JP3612588B2 - Method for measuring acetaldehyde - Google Patents
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- JP3612588B2 JP3612588B2 JP2000228332A JP2000228332A JP3612588B2 JP 3612588 B2 JP3612588 B2 JP 3612588B2 JP 2000228332 A JP2000228332 A JP 2000228332A JP 2000228332 A JP2000228332 A JP 2000228332A JP 3612588 B2 JP3612588 B2 JP 3612588B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、測定雰囲気中の他物質の影響を受けることなく、かつ温度、湿度の影響を補償し、検出対象物質であるアセトアルデヒドだけを、簡便迅速に、かつ連続的に測定することのできるアセトアルデヒドの測定方法である。
【０００２】
【従来の技術】
従来、気体中及び溶液中のアセトアルデヒドの高感度分析には、主にクロマトグラフ法が、また現場での作業環境の監視等には、より簡便な検知管法も使われている。クロマトグラフ法でのアセトアルデヒド物質の分析は、操作が煩雑で時間を要するため、熟練した技術者が行ってきた。一方、現場で実施可能な簡易検出法としては、発色試薬の呈色反応を利用した検知管法が用いられてきたが、干渉物質の影響を受けやすく、また変色を測定者が目視する際に誤差を生じやすい。さらに、気体中あるいは溶液中の測定には、それぞれ専用の測定機器をそろえる必要があった。また、公知既存の二分子膜を利用した水晶振動子による測定法も、対象ガスだけを測定することは難しく、そのガスの物理化学的特性の似たものまでも測定してしまうという問題があった。さらに、温度、湿度の影響を受けやすく、その補償をおこなった測定はなかった。
近年、物理化学的特性や分子構造の似たものを分離・吸着する素材として、分離・吸着したい分子の形状鋳型をもつ物質が報告されている。これは目的の物質共存下でモノマーと架橋剤をラジカル重合することにより目的の物質の形状を写し取った鋳型をもつ重合膜を形成させるものであるが、クロマトグラフ用担体として用いるのが一般的であった。
【０００３】
【発明が解決しようとする課題】
そこで本発明は、アセトアルデヒドを検出対象物質とし、この検出対象物質の形状の鋳型を有する鋳型重合膜を測定用素子とし、検出対象物質の形状の鋳型をもたない重合膜を参照用素子として用いることにより、気相中および液相中で、温度、湿度の影響を補償してアセトアルデヒドを高精度で測定する方法を提供することをその課題とする。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに到った。
即ち、本発明によれば、気相中又は液相中のアセトアルデヒドを測定する方法において、アセトアルデヒドの形状の鋳型を有する鋳型重合膜からなる測定用素子と、アセトアルデヒドの形状の鋳型を持たない以外は前記鋳型重合膜と実質的に同じ組成の非鋳型重合膜からなる参照用素子との組合わせをアセトアルデヒド測定手段として用いることからなり、該重合膜はメタクリル酸アルキルエステルとジビニル化合物とを、該メタクリル酸アルキルエステル１モル当り、該ジビニル化合物１〜１２モルの割合でビニル重合させて形成した重合膜であることを特徴とするアセトアルデヒドの測定方法が提供される。
【０００５】
【発明の実施の形態】
本発明においては、液相中又は気相中の検出対象物質としてのアセトアルデヒドを測定するための手段として、アセトアルデヒドの形状の鋳型を有する鋳型重合膜からなる測定用素子と、アセトアルデヒドの形状の鋳型の形状を持たない以外は前記鋳型重合膜と実質的に同じ組成の重合膜からなる参照用素子との組合わせを用いる。
前記鋳型重合膜は、アセトアルデヒドの分子形状に対応する鋳型を有する不溶性重合膜からなる。この鋳型重合膜を製造するには、ビニルモノマーとその架橋剤を含むモノマー混合溶液を作り、この溶液にアセトアルデヒドを溶解させ、更に重合開始剤を加え、これを液膜状に成形し、加熱重合させて不溶性重合膜とする。次に、この重合膜を水中で繰り返し洗浄して、アセトアルデヒドを溶出除去する。このようにして得られる重合膜は、その表面にアセトアルデヒドの形状の鋳型を有するものである。
一方、前記アセトアルデヒドの形状の鋳型を持たない以外は、実質的に同じ組成の非鋳型重合膜は、前記不溶性重合膜の製造方法において、アセトアルデヒドをモノマー混合溶液に溶解させない以外は同様にして製造することができる。
【０００６】
前記ビニルモノマーとしては、メタクリル酸メチル等のメタクリル酸アルキルエステルが用いられる。この場合、そのアルキル基としては、炭素数１〜６、好ましくは１〜３のアルキル基が用いられる。
前記架橋剤としては、２つのビニル基を持つ従来公知の各種ジビニル化合物が用いられる。このようなジビニル化合物としては、エチレングリコールジメタクリレートやジビニルベンゼン等が用いられる。このジビニル化合物としては、前記ビニル化合物と同族の化合物を用いるのが好ましい。架橋剤の使用割合は、ビニルモノマー１モル当り、１〜１２モル、好ましくは１〜２モルの割合である。
【０００７】
前記重合開始剤としては、ビニル重合に用いられている慣用のもの、通常、過酸化ラウロイル、過酸化ベンゾイル、クメンヒドロパーオキサイド等の有機過酸化物や、２，２−アゾビスイソブチロニトリル等のアゾ化合物が用いられる。この重合開始剤の使用割合は、ビニルモノマー１００重量部当り、通常、５〜３０重量部、好ましくは８〜２０重量部の割合である。
前記アセトアルデヒド使用量は、ビニルモノマー１００重量部当り、４〜４０重量部、好ましくは５〜１０重量部の割合である。
【０００８】
本発明の鋳型重合膜の製造においては、前記各成分を含む混合溶液を膜状体に保持して重合処理するが、この場合、重合溶媒を用いることができる。このような重合溶媒としては、蒸発除去の容易なもの、例えば、沸点５０〜１１０℃のもの、好ましくはクロロホルムが用いられる。
【０００９】
本発明で用いる好ましい鋳型及び非鋳型の重合膜は、メタクリル酸メチルとエチレングリコールジメタクリレートとからなり、該エチレングリコールジメタクリレートの割合が、メタクリル酸メチル１モル当り、０．５〜１２モル、好ましくは１〜２モルの割合であるモノマー混合物の重合体からなる不溶性重合膜である。
【００１０】
本発明の鋳型及び非鋳型の重合膜（以下、単に重合膜とも言う）は、それ単独で素子として用いることができるが、通常は、支持体上に付着支持させて用いられる。重合膜を単独で用いる場合、その厚さは１〜１００μｍ、好ましくは１０〜３０μｍである。その形状は特に制約されず、円形状、多角形状等の任意の形状であることができる。その大きさは、その測定雰囲気等に応じて適宜選定される。重合膜を支持体上に付着支持させて用いる場合、その重合膜の厚さは、０．０１〜１０μｍ、好ましくは０．０１〜０．１μｍである。支持体としては、プラスチック、ガラス、セラミックス、金属等の各種の固体から形成されるものが用いられる。本発明では、基体の形状は、特に制約されず、板体状、球体状、ペレット状、円柱状、中空体状、ハニカム体状等の各種の形状であることができる。その大きさは、測定雰囲気等に応じて適宜選定される。
【００１１】
本発明による鋳型重合膜は液相又は気相中に含まれるアセトアルデヒドのみを選択的に捕捉し、それ自体で又は基体に付着支持させた状態でアセトアルデヒド測定用素子として利用することができる。そして、この素子に捕捉されたアセトアルデヒド量を測定することにより、その液相又は気相中のアセトアルデヒド濃度を知ることができ、また、その測定を連続的に行うことにより、その濃度変化を知ることができる。鋳型重合膜に捕捉されたアセトアルデヒドの質量は、アセトアルデヒドを定量するための従来公知の物理的方法や化学的方法により測定することができる。
【００１２】
本発明においては、前記重合膜は、例えば、水晶振動子表面の少なくとも一部、例えば、片面又は両面に付着支持させることが好ましい。
このような重合膜を表面に有する水晶振動子は、その重合膜がアセトアルデヒドを捕捉したときに、その捕捉したアセトアルデヒドの質量に応じてその振動周波数を変化させるという特性を有する。従って、その重合膜を有する水晶振動子をアセトアルデヒド測定用素子として用い、その振動周波数を出力信号として測定することにより、気体中や液体中のアセトアルデヒド濃度及びその変化を連続的に測定することができる。この場合、アセトアルデヒドの形状の鋳型を有しない非鋳型重合膜を用いた以外は同様にして作製した実質的に同一組成の重合膜を表面に有する水晶振動子を参照用素子として同様に用いることにより、測定雰囲気中の温度や湿度等の影響を補償して、簡便迅速にアセトアルデヒドのみの濃度及び濃度変化を測定することができる。
なお、前記で用いる測定用素子に用いる水晶振動子及び参照用素子に用いる水晶振動子としては、好ましくは実質的に同一特性を有するものを用いる。
【００１３】
【実施例】
次に本発明を実施例により更に詳細に説明する。
【００１４】
実施例１
ビニル基を持ったモノマー、すなわちメタクリル酸メチル０．５ｍｌ、架橋剤、すなわちエチレングリコールジメタクリレート１０ｍｌ、及びクロロホルム１ｍｌを混合し、モノマー混合溶液を調製する。このモノマー混合溶液にアセトアルデヒド０．２ｍｌを溶解し、さらに重合開始剤として過酸化ラウロイル５０ｍｇを加えて、水晶振動子上に一定量を滴下した。これをガラスチューブオーブン中にて、９０℃で５時間加熱した。重合反応後、純水中で５回以上洗浄してアセトアルデヒドを前記複合体から溶出除去した。こうして水晶振動子を支持体とし、その表面にアセトアルデヒドの形状の鋳型を有する重合体膜で被覆された測定用素子Ａを得る。
次に、アセトアルデヒドを用いないこと以外は同様の操作を行い、アセトアルデヒドの形状の鋳型をもたない重合体膜で被覆された参照用素子Ｂを得る。
そして、作製した前記測定素子Ａを用いて、アセトアルデヒドの濃度検出・識別能力試験を行った。すなわち、濃度０．２ｍｌ／１０ｍｌのアセトアルデヒドとアセトンをそれぞれ鋳型重合膜を被覆した水晶振動子を設置した体積２０ｍｌのリン酸緩衝液を入れたセル中に滴下し、一定温度で自然拡散させた際の水晶振動子の周波数変化量から、アセトアルデヒドが鋳型重合膜に吸着した量を求めた。ここで調製した測定用素子Ａは、アセトアルデヒドに対する鋳型を持っており、アセトアルデヒドを選択的に吸着するが、その測定精度を高めるには、アセトアルデヒド以外の物質の影響や温度の影響を除外する必要がある。
この場合の測定用素子Ａの周波数変化量は、アセトアルデヒドと温度の影響を受けた出力となっており、そこから、アセトアルデヒド形状の鋳型をもたない重合体膜で被覆された参照素子Ｂにおけるアセトアルデヒドの影響は受けずに温度の影響のみを受けた状態の周波数変化量を差し引くことによって、鋳型に適合した吸着物質だけの吸着量を求めることができる。それぞれの溶液の添加量と周波数変化量の関係を図１に示す。この図から、分子構造が似たものを添加しても、その影響は現れずアセトアルデヒドの濃度だけを検知することができることがわかる。
【００１５】
実施例２
ビニル基を持ったモノマー、すなわちメタクリル酸メチル０．０５ｍｌ、架橋剤、すなわちエチレングリコールジメタクリレート１．３７ｍｌ、及びクロロホルム２．５ｍｌを混合し、モノマー混合溶液を調製する。このモノマー混合溶液にアセトアルデヒド０．０１ｍ１を溶解し、さらに重合開始剤として過酸化ラウロイル１０ｍｇを加えて、水晶振動子上に一定量を滴下する、これに１．０ｋＷ高出力高圧水銀灯を光源とする紫外線を１０分間照射後、一晩放置する。重合反応後、純水中で５回以上洗浄してアセトアルデヒドを前記複合体から溶出除去する。この方法によって水晶振動子を支持体とし、その表面にアセトアルデヒドの形状の鋳型を有する重合体膜からなる測定用素子Ａ−２を得る。
次に、アセトアルデヒドを用いないこと以外は同様の操作を行い、アセトアルデヒドの形状の鋳型をもたない重合体膜で被覆された参照用素子Ｂ−２を得る。
そして、作製した前記測定素子Ｂ−２を用いて、ガス濃度検出識別能力試験を行った。すなわち、０．１ｍｌのアセトアルデヒド、アセトン、クロロホルム、トリクロロエチレンをそれぞれ流量２００ｍｌ／ｍｉｎで、合成空気気流中に注入一定温度で自然気化させたものを、水晶振動子を設置したセル中に流したときの水晶振動子測定用素子Ａ−２の周波数変化量から、アセトアルデヒドの形状の鋳型を有する重合膜に吸着したアセトアルデヒド量を求めた。
ここで調製した素子Ａ−２は、アセトアルデヒドに対する鋳型を持っており、アセトアルデヒドを選択的に吸着するが、その測定精度を高めるには、アセトアルデヒド以外の物質の影響や温度、湿度の影響を除外する必要がある。
この場合の測定用素子Ａ−２の周波数変化量は、アセトアルデヒドとアセトアルデヒド以外の物質の影響や温度、湿度の影響をうけた出力となっており、そこから、アセトアルデヒド形状の鋳型をもたない重合体膜で被覆された参照素子Ｂ−２におけるアセトアルテヒドの影響は受けずに、アセトアルデヒド以外の物質の影響や温度、湿度の影響のみを受けた状態の周波数変化量を差し引くことによって、アセトアルデヒドだけの吸着量を求めることが可能となる。
【００１６】
【発明の効果】
本発明の方法によれば、気相中及び液相中のアセトアルデヒドの濃度及び濃度変化を連続的に測定することができる。
本発明では、特に、アセトアルデヒドの形状の鋳型重合膜を表面に有する水晶発振子を測定用素子として用いるとともに、アセトアルデヒドの形状の鋳型を有しない以外は前記鋳型重合膜と実質的に同じ組成の非鋳型重合膜を表面に有する水晶発振子を参照用素子として用いることにより、温度や湿度等の影響を補償してアセトアルデヒド濃度を０．１ｐｐｍ程度の高感度で測定することができる。
本発明は、アセトアルデヒド分析における省力化、分析精度の向上及び分析コストの低減等に大きく寄与するものである。
【図面の簡単な説明】
【図１】溶液中でのアセトアルデヒド、アセトン添加量に対する測定用素子と参照用素予の周波数変化量の差である。[0001]
BACKGROUND OF THE INVENTION
The present invention is not affected by other substances in the measurement atmosphere, compensates for the influence of temperature and humidity, and can measure only acetaldehyde as a detection target substance simply and quickly and continuously. This is a measurement method.
[0002]
[Prior art]
Conventionally, chromatographic methods are mainly used for high-sensitivity analysis of acetaldehyde in gases and solutions, and simpler detection tube methods are used for monitoring the working environment in the field. The analysis of the acetaldehyde substance by the chromatographic method has been performed by a skilled engineer because the operation is complicated and time-consuming. On the other hand, as a simple detection method that can be carried out in the field, a detector tube method using a color reaction of a coloring reagent has been used, but it is easily affected by interfering substances, and when a measurer visually observes discoloration. Prone to errors. Furthermore, for measurement in gas or solution, it was necessary to prepare dedicated measuring instruments. In addition, it is difficult to measure only a target gas using a known quartz crystal resonator method using a bilayer film, and it is difficult to measure even a gas having similar physicochemical characteristics. It was. Furthermore, it was easily affected by temperature and humidity, and there was no measurement that compensated for it.
In recent years, substances having a shape template of a molecule to be separated / adsorbed have been reported as materials for separating / adsorbing materials having similar physicochemical properties and molecular structures. In this method, a polymer film with a template that captures the shape of the target substance is formed by radical polymerization of the monomer and the crosslinking agent in the presence of the target substance, but it is generally used as a chromatographic carrier. there were.
[0003]
[Problems to be solved by the invention]
Therefore, the present invention uses acetaldehyde as a detection target substance, a template polymerization film having a template in the shape of this detection target substance as a measuring element, and a polymer film having no template in the shape of the detection target substance as a reference element. Accordingly, an object of the present invention is to provide a method for measuring acetaldehyde with high accuracy by compensating for the influence of temperature and humidity in a gas phase and a liquid phase.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, according to the present invention, in the method for measuring acetaldehyde in the gas phase or in the liquid phase, a measurement element comprising a template polymerized film having a template in the form of acetaldehyde and no template in the form of acetaldehyde are provided. The combination of the template polymerized film and a reference element comprising a non-template polymerized film having substantially the same composition is used as an acetaldehyde measuring means. The polymerized film comprises an alkyl methacrylate and a divinyl compound, There is provided a method for measuring acetaldehyde, which is a polymer film formed by vinyl polymerization at a ratio of 1 to 12 moles of the divinyl compound per mole of acid alkyl ester .
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, as a means for measuring acetaldehyde as a substance to be detected in a liquid phase or gas phase, a measuring element comprising a template polymerized film having a template in the form of acetaldehyde and a template in the form of acetaldehyde are used. A combination with a reference element made of a polymer film having substantially the same composition as the template polymer film except that it does not have a shape is used.
The template polymer film is an insoluble polymer film having a template corresponding to the molecular shape of acetaldehyde. In order to produce this template polymerized film, a monomer mixed solution containing a vinyl monomer and its crosslinking agent is prepared, acetaldehyde is dissolved in this solution, a polymerization initiator is further added, this is formed into a liquid film, and heat polymerization is performed. To form an insoluble polymer film. Next, this polymerized membrane is repeatedly washed in water to elute and remove acetaldehyde. The polymer film thus obtained has a template in the form of acetaldehyde on its surface.
On the other hand, a non-template polymerized membrane having substantially the same composition except that it does not have a template in the form of acetaldehyde is produced in the same manner as in the method for producing an insoluble polymer membrane except that acetaldehyde is not dissolved in a monomer mixed solution. be able to.
[0006]
Examples of the vinyl monomer, a methacrylic acid alkyl esters of methyl main methacrylic acid or the like is used. In this case, as the alkyl group, an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms is used.
As the crosslinking agent, various conventionally known divinyl compounds having two vinyl groups are used. As such a divinyl compound, ethylene glycol dimethacrylate, divinylbenzene, or the like is used. As this divinyl compound, it is preferable to use a compound of the same family as the vinyl compound. The ratio of the crosslinking agent used is 1 to 12 moles, preferably 1 to 2 moles per mole of vinyl monomer.
[0007]
Examples of the polymerization initiator include those commonly used for vinyl polymerization, usually organic peroxides such as lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, and 2,2-azobisisobutyronitrile. An azo compound such as The ratio of the polymerization initiator used is usually 5 to 30 parts by weight, preferably 8 to 20 parts by weight per 100 parts by weight of the vinyl monomer.
The amount of the acetaldehyde used is 4 to 40 parts by weight, preferably 5 to 10 parts by weight per 100 parts by weight of the vinyl monomer.
[0008]
In the production of the template polymerized film of the present invention, the mixed solution containing the above components is held in a film-like body and polymerized, and in this case, a polymerization solvent can be used. As such a polymerization solvent, one that can be easily removed by evaporation, for example, one having a boiling point of 50 to 110 ° C., preferably chloroform, is used.
[0009]
A preferred template and non-template polymerized film used in the present invention comprises methyl methacrylate and ethylene glycol dimethacrylate, and the ratio of the ethylene glycol dimethacrylate is preferably 0.5 to 12 moles per mole of methyl methacrylate. Is an insoluble polymer film made of a polymer of a monomer mixture having a ratio of 1 to 2 mol.
[0010]
The template and non-template polymerized film of the present invention (hereinafter also simply referred to as polymerized film) can be used alone as an element, but is usually used while being adhered and supported on a support. When the polymer film is used alone, the thickness is 1 to 100 μm, preferably 10 to 30 μm. The shape is not particularly limited, and can be any shape such as a circular shape or a polygonal shape. The size is appropriately selected according to the measurement atmosphere and the like. When the polymer film is used while being adhered and supported on a support, the thickness of the polymer film is 0.01 to 10 μm, preferably 0.01 to 0.1 μm. As the support, those formed from various solids such as plastic, glass, ceramics, and metal are used. In the present invention, the shape of the substrate is not particularly limited, and may be various shapes such as a plate shape, a sphere shape, a pellet shape, a columnar shape, a hollow shape, and a honeycomb shape. The size is appropriately selected according to the measurement atmosphere and the like.
[0011]
The template polymerized film according to the present invention can be used as an element for measuring acetaldehyde by selectively capturing only acetaldehyde contained in a liquid phase or a gas phase and adhering to and supporting the acetaldehyde on a substrate. And by measuring the amount of acetaldehyde trapped in this element, you can know the acetaldehyde concentration in the liquid phase or gas phase, and know the change in concentration by continuously measuring it. Can do. The mass of acetaldehyde trapped on the template polymerized membrane can be measured by a conventionally known physical method or chemical method for quantifying acetaldehyde.
[0012]
In the present invention, it is preferable that the polymer film is attached and supported on at least a part of the surface of the crystal unit, for example, one side or both sides.
The crystal resonator having such a polymer film on the surface has a characteristic that when the polymer film captures acetaldehyde, the vibration frequency is changed according to the mass of the trapped acetaldehyde. Therefore, the acetaldehyde concentration in gas or liquid and its change can be continuously measured by using the crystal resonator having the polymerized film as an element for measuring acetaldehyde and measuring the vibration frequency as an output signal. . In this case, a crystal resonator having a polymer film with substantially the same composition formed on the surface in the same manner except that a non-template polymer film that does not have a template in the form of acetaldehyde is used as a reference element. The concentration and concentration change of only acetaldehyde can be measured simply and quickly by compensating the influence of temperature, humidity, etc. in the measurement atmosphere.
Note that as the crystal resonator used for the measurement element and the crystal resonator used for the reference element, those having substantially the same characteristics are preferably used.
[0013]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0014]
Example 1
A monomer having a vinyl group, that is, 0.5 ml of methyl methacrylate, a cross-linking agent, that is, 10 ml of ethylene glycol dimethacrylate, and 1 ml of chloroform are mixed to prepare a monomer mixed solution. In this monomer mixed solution, 0.2 ml of acetaldehyde was dissolved, and 50 mg of lauroyl peroxide was further added as a polymerization initiator, and a predetermined amount was dropped onto the crystal resonator. This was heated in a glass tube oven at 90 ° C. for 5 hours. After the polymerization reaction, the acetaldehyde was eluted and removed from the complex by washing 5 times or more in pure water. In this way, a measuring element A is obtained in which the quartz resonator is used as a support and the surface thereof is coated with a polymer film having a template in the shape of acetaldehyde.
Next, the same operation is performed except that acetaldehyde is not used, and a reference element B covered with a polymer film having no template in the form of acetaldehyde is obtained.
And using the produced said measuring element A, the density | concentration detection and discrimination capability test of the acetaldehyde was done. That is, when acetaldehyde and acetone having a concentration of 0.2 ml / 10 ml were dropped into a cell containing a 20 ml phosphate buffer solution with a quartz resonator coated with a template polymerized film and allowed to spontaneously diffuse at a constant temperature. The amount of acetaldehyde adsorbed on the template polymer film was determined from the amount of change in the frequency of the quartz crystal. The measurement element A prepared here has a template for acetaldehyde and selectively adsorbs acetaldehyde. However, in order to increase the measurement accuracy, it is necessary to exclude the influence of substances other than acetaldehyde and the influence of temperature. is there.
The frequency change amount of the measuring element A in this case is an output affected by acetaldehyde and temperature, and from this, the acetaldehyde in the reference element B covered with the polymer film having no acetaldehyde-shaped template is obtained. By subtracting the amount of frequency change in the state of being affected only by the temperature without being affected by the above, it is possible to obtain the amount of adsorption of only the adsorbing material suitable for the template. The relationship between the amount of each solution added and the amount of frequency change is shown in FIG. From this figure, it can be seen that even if a substance having a similar molecular structure is added, the effect does not appear and only the concentration of acetaldehyde can be detected.
[0015]
Example 2
A monomer having a vinyl group, ie, 0.05 ml of methyl methacrylate, a crosslinking agent, ie, 1.37 ml of ethylene glycol dimethacrylate, and 2.5 ml of chloroform are mixed to prepare a monomer mixed solution. In this monomer mixed solution, 0.01 ml of acetaldehyde is dissolved, 10 mg of lauroyl peroxide is further added as a polymerization initiator, and a predetermined amount is dropped on a crystal resonator. A 1.0 kW high-power high-pressure mercury lamp is used as a light source. After 10 minutes of UV irradiation, leave overnight. After the polymerization reaction, the acetaldehyde is eluted and removed from the complex by washing 5 times or more in pure water. By this method, a measuring element A-2 made of a polymer film having a quartz resonator as a support and having a template in the shape of acetaldehyde on its surface is obtained.
Next, a similar operation is performed except that acetaldehyde is not used, and a reference element B-2 covered with a polymer film having no template in the form of acetaldehyde is obtained.
And the gas concentration detection discriminating ability test was done using the produced said measuring element B-2. That is, when 0.1 ml of acetaldehyde, acetone, chloroform, and trichlorethylene were each injected into a synthetic air stream at a flow rate of 200 ml / min and spontaneously vaporized at a constant temperature, they were passed through a cell in which a crystal unit was installed. The amount of acetaldehyde adsorbed on the polymer film having the acetaldehyde-shaped template was determined from the amount of change in the frequency of the crystal resonator measuring element A-2.
The element A-2 prepared here has a template for acetaldehyde and selectively adsorbs acetaldehyde, but in order to increase the measurement accuracy, the influence of substances other than acetaldehyde and the influence of temperature and humidity are excluded. There is a need.
The frequency change amount of the measuring element A-2 in this case is an output that is affected by the effects of acetaldehyde and substances other than acetaldehyde, and the influence of temperature and humidity. By subtracting the amount of frequency change in the state affected only by the influence of substances other than acetaldehyde and the influence of temperature and humidity without being affected by acetaldehyde in the reference element B-2 covered with the combined film, only acetaldehyde It is possible to determine the amount of adsorption.
[0016]
【The invention's effect】
According to the method of the present invention, the concentration and concentration change of acetaldehyde in the gas phase and the liquid phase can be continuously measured.
In the present invention, in particular, a crystal oscillator having a template polymer film in the form of acetaldehyde on the surface is used as a measuring element, and a non-crystal having a composition substantially the same as that of the template polymer film except that it does not have a template in the form of acetaldehyde. By using a crystal oscillator having a template polymer film on the surface as a reference element, it is possible to measure the acetaldehyde concentration with a high sensitivity of about 0.1 ppm by compensating for the influence of temperature, humidity and the like.
The present invention greatly contributes to labor saving in acetaldehyde analysis, improvement of analysis accuracy, reduction of analysis cost, and the like.
[Brief description of the drawings]
FIG. 1 is a difference in frequency change between a measuring element and a reference material with respect to the amounts of acetaldehyde and acetone added in a solution.
Claims (2)
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| JP2000228332A JP3612588B2 (en) | 2000-07-28 | 2000-07-28 | Method for measuring acetaldehyde |
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| JP2000228332A JP3612588B2 (en) | 2000-07-28 | 2000-07-28 | Method for measuring acetaldehyde |
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| JP3729181B2 (en) | 2003-03-14 | 2005-12-21 | セイコーエプソン株式会社 | Measuring method, measuring signal output circuit and measuring apparatus |
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