KR102173413B1 - Dye for sensing ammonia gas and sensing sensor using the same - Google Patents

Abstract

The present invention relates to an acid gas detection dye and an acid gas detection sensor comprising the same, and relates to an acid gas detection dye having excellent photostability and heat resistance, including a xanthene compound, and an acid gas detection sensor comprising the same. . The dye for detecting an acid gas of the present invention includes a xanthene-based compound, and has excellent photostability and heat resistance. In addition, the dye ink composition for detecting acid gas of the present invention has the effect of being able to apply the dye to various materials such as fiber, film, and paper. In addition, the sensor for detecting an acid gas of the present invention has excellent sensitivity in a hazardous gas environment including the dye.

Description

TECHNICAL FIELD [0002] Dye for acid gas detection and an acid gas detection sensor including the same

The present invention relates to an acid gas detection dye and an acid gas detection sensor comprising the same, and relates to an acid gas detection dye having excellent photostability and heat resistance, including a xanthene compound, and an acid gas detection sensor comprising the same. .

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.

In the case of the Foshan accident in Gumi on September 27, 2012, a worker slipped while the valve to which the pressure was applied and the valve to which the HF was transferred was opened and the HF leaked, resulting in 23 casualties and 50 billion won. It was a colostrum chemical contamination accident that caused damage to the property of the country.

As such, acid gas such as hydrofluoric acid (HF) has the characteristics of colorless, tasteless, and odorless, so when leaking, if people do not immediately recognize whether the leak has occurred, there is a problem that it can cause great damage to the human body and the surrounding environment.

In order to solve such a problem, a paint composition containing a pigment for detecting gas leakage in Korean Patent No. 10-0231611 relates to a pigment that detects gas leakage from a chemical reaction device by a color change of the pigment, and in particular, a platinum group metal oxide. , A gas leak detection pigment containing a particulate substrate having at least one selected from the group consisting of a hydroxide and a hydrated oxide on a surface, and a method for producing the same.

In addition, Patent Registration No. 10-0231611 discloses that at least one platinum group compound is present on the surface of the substrate, at least one platinum group compound is present on the surface of the substrate, and at least one surface coating agent is also present on the surface of the substrate. Is characterized in that it reacts with the leaked gas and discolors to a blackish color.

However, known dyes for detecting acid gas have a problem that they do not have sufficient photostability and heat resistance to be commercialized.

An object of the present invention is to provide a dye for detecting acid gas having excellent photostability and heat resistance, including a xanthene-based compound.

In addition, it is to provide a dye ink composition for detecting acid gas, which includes the dye and allows the dye to be applied to various materials such as fiber, film, and paper.

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

The present invention provides a dye for sensing an acid gas comprising a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

R ¹ to R ³ may be the same as or different from each other, and may be a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, or a 2-butyl chloride.

X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The present invention comprises 100 parts by weight of an acid gas detection dye comprising a compound represented by the following formula (1); 1,000 to 1,000,000 parts by weight of a solvent; Binder 100 to 10,000; And a plasticizer 100 to 10,000; provides a dye ink composition for detecting an acid gas comprising.

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

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 binder is ethyl cellulose, ethyl acetate, ethylene vinyl acetate, polyethylene, polypropylene, polystyrene, polyethylene glycol, polymethyl methacrylate And polyoxymethylene (Polyoxymethylene) may include at least one selected from.

The plasticizer is triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, dimethyl phthalate, Diethyl phthalate, diallyl phthalate, butyl cyclohexyl phthalate, diisoheptyl phthalate, 1,2-cyclohexane dicarboxylic acid diisononyl ester ( 1,2-Cyclohexane dicarboxylic acid diisononyl ester), cyclohexane-1,2-dicarboxylic acid-mono (hydroxyl-isononyl) ester [Cyclohexane-1,2-dicarboxylic acid-mono (hydroxyl-isononyl) ester] , Bis(2-ethylhexyl) adipate [Bis(2-ethylhexyl) adipate], diisononyl adipate, trioctyl trimellitate, tris(2-ethylhexyl) trimethylate[ Tris (2-ethylhexyl) trimellitate], glycerol (Glycerol) and propylene glycol (Propylene glycol) may include at least one selected from.

The acid-sensing dye ink composition may include 100 parts by weight of an acid gas-sensing dye containing the compound represented by Formula 1; 1,000 to 1,00,000 parts by weight of methanol; 1,000 to 1,00,000 parts by weight of dimethyl formamide (N,N-Dimethyl Formamide, DMF); 1,000 to 5,000 parts by weight of ethyl cellulose; And 1,000 to 5,000 parts by weight of triethyl citrate; may include.

The present invention provides an acid gas detection sensor including the compound represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ¹ and R ² are the same as or different from each other, and R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

The acid gas detection sensor may include a fabric in which the compound represented by Formula 2 is impregnated or coated.

The fabric is 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 comprises the steps of: (a) dissolving 2-hydroxycarbazole in a solvent and reacting with a deprotonating agent to prepare a deprotonated 2-hydroxycarbazole; (b) preparing an alkylated 2-hydroxycarbazole by adding an alkylating agent to the solution containing the deprotonated 2-hydroxycarbazole and reacting; And (c) reacting the alkylated 2-hydroxycarbazole with a halogenated phthalic anhydride and a catalyst to prepare a compound represented by the following Formula 1; Provides a way.

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

The solvent in step (a) is tetrahydrofuran (THF), dimethylformamide (N,N-Dimethyl Formamide, DMF), Diglyme, dimethyl sulfoxide (DMSO), and dimethoxyethane ( dimethoxyethane, DME) may contain at least one selected from.

The deprotonating agent of step (a) may include at least one selected from NaH, KH, NaOH, KOH, and n-butyllithium (n-BuLi).

The alkylating agent in step (b) is at least one selected from butyl chloride, butyl iodide, butyl bromide, propyl chloride, propyl iodide, propyl bromide, ethyl chloride, ethyl iodide, ethyl bromide, methyl chloride, methyl iodide, methyl bromide, and benzyl chloride. It may include.

The halogenated phthalic anhydride in step (c) is tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3,6-difluorophthalic anhydride (3,6- Difluorophthalic anhydride), 3-Fluorophthalic anhydride, and 4-Fluorophthalic anhydride.

The catalyst of step (c) is zinc chloride, methanesulfonic acid, zinc oxide, aluminum chloride, iron chloride, tin(IV) chloride), titanium tetrachloride, and hydrofluoric acid.

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

The manufacturing method of the acid gas detection sensor may include dissolving an acid gas detection dye represented by the following Formula 1 in a solvent, and then impregnating the fabric.

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

The manufacturing method of the acid gas detection sensor includes: 100 parts by weight of an acid gas detection dye comprising a compound represented by the following formula (1); 1,000 to 1,000,000 parts by weight of a solvent; Binder 100 to 10,000; And a plasticizer 100 to 10,000; may include the step of coating the dye ink composition for detecting an acid gas comprising the screen printing (screen printing) on the fabric.

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

The dye for detecting an acid gas of the present invention includes a xanthene-based compound, and has excellent photostability and heat resistance.

In addition, the dye ink composition for detecting acid gas of the present invention has the effect of being able to apply the dye to various materials such as fiber, film, and paper.

In addition, the sensor for detecting an acid gas of the present invention has excellent sensitivity in a hazardous gas environment including the dye.

1 is a photograph of a fabric coated with a dye for detecting an acid gas generated during the manufacturing process of Device Examples 1 and 2. (a: Device Example 1, b: Device Example 2)
1B is a photograph of a fabric coated with a dye for detecting an acid gas generated during the manufacturing process of Device Example 2.
2 is a UV-vis analysis result of a compound prepared according to Example 1.
3 is a result of injecting HCl gas into a fabric coated with a dye for detecting an acid gas generated during the manufacturing process of Device Examples 1 and 2; (a: Device Example 1, b: Device Example 2)
4 is a result of measuring characteristics of an acid gas detection sensor manufactured according to Device Example 1.
5 is a result of measuring the characteristics of an acid gas detection sensor manufactured according to Device Example 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 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.

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

"Heteroaryl group" means that the aryl group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, at least one ring among the fused rings may contain 1 to 4 hetero atoms.

In the aryl group and the heteroaryl group, the number of ring atoms is the sum of the number of carbon atoms and the number of non-carbon atoms.

When used in combination such as "alkylaryl group" or "arylalkyl group", the terms of each of the alkyl and aryl mentioned above have the meanings and contents indicated above.

The term "arylalkyl group" refers to an aryl substituted alkyl radical such as benzyl and is included in the alkyl group.

The term "alkylaryl group" refers to an alkyl substituted aryl radical and is included in an aryl group.

Hereinafter, the dye for detecting an acid gas of the present invention will be described in detail.

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

[Formula 1]

In Formula 1,

R ¹ , R ² , R ³ are the same as or different from each other, and R ¹ , R ² , R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group. ,

X is a halogen atom.

R ¹ to R ³ are the same as or different from each other, and may be a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, or a 2-butyl chloride, preferably a methyl group or a 2-butyl chloride. I can.

X may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a bromine atom.

Hereinafter, the dye ink composition for detecting an acid gas of the present invention will be described.

The dye ink composition for detecting an acid gas of the present invention comprises 100 parts by weight of a dye for detecting an acid gas comprising a compound represented by the following formula (1); 1,000 to 1,000,000 parts by weight of a solvent; Binder 100 to 10,000; And plasticizers 100 to 10,000;

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

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

The binder is ethyl cellulose, ethyl acetate, ethylene vinyl acetate, polyethylene, polypropylene, polystyrene, polyethylene glycol, polymethyl methacrylate , Polyoxymethylene, and the like, and preferably ethyl cellulose and/or ethyl acetate.

The plasticizers are triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, dimethyl phthalate, Diethyl phthalate, diallyl phthalate, butyl cyclohexyl phthalate, diisoheptyl phthalate, 1,2-cyclohexane dicarboxylic acid diisononyl ester ( 1,2-Cyclohexane dicarboxylic acid diisononyl ester), cyclohexane-1,2-dicarboxylic acid-mono (hydroxyl-isononyl) ester [Cyclohexane-1,2-dicarboxylic acid-mono (hydroxyl-isononyl) ester] , Bis(2-ethylhexyl) adipate [Bis(2-ethylhexyl) adipate], diisononyl adipate, trioctyl trimellitate, tris(2-ethylhexyl) trimethylate[ Tris (2-ethylhexyl) trimellitate], glycerol (Glycerol), propylene glycol (Propylene glycol), and the like, and preferably triethyl citrate.

The dye ink composition for acid detection is preferably

100 parts by weight of a dye for detecting an acid gas containing the compound represented by Formula 1;

1,000 to 1,00,000 parts by weight of methanol;

1,000 to 1,00,000 parts by weight of dimethyl formamide (N,N-Dimethyl Formamide, DMF);

1,000 to 5,000 parts by weight of ethyl cellulose; And

1,000 to 5,000 parts by weight of triethyl citrate;

Can include.

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

An acid gas detection sensor comprising a compound represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ¹ and R ² are the same as or different from each other, and R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

The acid gas detection sensor may include a fabric in which the compound represented by Formula 2 is impregnated or coated.

The structure of the compound represented by Chemical Formula 1 may be changed to Chemical Formula 2 by heat during the process of dipping or coating the fabric. In the process of dipping or coating, heat is applied to fix the dye on the fabric.Before heating, the fabric turns purple, so it is judged that the dye has the structure of Formula 1, and the color of the fabric turns almost colorless after heating. It is determined that the dye has the structure of Formula 2.

The fabric is polyester, polyurethane, polystylene, polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethylene oxide, Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyee It may include polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, polybutylene terephthalate, and the like. Preferably, the fabric may comprise polyester.

The compound represented by Formula 2 reacts as shown in Scheme 1 below after being exposed to an acid gas, thereby changing the structure of the compound and changing the color of the acid gas detection sensor.

[Scheme 1]

In the conventional acid gas detection sensor, halochromic dyes such as Phenolphthalein, Ethyl Orange, Cresol Red, p-Rosolic Acid, and Bromothymol Blue were used as dyes. However, when these dyes are impregnated into fabrics, their reactivity to gases is very low, so that only strong acid liquids or high concentration gases can be detected. In screen printing, the reactivity to acid gas is better than that of the salt sample, but since these dyes are water-soluble, there is a problem of water loss due to sweat, rain, washing, etc. In addition, there was a problem with poor visibility because the color change was not large.

However, the acid gas detection sensor of the present invention is excellent in reactivity to acid gas even during immersion and screen printing, and since it is an insoluble dye, it can have excellent fastness due to no fading. In addition, the compound represented by Formula 2 has a plate-like structure, has good association due to π-π stacking due to a benzene ring, and has more conjugation than other dyes, so it has excellent light resistance and heat resistance, which are problems of halochromic dyes. Have. As shown in Scheme 1, the compound represented by Chemical Formula 2 exhibits a light pink color, changes its structure after exposure to an acid gas, and exhibits a dark purple color to have excellent visibility.

Hereinafter, a method of manufacturing an acid gas detection dye according to the present invention will be described.

First, 2- Hydroxycarbazole (2- hydroxycarbazole ) In a solvent, With deprotonating agents React Deprotonated 2- Hydroxycarbazole To prepare (step a).

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

The deprotonating agent may include NaH, KH, NaOH, KOH, n-butyllithium (n-BuLi), and the like, preferably NaH.

Next, above Deprotonated 2- Hydroxycarbazole After adding an alkylating agent to the containing solution, the alkylated 2- Hydroxycarbazole To prepare (step b).

The alkylating agent may include butyl chloride, butyl iodide, butyl bromide, propyl chloride, propyl iodide, propyl bromide, ethyl chloride, ethyl iodide, ethyl bromide, methyl chloride, methyl iodide, methyl bromide, benzyl chloride, etc., preferably May include 2-butyl chloride.

Finally, the alkylated 2- Hydroxycarbazole Halogenated phthalic anhydride (halogenated phthalic anhydride) and a catalyst to prepare a compound represented by the following formula (1) (step c).

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

The halogenated phthalic anhydride is tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3,6-difluorophthalic anhydride, 3-Fluorophthalic anhydride, 4-Fluorophthalic anhydride, etc. may be included, and preferably tetrachlorophthalic anhydride may be included. have.

The catalyst is zinc chloride, methanesulfonic acid, zinc oxide, aluminum chloride, iron chloride, tin (IV) chloride, tetrachloride Titanium (Titanium tetrachloride), hydrofluoric acid (Hydrofluoric acid), and the like may be included, and preferably, zinc chloride may be included.

Hereinafter, a method of manufacturing the acid gas detection sensor of the present invention will be described.

The manufacturing method of the acid gas detection sensor of the present invention may include the step of dissolving a dye represented by the following Formula 1 in a solvent and then impregnating the fabric.

[Formula 1]

In Formula 1,

R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

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

The manufacturing method of the acid gas detection sensor of the present invention may include the step of coating the dye ink composition for acid detection on fabric by screen printing.

In the process of dipping or screen printing, the structure of the compound represented by Formula 1 may be changed to a compound represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R ¹ and R ² are the same as or different from each other, and R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,

X is a halogen atom.

[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 1: intermediate ( 1) of synthesis

10 mmol of 2-hydroxycarbazole was dissolved in a mixed solvent containing 20 ml of THF and 20 mmol of DMF, and 25 mmol of NaH was added, followed by reacting for 10 minutes under room temperature, anhydrous, and oxygen-free conditions. Next, after adding 11 mmol of butyl chloride, it was reacted at 50°C for 2 hours. Next, the temperature was cooled to 0° C., and 5 ml of distilled water was added, followed by drying. Next, it was purified through Silica gel column chromatography to obtain an intermediate (1). During the purification, the ratio of the developing solution was ethyl ether (Et2O):petroleum ether=1:4.

Manufacturing example 2: intermediate ( 2) of synthesis

Intermediate (1) 0.01 mol, tetrachlorophthalic anhydride 0.015 mol, and zinc chloride 0.01 mol were mixed, and reacted at 160° C. for 24 hours. Next, it was cooled to room temperature and the solidified reactant was completely dissolved in 5ml of DMF to obtain a reactant solution. 20 g of NaCl and 2 g of HCl were added to 200 ml of distilled water, and a precipitate was deposited by dropping the reactant solution dropwise while stirring. The precipitate was filtered and dried in vacuum for 24 hours.

After the drying, the intermediate (2) was obtained by purification through reverse phased silica gel column chromatography. In the above purification, the ratio of the developing solution was methanol:water:trifluoroacetic acid=95:5:0.1.

Example 1: Preparation of dye for detecting acid gas

Into 50 ml of methanol, 2 mmol of the intermediate (2) and 1.5 ml of H2SO4 were added and refluxed for 48 hours at 100° C. under an argon atmosphere. Next, it was cooled to room temperature and dried to obtain a reaction product. The reaction product was purified through reverse phased silica gel column chromatography to obtain a final material. During the purification, the ratio of the developing solution was methanol:water:trifluoroacetic acid=95:5:0.1.

device Example 1: Fabrication of sensor for detecting acid gas using dyeing

0.1 g of a dye for acid gas detection prepared according to Example 1 was dissolved in 100 ml of DMF, 2 g of Nylon6 fabric was added, and then heated at 100° C. for 1 hour. Next, after cooling to room temperature, washed with distilled water 5 times, and dried at room temperature for 24 hours to obtain a fabric dyed with the dye for detecting acid gas.

A photograph of the obtained fabric is shown in Fig. 1(a).

device Example 2: Fabrication of sensor for detecting acid gas using screen printing

After dissolving 2 g of ethyl cellulose in a solvent mixed with 10 g of methanol and 10 g of DMF, 0.1 g of a dye for detecting an acid gas and 3 g of triethyl citrate prepared according to Example 1 were added and dissolved to prepare a printing paste.

The printing paste was screen-printed on a polyester fabric, pre-drying at 80° C. for 10 minutes, washed 5 times with distilled water, and dried at room temperature. A photograph of the obtained fabric is shown in Fig. 1(b).

[Test Example]

Test example 1: UV- vis analysis

After dissolving the compound prepared according to Example 1 in dimethyl sulfoxide (DMSO), the result of UV-vis analysis is shown in FIG. 2.

Referring to FIG. 2, it can be seen that a portion of the visible light region in the range of 450-600 nm is absorbed, and in particular, strong absorption is performed at about 540 nm, resulting in red color. Through this, it was possible to confirm that the desired dye was synthesized, and it was possible to confirm the structure of the compound prepared according to Example 1 as it showed an absorption peak that a rhodamine-based dye generally has. For reference, 2-hydroxycarbazole is brown, and tetrachlorophthalic anhydride, which is phthalic anhydride, is colorless.

Test example 2: Confirmation of acid gas detection reaction

The results of injecting HCl gas into the sensors manufactured according to Device Examples 1 and 2 are shown in FIG. 3. 3A is a result of a sensor manufactured according to Device Example 1, and (b) is a result of a sensor manufactured according to Device Example 2.

Referring to FIG. 3, it can be seen that the color of the sensor for detecting the acid gas exposed to the HCl gas changes to purple.

Test example 3: Check sensor characteristics

The characteristics of the acid gas detection sensor manufactured according to Device Examples 1 and 2 were measured and shown in FIGS. 4 and 5. 4 and 5 are results obtained by measuring the color change rate and color intensity when exposed to 10 ppm of HCl acid gas to the acid gas detection sensor manufactured according to Device Examples 1 and 2 using a colorimeter. Color difference was measured by measuring the color change at 10 second intervals while continuously exposed to 10 ppm of HCl acid gas.

Referring to FIGS. 4 and 5, it can be observed that the acid gas detection sensor manufactured according to device examples 1 and 2 changes color immediately upon exposure to acid gas, and rapidly changes color even with a small amount of acid gas. there was.

Accordingly, it was found that the acid gas detection sensor of the present invention has superior sensitivity compared to the conventional acid gas detection sensor.

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 (20)

An acid gas detection dye comprising a compound represented by the following formula (1).
[Formula 1]

In Formula 1,
R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
X is a halogen atom. The method of claim 1,
R ¹ to R ³ are the same as or different from each other, and are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, or a 2-butyl chloride. The method of claim 1,
X is a dye for detecting acid gas, characterized in that a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. 100 parts by weight of an acid gas detection dye comprising a compound represented by the following formula (1);
1,000 to 1,000,000 parts by weight of a solvent;
100 to 10,000 parts by weight of a binder; And
100 to 10,000 parts by weight of a plasticizer;
A dye ink composition for detecting acid gas comprising.
[Formula 1]

In Formula 1,
R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
X is a halogen atom. 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) dye ink composition for detecting an acid gas, characterized in that it comprises at least one selected from. The method of claim 4,
The binder is ethyl cellulose, ethyl acetate, ethylene vinyl acetate, polyethylene, polypropylene, polystyrene, polyethylene glycol, polymethyl methacrylate And polyoxymethylene (Polyoxymethylene) dye ink composition for detecting an acid gas comprising at least one selected from. The method of claim 4,
The plasticizer is triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, dimethyl phthalate, Diethyl phthalate, diallyl phthalate, butyl cyclohexyl phthalate, diisoheptyl phthalate, 1,2-cyclohexane dicarboxylic acid diisononyl ester ( 1,2-Cyclohexane dicarboxylic acid diisononyl ester), cyclohexane-1,2-dicarboxylic acid-mono (hydroxyl-isononyl) ester [Cyclohexane-1,2-dicarboxylic acid-mono (hydroxyl-isononyl) ester] , Bis(2-ethylhexyl) adipate [Bis(2-ethylhexyl) adipate], diisononyl adipate, trioctyl trimellitate, tris(2-ethylhexyl) trimethylate[ Tris (2-ethylhexyl) trimellitate], glycerol (Glycerol) and propylene glycol (Propylene glycol), characterized in that it comprises at least one selected from the dye ink composition for detecting an acid gas. The method of claim 4, wherein the dye ink composition for acid detection,
100 parts by weight of a dye for detecting an acid gas containing the compound represented by Formula 1;
1,000 to 1,00,000 parts by weight of methanol;
1,000 to 1,00,000 parts by weight of dimethyl formamide (N,N-Dimethyl Formamide, DMF);
1,000 to 5,000 parts by weight of ethyl cellulose; And
1,000 to 5,000 parts by weight of triethyl citrate;
Dye ink composition for detecting an acid gas, characterized in that it comprises. An acid gas detection sensor comprising a compound represented by the following formula (2).
[Formula 2]

In Chemical Formula 2,
R ¹ and R ² are the same as or different from each other, and R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
X is a halogen atom. The method of claim 9,
The acid gas detection sensor, wherein the acid gas detection sensor comprises a fabric in which the compound represented by Formula 2 is impregnated or coated. The method of claim 10,
The fabric is polyester, polyurethane, polystylene, polyvinylalchol, polymethyl methacrylate, polylactic acid, polyethylene oxide, Polyvinyl acetate, polyacrylic acid, polycaprolactone, polyacrylonitrile, polyvinylpyrrolidone, polyvinylchloride, polycarbonate, polyee An acid gas detection sensor comprising at least one selected from polyetherimide, polyesthersulphone, polybenzimidazol, polyethylene terephthalate, and polybutylene terephthalate. (a) dissolving 2-hydroxycarbazole in a solvent and reacting with a deprotonating agent to prepare deprotonated 2-hydroxycarbazole;
(b) preparing an alkylated 2-hydroxycarbazole by adding an alkylating agent to the solution containing the deprotonated 2-hydroxycarbazole and reacting; And
(c) reacting the alkylated 2-hydroxycarbazole with halogenated phthalic anhydride and a catalyst to prepare a compound represented by the following formula (1);
Method for producing a dye for detecting acid gas containing.
[Formula 1]

In Formula 1,
R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
X is a halogen atom. The method of claim 12,
The solvent in step (a) is tetrahydrofuran (THF), dimethylformamide (N,N-Dimethyl Formamide, DMF), Diglyme, dimethyl sulfoxide (DMSO), and dimethoxyethane ( Dimethoxyethane, DME), a method for producing an acid gas detection dye comprising at least one selected from. The method of claim 12,
The method for producing a dye for detecting an acid gas, wherein the deprotonating agent of step (a) comprises at least one selected from NaH, KH, NaOH, KOH, and n-butyllithium (n-BuLi). The method of claim 12,
The alkylating agent in step (b) is at least one selected from butyl chloride, butyl iodide, butyl bromide, propyl chloride, propyl iodide, propyl bromide, ethyl chloride, ethyl iodide, ethyl bromide, methyl chloride, methyl iodide, methyl bromide, and benzyl chloride. A method for producing a dye for detecting acid gas, comprising a. The method of claim 12,
The halogenated phthalic anhydride in step (c) is tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3,6-difluorophthalic anhydride (3,6- Difluorophthalic anhydride), 3-fluorophthalic anhydride (3-fluorophthalic anhydride), and 4-fluorophthalic anhydride (4-Fluorophthalic anhydride) of a dye for detecting acid gas, characterized by containing at least one selected from Manufacturing method. The method of claim 12,
The catalyst of step (c) is zinc chloride, methanesulfonic acid, zinc oxide, aluminum chloride, iron chloride, tin(IV) chloride), titanium tetrachloride (Titanium tetrachloride), and hydrofluoric acid (Hydrofluoric acid). A method of manufacturing an acid gas detection sensor comprising the manufacturing method of the dye for detecting acid gas of claim 12. The method of claim 18, wherein the manufacturing method of the acid gas detection sensor,
A method of manufacturing an acid gas detection sensor comprising the step of dissolving an acid gas detection dye represented by the following formula (1) in a solvent and then impregnating the fabric.
[Formula 1]

In Formula 1,
R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
X is a halogen atom. The method of claim 18, wherein the manufacturing method of the acid gas detection sensor,
100 parts by weight of an acid gas detection dye comprising a compound represented by the following formula (1); 1,000 to 1,000,000 parts by weight of a solvent; 100 to 10,000 parts by weight of a binder; And 100 to 10,000 parts by weight of a plasticizer; The method of manufacturing an acid gas detection sensor comprising the step of coating the dye ink composition for detecting an acid gas containing the fabric by screen printing (screen printing).
[Formula 1]

In Formula 1,
R ¹ to R ³ are the same as or different from each other, and R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
X is a halogen atom.

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