Ketone scavenger

Abstract

To provide a scavenger capable of efficiently capturing ketones.SOLUTION: A ketone scavenger is contacted with a ketone, the ketone scavenger comprising a support carrying an aminooxyalkyl group by a chemical bond.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to ketone scavengers and uses thereof. [Background technology]

[0002] Various gaseous polluting compounds that cause bad odors are present in human living spaces such as inside a house or inside a vehicle, and there has been growing interest in removing these gaseous polluting compounds to obtain a comfortable environment. 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 cause discomfort to people due to their odor, but some compounds are also suspected to be carcinogenic, and there are concerns about their effects on the human body. Therefore, a method for efficiently removing aldehydes and ketones is required. Regarding aldehydes, a removal method by chemically reacting them with deodorants consisting of hydrazine derivatives, amines, inorganic adsorbents, etc. has been disclosed (see, for example, Patent Documents 1 to 3).

[0003] On the other hand, ketones are chemically more inactive than aldehydes, and therefore, The scavenger described in the patent has insufficient scavenging efficiency, and a scavenger capable of efficiently removing ketones is required. It is desired. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 4-358536 [Patent Document 2] Japanese Patent Application Publication No. 11-4879 [Patent Document 3] JP 2000-45175 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure has been made in view of the above-mentioned background art, and has an object to provide a scavenger capable of efficiently removing ketones. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems and discovered that a carrier having a specific aminooxyalkyl group supported thereon by chemical bonding, or a composition containing the carrier, can rapidly capture ketones, thereby completing the present invention.

[0007] That is, the present disclosure includes the following embodiments.

[0008] [1] A ketone scavenger comprising a carrier having an aminooxyalkyl group supported thereon by chemical bonding.

[0009] [2] The ketone scavenger according to the above [1], wherein the support having an aminooxyalkyl group supported thereon by a chemical bond is a support having any of the structures represented by the following general formula (2):

[0010] [ka]

[0011] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, multiple Rs may be the same or different. When m is 0, multiple Xs may be the same or different.) [3] The ketone scavenger according to the above [2], wherein R is a methyl group, and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0012] [4] The ketone scavenger according to [2] above, wherein n is 3.

[0013] [5] The ketone scavenger according to the above [1] or [2], wherein the carrier carrying an aminooxyalkyl group by chemical bonding is a reaction product between a compound represented by the following general formula (1) and an inorganic carrier or a polymer carrier having a hydroxyl group on the surface:

[0014] [ka]

[0015] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2, and n represents an integer of 1 to 12. When m is 0 or 1, multiple Xs may be the same or different. When m is 2, multiple Rs may be the same or different.) [6] The ketone scavenger according to the above [5], wherein R is a methyl group, and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0016] [7] The ketone scavenger according to [5] above, wherein n is 3.

[0017] [8] The ketone scavenger according to any one of the above [1] to [7], wherein the support is at least one selected from the group consisting of silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, and hydroxyapatite.

[0018] [9] The ketone scavenger according to any one of the above [1] to [7], wherein the carrier is silica gel.

[0019]

[10] A method for removing a ketone, comprising contacting a ketone with the ketone scavenger according to any one of the above [1] to [9].

[0020]

[11] A ketone-capturing structure having a substrate on the surface of which the ketone scavenger according to any one of [1] to [9] is attached.

[12] The ketone-capturing structure according to

[11] , wherein the substrate is at least one selected from the group consisting of fibers, sheets, wallpaper, sponges, beads, wood, plywood, and gypsum boards.

[0021]

[13] A method for removing ketones, comprising contacting the ketone-trapping structure according to

[11] or

[12] above with a ketone. Effect of the Invention

[0022] The scavenger according to one embodiment of the present disclosure quickly and continuously captures ketones, thereby reducing odors caused by ketones and improving the human living environment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present invention will be described in detail below. In this specification, the symbol "to" means a numerical range including both ends of the symbol.

[0024] A ketone scavenger according to one embodiment of the present disclosure includes a carrier having an aminooxyalkyl group supported thereon by chemical bonding.

[0025] The above-mentioned aminooxyalkyl group-supported carrier by chemical bonding is not particularly limited, but may be, for example, a carrier represented by the following general formula (2):

[0026] [ka]

[0027] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, multiple Rs may be the same or different. When m is 0, multiple Xs may be the same or different.) Examples of the carrier include a carrier having any of the structures shown below.

[0028] The alkyl group having 1 to 4 carbon atoms represented by R is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a tert-butyl group.

[0029] The R is preferably a methyl group, since the silane coupling reaction described below is efficient.

[0030] The alkoxy group having 1 to 4 carbon atoms represented by X is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropyloxy group, a 1-methylpropyloxy group, and a tert-butoxy group.

[0031] As the above-mentioned X, from the viewpoint of efficiency of the silane coupling reaction described later, a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.

[0032] The above m represents an integer of 0 to 2, and m' represents an integer of 0 or 1, with 0 or 1 being preferred in terms of the efficiency of the silane coupling reaction described below.

[0033] The above n represents an integer of 1 to 12, and is preferably an integer of 3 to 12, and more preferably 3, in that the aldehyde scavenging effect is excellent.

[0034] The above-mentioned aminooxyalkyl group-supported carrier by chemical bonding is not particularly limited, but may be, for example, a carrier represented by the following general formula (1):

[0035] [ka]

[0036] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2, and n represents an integer of 1 to 12. When m is 0 or 1, multiple Xs may be the same or different. When m is 2, multiple Rs may be the same or different.) It is preferable that the compound represented by the formula (hereinafter, also referred to as "silane coupling agent") is a reaction product obtained by mixing a compound represented by the formula (hereinafter, also referred to as "silane coupling reaction") with a carrier having a hydroxyl group on the surface.

[0037] That is, the support having the aminooxyalkyl group supported thereon by chemical bonding can be produced by reacting the above-mentioned silane coupling agent with a support having hydroxyl groups on its surface.

[0038] In the above silane coupling agent, the definitions and preferred ranges of R, X, and n are the same as those in the above general formula (2).

[0039] In the silane coupling agent, m represents an integer of 0 to 2. Regarding m, it is preferable that it is 0 or 1 in terms of efficiency of the silane coupling reaction.

[0040] The silane coupling agent may be a commercially available product, or may be synthesized according to the methods described in Organic Preparations and Procedures International, vol. 26, 1994, pp. 111-113, JP-A-7-233132, and Tetrahedron Letters, Vol. 46(14), 2005, pp. 7973-7975.

[0041] As described above, the ketone scavenger of the present invention is an aminooxyalkyl group [—(CH 2 )n-ONH 2A part or the whole of the aminooxyalkyl group may be in the form of a chemically acceptable salt with an inorganic acid or an organic acid.

[0042] The type of the salt is not particularly limited, and examples thereof include inorganic acid salts such as hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, and phosphate, and organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, and p-toluenesulfonate. As the salt, inorganic acid salts are preferable in that they are inexpensive, and hydrochloride is more preferable.

[0043] The amount of aminooxyalkyl groups supported on the support on which the above-mentioned aminooxyalkyl groups are supported by chemical bonds can be adjusted as desired depending on the purpose and is not particularly limited, but is preferably in the range of 0.01 to 10 mmol / g based on the unit weight of the support on which the aminooxyalkyl groups are supported by chemical bonds.

[0044] The above-mentioned carrier is not particularly limited, but examples thereof include a polymer carrier and an inorganic carrier.

[0045] Examples of the polymer carrier include, but are not limited to, styrene-based polymers (e.g., polystyrene, cross-linked polystyrene, etc.), polyolefins (e.g., polyethylene, polypropylene, etc.), poly(halogenated olefins) (e.g., polyvinyl chloride, polytetrafluoroethylene, etc.), nitrile-based polymers (e.g., polyacrylonitrile, etc.), (meth)acrylic polymers (e.g., polymethyl methacrylate, polyethyl acrylate, etc.), high molecular weight polysaccharides (e.g., cellulose, agarose, dextran, etc.), and the like.

[0046] The inorganic carrier is not particularly limited, but examples thereof include silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, and hydroxyapatite.

[0047] The carrier is preferably an inorganic carrier in that the above-mentioned silane coupling reaction is efficient, and more preferably silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, or hydroxyapatite, and even more preferably silica gel.

[0048] The carrier is preferably one having hydroxyl groups on its surface.

[0049] The shape of the carrier is not particularly limited, and examples thereof include spherical, granular, fibrous, granular, monolithic column, hollow fiber, membrane, etc. Regarding the shape, in terms of excellent aldehyde capture effect, spherical, membrane, granular, granular, or fibrous is preferable, and spherical, granular, or granular is more preferable.

[0050] The particle size of the spherical, granular, or particulate carrier is preferably within the range of an average particle size of 0.1 μm to 10 mm, and more preferably an average particle size of 1 μm to 100 μm in terms of good dispersibility in liquid.

[0051] The carrier may be either porous or non-porous, but is preferably porous in view of its excellent ketone capturing effect.

[0052] When the support is a porous support, the average pore size of the porous support is preferably from 1 nm to 1 μm, and more preferably from 1 nm to 300 nm in terms of excellent ketone capturing effect.

[0053] The ketone scavenger of the present invention can capture gaseous or liquid ketones and remove the ketones from the gas or liquid. Specifically, the ketone scavenger is brought into contact with a gas or liquid containing ketones, and the ketones in the gas or liquid are reacted with the ketone scavenger, thereby reducing the ketone concentration in the gas or liquid.

[0054] The ketones are not particularly limited, but examples thereof include dimethyl ketone (acetone), methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, isophorone, acetophenone, and benzophenone.

[0055] The gas is not particularly limited, but examples thereof include air, nitrogen, etc. The liquid is not particularly limited, but examples thereof include water, alcohol, etc.

[0056] In the gas containing ketones (the gas to be treated), the content of ketones contained in the gas is not particularly limited, but is preferably, for example, 1 ppm to 10,000 ppm, more preferably 1 ppm to 1,000 ppm, and even more preferably 1 ppm to 100 ppm.

[0057] In the liquid containing ketones (the liquid to be treated), the content of ketones contained in the liquid is not particularly limited, but is preferably 0.01 wt % to 50 wt %, more preferably 0.05 wt % to 10 wt %, and even more preferably 0.1 wt % to 5 wt %.

[0058] Another method of using the ketone scavenger is not particularly limited, but includes, for example, a method in which the ketone scavenger is used in a state in which it is attached to a substrate, and specifically, a method in which a substrate having the ketone scavenger attached to its surface is used as a ketone-capturing structure.

[0059] The ketone-capturing structure can be produced by applying or spraying the ketone scavenger to a substrate. The ketone scavenger can also be mixed with a binder resin and then applied or sprayed to a substrate to produce a ketone-capturing structure. The binder resin is not particularly limited, and examples thereof include acrylic ester resin, silicone resin, urethane resin, polyester resin, melamine resin, polypropylene resin, and fluororesin.

[0060] The ketone-trapping structure described above can capture odor-causing substances (including ketones) in a gas by exposure to the gas, thereby reducing the odor of the gas.

[0061] The substrate is not particularly limited, but examples thereof include fibers, sheets, wallpaper, sponges, beads, wood, plywood, and gypsum boards.

[0062] The material for the fiber, sheet, wallpaper, or sponge is not particularly limited, but examples thereof include polyester, polyamide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, fluorine-based resin, aramid resin, sulfone-based resin, rayon, acetate, cotton, wool, silk, hemp, glass, carbon, ceramics, silicone resin, polyimide resin, natural rubber, polyurethane, etc.

[0063] The ketone-capturing structure is not particularly limited, but examples thereof include clothing, curtains, carpets, wall coverings, automobile interior materials, furniture, and the like.

[0064] The amount of the ketone scavenger immobilized on the substrate can be adjusted as desired depending on the purpose, and is not particularly limited. The amount of the ketone scavenger immobilized on the substrate can be adjusted as desired depending on the purpose, and is preferably 0.1 to 200 g / m based on the unit area of ​​the substrate. 2 The range is preferably 0.5 to 75 g / m 2 It is more preferable that the range is . EXAMPLES

[0065] Hereinafter, one embodiment of the present disclosure will be described in more detail, but the present invention should not be construed as being limited to these examples. Unless otherwise specified, the reagents and the like used were commercially available products.

[0066] The analytical instruments and evaluation methods used in the examples are listed below.

[0067] <Acetone trapping test> 1.0 g of the ketone scavenger was mixed with 20 g of 0.5 wt% acetone aqueous solution, and the aggregates were loosened for 5 minutes using an ultrasonic cleaning device (ASU-M, manufactured by AS ONE Co., Ltd.) to obtain a suspension. The suspension was then passed through a syringe filter (DISMIC13HP, manufactured by ADVANTEC Co., Ltd.) with a mesh size of 0.45 μm to obtain an aqueous solution from which the aminooxy group-bearing carrier had been removed. 1 μL of the obtained aqueous solution was analyzed using a gas chromatograph (GC-2030, manufactured by Shimadzu Corporation), and the area value of acetone was recorded. An autosampler (AOC-30i, manufactured by Shimadzu Corporation) was used to inject the sample into the gas chromatograph. The acetone concentration after the capture test was calculated using the recorded area value of acetone and the calibration curve. Furthermore, the acetone capture rate [%] was calculated from the following formula.

[0068] Acetone capture rate [%] = [(initial acetone concentration - acetone concentration after capture test) ÷ initial acetone concentration] × 100.

[0069] <Methyl ethyl ketone capture test> 1.0 g of the ketone scavenger and 10 g of a 0.5 wt% aqueous solution of methyl ethyl ketone were mixed and stirred with a stirrer for 1 hour. The suspension was then passed through a syringe filter (Advantec, DISMIC13HP) with a mesh size of 0.45 μm to obtain an aqueous solution from which the aminooxy group-bearing carrier had been removed. 1 μL of the resulting aqueous solution was analyzed using a gas chromatograph (Shimadzu, GC-2030) and the area value of methyl ethyl ketone was recorded. An autosampler (Shimadzu, AOC-30i) was used to inject the sample into the gas chromatograph. Using the recorded area value of methyl ethyl ketone and the calibration curve, the methyl ethyl ketone concentration after the capture test was calculated. Furthermore, the methyl ethyl ketone capture rate [%] was calculated from the following formula.

[0070] Methyl ethyl ketone capture rate [%] = [(initial concentration of methyl ethyl ketone - concentration of methyl ethyl ketone after capture test) ÷ initial concentration of methyl ethyl ketone] × 100.

[0071] <Cyclohexanone capture test> Cyclohexanone was dissolved in water:N-methyl-2-pyrrolidone = 1:1 to obtain a 0.5% cyclohexanone solution. 1.0 g of the ketone scavenger and 10 g of a 0.5 wt% cyclohexanone solution were mixed and stirred with a stirrer for 1 hour. The suspension was then passed through a syringe filter (Advantec, DISMIC13HP) with a mesh size of 0.45 μm to obtain a solution from which the aminooxy group-supported carrier had been removed. 1 μL of the obtained solution was analyzed using a gas chromatograph (Shimadzu, GC-2030) and the area value of cyclohexanone was recorded. An autosampler (Shimadzu, AOC-30i) was used to inject the sample into the gas chromatograph. Using the recorded area value of cyclohexanone and the calibration curve, the cyclohexanone concentration after the capture test was calculated. Furthermore, the cyclohexanone capture rate [%] was calculated from the following formula.

[0072] Cyclohexanone capture rate [%] = [(initial cyclohexanone concentration - cyclohexanone concentration after capture test) ÷ initial cyclohexanone concentration] × 100.

[0073] Synthesis Example 1 A mixture of 19.94 g of silica gel (NIPGEL CX-400, manufactured by Tosoh Silica) having an average particle size of 4 μm and 173.4 g of toluene was treated under a nitrogen gas flow with a solution of the following formula (1a):

[0074] [ka]

[0075] A mixture of 8.08 g of a silane coupling agent represented by the formula (I) and 43.35 g of toluene was added dropwise and stirred at 25°C for 120 hours. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain a carrier carrying an aminooxyalkyl group by chemical bonding (hereinafter referred to as "aminooxy group-carrying carrier"). Elemental analysis of the resulting aminooxy group-carrying carrier revealed that the aminooxyalkyl group was contained in an amount of 1.5 mmol / g per unit mass of the aminooxy group-carrying carrier.

[0076] Example 1 An acetone trapping test was carried out using the aminooxy group-supported carrier obtained in Synthesis Example 1. The results are shown in Table 1.

[0077] As is clear from Table 1, the ketone scavenger of the present invention exhibited higher ketone scavenging performance than existing scavengers.

[0078] [Table 1]

[0079] Comparative Example 1 An acetone trapping test was carried out using silica gel (NIPGEL CX-400, manufactured by Tosoh Silica Co., Ltd.). The results are shown in Table 1.

[0080] Comparative Example 2 Acetone trapping tests were carried out using a commercially available inorganic aldehyde trapping agent (Kesmon NS750, manufactured by Toagosei Co., Ltd.). The results are shown in Table 1.

[0081] Example 2 When a methyl ethyl ketone capture test was carried out using the aminooxy group-supported carrier obtained in Synthesis Example 1, the MEK capture rate was 97%.

[0082] Example 3 When a cyclohexanone capture test was carried out using the aminooxy group-supported carrier obtained in Synthesis Example 1, the cyclohexanone capture rate was 99%.

Claims

1. A ketone scavenger comprising a carrier having an aminooxyalkyl group supported thereon by chemical bonding.

2. 2. The ketone scavenger according to claim 1, wherein the support having an aminooxyalkyl group supported thereon by a chemical bond is a support having any structure represented by the following general formula (2): 【Chemistry 1】 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, multiple Rs may be the same or different. When m is 0, multiple Xs may be the same or different.)

3. 3. The ketone scavenger according to claim 2, wherein R is a methyl group, and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

4. The ketone scavenger of claim 2 , wherein n is 3.

5. The ketone scavenger according to claim 1, wherein the carrier carrying an aminooxyalkyl group by chemical bonding is a reaction product between a compound represented by the following general formula (1) and an inorganic carrier or a polymer carrier having a hydroxyl group on the surface. 【Chemistry 2】 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2, and n represents an integer of 1 to 12. When m is 0 or 1, multiple Xs may be the same or different. When m is 2, multiple Rs may be the same or different.)

6. 6. The ketone scavenger according to claim 5, wherein R is a methyl group, and X is at least one selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

7. The ketone scavenger of claim 5 , wherein n is 3.

8. 8. The ketone scavenger according to claim 1, wherein the carrier is at least one selected from the group consisting of silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, and hydroxyapatite.

9. The ketone scavenger according to any one of claims 1 to 7, wherein the carrier is silica gel.

10. A method for removing a ketone, comprising contacting the ketone with the ketone scavenger according to any one of claims 1 to 9.

11. A ketone-trapping structure having a substrate having the ketone scavenger according to any one of claims 1 to 9 attached to its surface.

12. The ketone-trapping structure according to claim 11, wherein the substrate is at least one selected from the group consisting of fibers, sheets, wallpaper, sponges, beads, wood, plywood, and gypsum boards.

13. A method for removing a ketone, comprising contacting the ketone-trapping structure according to claim 11 or 12 with the ketone.

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