KR102163000B1 - Color change dye for ammonia gas detection and an ammonia gas detection sensor including the same - Google Patents

Abstract

The present invention relates to a color change dye for detecting ammonia gas and an ammonia gas detection sensor including the same, including a dimethyl phenol group, and a color change dye and ammonia gas for detecting ammonia gas having excellent sensitivity in a hazardous gas environment It relates to detection sensors. Unlike the prior art, the color change dye for detecting ammonia gas of the present invention includes a dimethyl phenol group, and thus has excellent sensitivity in a hazardous gas environment. In addition, the dye solution composition for detecting ammonia gas of the present invention has the effect of being able to apply the dye to various materials such as films, fibers, and paper. In addition, the sensor for detecting ammonia gas of the present invention has excellent sensitivity in a hazardous gas environment including the dye.

Description

Color change dye for ammonia gas detection and an ammonia gas detection sensor including the same

The present invention relates to a color change dye for detecting ammonia gas and an ammonia gas detection sensor including the same, including a dimethyl phenol group, and a color change dye and ammonia gas for detecting ammonia gas having excellent sensitivity in a hazardous gas environment It relates to detection sensors.

Recently, as interest in harmful gas and atmospheric environment existing in human life environment has increased, the need for a method that can easily detect environmentally harmful gas is recognized as important.

Among them, ammonia gas is an irritating odor that is harmful to the human body existing in the living environment, and the source of ammonia is not only agricultural sectors such as farmland and livestock breeding, but also sewage treatment plants and vehicle exhaust gas located near cities. The concentration is limited to 50 ppm.

In particular, ammonia is usually alkaline in the atmosphere, but reacts with acidic air pollutants such as nitric acid or sulfuric acid in the atmosphere and is involved in the formation of particulate matter such as ammonium nitrate (NH ₄ NO ₃ ) and ammonium sulfate (NH ₄ HSO ₄ ). .

These secondary-generated particulate matters are mostly microparticles (PM2.5), which lower the line of sight and have a potential adverse effect on human respiratory health. Therefore, it is urgent to develop a facility that can quickly detect the presence or leakage of ammonia gas and block it in advance.

Meanwhile, as a conventional ammonia gas detection technology, a gas sensor that detects low concentration ammonia gas by using a detection material in which Au is added to the WO ₃ parent material has been reported (T. Maekawa, K. Tamaki, N. Miura and N. Yamazoe, Chem. lett., p 639-642 (1992)).

Gas detection is possible because noble metal particles or metal oxide particles added to the metal oxide semiconductor material change the microstructure of the device (Heiland, G. and Kohl, D., Chem. Sen. Tech., 1, pp. 15-38(1998))(Oh, SW, Kim, YH, Yoo, DJ, SM and Park, SJ, Sens.Actuators B, 13, 400-403(1993)), due to increased sensitivity to combustible gases Ida (PJ Shaver, Appl. Phys. Lett., 11, 255 (1967)). Among them, noble metal catalysts act as electrical catalysts (Kim, C. S., Lad, R. J., and Tripp, C. P., Sens. Actuators B, 76, pp. 442-448 (2001)).

In addition, as a conventional ammonia gas detection technology, “a method of manufacturing a semiconductor thin film gas sensor for detecting ammonia gas and a sensor element” of Korean Patent Publication No. 2003-0061243 has been known.

An object of the present invention is to provide a color change dye for detecting ammonia gas having excellent sensitivity in a hazardous gas environment, including a dimethyl phenol group.

In addition, it is to provide a dye solution composition for detecting ammonia gas, including the dye, and allowing the dye to be applied to various materials such as film, fiber, and paper.

In addition, it is to provide a sensor for detecting ammonia gas having excellent sensitivity in a harmful gas environment including the dye.

The present invention provides a color changing dye for detecting ammonia gas comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

The compound may be represented by the following Chemical Formula 2 or 3.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C10 alkyl group.

R ¹ to R ⁴ may be an alkyl group.

The present invention comprises 0.01 to 0.1 parts by weight of a color change dye for ammonia gas detection comprising a compound represented by the following formula (1); 10 to 100 parts by weight of a solvent; And 1 to 10 parts by weight of a polymeric binder; It provides a dye solution composition for detecting ammonia gas.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

The solvent is methanol, dimethyl formamide (N,N-Dimethyl Formamide, DMF), tetrahydrofuran (THF), Diglyme, dimethyl sulfoxide (DMSO) and dimethoxyethane (dimethoxyethane, DME) may include one or more selected from.

The polymeric binder is ethyl cellulose, ethyl acetate, methyl cellulose, carboxy methyl cellulose, ethyl acetate, cellulose acetate, nitro cellulose, polyvinyl pinolidone, polyvinyl alcohol, polyacryl nitrile, polymethylmethacrelate and poly It may contain at least one selected from vinyl acetate.

The present invention provides a sensor for detecting ammonia gas comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

The ammonia gas detection sensor may include a polymer film including the compound represented by Formula 1 or a fiber coated with the compound represented by Formula 1.

The polymer film is a cellulose acetate (Cellulose Acetate, CA), ethyl cellulose (Ethyl Cellulose, EC), methyl cellulose (Methyl Cellulose, MC), carboxymethyl cellulose (Carboxymethyl Cellulose, CMC) polyethylene terephthalate (Polyethylene terephthalate, PET), Polyethylene imine (PEI) Polyethylene oxide (PEO), Polyvinylpyrrolidone (PVP), Polyvinyl acetate (PVAc), Polyvinyl alcohol (PVA), Polyvinyl Butyral (PVB), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polystyrene (PS) and polyvinylidene fluoride (PVDF) It may include one or more selected from among.

The fibers are polyester, polyurethane, polystylene, polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethylene oxide, Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyee It may include at least one selected from polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, and polybutylene terephthalate.

The present invention provides a method for producing a color change dye for detecting ammonia gas, which reacts a compound represented by the following formula (4) with a compound represented by the following formula (5) to prepare a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

[Formula 4]

[Formula 5]

The manufacturing method of the dye for detecting ammonia gas includes the steps of: (a) dissolving the compound represented by Formula 4 and the compound represented by Formula 5 in a solvent to prepare a mixed solution; (b) preparing a mixture by adding a catalyst to the mixed solution; And (c) heating the mixture to react.

The solvent is acetone, alcohol, acetone, alcohol, toluene, benzene, hexane, naphthalene, ethylbenzene, chlorobenzene, dichlorobenzene, dichloromethane, dimethylformamide, dimethylamine, dimethylacetamide, tetrachloromethane, cyclohexane, carbon tetrachloride It may be one or more selected from among.

The catalyst is at least one selected from H ₂ SO ₄ (Sulfuric acid), HCl (Hydrochloric acid), CH ₃ COOH (Acetic acid), HNO ₃ (Nitric Acid), Oleum (fuming sulfuric acid), HF (Hydrofluoric acid) I can.

Step c may be carried out at a temperature of 90 to 200 °C.

The present invention provides a method of manufacturing an ammonia gas detection sensor including the manufacturing method of the ammonia gas detection dye.

The method of manufacturing the ammonia gas detection sensor may include dissolving a compound represented by Formula 1 below in a solvent containing a polymer, and then spin coating on a substrate to prepare a polymer film.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

The manufacturing method of the ammonia gas detection sensor, 0.01 to 0.1 parts by weight of a color change dye for ammonia gas detection comprising a compound represented by the following formula (1); 10 to 100 parts by weight of a solvent; And 1 to 10 parts by weight of a polymeric binder; and coating a dye solution composition for detecting ammonia gas on the fiber by screen printing.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

Unlike the prior art, the color change dye for detecting ammonia gas of the present invention includes a dimethyl phenol group, and thus has excellent sensitivity in a hazardous gas environment.

In addition, the dye solution composition for detecting ammonia gas of the present invention has the effect of being able to apply the dye to various materials such as films, fibers, and paper.

In addition, the ammonia gas detection sensor of the present invention has excellent sensitivity in a hazardous gas environment including the dye.

1 is an FTIR analysis result of a compound prepared according to Example 1.
2 is an FTIR analysis result of a compound prepared according to Example 2.
3 is an NMR analysis result of a compound prepared according to Example 1.
4 is an NMR analysis result of a compound prepared according to Example 2.
5 is a result of UV-vis analysis of a polymer film prepared according to Film Example 1 before and after exposure to ammonia.
6 is a result of UV-vis analysis of a polymer film prepared according to Film Example 2 before and after exposure to ammonia.
7 is a structure of an ammonia gas detection sensor including a polymer film prepared according to Film Examples 1 and 2.
8 is a photograph showing a color change before and after exposure to ammonia gas of a polymer film prepared according to Film Examples 1 (Dye 1) and 2 (Dye 2).

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present invention.

However, the following description is not intended to limit the present invention to a specific embodiment, and in describing the present invention, when it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. .

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, elements, or combinations thereof described in the specification, but one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, actions, elements, or combinations thereof is not preliminarily excluded.

In addition, terms including ordinal numbers such as first and second to be used hereinafter may be used to describe various elements, but the elements are not limited by the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In addition, when a component is referred to as being "formed" or "stacked" on another component, it may be formed or stacked by being directly attached to the front surface or one surface on the surface of the other component. It should be understood that there may be more other components in the.

The "substituted" means that at least one hydrogen atom is deuterium, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C1 to C30 halogenated alkyl group, a C6 to C30 aryl group, a C1 to C30 heteroaryl group, C1 to C30 alkoxy group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryloxy group, silyloxy group (-OSiH ₃ ), -OSiR ¹ H ₂ (R ¹ is a C1 to C30 alkyl group or C6 to C30 aryl group), -OSiR ¹ R ² H (R ¹ and R ² are each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), -OSiR ¹ R ² R ³ , (R ¹ , R ² , and R ³ is each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), a C1 to C30 acyl group, a C2 to C30 acyloxy group, a C2 to C30 heteroaryloxy group, a C1 to C30 sulfonyl group, a C1 to C30 alkylthiol group , C6 to C30 arylthiol group, C1 to C30 heterocyclothiol group, C1 to C30 phosphate amide group, silyl group (-SiH ₃ ), -SiR ¹ H ₂ (R ¹ is a C1 to C30 alkyl group or C6 to C30 aryl group ), -SiR ¹ R ² H (R ¹ and R ² are each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), -SiR ¹ R ² R ³ , (R ¹ , R ² , and R ³ are each Independently, a C1 to C30 alkyl group or a C6 to C30 aryl group), an amine group-NRR' (wherein R and R'are each independently selected from the group consisting of a hydrogen atom, a C1 to C30 alkyl group, and a C6 to C30 aryl group Is a substituent), a carboxyl group, a halogen group, a cyano group, a nitro group, an azo group, and a substituent selected from the group consisting of a hydroxy group.

In addition, two adjacent substituents among the substituents may be fused to form a saturated or unsaturated ring.

In addition, the range of carbon number of the alkyl group or aryl group in the "substituted or unsubstituted C1 to C30 alkyl group" or "substituted or unsubstituted C6 to C30 aryl group" etc. is unsubstituted without considering the portion where the substituent is substituted It refers to the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when viewed as being formed. For example, a phenyl group in which a butyl group is substituted in the para position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

In the present specification, "hydrogen" refers to singlet hydrogen, dihydrogen, or tritium unless otherwise defined.

In the present specification, "alkyl (alkyl) group" refers to an aliphatic hydrocarbon group unless otherwise defined.

The alkyl group may be a "saturated alkyl group" that does not contain any double bonds or triple bonds.

The alkyl group may be an "unsaturated alkyl group" including at least one double bond or triple bond.

The alkyl group may be a C1 to C50 alkyl group. More specifically, the alkyl group may be a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C6 alkyl group.

For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. It indicates that it is selected from the group consisting of.

For specific examples, the alkyl group is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, propenyl group, butenyl group, cyclopropyl group, cyclo It means a butyl group, a cyclopentyl group, a cyclohexyl group, etc.

“Cycloalkyl groups” include monocyclic or fused ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

In the "alkoxy group", the alkyl group portion in the chain is the same as that of the alkyl group.

Hereinafter, a color change dye for detecting ammonia gas of the present invention will be described in detail.

The color change dye for detecting ammonia gas of the present invention includes a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

The compound may be represented by the following Chemical Formula 2 or 3.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C10 alkyl group.

R ¹ to R ⁴ may preferably be an alkyl group.

Hereinafter, a dye solution composition for detecting ammonia gas of the present invention will be described.

The dye solution composition for detecting ammonia gas of the present invention comprises 0.01 to 0.1 parts by weight of a color change dye for detecting ammonia gas comprising a compound represented by the following Formula 1; 10 to 100 parts by weight of a solvent; And 1 to 10 parts by weight of a polymeric binder.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

The solvent is methanol, dimethylformamide (N,N-Dimethyl Formamide, DMF), tetrahydrofuran (THF), Diglyme, dimethyl sulfoxide (DMSO), dimethoxyethane, DME) and the like are possible, but preferably methanol and dimethylformamide.

The polymeric binder is ethyl cellulose, methyl cellulose, carboxy methyl cellulose, ethyl acetate, cellulose acetate, nitro cellulose, polyvinyl pinolidone, polyvinyl alcohol, polyacryl nitrile, polymethyl methacrelate, polyvinyl acetate, etc. Although this is possible, it may be preferably ethyl cellulose.

The dye solution composition for detecting ammonia gas may additionally include a plasticizer, and the plasticizer may include triethyl citrate, dibutyl phthalate, diisononyl phthalate, and diiso Diisodecyl phthalate, Benzyl butyl phthalate, polyalkylene adipates, diethylhexyl phthalate, tris(2-ethylhexyl)trimelate Tris(2-ethylhexyl) ) Trimellitate, etc., may be preferably triethyl citrate.

Hereinafter, an ammonia gas detection sensor of the present invention will be described.

The ammonia gas detection sensor of the present invention includes a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

The ammonia gas detection sensor may include a polymer film including the compound represented by Formula 1 or a fiber coated with the compound represented by Formula 1.

The polymer film is cellulose acetate (Cellulose Acetate, CA), ethyl cellulose (Ethyl Cellulose, EC), methyl cellulose (Methyl Cellulose, MC), carboxymethyl cellulose (Carboxymethyl Cellulose, CMC) polyethylene terephthalate (Polyethylene terephthalate, PET), Polyethylene imine (PEI) Polyethylene oxide (PEO), Polyvinylpyrrolidone (PVP), Polyvinyl acetate (PVAc), Polyvinyl alcohol (PVA), Polyvinyl Butyral (PVB), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polystyrene (PS), polyvinylidene fluoride (PVDF) And the like, and preferably, a cellulose-based polymer or polyvinyl pinolidone.

The fibers are polyester, polyurethane, polystylene, polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethylene oxide, Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyee It may be a polyetherimide (polyetherimide), polyether sulfone (polyesthersulphone), polybenzimidazol (polybenzimidazol), polyethylene terephthalate, polybutylene terephthalate, and the like, preferably polyester.

Hereinafter, a method of manufacturing a color changing dye for detecting ammonia gas according to the present invention will be described.

A compound represented by the following Formula 1 is prepared by reacting a compound represented by the following Formula 4 with a compound represented by the following Formula 5.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are the same as or different from each other, and R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or a substituted or unsubstituted C1 to C10 alkyl group.

[Formula 4]

[Formula 5]

Specifically, the method of preparing a color change dye for detecting ammonia gas comprises the steps of: (a) dissolving the compound represented by Formula 4 and the compound represented by Formula 5 in a solvent to prepare a mixed solution; (b) preparing a mixture by adding a catalyst to the mixed solution; And (c) heating the mixture to react.

The solvent may include acetone, alcohol, toluene, benzene, hexane, naphthalene, ethylbenzene, chlorobenzene, dichlorobenzene, dichloromethane, dimethylformamide, dimethylamine, dimethylacetamide, tetrachloromethane, cyclohexane, carbon tetrachloride, etc. I can.

The catalyst is H ₂ SO ₄ (Sulfuric acid), HCl (Hydrochloric acid), CH ₃ COOH (Acetic acid), HNO ₃ (Nitric Acid), H ₂ SO ₄ (Sulfuric acid), Oleum (fuming sulfuric acid), HF (Hydrofluoric acid) and the like may be included.

Step c may be performed at a temperature of 90 to 200°C, but is not limited thereto. The temperature may vary depending on the type of catalyst.

Hereinafter, a method of manufacturing an ammonia gas sensing sensor including a method of manufacturing a color changing dye for sensing ammonia gas according to the present invention will be described.

The ammonia gas detection sensor of the present invention may be prepared by forming a polymer film including the compound represented by Formula 1 or coating the compound represented by Formula 1 on fibers.

Specifically, the polymer film may be prepared by dissolving the compound represented by Chemical Formula 1 in a solvent containing a polymer and then spin coating on a substrate.

The polymer is cellulose acetate (Cellulose Acetate, CA), ethyl cellulose (Ethyl Cellulose, EC), methyl cellulose (MC), carboxymethyl cellulose (CMC), polyethylene terephthalate (PET), Polyethylene imine (PEI) Polyethylene oxide (PEO), Polyvinylpyrrolidone (PVP), Polyvinyl acetate (PVAc), Polyvinyl alcohol (PVA), Polyvinyl Butyral (PVB), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polystyrene (PS), polyvinylidene fluoride (PVDF) Etc. are possible.

The solvent may include acetone, alcohol, toluene, benzene, hexane, naphthalene, ethylbenzene, chlorobenzene, dichlorobenzene, dichloromethane, dimethylformamide, dimethylamine, dimethylacetamide, tetrachloromethane, cyclohexane, carbon tetrachloride, etc. I can.

The method of coating the fiber with the compound represented by Formula 1 may include, specifically, 0.01 to 0.1 parts by weight of a color change dye for detecting ammonia gas containing the compound represented by Formula 1; 10 to 100 parts by weight of a solvent; And 1 to 10 parts by weight of a polymeric binder; it may be a method of coating the fiber by screen printing a dye solution composition for detecting ammonia gas.

The solvent is methanol, dimethylformamide (N,N-Dimethyl Formamide, DMF), tetrahydrofuran (THF), Diglyme, dimethyl sulfoxide (DMSO), dimethoxyethane, DME) and the like, but preferably methanol and dimethylformamide.

The polymer binder is ethyl cellulose, ethyl acetate The polymer binder is ethyl cellulose, methyl cellulose, carboxy methyl cellulose, ethyl acetate, cellulose acetate, nitro cellulose, polyvinyl pinolidone, polyvinyl alcohol, polyacryl nitrile, polymethyl Metaacrelate, polyvinyl acetate, etc. may be included, but preferably ethyl cellulose may be included.

The dye solution composition for detecting ammonia gas may additionally include a plasticizer, and the plasticizer may include triethyl citrate, dibutyl phthalate, diisononyl phthalate, and diiso Diisodecyl phthalate, Benzyl butyl phthalate, polyalkylene adipates, diethylhexyl phthalate, tri(2-ethylhexyl) trimelate (Tris(2- ethylhexyl) Trimellitate), and the like, preferably triethyl citrate.

The fibers are polyester, polyurethane, polystylene, polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethylene oxide, Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyee It may be a polyetherimide (polyetherimide), polyether sulfone (polyesthersulphone), polybenzimidazol (polybenzimidazol), polyethylene terephthalate, polybutylene terephthalate, and the like, preferably polyester.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes, and the scope of the present invention is not limited thereby.

Manufacturing example : Intermediate ( 1) of synthesis

Intermediate (1) was synthesized by refluxing O-Slfobenzimide 2mmol (3.6635g) in H ₂ SO ₄ 6mmol (5.8847g) for 2 hours in a nitrogen atmosphere at 140°C.

Example One

2,3-dimethylphenol (2,3-dimethylpehnol) 2.2mmol (1.727g) was added to the intermediate (1) 3.5mmol (4.121g) prepared according to Preparation Example, and maintained at 140 ℃ in a nitrogen atmosphere. It was refluxed for 6 hours. After the reaction product was cooled to room temperature, 100 mL of ultrapure distilled water of 90°C or higher was added and transferred to a flask to prepare an intermediate (2). The intermediate (2) was stored frozen for 24 hours and then evaporated at 90° C. for 30 minutes to prepare an intermediate (3). The intermediate (3) was filtered several times in 50 mL of benzene and 100 mL of ethyl ether, and then evaporated again at 90° C. for 30 minutes to prepare an intermediate (4). Intermediate (4) was neutralized to a pH of 7 by adding 30wt% sodium carbonate aqueous solution prepared using ultrapure distilled water at 90°C, and then 50 μl of HCl was added to prepare intermediate (5). The intermediate (5) was stored frozen for 24 hours, filtered several times, evaporated at 90° C. for 30 minutes, and vacuum dried at 100° C. for 24 hours to obtain a final material. (Yield: 32%)

Example 2

2,6-dimethylphenol (2,6-dimethylpehnol) 2.2mmol (1.792g) was added to the intermediate (1) 3.5mmol (4.121g) prepared according to the preparation example, and the temperature was maintained at 150 ℃ and in a nitrogen atmosphere. It was refluxed for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100 mL of distilled water at 90° C. was added and transferred to a flask to prepare an intermediate (2). The intermediate (2) was stored frozen for 24 hours and then evaporated at 90° C. for 30 minutes to prepare an intermediate (3). The intermediate (3) was filtered several times with 50 mL of benzene and 100 mL of ethyl ether, and then evaporated again at 90° C. for 30 minutes to prepare an intermediate (4). Intermediate (4) was neutralized to a pH of 7 by adding 30wt% aqueous sodium carbonate solution prepared using ultrapure distilled water at 90°C, and then 50 μl of HCl was added to prepare intermediate (5). The intermediate (5) was stored frozen for 24 hours, filtered several times, evaporated at 90° C. for 30 minutes, and vacuum dried at 100° C. for 24 hours to obtain a final material. (Yield: 38%)

Comparative example

Bromophenol blue was used as a comparative example.

film Example One

SiO ₂ A 2cm x 2cm quartz glass was prepared. The glass was washed in a glass cleaning solution at 60° C. for 30 minutes, and then ultrasonically washed in acetone for 30 minutes to remove foreign substances remaining on the surface. Next, in order to remove the residual solvent, the residual solvents were sufficiently washed several times using ultrapure distilled water, and then dried in an oven at 60° C. for 30 minutes. On the dried glass, 0.02 g of the dye prepared according to Example 1 was dissolved in a solvent containing 10 wt% of cellulose acetate, and a mixture of acetone, ultrapure distilled water, and alcohol in a weight ratio of 9:0.5:0.5 to be dissolved. A polymer film was formed by spin coating at 1,000 Rpm for 30 seconds.

film Example 2

A polymer film was prepared in the same manner as in Film Example 1, except that the compound prepared according to Example 2 was used instead of the compound prepared according to Example 1.

film Comparative example

A polymer film was prepared in the same manner as in Film Example 1, except that bromophenol blue of Comparative Example was used instead of the compound prepared according to Example 1.

fiber Example One

After dissolving 2 g of ethyl cellulose in a solvent in which 10 g of methanol and 10 g of DMF were mixed, 0.1 g of the compound prepared according to Example 1 and 3 g of triethyl citrate were added and dissolved to prepare a printing paste.

The printing paste was screen-printed on polyester fiber, pre-drying at 80° C. for 10 minutes, washed with distilled water 5 times, and dried at room temperature to prepare ammonia gas sensing fiber.

fiber Example 2

Ammonia gas sensing fiber was prepared in the same manner as in Fiber Example 1, except that the compound prepared according to Example 2 was used instead of the compound prepared according to Example 1, and nylon 6 was used instead of the polyester fiber. .

fiber Comparative example

Ammonia gas sensing fibers were prepared in the same manner as in Fiber Example 1, except that bromophenol blue of Comparative Example was used instead of the compound prepared according to Example 1.

[Test Example]

Test example 1: structural analysis

The fourier transform infrared ray (FTIR) analysis results of the dyes prepared according to Examples 1 and 2 are shown in FIGS. 1 and 2, and the NMR analysis results are shown in FIGS. 3 and 4. The results of UV-vis analysis before and after exposure to ammonia of the polymer films prepared according to Film Examples 1 and 2 are shown in FIGS. 5 and 6.

The structure of the dye of the present invention can be confirmed through FIGS. 1 to 4, and changes in the structure of the dye of the present invention according to the exposure of ammonia gas through FIGS. 5 and 6.

Test example 2: Check film properties

The structure of an ammonia gas detection sensor including a polymer film prepared according to Film Examples 1 and 2 is shown in FIG. 7, and prepared according to Film Examples 1 (Dye 1) and 2 (Dye 2) using the sensor The properties of the polymer film were analyzed and shown in FIG. 8.

Referring to FIG. 7, the basic structure of the ammonia gas detection sensor includes an inlet and an outlet through which ammonia gas can enter and exit. A sensor capable of detecting ammonia gas is installed on the upper part, and a humidity sensor is installed inside to measure the concentration of ammonia gas and relative humidity at the same time. In FIG. 8, a polymer film prepared according to Film Examples 1 and 2 was suspended inside the ammonia gas detection sensor, and then ammonia gas was injected into the inside.

Referring to FIG. 8, it can be seen that the color of the film is changed in the polymer film prepared according to Film Examples 1 and 2 at a concentration of 50 ppm ammonia gas.

Therefore, it was found that the ammonia gas detection sensor of the present invention has excellent sensitivity.

Test example 3: Check the properties of polymer films and fibers for detecting ammonia gas

The properties of the ammonia gas sensing films prepared according to Film Examples 1 and 2 and Comparative Film Examples were analyzed and shown in Table 1 below.

division Film Example 1 Film Example 2 Film Comparative Example △at 10s △E _max Color change △at 10s △E _max Color change △at 10s △E _max Color change 0ppm - - X - - X - - X 1ppm 12.73 32.72 O 10.72 21.72 O 4.73 2.72 X 3ppm 32.89 42.16 O 22.81 23.11 O 7.89 6.16 X 5ppm 35.15 43.32 O 29.12 25.33 O 9.17 8.32 X 10ppm 37.02 47.11 O 32.03 28.14 O 19.01 20.11 O 50ppm 39.60 44.38 O 34.62 32.32 O 39.42 41.23 O 100ppm 40.12 43.56 O 37.11 33.21 O 38.12 39.21 O

The characteristics of the ammonia gas sensing fibers prepared according to Fiber Examples 1 and 2 and Comparative Fiber Examples were analyzed and shown in Table 2 below.

division Fiber Example 1 Fiber Example 2 Fiber Comparative Example △at 10s △E _max Color change △at 10s △E _max Color change △at 10s △E _max Color change 0ppm - - X - - X - - X 1ppm 11.31 22.61 O 13.92 19.32 O 3.12 4.59 X 3ppm 29.81 32.11 O 27.11 24.12 O 5.56 6.13 X 5ppm 35.11 45.22 O 33.10 28.33 O 7.21 8.61 X 10ppm 38.24 49.19 O 38.23 32.02 O 17.03 29.01 O 50ppm 41.32 48.87 O 40.64 33.52 O 36.92 38.28 O 100ppm 43.34 47.53 O 41.16 34.03 O 39.82 35.16 O

Referring to Tables 1 and 2, it can be seen that the colors of the ammonia gas sensing films and fibers prepared according to Film Examples 1 and 2 and Fiber Examples 1 and 2 change as the gas concentration increases.

Accordingly, it was found that the ammonia gas sensing film and fiber of the present invention had superior sensitivity compared to the comparative example.

The scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (18)

A color change dye for detecting ammonia gas comprising at least one of the compounds represented by the following Chemical Formulas 2 or 3.
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
R ¹ to R ⁴ are alkyl groups. delete delete 0.01 to 0.1 parts by weight of a color change dye for detecting ammonia gas containing at least one of the compounds represented by the following Formulas 2 or 3;
10 to 100 parts by weight of a solvent; And
1 to 10 parts by weight of a polymeric binder;
A dye solution composition for detecting ammonia gas comprising.
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
R ¹ to R ⁴ are alkyl groups. The method of claim 4,
The solvent is methanol, dimethyl formamide (N,N-Dimethyl Formamide, DMF), tetrahydrofuran (THF), Diglyme, dimethyl sulfoxide (DMSO) and dimethoxyethane (dimethoxyethane, DME) a dye solution composition for detecting ammonia gas, characterized in that it comprises at least one selected from. The method of claim 4,
The polymeric binder is ethyl cellulose, ethyl acetate, methyl cellulose, carboxy methyl cellulose, ethyl acetate, cellulose acetate, nitro cellulose, polyvinyl pinolidone, polyvinyl alcohol, polyacryl nitrile, polymethylmethacrelate and poly A dye solution composition for detecting ammonia gas, comprising at least one selected from vinyl acetate. Ammonia gas detection sensor comprising at least one of the compounds represented by the following formula (2) or (3).
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
R ¹ to R ⁴ are alkyl groups. The method of claim 7,
Ammonia, characterized in that the ammonia gas detection sensor includes a polymer film containing at least one of the compounds represented by Formula 2 or 3 or a fiber coated with at least one of the compounds represented by Formula 2 or 3 Gas detection sensor. The method of claim 8,
The polymer film is a cellulose acetate (Cellulose Acetate, CA), ethyl cellulose (Ethyl Cellulose, EC), methyl cellulose (Methyl Cellulose, MC), carboxymethyl cellulose (Carboxymethyl Cellulose, CMC) polyethylene terephthalate (Polyethylene terephthalate, PET), Polyethylene imine (PEI) Polyethylene oxide (PEO), Polyvinylpyrrolidone (PVP), Polyvinyl acetate (PVAc), Polyvinyl alcohol (PVA), Polyvinyl Butyral (PVB), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polystyrene (PS) and polyvinylidene fluoride (PVDF) Ammonia gas detection sensor comprising at least one selected from among. The method of claim 8,
The fibers are polyester, polyurethane, polystylene, polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethylene oxide, Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyee Ammonia gas detection sensor comprising at least one selected from polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate and polybutylene terephthalate. A method of producing a color change dye for detecting ammonia gas by reacting a compound represented by the following Formula 4 with a compound represented by the following Formula 5 to prepare a compound represented by the following Formula 2 or 3.
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
R ¹ to R ⁴ are alkyl groups.
[Formula 4]

[Formula 5]

In Chemical Formula 5,
R ¹ to R ⁴ are each independently a hydrogen atom, a hydroxy group, or an alkyl group. The method of claim 11,
The manufacturing method of the dye for detecting ammonia gas
(a) preparing a mixed solution by dissolving the compound represented by Formula 4 and the compound represented by Formula 5 in a solvent;
(b) preparing a mixture by adding a catalyst to the mixed solution; And
(c) heating the mixture to react. A method for producing a color change dye for detecting ammonia gas, comprising: The method of claim 12,
The solvent is acetone, alcohol, acetone, alcohol, toluene, benzene, hexane, naphthalene, ethylbenzene, chlorobenzene, dichlorobenzene, dichloromethane, dimethylformamide, dimethylamine, dimethylacetamide, tetrachloromethane, cyclohexane, carbon tetrachloride Method for producing a color change dye for detecting ammonia gas, characterized in that at least one selected from. The method of claim 12,
The catalyst is at least one selected from H ₂ SO ₄ (Sulfuric acid), HCl (Hydrochloric acid), CH ₃ COOH (Acetic acid), HNO ₃ (Nitric Acid), Oleum (fuming sulfuric acid), HF (Hydrofluoric acid) Method for producing a color change dye for detecting ammonia gas, characterized in that. The method of claim 12,
Step c is a method for producing a color change dye for detecting ammonia gas, characterized in that carried out at a temperature of 90 to 200 ℃. A method of manufacturing an ammonia gas sensing sensor comprising the method of manufacturing a dye for sensing ammonia gas of claim 11. The method of claim 16, wherein the method of manufacturing the ammonia gas detection sensor,
A method for manufacturing an ammonia gas detection sensor comprising the step of dissolving at least one of the compounds represented by the following formulas 2 or 3 in a solvent containing a polymer and then spin coating on a substrate to prepare a polymer film .
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
R ¹ to R ⁴ are alkyl groups. The method of claim 16, wherein the method of manufacturing the ammonia gas detection sensor,
0.01 to 0.1 parts by weight of a color change dye for detecting ammonia gas containing at least one of the compounds represented by the following Formulas 2 or 3; 10 to 100 parts by weight of a solvent; And 1 to 10 parts by weight of a polymeric binder; A method of manufacturing an ammonia gas detection sensor comprising the step of coating a dye solution composition for detecting ammonia gas comprising a fiber by screen printing.
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
R ¹ to R ⁴ are alkyl groups.

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