JP7215236B2 - Amine scavenger - Google Patents

Description

The present invention relates to a trapping agent for amines.

Polyurethane resins are produced using polyol and polyisocyanate as main raw materials, and are used in various fields due to their excellent properties. Among them, in the automobile field, foamed polyurethane called foam is used for cushion materials inside seats, headrests, armrests, steering wheels, and other automobile interior materials, and is in great demand.

Amines function as catalysts in the skeleton formation (resinification) of polyurethane foams and in the foaming/expansion reaction (foaming), and are essential substances for foam production. However, amine catalysts gradually volatilize from polyurethane foam after production, causing problems such as odor, eye irritation, discoloration and cloudiness of interior materials, and fogging of glass. is required.

As a method for removing amines, a method of washing with hydrochloric acid or the like, a method of blowing in hydrochloric acid gas for neutralization, and the like have been disclosed (see, for example, Patent Documents 1 and 2).

However, the methods described in these patent documents have a problem that removal of amine hydrochloride is insufficient.

JP-A-55-86814 JP-A-57-80438

SUMMARY OF THE INVENTION The present invention has been made in view of the background art described above, and an object of the present invention is to provide an amine scavenger that rapidly and continuously captures amines.

The present inventors have made intensive studies to solve the above problems, and found that an amine scavenger containing a specific carboxyl group-containing O-substituted hydroxylamine or a chemically acceptable salt thereof rapidly decomposes amines. The present invention was completed by discovering that it is possible to capture both effectively and continuously.

That is, the present invention has the following gists.

[1]
An amine scavenger comprising one or more carboxy group-containing O-substituted monohydroxylamines or chemically acceptable salts thereof.

[2]
The amine scavenger according to [1], which comprises one or more carboxy group-containing O-substituted monohydroxylamines represented by the following general formula (1) or chemically acceptable salts thereof.

(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. When n is an integer of 2 to 6, multiple 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 amine scavenger according to [1] or [2], characterized in that

[4]
A method for removing amines, which comprises using the amine scavenger according to any one of [1] to [3].

The amine scavenger of the present invention rapidly and persistently scavenges amines. As a result, amines harmful to the human body can be reduced, and the living environment for humans can be improved.

The amine scavenger of the present invention is characterized by containing one or more carboxy group-containing O-substituted monohydroxylamines or chemically acceptable salts thereof.

In general formula (1) above, 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; When n is an integer of 2 to 6, multiple R's 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. Furthermore, a part of the carboxyl group may be a carboxylate, but since the amine scavenger of the present invention becomes alkaline, the scavenging effect is reduced. preferably. The type of carboxylate is not particularly limited, but examples thereof include lithium salts, sodium salts, potassium salts, alkali metal salts such as cesium salts, and ammonium salts.

The amine 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 an arbitrary solvent to obtain a liquid amine scavenger. carboxy group-containing O-substituted monohydroxylamines or the above liquid amine scavengers supported on any carrier and used as solid amine scavengers, or kneaded into rubber or the like. can be done. In addition, by applying these scavengers to materials such as polyurethane foam, it is possible to suppress the release of amines from the material into the environment.

The amount of the carboxy group-containing O-substituted monohydroxylamine dissolved in the solvent when preparing the liquid amine scavenger of the present invention can be arbitrarily adjusted according to the purpose, and is not particularly limited. A range of 1 to 50% is preferred, and a range of 3 to 30% is more preferred, relative to the liquid amine scavenger of the invention.

As the carrier for supporting the carboxy group-containing O-substituted monohydroxylamines in preparing the solid amine 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 amine scavenger of the present invention is not particularly limited. Hollow fibers, membranous (e.g., flat membranes, etc.) shapes generally used as separation substrates can be used, and among these, spherical, membranous, granular, granular, or fibrous shapes can be used. is preferred. 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 amine scavenger 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 used, and a range of 1 nm to 300 nm is preferable from the viewpoint of the amine trapping rate.

The method for preparing the solid amine scavenger of the present invention is not particularly limited. A method of immobilizing by allowing the

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 carboxy group-containing O-substituted monohydroxylamine supported on the carrier can be arbitrarily adjusted depending on the purpose, and is not particularly limited, but the amount of the carboxy group-containing O-substituted monohydroxylamine is from 1 to A range of 50% by weight is preferred, and a range of 3-30% by weight is more preferred.

Objects to be captured by the amine scavenger of the present invention are not particularly limited as long as they are amines. Examples of primary amines include methylamine, ethylamine and propylamine, and secondary amines include dimethylamine, diethylamine and dipropyl. amines and piperazines, and tertiary amines include trimethylamine, triethylamine, tripropylamine, diethylenetriamine and triethylenediamine. Ammonia is also captured.

1 is a diagram showing the amount of triethylenediamine released per 1 g of polyurethane foam in Example 1 and Comparative Examples 1 and 2. FIG.

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

Example 1 (Amine scavenging test from polyurethane foam)
A polyurethane foam (length 3 cm, width 1 cm, thickness 1 cm) was coated with an aqueous solution of a scavenger containing 3% by weight of (aminooxy)acetic acid at a rate of 10 g/m ² and dried at room temperature for 24 hours. After heating this polyurethane foam in a 10 mL vial at 85° C. for 15 minutes, the gas in the vial was analyzed with an electronic olfactory system (device name: Flash GC nose HERACLES II, manufactured by Alpha Moss Japan). Triethylenediamine release was less than 0.1 μg.

Comparative example 1
As a result of carrying out in the same manner as in Example 1 except that no scavenger was used, the amount of triethylenediamine released per 1 g of polyurethane foam was 81 μg.

Comparative example 2
The procedure of Example 1 was repeated except that an aqueous solution containing 5% by weight of dihydrazide adipic acid was used as a scavenger.

The amine scavenger of the present invention rapidly and persistently scavenges amines. As a result, amines harmful to the human body can be reduced, and the living environment for humans can be improved.

Claims (4)

An amine scavenger comprising an aqueous solution containing 1 to 50% by weight of (aminooxy)acetic acid . A method for removing amines in polyurethane foam, characterized in that the amine scavenger of claim 1 is used in polyurethane foam. A solid amine scavenger comprising the amine scavenger of claim 1 supported on a substrate. 4. The solid amine scavenger of claim 3, wherein said substrate is polyurethane foam.

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