JP2006010390A - Trapping material for carbonyl compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a trapping material for a carbonyl compound for use in a sampler which is supported on the ion exchange group, which is introduced into a porous carrier comprising porous crosslinked polymer particles through a functional group becoming a spacer such as an alkyl group or an allyl group, by an ion bond, and can selectively and efficiently trap especially aldehydes or ketones to stably adsorb, concentrate and elute them under a high humidity environment. <P>SOLUTION: In the trapping material for the carbonyl compound, the porous carrier having the ion exchange group, on which a trapping material for trapping the carbonyl compound is supported, comprises porous crosslinked polymer particles. This trapping material is respresented by R<SB>1</SB>-ONH<SB>2</SB>or R<SB>2</SB>-NH-NH<SB>2</SB>(wherein R<SB>1</SB>and R<SB>2</SB>are each a derivative of a phenyl group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a sampling material for a carbonyl compound for a sampler that selectively and efficiently collects carbonyl compounds, particularly aldehydes or ketones, and that can stably adsorb, concentrate and elute even in a high humidity environment.

  When air pollution is caused by harmful chemical substances (formaldehydes, VOCs, etc.), even if it is a trace amount of ppb order, long-term exposure may cause serious problems such as chronic damage and carcinogenesis. In addition, it has been pointed out that it is related to Sick House Syndrome, which has been highlighted as a social issue in recent years, and it is listed as a substance to be measured in the Housing Quality Assurance Law, School Insurance Law, Building Standard Law, etc. With sick house syndrome, harmful chemical substances (formaldehydes, VOCs, etc.) are diffused from building materials, household goods, combustion equipment, etc., and together with the high airtightness of houses, indoor air is polluted, and residents are It is a phenomenon that causes pain in the eyes, nose, throat, nausea, dizziness, and health problems such as asthma.

  Cartridges for measuring aldehydes are commercially available or reported as methods for analyzing volatile carbonyl compounds in the atmosphere, especially formaldehyde and acetaldehyde. As carbonyl compound collectors used in aldehydes measurement cartridges, silica gel impregnated with 2,4-dinitrophenylhydrazine (DNPH), O- (4-trifluoromethoxybenzyl) hydroxylamine (TFBA) ) Is held on silica gel into which an ion exchange group is introduced (Patent Document 1). However, as described above, when supported on silica gel into which ion exchange groups have been introduced, a water film is formed on the surface of the silica gel, which is the support, at high humidity (85 to 90% or more). In some cases, a sufficient collection effect could not be obtained. In particular, TFBA is bonded to silica gel by ionic bonds, but the amino group that reacts with the carbonyl group is on the inside and the phenyl group derivative is on the outside, resulting in steric hindrance, so it reacts with carbonyl compounds in the air. There was a drawback that it was difficult to do. DNPH is supported on silica gel in the form of phosphate, but there is a disadvantage that unreacted DNPH flows out during extraction.

JP 2002-195990 A

  Under these circumstances, the present inventors used a trapping material for trapping carbonyl compounds as a functional group serving as a spacer such as an alkyl group or an allyl group on a porous carrier made of porous crosslinked polymer particles. By supporting the ion exchange groups introduced via the ionic bond with an ionic bond, a water film cannot be formed on the surface of the support even in a high humidity environment, and the carbonyl compound trap enables efficient and stable collection. Gathering was established.

  The present invention solves the problems in the conventional carbonyl compound collector, selectively and efficiently collects carbonyl compounds, particularly aldehydes or ketones, and stably adsorbs and concentrates them even in a high humidity environment. The purpose of the present invention is to provide a carbonyl compound collector for samplers that can be eluted and no excess unreacted reagent flows out during elution.

  The inventors of the present invention have introduced a trapping material for trapping a carbonyl compound into an ion exchange group introduced into a porous carrier made of porous crosslinked polymer particles through a functional group serving as a spacer such as an alkyl group or an allyl group. The present invention has been completed by finding that it can be stably collected in any environment with high humidity and other changes by supporting it with ionic bonds.

That is, the present invention relates to the following inventions.
<1> A carbonyl compound collecting material in which a collecting material for collecting a carbonyl compound is supported on a porous carrier.
<2> The carbonyl compound trapping material according to <1>, wherein the porous carrier comprises porous crosslinked polymer particles.
<3> The carbonyl compound trapping material according to <1>, wherein the porous carrier has an ion exchange group.
<4> The collector for a carbonyl compound according to <1>, wherein the collector for collecting the carbonyl compound is represented by R ₁ —ONH ₂ or R ₂ —NH—NH ₂ .
<5> The carbonyl compound trapping material according to <1>, wherein R ₁ and R ₂ are each a phenyl group derivative.
<6> The carbonyl compound according to <1>, wherein the ion exchange group of the porous carrier is bonded to the porous crosslinked polymer particle through a functional group serving as a spacer such as an alkyl group or an allyl group. Collection material.
<7> The collector for a carbonyl compound according to <1>, wherein the ion exchange group of the porous carrier is an acid group.
<8> The carbonyl compound trapping material according to <1>, wherein the acid group is a sulfone group or a phosphate group.

  In the present invention, a collector for collecting a carbonyl compound is ion-bonded to an ion exchange group introduced through a functional group serving as a spacer such as an alkyl group or an allyl group into a porous carrier made of porous crosslinked polymer particles. A sampler capable of selectively collecting aldehydes and ketones selectively and stably adsorbing, concentrating and eluting even in high humidity environments. It is to provide a carbonyl compound collector.

In the present invention, a collector for collecting a carbonyl compound is ion-bonded to an ion exchange group introduced through a functional group serving as a spacer such as an alkyl group or an allyl group into a porous carrier made of porous crosslinked polymer particles. In accordance with the present invention, there is provided a carbonyl compound collector that enables efficient and stable collection under any environment that changes such as high humidity. Provided.
Hereinafter, embodiments of the present invention will be described in detail.

The trapping material for trapping the carbonyl compound described in this patent can be represented by the structural formula R ₁ —ONH ₂ or R ₂ —NH—NH ₂ and forms an imine with the carbonyl compound in the air. For example, O- (4-trifluoromethoxybenzyl) hydroxylamine (TFBA), 2,4-dinitrophenylhydrazine (DNPH), triethanolamine, and the like can be used.

  Examples of the base gel for supporting the trapping material include a cation exchange resin, and a non-crosslinkable monomer and a crosslinkable polyvinyl monomer are used in the production method. The cation exchange resin particles preferably have an average particle diameter of an adsorbent used for passive sampling of 80 to 1000 μm, and more preferably 100 to 500 μm. If it exceeds 1000 µm, the specific surface area becomes small, and the amount of adsorption tends to decrease. On the other hand, if it is less than 80 μm, it tends to be difficult to contact the measurement chemical substance, and the amount of adsorption tends to decrease.

  Examples of the non-crosslinkable monomer include (meth) acrylate having only one vinyl group, such as (meth) acrylic acid, glycidyl (meth) acrylate, glycidyl clonate, glycidyl itaconate, Glycidyl fumarate, glycidyl malate, their halides, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, tetramethylol methanetri (meth) acrylate, vinyl Examples include cyclohexene monooxide (1,2-epoxy-4-vinylcyclohexane), epoxidized polybutadiene, 3,4-epoxycyclohexylmethyl acrylate, and the like. These may be used alone or in combination of two or more. The amount of the non-crosslinkable monomer used is preferably 60 to 90% by weight, more preferably 65 to 80% by weight. If the amount used is less than 60% by weight, the amount of exchange group introduced tends to be insufficient, and if it exceeds 90% by weight, the weather resistance tends to decrease.

  The purity of the crosslinkable polyvinyl monomer particles used in the present invention is not particularly limited, but those having a purity of 50% or more are preferably used.

Examples of the crosslinkable polyvinyl monomer used in the present invention include alkylene glycol divinyl esters such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, polyethylene glycol diacrylate, and polyethylene. Polyalkylene glycol divinyl ester such as glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, glycerin di or triacrylate, glycerin di or trimethacrylate, trimethylol propane di or triacrylate, trimethylol propane di- Or trimethacrylate, tetramethylolmethane di, tri or teto Acrylate, tetramethylol methane di, tri or tetra methacrylate, ethylene glycol diallyl ether, propylene glycol diallyl ether, polyethylene glycol diallyl ether, polypropylene glycol diallyl ether, glycerol di or triallyl ether, trimethylolpropane di or triallyl ether , Tetramethylolmethane di, tri or tetraallyl ether, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dimethacrylate Cyclopentenyl, dicyclopentenyloxyethyl methacrylate, N-vinyl-2-pyrrolidone acid, methacrylonitrile, methacrylamide, N-methylol methacrylamide, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 2-hydroxy-3-phenyl methacrylate Vinyl monomers such as oxypropyl are aromatic monomers such as styrene, methylstyrene, monovinylethylbenzene, aminostyrene, diphenylstyrene, vinylbiphenyl, vinylnaphthalene, divinylnaphthalene, diphenylethylene, vinylphenanthrene, and chloromethylstyrene. The body is mentioned.
These compounds can be used alone or in combination of two or more.

  In aqueous suspension polymerization, suspension polymerization is carried out in an aqueous medium. As this aqueous medium, water is essential and water-soluble organic solvents are used as long as they do not impair the stability of the suspension system. You may use the water which melt | dissolved.

  The aqueous suspension polymerization is carried out in the presence of a polymerization initiator. As a polymerization initiator, a peroxide radical initiator and an azo radical initiator are preferable. For example, benzoyl peroxide, 2-ethylhexyl perbenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, lauroyl peroxide. , Di-tert-butyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, 4,4,6-trimethylcyclohexanone di-tert-butyl peroxyketal, cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, cyclohexanone di-tert-butyl peroxy ketal, acetone di Peroxide radical polymerization initiators such as tert-butyl peroxyketal and diisopropyl hydroperoxide, 2,2′-azobisisobutyronite 2,2,2'-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2 '-Azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile, 2,2 Azo polymerization initiators such as' -azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane) It is done. One or more of these polymerization initiators can be used.

  The radical polymerization initiator is used in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the monomer having one vinyl group. When the amount used is less than 0.05 parts by weight, the polymerization time becomes long, and unreacted monomers remain in the polymer fine particles, which is not preferable. On the other hand, when the amount used exceeds 10 parts by weight, not only the polymerization initiator is wasted, but also heat generation control during polymerization is difficult and problems such as insufficient molecular chain length occur. The amount used is appropriately determined depending on the type of the monomer, but is preferably 0.1 to 4.0% by weight based on the total amount of monomers. The aqueous medium is preferably used 1 to 50 times by weight based on the total amount of the components (a) and (b) and the organic solvent. In this case, water is used as the aqueous medium, but water containing a water-soluble organic solvent dissolved in a range that does not impair the stability of the suspension system may be used.

  By adding an organic solvent that is insoluble or hardly soluble in water during the polymerization, the resulting crosslinked copolymer particles can be made porous. The water-insoluble or hardly soluble organic solvent used in the present invention has a solubility of 15 g or less with respect to 100 g of water at 25 ° C., for example, toluene, xylene, ethylbenzene, diethylbenzene, heptanol, isoamyl alcohol, acetic acid. Known materials such as aliphatic or aromatic esters such as ethyl, butyl acetate, dimethyl phthalate and diethyl phthalate, ethylene glycol monoethyl ether acetate, hexane, octane and decane can be used. These organic solvents are properly used depending on the type of monomer that is the base of the polymer to be obtained, and may be used alone or in admixture of two or more.

  The blending ratio of these organic solvents is 5 to 300% by weight, preferably 20 to 200% by weight, more preferably 50 to 100% by weight based on the total amount of vinyl monomers from the viewpoint of porosity. If the blending ratio is less than 5% by weight or exceeds 300% by weight, it becomes difficult to obtain desired porosity.

  The polymerization reaction is usually allowed to proceed for 5 to 10 hours in a temperature range of 60 to 90 ° C. The spherical particles having a particle diameter of 1 to 200 μm, preferably 3 to 25 μm, obtained as described above are classified and used as necessary.

With respect to the spherical particles obtained above, the exchange group is preferably a strongly acidic group, and more preferably a sulfone group or a phosphate group is introduced. Examples of the introduction method include a method of coating the carrier with a sulfone group-containing polymer, a method of chemically bonding to the carrier, and the like. From the viewpoint of durability, a method of chemically bonding to the carrier is preferable. Examples of the method of chemically bonding with the carrier include a method of synthesizing a carrier having an epoxy group according to the above method, reacting a sulfone group or a phosphate group, and introducing a sulfone group or a phosphate group.
For example, when introducing a phosphoric acid group, porous crosslinked polymer particles are reacted with phosphoric acid. In this reaction, 15 parts by weight or more of an aqueous phosphoric acid solution is used with respect to 1 part by weight of porous crosslinked polymer particles having a glycidyl group. The reaction solvent is not particularly limited as long as it dissolves phosphoric acid and does not introduce an anion exchange group by reacting with a glycidyl group. The concentration of the phosphoric acid aqueous solution is 0.01% by weight or more, preferably 1% by weight or more, and can be used in the range up to 100% by weight (concentrated phosphoric acid).

  The reaction is carried out at 30 to 200 ° C., preferably 50 to 90 ° C., for several minutes to 10 hours. When the reaction is performed under the above reaction conditions, the phosphate group introduction reaction and the hydrolysis reaction occur competitively. By adjusting the concentration of the phosphoric acid aqueous solution, this competitive reaction can be controlled, and quantitative introduction of phosphate groups can be achieved. Can be easily performed.

  The method of coating the porous crosslinked polymer particles is not particularly limited, but a method of dissolving the adsorbent in an organic solvent or water and impregnating the porous crosslinked polymer particles while ionic bonding is preferable. The collecting material for collecting an excessive amount of the carbonyl compound can be easily removed with an organic solvent such as acetonitrile.

  Hereinafter, the present invention will be described by way of examples.

Example 1
(A) Production of crosslinked polymer particles having glycidyl ester groups 130 g of vinylcyclohexene monooxide, 60 g of tetramethylolmethane methacrylate, 180 g of butyl acetate, 120 g of isoamyl alcohol and 0.7 g of azobisisobutyronitrile are added to 1000 ml of ion-exchanged water. And the pH was adjusted to 7-8 using an aqueous sodium hydride solution while stirring. Thereafter, a polymerization reaction was carried out at 70 ° C. for 6 hours. After the reaction product was cooled, the produced copolymer particles were collected by filtration and washed successively with methanol and water. Subsequently, it was air-dried for one day and further put in a vacuum dryer at 80 ° C. for 6 hours. The dried particles were classified to obtain 80 g of porous crosslinked polymer particles having a thickness of 150 μm.
(b) Phosphoric acid group introduction reaction 20 g of the porous crosslinked polymer particles obtained in (a) were placed in 300 ml of concentrated phosphoric acid and stirred well. This was heated at 60 ° C. and stirred for 3 hours to carry out the reaction. After the reaction, the mixture was cooled, and the resulting porous crosslinked polymer particles were washed with ion exchange water until neutral. Thereafter, decantation was performed 5 times using ion-exchanged water to remove fine particles.
(C) Measurement of the amount of exchange groups The porous crosslinked polymer particles obtained in (b) were placed in a vacuum dryer and dried at 80 ° C. for 6 hours, 1 g of which was packed into a column to obtain a column filler. This was washed with a 0.1 hydrochloric acid aqueous solution, and further washed with ion exchange water until the washing solution became neutral. It was then washed with 20 ml of 0.1N aqueous sodium hydroxide and the filtrate was recovered. This filtrate was titrated with a 0.1N hydrochloric acid aqueous solution, and the amount of exchange groups was determined by the following formula. As a result, it was 1.8 meq / g.
X = (20−Y) × 0.1 / Z
[Wherein, X represents the exchange group amount (meq / g), Y represents the titration amount (ml), and Z represents the column packing amount (g)]
(d) Adsorbent coating The adsorbent was coated under a nitrogen stream. In a 500 mL separable flask, 40 g of 2,4-dinitrophenylhydrazine (DNPH) dissolved in 200 mL of acetonitrile was dispersed in 80 g of the porous crosslinked polymer particles obtained in (c) with an average particle diameter of 150 μm. -The mixture was stirred for 30 minutes at a rotation speed of 200 rpm using a tar and a stirring blade. This dispersion was subjected to suction filtration using a glass filter, and then washed twice with 200 mL of acetonitrile. The filtrate was collected and dried under reduced pressure at 0.1 mPa or less for 8 hours.
100 mg of this adsorbent was washed with acetonitrile in a commercially available DSD-DNPH (manufactured by SPELCO) container and filled into a dry sample to produce an adsorption tube for passive sampling.
The adsorption tube was placed on a stand, and passive sampling of formaldehyde was performed indoors for 24 hours. After sampling, formaldehyde adsorbed on the adsorbent and derivatized with 2,4-dinitrophenylhydrazine (DNPH) was eluted with acetonitrile using a multipipette (Eppendorf) and made up to 5 ml. At this time, the time from the start of elution to the end of the constant volume (time to elute 5 ml) was measured and found to be 3.1 minutes. The eluted 2,4-dinitrophenylhydrazine (DNPH) derivative of formaldehyde was quantified by liquid chromatography.
The evaluation conditions are column: GL-OP100, eluent: acetonitrile / water = 60/40, sample size: 50 μL, flow rate: 1 ml / min detector absorbance (366 nm).

Comparative Example 1
A passive passive sampler DSD-DNPH (manufactured by SPELCO) was placed on a stand and passive sampling of formaldehyde was performed indoors for 24 hours. After sampling, formaldehyde adsorbed on the adsorbent and derivatized with 2,4-dinitrophenylhydrazine (DNPH) was eluted with acetonitrile using a multipipette (Eppendorf) and made up to 5 ml. At this time, the time from the start of elution to the end of the constant volume (time to elute 5 ml) was measured and found to be 3.0 minutes. The eluted 2,4-dinitrophenylhydrazine (DNPH) derivative of formaldehyde was quantified by liquid chromatography. Evaluation conditions used the same method as in Example 1.

Comparative Example 2
A commercially available active sampler “XposurAldehydeSampler” (Waters) was connected to a suction pump, and active sampling of formaldehyde in the room was performed at 100 ml / min for 24 hours. After sampling, formaldehyde adsorbed on the adsorbent and derivatized with 2,4-dinitrophenylhydrazine (DNPH) was eluted with acetonitrile using a multipipette (Eppendorf) and made up to 5 ml. The eluted 2,4-dinitrophenylhydrazine (DNPH) derivative of formaldehyde was quantified by liquid chromatography. As evaluation conditions, the same method as in Example 1 was used.

As a result of the measurement of the sampler installed in approximately the same place in the room adjusted to 70% humidity by the method of this example and the comparative example, and the sampler installed in approximately the same place in the room adjusted to 90% humidity. The measurement results are shown in Table 1. As a result, a decrease in the collection rate at high humidity is recognized in all cases, but it can be seen that the embodiment of the present invention is hardly affected by humidity.

Claims (8)

A collector for carbonyl compounds, in which a collector for collecting carbonyl compounds is supported on a porous carrier. 2. The carbonyl compound trapping material according to claim 1, wherein the porous carrier is composed of porous crosslinked polymer particles. 2. The carbonyl compound collector according to claim 1, wherein the porous carrier has an ion exchange group. _{2. The} collector for a carbonyl compound according to claim 1, wherein the collector for collecting the carbonyl compound is represented by R ₁ —ONH ₂ or R ₂ —NH—NH ₂ . _2. The carbonyl compound collector according to claim 1, wherein R ₁ and R ₂ are each a phenyl group derivative. 2. The trap for a carbonyl compound according to claim 1, wherein the ion exchange group of the porous carrier is bonded to the porous crosslinked polymer particle through a functional group serving as a spacer such as an alkyl group or an allyl group. Wood. 2. The collector for a carbonyl compound according to claim 1, wherein the ion exchange group of the porous carrier is an acid group. 2. The collector for a carbonyl compound according to claim 1, wherein the acid group is a sulfone group or a phosphate group.