JP2023012046A - Ketone scavenger and applications therefor - Google Patents

Abstract

To provide a scavenger that can efficiently trap a ketone.SOLUTION: A ketone scavenger comprises a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof.SELECTED DRAWING: None

Description

The present invention relates to a ketone scavenger and its use.

Various gaseous pollutant compounds that cause offensive odors exist in human living spaces such as houses and vehicle interiors. I'm starting to be able to do it. For example, aldehydes and ketones are contained in various odors such as cigarette smoke, body odor, pet odor, mold odor, paint odor, and printing odor. Aldehydes and ketones not only make people feel uncomfortable due to their odors, but are also suspected to be carcinogenic depending on the compounds, raising concerns about their effects on the human body. Therefore, a method for efficiently removing aldehydes and ketones is desired.

As for aldehydes, methods for removing them by chemically reacting them with a deodorant composed of hydrazine derivatives, amines, amino acids, urea derivatives, or the like have been disclosed (see, for example, Patent Documents 1 to 3).

JP-A-4-358536 JP-A-11-4879 Japanese Patent Application Laid-Open No. 2012-120708

On the other hand, since ketones are chemically more inert than aldehydes, the trapping efficiency of the scavengers described in the prior art documents is insufficient, and scavengers capable of efficiently removing ketones are desired. ing.

The present invention has been made in view of the background art described above, and an object of the present invention is to provide a scavenger capable of efficiently removing ketones.

The present inventors have made intensive studies to solve the above problems, and as a result, a specific carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof, or a composition containing the same , and found that ketones can be rapidly captured, and completed the present invention.

That is, the present invention has the following gists.
[1]
A ketone scavenger comprising a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof.
[2]
The ketone scavenger according to [1], wherein the carboxy group-containing O-substituted monohydroxylamine is a compound represented by the following general formula (1).

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. n represents an integer of 1 to 6. Plural R may be the same or different.)
[3]
In general formula (1), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, or a phenyl group; The ketone scavenger according to [2], characterized in that
[4]
The ketone scavenger according to [1], wherein the carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof is aminooxyacetic acid or a chemically acceptable salt thereof.
[5]
The ketone scavenger according to any one of [1] to [4], wherein the content of carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof is 0.01 to 30% by weight.
[6]
A ketone scavenger comprising an aqueous solution containing aminooxyacetic acid or a chemically acceptable salt thereof, wherein the concentration of aminooxyacetic acid or a chemically acceptable salt thereof is 0.1 to 10% by weight.
[7]
A method for removing ketones, which comprises using the ketone scavenger according to any one of [1] to [6].
[8]
In gas, characterized in that the ketone scavenger according to any one of [1] to [6] is brought into contact with a gas containing ketones, and the ketones in the gas are reacted with the aminooxyacetic acid. method of reducing the ketones concentration of.

The scavenger of the present invention captures ketones rapidly and continuously. As a result, the odor derived from ketones can be reduced, and the human living environment can be improved.

The ketone scavenger of the present invention is characterized by containing a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof.

The carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof is not particularly limited, but for example, the compound represented by the above general formula (1) or a chemically Acceptable salts may be mentioned. Further, the carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof is preferably aminooxyacetic acid or a chemically acceptable salt thereof.

In the carboxy group-containing O-substituted monohydroxylamine represented by the general formula (1), R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 to 15 carbon atoms. represents an arylalkyl group. n represents an integer of 1 to 6; Plural Rs may be the same or different.

The alkyl group having 1 to 18 carbon atoms may be a linear, branched or cyclic alkyl group, and is not particularly limited, but examples include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl. group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group (cetyl group), heptadecyl group, octadecyl group (stearyl group), oleyl group, elaidyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group , cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like.

Examples of the aryl group having 6 to 14 carbon atoms include, but are not limited to, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, cumenyl group, vinylphenyl group, biphenylyl group and phenanthryl group.

The arylalkyl group having 7 to 15 carbon atoms is not particularly limited, but examples include benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, anthrylmethyl group, tolylmethyl group, xylylmethyl group, cumenylmethyl group, vinylphenyl A methyl group, a biphenylylmethyl group, a phenanthrylmethyl group and the like can be mentioned.

Among these, in general formula (1), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, and a phenyl group. Carboxy group-containing O-substituted monohydroxylamines are particularly preferred.

Some or all of the hydroxylamino groups of the carboxyl group-containing O-substituted monohydroxylamine may be chemically acceptable salts with inorganic or organic acids. The type of salt is not particularly limited, but examples include hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, and phosphoric acid. Inorganic acid salts such as salts, organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, tosylate, etc. In that respect, inorganic acid salts are preferred, and hydrochlorides are more preferred.

In addition, the carboxy group of the above carboxy group-containing O-substituted monohydroxylamine may form an intramolecular salt with an intramolecular hydroxylamino group, or may form an intermolecular salt.

Moreover, some or all of the carboxy groups may be carboxylates. The type of carboxylate is not particularly limited, but examples thereof include alkali metal salts such as lithium salts, sodium salts, potassium salts and cesium salts, and ammonium salts. The amine that forms the ammonium salt is not particularly limited, but examples include ammonia, polyethyleneimine, ethanolamine, diethanolamine, triethanolamine, trishydroxymethylaminomethane, ethylenediamine, diethylenetriamine, triethylenediamine, triethylenetetramine, and tetraethylene. pentamine, pentaethylenehexamine, ethylenediamine-N,N,N',N'-tetraethanol, 1,4-piperazinediethanol, 1-(2,3-dihydroxypropyl)piperazine, 2-hydroxymethyltriethylenediamine, piperazine, and N-(2-aminoethyl)piperazine.

The ketone scavenger of the present invention can be used in any form depending on the purpose and application. For example, a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof (hereinafter referred to as "carboxy group-containing O-substituted monohydroxylamines") is dissolved in any solvent and used as a liquid scavenger. Alternatively, the carboxy group-containing O-substituted monohydroxylamines or the liquid scavenger can be supported on any carrier and used as a solid scavenger.

The amount of the carboxyl group-containing O-substituted monohydroxylamine dissolved in the solvent when preparing the liquid scavenger of the present invention can be arbitrarily adjusted according to the purpose, and is not particularly limited, but is 0.00. A range of 01 to 30% by weight is preferred, and a range of 0.1 to 10% by weight is more preferred.

The solvent for dissolving the carboxy group-containing O-substituted monohydroxylamines in preparing the liquid scavenger of the present invention is not particularly limited, but examples thereof include water, methanol, ethanol and toluene. The solvent may be a single solvent or a mixed solvent. Among these, water, which is inexpensive and harmless to the human body, is particularly preferred.

As the carrier for supporting the carboxy group-containing O-substituted monohydroxylamines in preparing the solid scavenger of the present invention, any carrier that is insoluble in water can be used without particular limitation. Examples of polymer carriers include styrene polymers such as polystyrene and crosslinked polystyrene; polyolefins such as polyethylene and polypropylene; poly(halogenated olefins) such as polyvinyl chloride and polytetrafluoroethylene; nitrile polymers such as polyacrylonitrile; Examples include (meth)acrylic polymers such as methyl methacrylate and polyethyl acrylate, and high molecular weight polysaccharides such as cellulose, agarose, and dextran. Examples of inorganic carriers include activated carbon, silica gel, diatomaceous earth, hydroxyapatite, alumina, and titanium oxide. , magnesia, and polysiloxane.

Here, crosslinked polystyrene includes monovinyl aromatic compounds such as styrene, vinyltoluene, vinylxylene, and vinylnaphthalene, and divinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, trivinylbenzene, bisvinyldiphenyl, bisvinylphenylethane, and the like. These copolymers may be copolymerized with methacrylic acid esters such as glycerol methacrylate and ethylene glycol dimethacrylate.

The shape of the carrier used in the preparation of the solid capture agent of the present invention is not particularly limited. Shapes commonly used as separation substrates, such as threads and membranes (e.g., flat membranes), can be used, and among these, spherical, membranous, granular, granular, or fibrous shapes preferable. Spherical, granular, or granular carriers are particularly preferably used because the volume used can be freely set when used in a column method or a batch method.

As for the particle size of the spherical, granular, or granular carrier, those having an average particle size in the range of 1 μm to 10 mm are generally usable, and the range of 2 μm to 1 mm is preferable.

The carrier used in preparing the solid capture agent of the present invention may be porous or non-porous. As the average pore diameter of the porous carrier, one having an average pore diameter of 1 nm to 1 μm can be generally used, and a range of 1 nm to 300 nm is preferable from the viewpoint of the ketone trapping rate.

The method for preparing the solid scavenger of the present invention is not particularly limited. A method of immobilization can be mentioned.

The method of immobilizing the carboxy group-containing O-substituted monohydroxylamines by physical adsorption is not particularly limited. Then, the carrier is added, the carrier is impregnated with the carboxyl group-containing O-substituted monohydroxylamine, and the solvent is distilled off.

The amount of the carboxyl group-containing O-substituted monohydroxylamine supported on the carrier can be arbitrarily adjusted according to the purpose, and is not particularly limited, but is preferably in the range of 0.01 to 30% by weight. A range of .1 to 10% by weight is more preferred.

The ketone scavenger of the present invention can capture gaseous ketones and remove the ketones from the gas. More specifically, the ketone scavenger is brought into contact with a gas containing ketones, and the ketones in the gas react with the ketone scavenger, thereby reducing the concentration of ketones in the gas. can be made

Examples of the ketones include, but are not limited to, dimethyl ketone (acetone), methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopropanone, cyclobutanone, cyclopentanone, Examples include cyclohexanone, isophorone, acetophenone, benzophenone, etc. Among these, acetone is preferred.

The gas is not particularly limited, but examples include air, nitrogen, and the like. Of these, air is preferred.

In the gas containing ketones (gas to be treated), the content of ketones contained in the gas is not particularly limited, but for example, it is preferably 1 ppm to 10,000 ppm. , more preferably 1 ppm to 1,000 ppm, more preferably 1 ppm to 100 ppm.

The present invention will be specifically described below, but the present invention should not be construed as being limited to these examples.

Example 1
1 L of nitrogen gas containing acetone gas with a volume concentration of 3.8 ppm was injected into a 2-L Tedlar (registered trademark) bag that had been degassed under reduced pressure. 100 μL of a 3% by weight aqueous solution of aminooxyacetic acid (manufactured by Sigma-Aldrich) as a ketone scavenger was injected into the Tedlar bag. After heating at 65 ° C. for 10 minutes, the gas in the Tedlar bag was transferred to Presep-C DNPH (2,4-dinitrophenylhydrazine (DNPH)-supported ketone analysis collection tube, manufactured by Wako Pure Chemical Industries) cartridge. adsorbed. The DNPH-ketone condensate is eluted from this cartridge with acetonitrile, and the DNPH-ketone condensate in the eluate is quantified by a liquid chromatograph (device name: Agilent 1220 Infinity LC, manufactured by Agilent Technologies) and collected in the cartridge. acetone was calculated. From the amount of acetone collected in the cartridge, the residual acetone concentration (residual ketone concentration) in the Tedlar bag after the heating treatment was calculated. Further, from the residual acetone concentration, the acetone capture rate (ketone capture rate) of the ketone scavenger of the present invention was calculated from the following equation.

Ketone capture rate [%]={(initial concentration−residual concentration)÷initial concentration}×100.

Comparative example 1
In Example 1, the same operation as in Example 1 was performed except that 100 μL of pure water was used instead of 100 μL of 3% by weight aqueous solution of aminooxyacetic acid, and the ketone residual concentration and ketone capture rate were calculated.

Example 2
In Example 1, the same operation as in Example 1 except that 1 L of nitrogen gas containing methyl ethyl ketone gas with a volume concentration of 3.4 ppm was used instead of 1 L of nitrogen gas containing acetone gas with a volume concentration of 3.8 ppm. was performed to calculate the ketone residual concentration and the ketone capture rate.

Comparative example 2
In Example 1, instead of 1 L of nitrogen gas containing acetone gas with a volume concentration of 3.8 ppm, 1 L of nitrogen gas containing methyl ethyl ketone gas with a volume concentration of 3.4 ppm was used, and a 3% by weight aqueous solution of aminooxyacetic acid was used. The same operation as in Example 1 was performed except that 100 μL of pure water was used instead of 100 μL, and the ketone residual concentration and ketone capture rate were calculated.

Example 3
0.2 g of a 3% by weight aqueous solution of aminooxyacetic acid was applied to a cotton cloth (10×10 cm), heated at 65° C. for 20 minutes, and then dried overnight at room temperature to prepare a test cloth. After enclosing this test cloth in a Tedlar bag with a volume of 2 L and degassing under reduced pressure, 1 L of nitrogen gas containing acetone gas with a volume concentration of 43 ppm was injected. After standing at room temperature for 1 hour, the ketone residual concentration and ketone capture rate were calculated in the same manner as in Example 1.

Comparative example 3
In Example 3, the same operation as in Example 3 was performed except that 0.2 g of a 3% by weight aqueous solution of adipic acid dihydrazide was used instead of 0.2 g of the 3% by weight aqueous solution of aminooxyacetic acid. and the ketone capture rate were calculated.

Comparative example 4
In Example 3, the same operation as in Example 3 was performed except that uncoated cotton bleached cotton was used instead of the test cloth, and the residual ketone concentration and ketone capture rate were calculated.

Example 4
In Example 3, the same operation as in Example 3 was performed except that nitrogen gas containing diacetyl with a volume concentration of 41 ppm was used instead of nitrogen gas containing acetone gas with a volume concentration of 43 ppm. , and the ketone capture rate were calculated.

Comparative example 5
In Example 3, instead of nitrogen gas containing acetone gas with a volume concentration of 43 ppm, nitrogen gas containing diacetyl with a volume concentration of 41 ppm was used, and instead of 0.2 g of 3% by weight aqueous solution of aminooxyacetic acid, The same operation as in Example 3 was performed except that 0.2 g of a 3% by weight aqueous solution of adipic acid dihydrazide was used, and the ketone residual concentration and ketone capture rate were calculated.

Comparative example 6
In Example 3, instead of nitrogen gas containing acetone gas with a volume concentration of 43 ppm, nitrogen gas containing diacetyl with a volume concentration of 41 ppm was used, and uncoated cotton was used instead of the test cloth. Except for this, the same operation as in Example 3 was performed, and the ketone residual concentration and the ketone capture rate were calculated.

The results of Examples 1-4 and Comparative Examples 1-6 are shown in Tables 1-4. As is clear from Tables 1 to 4, the scavengers of the present invention exhibited higher ketone scavenging ability compared to existing scavengers.

Claims (8)

A ketone scavenger comprising a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof. The ketone scavenger according to claim 1, wherein the carboxy group-containing O-substituted monohydroxylamine is a compound represented by the following general formula (1).

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. n represents an integer of 1 to 6. Plural R may be the same or different.) In general formula (1), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, or a phenyl group; The ketone scavenger according to claim 2, characterized in that A ketone scavenger according to claim 1, characterized in that the carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof is aminooxyacetic acid or a chemically acceptable salt thereof. The ketone scavenger according to any one of claims 1 to 4, wherein the content of the carboxy group-containing O-substituted monohydroxylamine or its chemically acceptable salt is 0.01 to 30% by weight. A ketone scavenger comprising an aqueous solution containing aminooxyacetic acid or a chemically acceptable salt thereof, wherein the concentration of aminooxyacetic acid or a chemically acceptable salt thereof is 0.1 to 10% by weight. A method for removing ketones, which comprises using the ketone scavenger according to any one of claims 1 to 6. A ketone in a gas, characterized in that the ketone scavenger according to any one of claims 1 to 6 is brought into contact with a gas containing ketones, and the ketones in the gas are reacted with the ketone scavenger. A method for reducing analog concentration.