Polymer composite material including metalloporphyrin complex, color change sensor using polymer composite material, and manufacturing method therefor

Abstract

Disclosed are: a polymer composite material including a metalloporphyrin complex; a color change sensor using the polymer composite material; and a manufacturing method therefor. The member for a color change sensor as a polymer composite material according to an embodiment may include a flexible color change sensor film based on a polymer composite material in which a metallporphyrin complex is uniformly dispersed. In this regard, the metalloporphyrin complex can be formed by complexing a plurality of metal ions with a porphyrin organic material including a plurality of pyridyl groups through chelation.

Description

Polymer composite material containing a metal-porphyrin complex, color change sensor using the polymer composite material, and method for manufacturing the same

[0001] Embodiments of the present invention relate to a polymer composite material containing a metal-porphyrin complex, a color change sensor using the polymer composite material, and a method for manufacturing the same.

[0002] Electrochemical sensors offer the advantage of quantitative detection of target components, but they suffer from the disadvantage of being unusable once their power supply runs out. Furthermore, their high power consumption limits their use as portable sensors.

[0003] Provided are a polymer composite material containing a metalloporphyrin complex, a color change sensor using the polymer composite material, and a method for manufacturing the same.

[0004] The present invention provides a color change sensor component having a color change characteristic upon exposure to an acidic gas, a color change sensor, and a method for manufacturing the same, by additionally complexing a polymer with a metal-porphyrin complex synthesized by chelating a metal with a porphyrin molecule having a large ring structure.

[0005] A flexible color change sensor film based on a polymer composite material in which a metal-porphyrin complex is uniformly dispersed is provided, wherein the metal-porphyrin complex is formed by complexing a plurality of metal ions through chelation with a porphyrin organic material containing a plurality of pyridyl groups.

[0006] According to one side, the above-mentioned porphyrin organic material may be characterized by having four pyrrole functional groups in a ring structure and including one or more pyridyl groups containing unshared electron pairs as ligands.

[0007] According to another aspect, the metal ion is Be2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , Fe 2+ , Cd 2+ , Cr 2+ , Co 2+ , Cu 2+ , Pb 2+ , Mn 2+ , Hg 2+ , Ni 2+ , Pt 2+ , Sn 2+ , and Zn 2+ It can be characterized as one of the following.

[0008] According to another aspect, the polymer forming the polymer composite material may be characterized by including at least one of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonates), PES (polyethersulfone), PI (polyimide), COC (cyclic olefin copolymer), and PDMS (poly-di-methyl-siloxane).

[0009] According to another aspect, the polymer forming the polymer composite material may be characterized by including at least one of elastomers such as styrene-butadiene block copolymers, polyisoprene, polybutadiene, ethylene propylene rubber, ethylene propylene diene rubber, silicone elastomers, fluoroelastomers, polyurethane elastomers, and nitrile rubbers.

[0010] According to another aspect, the weight ratio between the metal-porphyrin complex and the polymer forming the polymer composite material may be characterized as being within a range of 0.001 to 10.

[0011] According to another aspect, the thickness of the flexible color change sensor film may be characterized as being in the range of 10 μm to 10 mm.

[0012] According to another aspect, the metal-porphyrin complex may be characterized in that it is bonded through chemical interaction with an acidic gas including at least one of chlorine (HCl), perchloric acid (HClO4), chloric acid (HClO3), chlorous acid (HClO2), hypochlorous acid (HClO), nitric acid (HNO3), sulfuric acid (H2SO4), nitrogen trifluoride (NF3), nitrous oxide (N2O), and hydrogen fluoride (HF).

[0013] According to another aspect, the flexible color change sensor film may be characterized by exhibiting a color change in an acidity (pH) range of 1 to 7.

[0014] A method for manufacturing a color change sensor member is provided, comprising: (a) preparing a metal-porphyrin complex by using a chelation reaction of a metal ion to a porphyrin containing a pyridyl functional group; (b) preparing a mixed polymer solution containing the metal-porphyrin by mixing the metal-porphyrin complex with a polymer solution; (c) removing air bubbles contained in the mixed polymer solution containing the metal-porphyrin complex; and (d) preparing a mechanically stable and physically flexible film through a curing process of the mixed polymer solution containing the metal-porphyrin complex.

[0015] A polymer composite material containing a metalloporphyrin complex, a color change sensor using the polymer composite material, and a method for manufacturing the same can be provided.

[0016] A color change sensor component having a color change characteristic upon exposure to an acidic gas, a color change sensor, and a method for manufacturing the same can be provided by additionally complexing a polymer with a metal-porphyrin complex synthesized by chelating a metal with a porphyrin molecule having a large ring structure.

[0017] FIG. 1 is a drawing showing an example of a component for an acid gas color change sensor using a polymer composite material sensing material in which a metal-porphyrin complex is uniformly dispersed, according to one embodiment of the present invention.

[0018] FIG. 2 is a drawing showing an example of a process for manufacturing a member for an acid gas color change sensor using a polymer composite material sensing material in which a metal-porphyrin complex is uniformly dispersed, according to one embodiment of the present invention.

[0019] FIG. 3 is a flowchart illustrating an example of a method for manufacturing a member for a color change sensor according to one embodiment of the present invention.

[0020] FIG. 4 is a Fourier transform infrared spectroscopy (FTIR) graph of a metal-porphyrin complex manufactured according to Example 1 of the present invention.

[0021] FIG. 5 is a drawing showing the color change according to the addition of hydrogen chloride (HCl) to a metal-porphyrin complex manufactured according to Example 1 of the present invention.

[0022] FIG. 6 is a drawing showing an image in which a metal-porphyrin complex manufactured according to Example 2 of the present invention is uniformly complexed with an elastic polymer solution.

[0023] FIG. 7 is a drawing showing an image of a member for a color change sensor manufactured according to Example 2 of the present invention.

[0024] Figure 8 is a drawing showing an image of an elastic polymer manufactured according to Comparative Example 1 of the present invention.

[0025] FIG. 9 is a drawing showing an image showing the color change of an elastic polymer composite material in which a metal-porphyrin complex in which various metals are chelated is uniformly dispersed before and after exposure to hydrogen chloride (HCl), an acidic gas, in Experimental Example 1 of the present invention.

[0026] Figure 10 is a graph quantitatively analyzing the color change of an elastic polymer composite material in which a metal-porphyrin complex in which various metals are chelated is uniformly dispersed before and after exposure to hydrogen chloride (HCl), an acidic gas, in Experimental Example 1 of the present invention.

[0027] Figure 11 is a drawing showing an image showing the color change according to the concentration of hydrogen chloride (HCl), an acidic gas, of an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed in Experimental Example 2 of the present invention.

[0028] Figure 12 is a graph quantitatively analyzing the color change according to the concentration of hydrogen chloride (HCl), an acidic gas, of an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed in Experimental Example 2 of the present invention.

[0029] FIG. 13 is a drawing showing an image showing the color change for hydrogen chloride (HCl), an acidic gas, according to the thickness of a color change sensor film manufactured using an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed, in Experimental Example 3 of the present invention.

[0030] Figure 14 is a graph quantitatively analyzing the color change for hydrogen chloride (HCl), an acidic gas, according to the thickness of a color change sensor film manufactured using an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed, in Experimental Example 3 of the present invention.

[0031] Hereinafter, the detailed description will be given with reference to the attached drawings.

[0032] Embodiments of the present invention relate to a color change sensor component having a color change characteristic according to exposure to an acidic gas, a color change sensor, and a method for manufacturing the same, which is synthesized by chelating a metal to a porphyrin molecule having a macrocyclic structure and further complexing the metal-porphyrin complex with a polymer. The color change sensor is characterized by the color change characteristic exhibited by the chemical interaction between the metal-porphyrin complex and the acidic gas. Specifically, the porphyrin molecule of the metal-porphyrin complex is characterized by containing a plurality of pyridyl groups, and is characterized by the color change characteristic exhibited by reacting the unshared electron pair contained in the pyridyl groups with the acidic gas. In addition, by chelating the metal, the electron distribution within the metal-porphyrin complex can be changed, thereby modifying the optical properties, and therefore, metal-porphyrin complexes exhibiting various colors can be synthesized, and the color change sensor is characterized by the characteristic of exhibiting a color change characteristic after reacting with an acidic gas depending on the metal component. The metal-porphyrin complex can be used as a flexible color-changing sensor by complexing with a polymer, and is characterized by being able to be used to detect trace amounts of acidic gases generated from rough surfaces or curved edges.

[0033] FIG. 1 is a drawing showing an example of a component for an acidic gas color change sensor using a polymer composite material sensing material in which a metal-porphyrin complex is uniformly dispersed according to an embodiment of the present invention, and FIG. 2 is a drawing showing an example of a process for manufacturing a component for an acidic gas color change sensor using a polymer composite material sensing material in which a metal-porphyrin complex is uniformly dispersed according to an embodiment of the present invention. FIG. 1 shows an example of a polymer composite material (110) including a metal-porphyrin complex (120). At this time, the metal-porphyrin complex (120) includes a porphyrin-based organic molecule which is a macrocyclic structure containing four pyrrole functional groups (140) as a plurality of pyridyl groups, and when the metal (130) is additionally chelated to the porphyrin-based organic molecule, the internal electron distribution of the organic molecule is changed so that when it chemically interacts with an acidic gas molecule, different color changes can be exhibited depending on the type of metal. To this end, as shown in FIG. 2, a mixed polymer solution (210) prepared by mixing the metal-porphyrin complex (120) with a solution in which a polymer (150) is dissolved is poured into a petri dish (220), and then air bubbles are removed under low pressure and then cured, thereby manufacturing a member for a color change sensor which is a polymer composite material (110).

[0034] More specifically, the color change sensor member according to embodiments of the present invention can be utilized in a non-powered, real-time color change sensor that can detect hazardous gas leaks early by inducing a color change through a chemical interaction between a macrocyclic molecule containing an unshared electron pair and an acidic gas component. The color change sensor member includes an organic molecule based on porphyrin, which is a macrocyclic structure containing a plurality of pyridyl groups. When a metal is additionally chelated to the porphyrin-based organic molecule, the internal electron distribution of the organic molecule is changed, and when a chemical interaction occurs with an acidic gas molecule, different color changes can be exhibited depending on the type of metal. The porphyrin (metal-porphyrin) complex with the metal chelated therein can be uniformly dispersed in a polymer, and can be manufactured into a color change sensor having a mechanically stable and flexible film structure through a polymer curing process, so that it can be attached to a rough surface or a curved edge to detect a trace amount of hazardous environmental gas leaking.

[0035] A color change sensor component comprises a porphyrin-based organic molecule functionalized with a plurality of pyridyl groups and a metal-porphyrin complex chelated with a metal, wherein the metal-porphyrin complex is uniformly dispersed in a mechanically flexible polymer and can change color through chemical interaction with an acidic gas.

[0036] Metal-porphyrin complexes contain a porphyrin structure and can include multiple pyridyl groups as ligands. Porphyrins can form metal-porphyrin complex compounds by chelation with multiple cations. The metal-porphyrin complexes can include pyridyl groups with unshared electron pairs. The unshared electron pairs contained in the pyridyl groups can change the color of the metal-pyridyl complex through chemical interactions with acidic gas molecules. Therefore, metal-pyridyl complexes can be uniformly dispersed in mechanically flexible polymers and utilized as color-changing sensor materials that react with acidic gases to change color. Because polymers exhibit mechanical flexibility, they can be applied to rough surfaces or curved edges to detect trace amounts of acidic gases. A polymer composite color-changing sensor in which a metal-porphyrin complex is dispersed can be utilized as a color-changing sensor for non-powered gas detection.

[0037] The color change characteristics of polymer composites with dispersed metal-porphyrin complexes can be caused by the chemical interaction between the unshared electron pairs of the pyridyl groups contained in the metal-porphyrin complex and the acidic gas. The chemical reaction between the unshared electron pairs and the acidic gas can occur through hydrogen bonding, protonation, and coordination bonding. For example, the pH of the gas changes depending on the concentration of the acidic gas, and the color can change depending on the protonation reaction of the metal-porphyrin complex. Since the chemical properties of the metal-porphyrin complex vary depending on the type of chelated metal, different color changes can occur in response to acidic gases depending on the type of metal. The color change can occur when an acidic gas penetrates into the polymer composite with uniformly dispersed metal-porphyrin and chemically reacts with the metal-porphyrin complex.

[0038] A component for a color-change sensor can be fabricated by uniformly dispersing a metal-porphyrin complex in a polymer. The polymer can exhibit a liquid phase before curing, and after curing, it can exhibit mechanical stability and physical flexibility. Color-change characteristics can vary depending on the thickness of the polymer.

[0039] In embodiments of the present invention, a color change sensor member for acidic gas detection based on a polymer composite material in which a metal-porphyrin complex is uniformly dispersed may include a flexible color change sensor film based on a polymer composite material in which a metal-porphyrin complex is uniformly dispersed. In this case, the metal-porphyrin complex may be formed by complexing a plurality of metal ions through chelation with a porphyrin organic material containing a plurality of pyridyl groups. In this case, the flexible color change sensor member can be easily applied to a rough surface or a curved edge part. Therefore, it is possible to provide a color change sensor that can detect an acidic gas minutely exposed on a rough surface or a curved edge part to which the color change sensor member is applied through a chemical interaction between the color change sensor member and the acidic gas.

[0040] Here, the porphyrin may include a heterocyclic macrocycle organic compound based on a heterocyclic ring structure composed of four pyrrole groups. Furthermore, the porphyrin may further include multiple organic ligands. These porphyrins include multiple pyridyl groups as ligands, and the pyridyl groups contain unshared electron pairs, allowing them to chemically interact with acidic gas components.

[0041] For example, porphyrin binds to various metal ions (Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , Fe2+ , Cd 2+ , Cr 2+ , Co 2+ , Cu 2+ , Pb 2+ , Mn 2+ , Hg 2+ , Ni 2+ , Pt 2+ , Sn 2+ , Zn 2+ ) can be complexed with components to form a metal-porphyrin complex.

[0042] Additionally, the polymer may include at least one of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonates (PC), polyethersulfone (PES), polyimide (PI), cyclic olefin copolymer (COC), and poly-di-methyl-siloxane (PDMS).

[0043] In another embodiment, the polymer can include at least one of elastomers such as styrene-butadiene block copolymers, polyisoprene, polybutadiene, ethylene propylene rubber, ethylene propylene diene rubber, silicone elastomers, fluoroelastomers, polyurethane elastomers, and nitrile rubbers.

[0044] Additionally, the polymer may further include a curing agent, and may form a mechanically stable flexible film through a curing process.

[0045] The metal-porphyrin complex can be complexed with the aforementioned polymer and, through a curing process, can be uniformly dispersed within a flexible polymer film. At this time, the thickness of the polymer film including the metal-porphyrin complex can be within the range of 10 μm to 10 mm.

[0046] As described above, the metal-porphyrin complex of the polymer film including the metal-porphyrin complex can combine through chemical interaction with an acidic gas, and a color change can appear accordingly. The acidic gas can include at least one of chlorine (HCl), perchloric acid (HClO4), chloric acid (HClO3), chlorous acid (HClO2), hypochlorous acid (HClO), nitric acid (HNO3), sulfuric acid (H2SO4), nitrogen trifluoride (NF3), nitrous oxide (N2O), and hydrogen fluoride (HF). At this time, the polymer film including the metal-porphyrin complex can exhibit a chemical interaction in the acidity (pH) range of 1 to 7 of the acidic gas. In this case, the color of the polymer film including the metal-porphyrin complex can change due to the chemical interaction.

[0047] FIG. 3 is a flowchart illustrating an example of a method for manufacturing a member for a color change sensor according to an embodiment of the present invention. The manufacturing method according to the present embodiment may include a step (310) of manufacturing a metal-porphyrin complex by using a chelation reaction of a metal ion for porphyrin containing a pyridyl functional group, a step (320) of mixing the metal-porphyrin complex with a polymer solution to manufacture a mixed polymer solution containing the metal-porphyrin, a step (330) of removing air bubbles contained in the mixed polymer solution containing the metal-porphyrin complex, and a step (340) of manufacturing a mechanically stable and physically flexible film through a curing process of the mixed polymer solution containing the metal-porphyrin complex. Thereafter, a color change sensor capable of detecting an acidic gas can be manufactured using the film as a polymer composite material in which the metal-porphyrin complex is uniformly dispersed.

[0048] In step (310), a porphyrin-based organic molecule can be manufactured by additionally functionalizing a pyridyl group on a porphyrin-based organic molecule to include a plurality of pyridyl groups. At this time, Be is added to the porphyrin-based organic molecule (receptor). 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , Fe 2+ , Cd 2+ , Cr 2+ , Co 2+ , Cu 2+ , Pb 2+ , Mn 2+ , Hg 2+ , Ni 2+ , Pt 2+ , Sn 2+ and Zn 2+ A metal-receptor complex can be prepared by chelating at least one metal ion.

[0049] In step (320), a metal-porphyrin complex is added to a solution in which a polymer is dispersed, and a mixed solution can be prepared by uniformly mixing through a stirring process. At this time, the weight ratio between the metal-porphyrin complex and the polymer can be included in the range of 0.001 to 10. In addition, the solvent in which the polymer is dissolved can include a solvent selected from ethanol, methanol, propanol, butanol, isopropyl alcohol (IPA), dimethylformamide (DMF), acetone, acetonitrile, toluene, tetrahydrofuran, 1,2-dichlorobenzene, water, and mixtures thereof.

[0050] In step (330), bubbles contained in a mixed solution in which a metal-porphyrin complex and a polymer are complexed are removed at low pressure to produce a mixed solution that does not contain bubbles.

[0051] In step (340), a curing agent is additionally added to the polymer solution containing the metal-porphyrin complex to produce a mechanically stable and physically flexible film after the curing process. At this time, the polymer solution containing the metal-porphyrin complex can be cured using a UV (ultraviolet) light source to produce a mechanically stable and physically flexible film. Depending on the embodiment, the curing process can use an optical curing process or a thermal curing process. For example, the polymer solution containing the metal-porphyrin complex can be thermally cured at a temperature range of 25°C to 200°C to produce a mechanically stable and physically flexible film. At this time, the thickness of the film containing the polymer composite material in which the metal-porphyrin complex is uniformly dispersed can be included in the range of 10 μm to 10 mm.

[0052] The manufactured color change sensor member and / or the color change sensor manufactured using the manufactured color change sensor member can provide color change characteristics as the color of the polymer composite material in which a metal-porphyrin complex containing a plurality of pyridyl groups is uniformly dispersed changes through chemical interaction with a plurality of harmful acidic gases. As described above, the color change sensor member and / or the color change sensor can detect an acidic gas through a color change in the acidity (pH) range of 1 to 7. In addition, the structure of the flexible film provides an advantage in that the color change sensor member and / or the color change sensor can be easily placed on a rough surface or a curved edge, and even a trace amount of harmful acidic gas leaking from the rough surface or the curved edge can be detected in real time.

[0053] Example 1: Synthesis of metal-porphyrin complexes through chelation of various metal ions with macrocyclic porphyrin-based molecules containing pyridyl groups.

[0054] In order to synthesize a metal-porphyrin complex, a metal ion was chelated to a macrocyclic porphyrin (5,10,15,20-Tetrakis-(4-pyridyl)-21,23H-porphine; TPyP) containing multiple pyridyl groups to synthesize a metal-porphyrin complex. In this example, Zn 2+ , Mn 2+ , Co 2+ , Fe 2+ and Cu 2+ A metal-porphyrin complex was synthesized through a chelating reaction with TPyP using Zn as a metal ion. Specifically, Zn 2+ In order to synthesize the chelated zinc-porphyrin complex (ZnTPyP), a solution of Zn(CH3COO)2·2H2O completely dissolved in 6 mL of methanol (MeOH) was mixed with 24 mL of chloroform (CHCl3) solution containing TPyP, and the mixed solution was heated to 65°C and refluxed for 24 h to proceed with the chemical reaction. After the reaction was completed, the solvent was removed using a rotary evaporator, and the residue was washed with water and dried in a vacuum oven to obtain zinc-porphyrin (ZnTPyP). In the same manner, Co 2+ Wow Cu 2+ In order to synthesize chelated cobalt-porphyrin (CoTPyP) and copper-porphyrin (CuTPyP), chemical reactions were carried out using Co(CH3COO)2·4H2O and Cu(CH3COO)2·H2O through the same experimental process as above, and cobalt-porphyrin and copper-porphyrin were obtained.

[0055] Also, Fe 2+To synthesize the chelated iron-porphyrin complex FeTPyP, FeCl2·4H2O and TPyP were dissolved in 20 mL of DMF, and the solution was heated to 160°C for 24 h and refluxed to initiate the chemical reaction. After the reaction was completed, the solvent was removed using a rotary evaporator, and the residue was washed with water and dried in a vacuum oven to obtain iron-porphyrin. In the same manner, Mn 2+ In order to synthesize chelated manganese-porphyrin (MnTPyP), the above experimental process was repeated using MnCl2 to obtain manganese-porphyrin. Meanwhile, in synthesizing the metal-porphyrin complex, including the metal ion utilized in Example 1, Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , Fe 2+ , Cd 2+ , Cr 2+ , Co 2+ , Cu 2+ , Pb 2+ , Mn 2+ , Hg 2+ , Ni 2+ , Pt 2+ , Sn 2+ , Zn 2+ Various metal-porphyrin complexes can be synthesized by utilizing various precursors such as .

[0056] Figure 4 is a Fourier Transform Infrared Spectroscopy (FTIR) graph of a metal-porphyrin complex manufactured according to Example 1 of the present invention. The graph of Figure 4 is intended to clarify that the metal-porphyrin complex was formed by chelating a metal ion to porphyrin (TPyP). After the metal ion was chelated to porphyrin (TPyP), the FTIR spectrum was obtained at 3309 cm -1The metal ion chelation was confirmed by the disappearance of the pyrrole NH vibration of porphyrin (TPyP) that appears in .

[0057] FIG. 5 is a drawing showing the color change according to the addition of hydrogen chloride (HCl) to a metal-porphyrin complex manufactured according to Example 1 of the present invention. In the example of FIG. 5, when zinc-porphyrin (ZnTPyP) was dissolved in an aqueous solution at pH 3 and a small amount of hydrogen chloride (HCl) was added, it can be observed that the color of the aqueous solution changed from purple to green. This color change can be achieved by protonation of the pyridyl group of zinc-porphyrin (ZnTPyP).

[0058] Example 2: Fabrication of a color-changing sensor composite material by mixing a metal-porphyrin complex and an elastomeric polymer.

[0059] To uniformly mix the elastomeric polymer and the metal-porphyrin complex, 20 mg of the metal-porphyrin complex was dispersed in 1 mL of dichloromethane (DCM). In this example, poly-dimethylsiloxane (PDMS) was used as the elastomeric polymer. The metal-porphyrin complex dispersion solution was prepared by uniformly mixing 10 g of PDMS solution and 1 g of curing agent, and then using a vacuum pump to remove air bubbles in the solution. The DCM solvent used to disperse the metal-porphyrin complex can also be removed. Afterwards, the mixed solution is poured into a petri dish and cured, so that a color-change sensor with a flexible film structure can be manufactured. In addition, the thickness of the film can be controlled by adjusting the amount poured into the petri dish. The cured PDMS film in the petri dish is elastic and can be easily peeled off from the petri dish.

[0060] Figure 6 is a drawing showing an image in which a metal-porphyrin complex manufactured according to Example 2 of the present invention is uniformly complexed with an elastomeric polymer solution. Figure 6 shows a mixed solution in which air bubbles have been completely removed after ZnTPyP has been uniformly mixed into the PDMS solution. The mixed solution exhibits a color similar to that of ZnTPyP powder.

[0061] Fig. 7 is a drawing showing an image of a component for a color change sensor manufactured according to Example 2 of the present invention. Fig. 7 shows an image of PDMS containing ZnTPyP cured in a petri dish. The petri dish used in this example has a diameter of 5 cm, and PDMS having the same diameter as the petri dish can be manufactured.

[0062] Comparative Example 1: Fabrication of a Color-Change Sensor Using a Pure Elastic Polymer Without a Metal-Porphyrin Complex

[0063] In order to compare the color change after reaction with acidic gas of an elastomeric polymer with or without a metal-porphyrin complex, a pure elastomeric polymer without a metal-porphyrin complex was produced. In this comparative example 1, the step of mixing the metal-porphyrin complex solution into the PDMS solution was omitted, and the PDMS solution and curing agent were mixed, poured into a petri dish, and cured to produce a pure elastomeric polymer.

[0064] Figure 8 is a drawing showing an image of an elastomeric polymer manufactured according to Comparative Example 1 of the present invention. PDMS without metal-porphyrin exhibits colorless and transparent optical properties.

[0065] Experimental Example 1: Evaluation of color change characteristics for acidic gases according to metal type of the color change sensor manufactured according to Examples 1, 2, and Comparative Example 1

[0066] In this Experimental Example 1, a PDMS color change sensor including a metal-porphyrin complex manufactured according to the previous Example 2 and a PDMS color change sensor not including a metal-porphyrin complex manufactured according to Comparative Example 1 are used to describe a method and evaluation of the detection characteristics for acid gases through color change of the color change sensor.

[0067] The sensitivity of the PDMS color change sensor was evaluated by observing the color change before and after exposure to acidic gas. In Experimental Example 1, to expose the PDMS color change sensor to acidic gas, 1 mL of hydrogen chloride solution (HCl, 37% aqueous solution) was added to a 5 mL vial, and the PDMS color change sensor was attached to the inlet of the vial to react with the hydrogen chloride gas that volatilized from the hydrogen chloride solution at room temperature. In addition, in order to express the color change in a specific numerical value, a photograph of the color change sensor was taken under the same conditions, and then the RGB (Red, Green, Blue) values ​​were extracted using ImageJ software. In addition, the RGB values ​​were converted to CIE color coordinates. The CIE color coordinates are expressed as L*, a*, and b*, where L* is the brightness, a* is the degree of red and green, and b* is a three-dimensional space coordinate representing the degree of yellow and blue. The color change sensitivity is expressed as ΔRGB = |(R inital - R exposure )| + |(G inital - G exposure )| + |(B inital - B exposure )| can be calculated, where R inital , G inital , B inital RGB values ​​before exposure to acid gas, R exposure , G exposure , B exposure can represent the RGB values ​​after exposure to acidic gas, respectively. Also, the color change sensitivity ΔE = [(L* initial - L* exposure ) 2 + (a*initial - a* exposure ) 2 + (b* initial - b* exposure ) 2 ] 1 / 2 can be calculated as , where L* initial , a* initial , b* initial L*, a*, b* values ​​before exposure to acid gas, L* exposure , a* exposure , b* exposure can represent the L*, a*, and b* values ​​respectively after exposure to acidic gas.

[0068] Figure 9 is a drawing showing an image showing the color change of an elastic polymer composite material in which various metal-chelated metal-porphyrin complexes are uniformly dispersed, before and after exposure to hydrogen chloride (HCl), an acidic gas, in Experimental Example 1 of the present invention. It can be confirmed with the naked eye that PDMS containing metal-porphyrin complexes exhibited a color change, but pure PDMS did not show a color change.

[0069] Figure 10 is a graph quantitatively analyzing the color change of an elastic polymer composite material in which various metal-chelated metal-porphyrin complexes are uniformly dispersed in Experimental Example 1 of the present invention before and after exposure to hydrogen chloride (HCl), an acidic gas. In Figure 10, the color change shown in Figure 9 is quantified as ΔRGB and ΔE, calculated as color change sensitivity, and plotted as a graph. When compared numerically, zinc-porphyrin (ZnTPyP) showed the highest ΔRGB and ΔE values.

[0070] Experimental Example 2: Evaluation of color change characteristics according to acid gas concentration of color change sensors manufactured according to Examples 1, 2, and Comparative Example 1

[0071] In this Experimental Example 2, the color change sensitivity according to the concentration of acidic gas of each of a PDMS color change sensor including zinc-porphyrin (ZnTPyP) manufactured according to Example 2 and a PDMS color change sensor not including a metal-porphyrin complex manufactured according to Comparative Example 1 is described.

[0072] The sensitivity characteristics of the PDMS color change sensor were determined by observing the color change before and after exposure to acidic gas. In Experimental Example 2, in order to expose the PDMS color change sensor to acidic gas, 1 mL of hydrogen chloride solution (HCl, 37% aqueous solution) was diluted with water and injected into a 5 mL vial. The PDMS color change sensor was attached to the inlet of the vial and allowed to react with the hydrogen chloride (HCl) gas that volatilized from the hydrogen chloride (HCl) solution at room temperature for 3 minutes. In addition, in order to express the color change in a specific numerical value, a photograph of the color change sensor was taken under the same conditions and the RGB values ​​were extracted using ImageJ software.

[0073] FIG. 11 is a drawing showing an image showing the color change according to the concentration of hydrogen chloride (HCl), an acidic gas, of an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed in Experimental Example 2 of the present invention. FIG. 11 shows an image showing the color change after exposing PDMS containing zinc-porphyrin (ZnTPyP) to hydrogen chloride (HCl) gas using hydrogen chloride (HCl) aqueous solutions of different concentrations. It can be confirmed that the color changes from brown to green when exposed to hydrogen chloride (HCl). In addition, it can be confirmed that the higher the concentration of hydrogen chloride (HCl) aqueous solution, the more distinct the color change when exposed to hydrogen chloride (HCl) gas for 3 minutes.

[0074] Fig. 12 is a graph quantitatively analyzing the color change according to the concentration of hydrogen chloride (HCl), an acidic gas, of an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed in Experimental Example 2 of the present invention. Fig. 12 shows a graph calculated by calculating (R+G+B) / 3 of a color change sensor exposed to different concentrations of hydrogen chloride (HCl) in order to confirm the tendency of color change of PDMS containing zinc-porphyrin (ZnTPyP) according to the concentration of hydrogen chloride (HCl) aqueous solution. Before exposure to hydrogen chloride (HCl), (R+G+B) / 3 was 117.22, and upon exposure to hydrogen chloride (HCl) gas, (R+G+B) / 3 gradually decreased, and when exposed to hydrogen chloride (HCl) gas generated from a 37% aqueous hydrogen chloride (HCl) solution, (R+G+B) / 3 decreased to 90.64.

[0075] Experimental Example 3: Evaluation of color change characteristics for acidic gases according to thickness of color change sensors manufactured according to Examples 1, 2, and Comparative Example 1.

[0076] In this Experimental Example 3, the color change sensitivity in response to acidic gas according to the thickness of the PDMS color change sensor including zinc-porphyrin (ZnTPyP) manufactured according to Example 2 and the PDMS color change sensor manufactured according to Comparative Example 1 is described.

[0077] The sensitivity characteristics of the PDMS color change sensor were determined by observing the color change before and after exposure to acidic gas. In Experimental Example 3, PDMS color change sensors of different thicknesses were prepared, and acidic gas was exposed to the color change sensor in the same manner as Experimental Example 1. In addition, in order to express the color change in specific numbers, photographs of the color change sensor were taken under the same conditions, and then the RGB values ​​were extracted using ImageJ software, and then converted to the CIE color coordinates L*, a*, b*.

[0078] Fig. 13 is a drawing showing an image showing the color change in response to hydrogen chloride (HCl), an acidic gas, according to the thickness of a color change sensor film manufactured using an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed, in Experimental Example 3 of the present invention. Fig. 13 shows images before and after exposure to hydrogen chloride (HCl) gas according to the thickness of the color change sensor. It can be observed with the naked eye that the color change sensor changes from brown to green after exposure to hydrogen chloride (HCl).

[0079] Fig. 14 is a graph quantitatively analyzing the color change for hydrogen chloride (HCl), an acidic gas, according to the thickness of a color change sensor film manufactured using an elastic polymer composite material in which a zinc-porphyrin complex is uniformly dispersed, in Experimental Example 3 of the present invention. Fig. 14 shows the color change sensitivity ΔRGB and ΔE of the color change sensor for hydrogen chloride (HCl) gas as a graph according to the thickness of the sensor. It can be confirmed that ΔRGB decreases as the thickness increases. In addition, ΔE shows a maximum value at a thickness of 0.26 cm.

[0080] As such, according to embodiments of the present invention, a metal-porphyrin complex can be formed through a chelation process between a metal and porphyrin having a macrocyclic molecular structure including a pyridyl group, and the metal-porphyrin complex can be uniformly mixed with a polymer to form a complex, so that a color change sensor member having a mechanically stable flexible film structure can be manufactured through a curing process of the polymer including the metal-porphyrin complex. The color change sensor member can detect an acidic gas through a color change through a chemical interaction with an unshared electron pair of a pyridyl group upon exposure to the acidic gas.

[0081]

[0082]

[0083] Although the embodiments described above have been described by way of limited examples and drawings, those skilled in the art will appreciate that various modifications and variations can be made based on the above teachings. For example, appropriate results can still be achieved even if the described techniques are performed in a different order than described, and / or components of the described systems, structures, devices, circuits, etc. are combined or combined in a different manner than described, or are replaced or substituted with other components or equivalents.

[0084] Therefore, other implementations, other embodiments, and equivalents to the claims also fall within the scope of the claims set forth below.

Claims

1. A flexible color-changing sensor film based on a polymer composite material in which a metalloporphyrin complex is uniformly dispersed, The above metal-porphyrin complex is formed by complexing a plurality of metal ions through chelation with a porphyrin organic material containing a plurality of pyridyl groups. A component for a color change sensor characterized by:

2. In paragraph 1, The above porphyrin organic material is a color change sensor material characterized in that it comprises four pyrrole functional groups in a ring structure and at least one pyridyl group containing an unshared electron pair as a ligand.

3. In paragraph 1, The above metal ion is Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , Fe 2+ , Cd 2+ , Cr 2+ , Co 2+ , Cu 2+ , Pb 2+ , Mn 2+ , Hg 2+ , Ni 2+ , Pt 2+ , Sn 2+ , and Zn 2+ A color change sensor member characterized by being one of the following.

4. In paragraph 1, A color change sensor member characterized in that the polymer forming the polymer composite material includes at least one of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonates), PES (polyethersulfone), PI (polyimide), COC (cyclic olefin copolymer), and PDMS (poly-di-methyl-siloxane).

5. In paragraph 1, A color change sensor member characterized in that the polymer forming the polymer composite material comprises at least one of elastomers such as styrene-butadiene block copolymers, polyisoprene, polybutadiene, ethylene propylene rubber, ethylene propylene diene rubber, silicone elastomers, fluoroelastomers, polyurethane elastomers, and nitrile rubbers.

6. In paragraph 1, A color change sensor component characterized in that the weight ratio between the metal-porphyrin complex and the polymer forming the polymer composite material is within a range of 0.001 to 10.

7. In paragraph 1, A member for a color change sensor, characterized in that the thickness of the flexible color change sensor film is in the range of 10 μm to 10 mm.

8. In paragraph 1, A color change sensor member characterized in that the metal-porphyrin complex is bonded through chemical interaction with an acid gas containing at least one of chlorine (HCl), perchloric acid (HClO4), chloric acid (HClO3), chlorous acid (HClO2), hypochlorous acid (HClO), nitric acid (HNO3), sulfuric acid (H2SO4), nitrogen trifluoride (NF3), nitrous oxide (N2O), and hydrogen fluoride (HF).

9. In paragraph 1, A color change sensor member characterized in that the flexible color change sensor film exhibits a color change in an acidity (pH) range of 1 to 7. 10.(a) A step of preparing a metal-porphyrin complex by using a chelating reaction of a metal ion to a porphyrin containing a pyridyl functional group; (b) a step of mixing the metal-porphyrin complex with a polymer solution to prepare a mixed polymer solution containing metal-porphyrin; (c) a step of removing air bubbles contained in the mixed polymer solution containing the metal-porphyrin complex; and (d) a step of manufacturing a mechanically stable and physically flexible film through a curing process of a mixed polymer solution containing the metal-porphyrin complex; A method for manufacturing a member for a color change sensor including:

11. In paragraph 10, In step (b) above, A method for manufacturing a member for a color change sensor, characterized in that the solvent of the polymer solution comprises a solvent selected from ethanol, methanol, propanol, butanol, isopropyl alcohol (IPA), dimethylformamide (DMF), acetone, acetonitrile, toluene, tetrahydrofuran, 1,2-dichlorobenzene, water, and mixtures thereof.

12. In paragraph 10, In step (c) above, A method for manufacturing a color change sensor member characterized by removing air bubbles contained in the mixed polymer solution in which the metal-porphyrin complex and the polymer are complexed at low pressure.

13. In paragraph 10, Prior to step (d) above, A method for manufacturing a color change sensor member, characterized in that a curing agent is additionally added to the above mixed polymer solution to form a mechanically stable and physically flexible film after the above curing process.

14. In paragraph 10, In step (d) above, A method for manufacturing a member for a color change sensor, characterized in that the above curing process forms a mechanically stable and physically flexible film using an optical curing or thermal curing process.

15. In paragraph 14, In step (d) above, A method for manufacturing a member for a color change sensor, characterized in that the thermal curing process is performed in a temperature range of 25°C to 200°C to form a mechanically stable and physically flexible film.

16. In paragraph 10, (e) A step of manufacturing a color change sensor that detects acid gas using the above film. A method for manufacturing a member for a color change sensor further comprising:

17. In paragraph 10, The above film is used as a color change sensor that detects acid gas leaking minutely from a rough surface or curved corner through real-time color change. A method for manufacturing a member for a color change sensor characterized by:

Images