperature for 1min, centrifuging for 8min (the centrifugation rate is 7000 r/min) by using a centrifuge, removing supernatant, washing for three times by using a mixed solvent (the volume ratio of absolute ethyl alcohol to deionized water is 9); drying the collected solid particles at room temperature to obtain metal organic framework Co-BTC powder;
(2) Adding 80mg of the metal organic framework Co-BTC powder into 2.6mL of acetone, sealing by using a preservative film, putting into an ultrasonic water bath, and performing ultrasonic treatment for 40min to uniformly disperse the powder to obtain Co-BTC/acetone dispersion liquid;
(3) Weighing 1.6g PVB and dissolving it in 18.4g DMF, stirring thoroughly to dissolve it completely, to obtain a DMF solution containing 8.0wt% PVB; adding 2g of PVB-containing DMF solution into the Co-BTC/acetone dispersion liquid, and performing ultrasonic dispersion for 40min to obtain a membrane casting liquid;
(4) And dropwise adding the casting solution on the surface of a glass sheet, and heating in an oven at 80 ℃ for 4h to evaporate the solvent to obtain the Co-BTC/PVB composite film with the thermoreversible discoloration property, wherein the thickness of the Co-BTC/PVB composite film is 37.3 mu m.
Example two:
the embodiment of the invention relates to a preparation method of a Co-BTC/high molecular polymer composite membrane with a thermoreversible color change property, which comprises the following steps:
(1) Co-BTC powder for preparing metal organic frame by solution reaction method
Respectively dissolving 1.23g of cobalt acetate tetrahydrate and 0.58g of trimesic acid in 10mL of deionized water and 90mL of absolute ethanol solvent to obtain 0.49mol/L cobalt acetate tetrahydrate aqueous solution and 0.031mol/L trimesic acid ethanol solution; slowly dripping cobalt acetate tetrahydrate aqueous solution into the trimesic acid ethanol solution under the stirring state, carrying out ultrasonic reaction at room temperature for 30s, centrifuging for 10min (the centrifugation rate is 6000 r/min) by using a centrifuge, removing supernatant, washing for three times by using a mixed solvent (the volume ratio of absolute ethyl alcohol to deionized water is 9); drying the collected solid particles at room temperature to obtain metal organic framework Co-BTC powder;
(2) Adding 75mg of the metal organic framework Co-BTC powder into 2.5mL of acetone, sealing the mixture by using a preservative film, putting the mixture into an ultrasonic water bath, and carrying out ultrasonic treatment for 30min to uniformly disperse the mixture to obtain a Co-BTC/acetone dispersion solution;
(3) Weighing 1.5g PVB and dissolving in 18.5g DMF, and stirring thoroughly to dissolve completely to obtain a DMF solution containing 7.5wt% PVB; adding 4g of PVB-containing DMF solution into the Co-BTC/acetone dispersion liquid, and performing ultrasonic dispersion for 30min to obtain a membrane casting liquid;
(4) And dropwise adding the casting solution on the surface of a glass sheet, and heating in a 60 ℃ oven for 8 hours to evaporate the solvent to obtain the Co-BTC/PVB composite film with the thermoreversible color change property, wherein the thickness of the Co-BTC/PVB composite film is 22.1 mu m.
Example three:
the embodiment of the invention relates to a preparation method of a Co-BTC/high molecular polymer composite membrane with a thermoreversible color change property, which comprises the following steps:
(1) Co-BTC powder for preparing metal organic frame by solution reaction method
Respectively dissolving 1.58g of cobalt acetate tetrahydrate and 0.70g of trimesic acid in 10mL of deionized water and 90mL of absolute ethanol solvent to obtain 0.63mol/L cobalt acetate tetrahydrate aqueous solution and 0.037mol/L trimesic acid ethanol solution; slowly dripping cobalt acetate tetrahydrate aqueous solution into trimesic acid ethanol solution under the stirring state, performing ultrasonic reaction at room temperature for 5min, centrifuging for 6min (the centrifugation rate is 6500 r/min) by using a centrifuge, removing supernatant, washing for three times by using a mixed solvent (the volume ratio of absolute ethyl alcohol to deionized water is 9; drying the collected solid particles at room temperature to obtain metal organic framework Co-BTC powder;
(2) Adding 60mg of the metal organic framework Co-BTC powder into 2.0mL of acetone, sealing by using a preservative film, putting into an ultrasonic water bath, and performing ultrasonic treatment for 40min to uniformly disperse the powder to obtain a Co-BTC/acetone dispersion solution;
(3) Weighing 1.2g PVB and dissolving it in 18.8g DMF, stirring thoroughly to dissolve it completely, to obtain a DMF solution containing 6.0wt% PVB; adding 6g of PVB-containing DMF solution into the Co-BTC/acetone dispersion liquid, and performing ultrasonic dispersion for 60min to obtain a membrane casting liquid;
(4) And dropwise adding the casting solution on the surface of a glass sheet, heating in a 70 ℃ oven for 5 hours to evaporate the solvent, thus obtaining the Co-BTC/PVB composite membrane with the thermoreversible color change property, wherein the thickness is 7.5 mu m.
The color of the Co-BTC/PVB composite membrane prepared by the embodiment of the invention is pink at 25 ℃ (see figure 1 a), and the R.G.B values are R =163, G =139 and B =153; the color changes to violet at 55 ℃ (see fig. 1B) with r.g.b values of R =139, G =114, B =154. As the temperature further increased, the color became darker, becoming dark purple at 70 ℃ (see fig. 1 c), with r.g.b values of R =124, G =103, B =160.
Claims (7)
1. A Co-BTC/high molecular polymer composite membrane with thermoreversible color changing property is characterized in that: comprises a metal organic framework and a high molecular polymer; the metal organic framework is Co-BTC and is generated by the reaction of metal salt cobalt acetate tetrahydrate and organic ligand trimesic acid; the high molecular polymer is polyvinyl butyral and polyvinylidene fluoride; the mass fraction of the metal organic framework Co-BTC in the composite membrane is 5.0-40 wt%.
2. The Co-BTC/high molecular polymer composite film having a thermoreversible color change property according to claim 1, wherein: the molar ratio of the tetrahydrate cobalt acetate to the trimesic acid is 1.5-2: 1.
3. The method for preparing a Co-BTC/high molecular polymer composite film having a thermoreversible color property according to claim 1 or 2, comprising the steps of:
(1) Co-BTC powder for preparing metal organic frame by solution reaction method
Respectively dissolving the metal salt cobalt acetate tetrahydrate and the organic ligand trimesic acid into deionized water and absolute ethyl alcohol to obtain a trimesic acid ethyl alcohol solution with the molar concentration of 0.02-0.05 mol/L and a cobalt acetate tetrahydrate aqueous solution with the molar concentration of 0.27-0.90 mol/L; then dropwise adding the cobalt acetate tetrahydrate aqueous solution into a trimesic acid ethanol solution, performing ultrasonic reaction, centrifuging, washing and drying to obtain metal organic framework Co-BTC powder;
(2) Dispersing Co-BTC powder of the metal organic framework in acetone by ultrasound according to the ratio of Co-BTC powder to acetone = 0.06-0.1 g: 2.0-3.3 mL to obtain Co-BTC/acetone dispersion liquid;
(3) Dissolving the high molecular polymer in DMF to obtain a high molecular polymer DMF solution containing 4.0-10 wt% of the high molecular polymer, and then adding the high molecular polymer DMF solution into the Co-BTC/acetone dispersion solution to obtain a membrane casting solution;
(4) And dropwise adding the casting solution on the smooth surface of the substrate, and heating in an oven to evaporate the solvent to obtain the Co-BTC/high-molecular polymer composite film with the thermo-reversible color change property.
4. The method for preparing a metal organic framework/high molecular polymer composite film having a thermoreversible color property according to claim 3, wherein: the ultrasonic reaction time in the step (1) is 10 s-20 min; the grain diameter of the metal organic framework Co-BTC powder is 30-350 nm.
5. The method for preparing a metal organic framework/high molecular polymer composite film having a thermoreversible color property according to claim 3, wherein: the ultrasonic dispersion time in the step (2) is 30-90 min.
6. The method for preparing a metal organic framework/high molecular polymer composite film having a thermoreversible color property according to claim 3, wherein: the heating temperature in the step (4) is 50-100 ℃.
7. The product obtained by the production method according to any one of claims 3 to 6, characterized in that: the thickness of the prepared composite film is 5-40 μm, the color is pink at 25 ℃, and the R.G.B value is R = 162-177, G = 137-158, B = 151-173; a purple color at 55 ℃, wherein the R.G.B value is R = 137-167, G = 112-155, B = 152-175; as the temperature further increases, the color changes to dark purple at 70 ℃ and above, and the r.g.b values thereof are R =117 to 138, G =96 to 127, and B =153 to 168.
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