JP4584703B2 - Sheet or polymer solid having molecular adsorption function, and production method thereof - Google Patents
Sheet or polymer solid having molecular adsorption function, and production method thereof Download PDFInfo
- Publication number
- JP4584703B2 JP4584703B2 JP2004373755A JP2004373755A JP4584703B2 JP 4584703 B2 JP4584703 B2 JP 4584703B2 JP 2004373755 A JP2004373755 A JP 2004373755A JP 2004373755 A JP2004373755 A JP 2004373755A JP 4584703 B2 JP4584703 B2 JP 4584703B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- sheet
- template molecule
- solvent
- molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、空気中および水中に存在する、内分泌攪乱物質や有害化学物質等の分子状物質を吸着除去するために用いられるシート、またはポリマー固形物に関するものである。 The present invention relates to a sheet or polymer solid used for adsorbing and removing molecular substances such as endocrine disrupting substances and harmful chemical substances present in air and water.
環境中に存在しているアルキルフェノール類やビスフェノールＡなどの分子状物質は、内分泌攪乱物質として生態系に影響をおよぼすことが知られている。これらの物質は、環境中の濃度が非常に低濃度であっても悪影響をおよぼすため、これらを問題とならないレベルまで除去するためには、これらの物質を選択的に高効率で吸着除去する材料が必要とされる。 It is known that molecular substances such as alkylphenols and bisphenol A present in the environment affect the ecosystem as endocrine disruptors. Since these substances have adverse effects even if the concentration in the environment is very low, in order to remove them to a level that does not cause a problem, materials that selectively adsorb and remove these substances with high efficiency Is needed.
近年、特定の分子を選択的に吸着する材料として、分子インプリント法を用いたインプリントポリマーが注目されており、選択的分子捕捉の例が提案されている。分子インプリント法とは、吸着対象分子をポリマー材料内に鋳型として包接させた後で、前記鋳型を除去することにより、鋳型の認識部位を形成させる方法である。 In recent years, an imprint polymer using a molecular imprint method has attracted attention as a material that selectively adsorbs specific molecules, and an example of selective molecular capture has been proposed. The molecular imprint method is a method in which a recognition site of a template is formed by removing the template after the adsorption target molecule is included in the polymer material as a template.
分子インプリント法を用いた選択的吸着材料として、特許文献１および特許文献２においては、鋳型分子とポリマーを溶媒に溶解させ、この溶液からキャスト法を用いてフィルムを形成させることにより得られるインプリントポリマー膜材料について提案している。しかし、これらポリマー膜の作製においては、ポリマー樹脂の選定段階で鋳型分子と結合可能なものが優先されるので、必ずしも後加工性や使用性に適合するものではなく、応用性、汎用性が乏しい。さらに、吸着を効率的に行うためには、微細化したり多孔化したりするなどして材料の表面積を大きくする必要があるが、微細化した場合には、使用時に材料自体が脱落や飛散するなどの問題があり、多孔化した場合には、使用のために必要な材料強度が得られなくなるという問題がある。 As a selective adsorption material using the molecular imprint method, Patent Document 1 and Patent Document 2 disclose an imprint obtained by dissolving a template molecule and a polymer in a solvent and forming a film from the solution using a casting method. We have proposed printed polymer film materials. However, in the production of these polymer films, priority is given to those capable of binding to the template molecule at the stage of selection of the polymer resin, so it is not necessarily compatible with post-processing properties and usability, and is poor in applicability and versatility. . Furthermore, in order to efficiently perform adsorption, it is necessary to increase the surface area of the material by making it finer or porous, etc., but if the material is made finer, the material itself may fall off or scatter during use. There is a problem that when the material is made porous, the material strength required for use cannot be obtained.
また、ポリマー内にある鋳型分子の認識部位は、水酸基、アミノ基、カルボキシル基などの極性基であり、このような極性基を有するポリマーを溶解させるためには、通常、アルコール、ケトンなどの比較的極性の高い溶媒を用いる必要がある。しかし、このような極性の高い溶媒を用いた場合、鋳型とポリマー間に働く水素結合やイオン結合などの相互作用が阻害されるために、ポリマー内に鋳型の認識部位がうまく形成されず、鋳型の認識能力が低下するという問題がある。
本発明が解決しようとする課題は、特定の分子状汚染物質を選択的に除去し、さらに後加工性、使用性に優れた分子吸着機能を有したシートおよびポリマー固形物を提供することである。 The problem to be solved by the present invention is to provide a sheet and a polymer solid having a molecular adsorption function that selectively removes specific molecular contaminants and is excellent in post-processability and usability. .
本発明者は、上記課題を解決するため鋭意研究を重ねた結果、鋳型分子とポリマーを溶媒に溶解させる段階を含む分子インプリント法を利用してシート面上に鋳型分子の認識部位が形成されているポリマーを担持している分子吸着機能を有するシートまたは前記ポリマーよりなるポリマー固体において、溶解されるポリマーはエチレン−酢酸ビニル共重合物（以下、単に「ポリマー」と略記することもある。）であり、該ポリマーが、鋳型分子と結合可能な官能基を有し、そして溶媒が３．０以下の比誘電率を有することで、上記課題が解決できることを見出した。ここで担持とは、ポリマーがシート面上に脱落・飛散なく強固に付着した状態を言う。
As a result of intensive studies to solve the above problems, the present inventor has formed a recognition site for a template molecule on a sheet surface using a molecular imprint method including a step of dissolving a template molecule and a polymer in a solvent. The polymer to be dissolved in the polymer solid sheet made of the polymer or the polymer adsorbing sheet carrying the polymer is an ethylene-vinyl acetate copolymer (hereinafter sometimes simply referred to as “polymer”). It has been found that the above-mentioned problems can be solved when the polymer has a functional group capable of binding to a template molecule and the solvent has a relative dielectric constant of 3.0 or less. Here, the term “support” refers to a state in which the polymer is firmly attached to the sheet surface without dropping off or scattering.
この様な構成をとることにより、本発明のシートまたはポリマー固体によれば、特定の分子を選択的に除去し、さらに後加工性、使用性に優れた、分子吸着機能を有したシートまたはポリマー固体を提供することができる。 By adopting such a configuration, according to the sheet or polymer solid of the present invention, a specific molecule is selectively removed, and further, a sheet or polymer having a molecular adsorption function that is excellent in post-processing property and usability. A solid can be provided.
以下に、本発明をさらに詳細に説明する。 The present invention is described in further detail below.
本発明における分子インプリント法は、ポリマーの組織化を利用した方法である。まず、鋳型分子と結合可能な官能基を有するポリマー樹脂と鋳型分子を溶媒に溶解させ、これらの混合溶液を調製する。次に、この溶液から溶媒を除去することでポリマー皮膜を形成させる。この段階では、鋳型分子はポリマー皮膜中にポリマー皮膜中の官能基と結合した形で存在している。こうして得られたポリマー皮膜から鋳型分子を除去することで、ポリマー皮膜中に鋳型分子の認識部位が形成される。このようにして、鋳型分子を選択的に吸着除去可能なインプリントポリマー皮膜を得ることができる。 The molecular imprinting method in the present invention is a method utilizing the organization of polymers. First, a polymer resin having a functional group capable of binding to a template molecule and the template molecule are dissolved in a solvent to prepare a mixed solution thereof. Next, a polymer film is formed by removing the solvent from the solution. At this stage, the template molecule is present in the polymer film in a form bonded to the functional group in the polymer film. By removing the template molecule from the polymer film thus obtained, a recognition site for the template molecule is formed in the polymer film. In this way, an imprinted polymer film capable of selectively adsorbing and removing template molecules can be obtained.
本発明で用いられるポリマー樹脂と鋳型分子を溶解させる溶媒には、ポリマー樹脂と鋳型分子の間の相互作用を阻害しない、極性の低い溶媒を用いる。溶媒の極性を示す指標としては、物質の電気のためやすさの指標である比誘電率があり、極性の低い溶媒ほど、その比誘電率の値は低くなる。本発明における極性の低い溶媒としては、比誘電率が３．０以下の溶媒が用いられ、例えば、ベンゼン（比誘電率：２．３）、トルエン（比誘電率：２．４）、シクロヘキサン（比誘電率：２．０）、四塩化炭素（比誘電率：２．２）などが挙げられる。このような、比誘電率が３．０以下の十分に極性の低い溶媒を用いた場合、ポリマー樹脂中の官能基と鋳型分子との間に働く水素結合などの相互作用をほとんど阻害せず、認識部位を効率よく形成することが可能となる。一方、比誘電率が３．０よりも高くなると、ポリマー樹脂中の官能基と鋳型分子との間の相互作用は阻害されていき、認識部位をうまく形成することができなくなる。 As the solvent for dissolving the polymer resin and the template molecule used in the present invention, a low polarity solvent that does not inhibit the interaction between the polymer resin and the template molecule is used. As an index indicating the polarity of the solvent, there is a relative dielectric constant which is an index of the ease of electricity of the substance, and the lower the solvent, the lower the value of the relative dielectric constant. As the low polarity solvent in the present invention, a solvent having a relative dielectric constant of 3.0 or less is used. For example, benzene (relative dielectric constant: 2.3), toluene (relative dielectric constant: 2.4), cyclohexane ( Specific dielectric constant: 2.0), carbon tetrachloride (relative dielectric constant: 2.2), and the like. When such a low-polarity solvent having a relative dielectric constant of 3.0 or less is used, it hardly inhibits the interaction such as hydrogen bonding that acts between the functional group in the polymer resin and the template molecule, A recognition site can be formed efficiently. On the other hand, when the relative dielectric constant is higher than 3.0, the interaction between the functional group in the polymer resin and the template molecule is inhibited, and the recognition site cannot be successfully formed.
上記のように、比誘電率が３．０以下である溶媒を用いると、インプリント法による認識部位の形成を効率よく行うことができるが、この方法を用いるためには、ポリマー樹脂が、比誘電率が３．０以下の溶媒に可溶であることと、かつ、鋳型分子と結合可能な官能基を有することを兼ね備えたものである必要がある。そこで検討を重ねた結果、本発明者らは、エチレン−酢酸ビニル共重合物が上記の条件を満たす材料であることを見出した。エチレン−酢酸ビニル共重合物は、アルキルフェノール類などに含まれる水酸基と水素結合可能なカルボニル基を有しており、ベンゼン、トルエン、シクロヘキサン、四塩化炭素など極性の低い比誘電率が３．０以下である溶媒にも可溶である。 As described above, when a solvent having a relative dielectric constant of 3.0 or less is used, formation of a recognition site by an imprint method can be efficiently performed. It must be soluble in a solvent having a dielectric constant of 3.0 or less and have a functional group capable of binding to a template molecule. As a result of repeated studies, the present inventors have found that an ethylene-vinyl acetate copolymer is a material that satisfies the above conditions. The ethylene-vinyl acetate copolymer has a carbonyl group capable of hydrogen bonding with a hydroxyl group contained in alkylphenols and the like, and has a low relative dielectric constant of 3.0 or less, such as benzene, toluene, cyclohexane, and carbon tetrachloride. It is also soluble in the solvent.
捕捉対象である鋳型分子としては、内分泌攪乱物質として問題視されている、ビスフェノールA、アルキルフェノール類、フタル酸エステル類などが挙げられる。 Examples of template molecules to be captured include bisphenol A, alkylphenols, and phthalates that are regarded as problematic as endocrine disruptors.
本発明は、分子の選択的吸着能力を有するインプリントポリマー皮膜を、所定のシート基材中あるいは基材上に担持させたものである。これまでに提案されたインプリントポリマーは、ほとんどがフィルム状または粉体状のものであり、表面積を大きくして認識部位を多くするためには、薄膜化、多孔化、微粒子化などが必要となる。しかし、これらの操作は、ポリマー自体の強度を大きく低下させたり、実際の使用において脱離や飛散などの問題を引き起こしたりする。一方、インプリントポリマーをシート基材に担持させた本発明のシートは、基材と同じ強度を有しており、使用時の脱離や飛散などの心配もない。さらに、基材が繊維状構造物である場合、インプリントポリマーの表面積は非常に大きくなり、主体繊維に繊維径がミクロン〜サブミクロンオーダーである極細ガラス繊維を用いれば、表面積はさらに大きくなる。 In the present invention, an imprinted polymer film having a selective adsorption ability of molecules is supported in or on a predetermined sheet base material. Most of the imprint polymers proposed so far are in the form of a film or powder, and in order to increase the surface area and increase the number of recognition sites, it is necessary to make the film thinner, porous, or fine particles. Become. However, these operations greatly reduce the strength of the polymer itself, or cause problems such as detachment and scattering in actual use. On the other hand, the sheet of the present invention in which an imprint polymer is supported on a sheet base material has the same strength as the base material, and there is no concern about separation or scattering during use. Furthermore, when the base material is a fibrous structure, the surface area of the imprint polymer is very large, and if ultrafine glass fibers having a fiber diameter of the order of micron to submicron are used as the main fiber, the surface area is further increased.
本発明のシートの製造方法としては、特に限定はしないが、例えば、シート基材、例えば紙、不織布、織製または編製布などの繊維状構造物に鋳型分子とポリマー樹脂の混合溶液をロール塗工処理、または浸漬、スプレー等の含浸処理を行う方法が挙げられる。次工程のポリマー皮膜を形成させる方法としては、鋳型分子が揮発しない条件において溶媒を揮発させて乾燥皮膜を形成する方法、ポリマー樹脂の溶解度が低い溶媒に浸漬して相転移させて皮膜を形成する方法等が挙げられる。また、ポリマー皮膜中の鋳型分子を除去する方法としては、溶媒を用いて洗浄除去する方法、減圧や加熱などにより揮発除去する方法等が挙げられる。シート基材に対するインプリントポリマー皮膜の付着量は、同皮膜の吸着特性に応じて設計される。 The method for producing the sheet of the present invention is not particularly limited. For example, a sheet base material such as paper, nonwoven fabric, woven fabric or knitted fabric is roll-coated with a mixed solution of a template molecule and a polymer resin. The method of performing an impregnation process, such as a construction process or immersion and a spray, is mentioned. As a method for forming a polymer film in the next step, a method of forming a dry film by volatilizing the solvent under conditions where the template molecule does not volatilize, a film is formed by immersing in a solvent having a low solubility of the polymer resin to cause phase transition. Methods and the like. Examples of the method for removing the template molecules in the polymer film include a method for washing and removing using a solvent, a method for removing by volatilization by reducing pressure or heating, and the like. The amount of the imprint polymer film attached to the sheet substrate is designed according to the adsorption characteristics of the film.
本発明の分子吸着機能を有するシートは、シート形状をしているため加工性、使用性に優れ、プリーツ加工やハニカム加工することにより液体用または気体用の濾過材として使用したり、また、壁紙として使用したりできる。 The sheet having a molecular adsorption function of the present invention is excellent in processability and usability because it has a sheet shape, and can be used as a filtering material for liquid or gas by pleating or honeycomb processing, or wallpaper. Or can be used as
本発明の方法により、比誘電率３．０以下の溶媒に可溶なポリマーを用いて作成したインプリントポリマーを、繊維、膜、成形体などのポリマー固形物に成形して使用することももちろん可能である。さらに粉末などの固形物として成形した場合には、使用時の脱落・飛散を防止しながら表面積を大きくする必要がある。
実施例：
以下に、本発明を実施例および比較例により、さらに具体的に説明するが、本発明はこれにより何ら限定されるものではない。
Of course, an imprint polymer prepared by using a polymer soluble in a solvent having a relative dielectric constant of 3.0 or less by the method of the present invention can be used by molding it into a polymer solid such as a fiber, film, or molded product. Is possible. Furthermore, when it is molded as a solid material such as a powder, it is necessary to increase the surface area while preventing dropout and scattering during use.
Example:
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto.
（インプリント処理）
平均繊維径０．６５μｍの極細ガラス繊維６０重量％、平均繊維径２．７０μｍの極細ガラス繊維３５重量％、平均繊維径６μｍのチョップドガラス繊維５重量％を、濃度０．５％、硫酸酸性ｐＨ２．５でパルパーにて離解した後、手抄筒を用いて抄紙し、１２０℃×１０分間乾燥させてシートを得た。次に、エチレン／酢酸ビニル共重合体２５（製造元：和光純薬工業（株））と、鋳型分子となるｐ−ｔ−ブチルフェノール（製造元：和光純薬工業（株））を重量比で２：１となるようにトルエン（比誘電率：２．４）に溶解させた溶液を前記シートに付与し、余分な液を吸引濾過により除去した後、真空下でトルエンを蒸発させた。次に、このシートをアセトンで洗浄し、ｐ−ｔ−ブチルフェノールを除去した。こうして、目付重量７０ｇ／ｍ２、樹脂付着量７．０重量％のシートを得た。
(Imprint process)
60% by weight of ultrafine glass fiber having an average fiber diameter of 0.65 μm, 35% by weight of ultrafine glass fiber having an average fiber diameter of 2.70 μm, 5% by weight of chopped glass fiber having an average fiber diameter of 6 μm, concentration 0.5%, sulfuric acid pH 2 After separating with a pulper at .5, paper was made using a hand-made cylinder and dried at 120 ° C. for 10 minutes to obtain a sheet. Next, ethylene / vinyl acetate copolymer 25 (manufacturer: Wako Pure Chemical Industries, Ltd.) and pt-butylphenol (manufacturer: Wako Pure Chemical Industries, Ltd.) as a template molecule were used at a weight ratio of 2: A solution dissolved in toluene (relative dielectric constant: 2.4) so as to be 1 was applied to the sheet, excess liquid was removed by suction filtration, and then toluene was evaporated under vacuum. Next, this sheet was washed with acetone to remove pt-butylphenol. Thus, a sheet having a weight per unit area of 70 g / m 2 and a resin adhesion amount of 7.0% by weight was obtained.
（インプリント処理なし）
平均繊維径０．６５μｍの極細ガラス繊維６０重量％、平均繊維径２．７０μｍの極細ガラス繊維３５重量％、平均繊維径６μｍのチョップドガラス繊維５重量％を、濃度０．５％、硫酸酸性ｐＨ２．５でパルパーにて離解した後、手抄筒を用いて抄紙し、１２０℃×１０分間乾燥させてシートを得た。次に、エチレン／酢酸ビニル共重合体２５（製造元：和光純薬工業（株））のみをトルエンに溶解させた溶液を前記シートに付与し、余分な液を吸引濾過により除去した後、真空下でトルエンを蒸発させた。次に、条件を同一にするために、実施例１と同様にシートをアセトンで洗浄した。こうして、目付重量７０ｇ／ｍ２、樹脂付着量７．１重量％のシートを得た。
(No imprint process)
60% by weight of ultrafine glass fiber having an average fiber diameter of 0.65 μm, 35% by weight of ultrafine glass fiber having an average fiber diameter of 2.70 μm, 5% by weight of chopped glass fiber having an average fiber diameter of 6 μm, concentration 0.5%, sulfuric acid pH 2 After separating with a pulper at .5, paper was made using a hand-made cylinder and dried at 120 ° C. for 10 minutes to obtain a sheet. Next, a solution in which only ethylene / vinyl acetate copolymer 25 (manufacturer: Wako Pure Chemical Industries, Ltd.) was dissolved in toluene was applied to the sheet, and the excess liquid was removed by suction filtration, and then, under vacuum The toluene was evaporated. Next, in order to make the conditions the same, the sheet was washed with acetone as in Example 1. Thus, a sheet having a weight per unit area of 70 g / m 2 and a resin adhesion amount of 7.1% by weight was obtained.
（インプリント処理あり；溶媒として比誘電率４．３のジエチルエーテルを使用）
平均繊維径０．６５μｍの極細ガラス繊維６０重量％、平均繊維径２．７０μｍの極細ガラス繊維３５重量％、平均繊維径６μｍのチョップドガラス繊維５重量％を、濃度０．５％、硫酸酸性ｐＨ２．５でパルパーにて離解した後、手抄筒を用いて抄紙し、１２０℃×１０分間乾燥させてシートを得た。次に、エチレン／酢酸ビニル共重合体２５（製造元：和光純薬工業（株））と、鋳型分子となるｐ−ｔ−ブチルフェノール（製造元：和光純薬工業（株））を重量比で２：１となるようにジエチルエーテル（比誘電率：４．３）に溶解させた溶液を前記シートに付与し、余分な液を吸引濾過により除去した後、真空下でジエチルエーテルを蒸発させた。次に、このシートをアセトンで洗浄し、ｐ−ｔ−ブチルフェノールを除去した。こうして、目付重量７０ｇ／ｍ２、樹脂付着量７．１重量％のシートを得た。
（シートの吸着性能の評価）：
シートの吸着性能の評価は、以下のようにして行った。まずシートを直径２５ｍｍの円形に切り抜き、フィルターホルダーで固定した。これを用いて、濃度１００ｍｇ／L・のｐ−ｔ−ブチルフェノール／アセトン溶液２ｍｌを濾過した。濾過前後の溶液をガスクロマトグラフに導入して、各溶液中のｐ−ｔ−ブチルフェノール量を測定し、ｐ−ｔ−ブチルフェノール除去率（％）を計算した。
(With imprint treatment; use diethyl ether with relative permittivity of 4.3 as solvent)
60% by weight of ultrafine glass fiber having an average fiber diameter of 0.65 μm, 35% by weight of ultrafine glass fiber having an average fiber diameter of 2.70 μm, 5% by weight of chopped glass fiber having an average fiber diameter of 6 μm, concentration 0.5%, sulfuric acid pH 2 After separating with a pulper at .5, paper was made using a hand-made cylinder and dried at 120 ° C. for 10 minutes to obtain a sheet. Next, ethylene / vinyl acetate copolymer 25 (manufacturer: Wako Pure Chemical Industries, Ltd.) and pt-butylphenol (manufacturer: Wako Pure Chemical Industries, Ltd.) as a template molecule were used at a weight ratio of 2: A solution dissolved in diethyl ether (relative dielectric constant: 4.3) so as to be 1 was applied to the sheet, excess liquid was removed by suction filtration, and then diethyl ether was evaporated under vacuum. Next, this sheet was washed with acetone to remove pt-butylphenol. In this way, a sheet having a basis weight of 70 g / m 2 and a resin adhesion amount of 7.1% by weight was obtained.
(Evaluation of sheet adsorption performance):
Evaluation of the adsorption | suction performance of a sheet | seat was performed as follows. First, the sheet was cut into a circle with a diameter of 25 mm and fixed with a filter holder. Using this, 2 ml of a pt-butylphenol / acetone solution having a concentration of 100 mg / L · was filtered. The solution before and after filtration was introduced into a gas chromatograph, the amount of pt- butylphenol in each solution was measured, and the pt-butylphenol removal rate (%) was calculated.
シートの鋳型保持能力は、以下のようにして行った。前記の吸着性能評価に用いたシートをフィルターホルダーより取り出し、室温で３０分間放置してアセトンを蒸発させた後、シートに保持されている ｐ−ｔ−ブチルフェノールをヘリウム気流中で２５０℃で加熱して脱着させ、これを捕集濃縮し、ガスクロマトグラフに導入して、シート上に保持された ｐ−ｔ−ブチルフェノール量を測定した。次に、フィルターホルダーより取り出してから室温で１００時間放置した後のシートについても同様の測定を行った。各シートで測定された保持量から、１００時間後におけるシート上のｐ−ｔ−ブチルフェノール保持率（％）を計算した。 The mold holding ability of the sheet was performed as follows. The sheet used for the evaluation of the adsorption performance was taken out from the filter holder, allowed to stand at room temperature for 30 minutes to evaporate acetone, and then the pt-butylphenol held on the sheet was heated at 250 ° C. in a helium stream. The sample was collected and concentrated, introduced into a gas chromatograph, and the amount of pt-butylphenol retained on the sheet was measured. Next, the same measurement was performed on the sheet after being taken out of the filter holder and allowed to stand at room temperature for 100 hours. From the holding amount measured on each sheet, the pt-butylphenol holding ratio (%) on the sheet after 100 hours was calculated.
実施例および比較例の評価結果を表１に示す。 The evaluation results of Examples and Comparative Examples are shown in Table 1.
インプリント処理を施した実施例１においては、インプリント処理を施していない比較例１に比べて、ｐ−ｔ−ブチルフェノール除去率が高く、インプリントによる認識部位形成の効果が見られる。また、シート上のｐ−ｔ−ブチルフェノール保持率も非常に高く、ｐ−ｔ−ブチルフェノールが認識部位において強く結合していることがわかる。
In Example 1 where imprint processing was performed, the removal rate of pt-butylphenol was higher than that of Comparative Example 1 where imprint processing was not performed, and the effect of forming recognition sites by imprinting was observed. Moreover, the pt- butylphenol retention rate on a sheet | seat is also very high, and it turns out that pt-butylphenol has couple | bonded strongly in the recognition part.
一方、比較例１においても、３０％程度のｐ−ｔ−ブチルフェノールが除去されているが、ｐ−ｔ−ブチルフェノール保持率が低いことから、シートとの吸着力が弱いことを示している。そのため、連続的な濾過を行った場合、吸着された分子の再脱離が起こることが予想される。 On the other hand, in Comparative Example 1, about 30% of pt-butylphenol was removed, but the pt-butylphenol retention rate was low, indicating that the adsorptive power with the sheet was weak. Therefore, when continuous filtration is performed, resorption of adsorbed molecules is expected to occur.
また、溶媒としてジエチルエーテルを用いた比較例２においては、インプリント処理を施していない比較例１に比べて、ｐ−ｔ−ブチルフェノール除去率およびｐ−ｔ−ブチルフェノール保持率ともに高くなっていることから、インプリントによる効果がみられている。しかし溶媒としてトルエンを用いた実施例１に比べて、インプリントの効果はかなり低くなっている。このことより、インプリントの効果を強くするためには、比誘電率の低い溶媒を用いることが重要である。
Further, in Comparative Example 2 using diethyl ether as a solvent, it is compared with Comparative Example 1 not subjected to imprinting, higher p-t-butylphenol removal rate and p-t-butylphenol retention together Therefore, the effect by imprint is seen. However, the imprinting effect is considerably lower than in Example 1 using toluene as the solvent. For this reason, it is important to use a solvent having a low dielectric constant in order to enhance the imprinting effect.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004373755A JP4584703B2 (en) | 2004-12-24 | 2004-12-24 | Sheet or polymer solid having molecular adsorption function, and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004373755A JP4584703B2 (en) | 2004-12-24 | 2004-12-24 | Sheet or polymer solid having molecular adsorption function, and production method thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2006175407A JP2006175407A (en) | 2006-07-06 |
| JP2006175407A5 JP2006175407A5 (en) | 2008-01-10 |
| JP4584703B2 true JP4584703B2 (en) | 2010-11-24 |
Family
ID=36730006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004373755A Expired - Fee Related JP4584703B2 (en) | 2004-12-24 | 2004-12-24 | Sheet or polymer solid having molecular adsorption function, and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4584703B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5105423B2 (en) * | 2008-01-23 | 2012-12-26 | 北越紀州製紙株式会社 | Fiber sheet with molecular adsorption function |
| KR102450952B1 (en) * | 2020-08-11 | 2022-10-04 | 부산대학교 산학협력단 | Polymer material-based sheet including molecular imprinted polymer material layer having perforated structure, method for manufacturing the same, and device using the polymer material-based sheet |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4122540B2 (en) * | 1997-07-17 | 2008-07-23 | 日立化成工業株式会社 | Building material board that is mounted with a seat for environmental cleaning |
| JP3399373B2 (en) * | 1998-10-02 | 2003-04-21 | 東洋インキ製造株式会社 | Polymer material having the property of selectively capturing relatively low molecular compounds, coating material containing the same, separation method using the same, separation material, detection method of functional compound, etc. and detection material |
| JP2001212456A (en) * | 2000-02-07 | 2001-08-07 | Toyo Ink Mfg Co Ltd | Polymer material having characteristics of selectively capturing target substance, separation method, separation material and selective solid phase extraction method |
| JP2002131302A (en) * | 2000-10-30 | 2002-05-09 | Toyo Ink Mfg Co Ltd | Method for treating biological fluid and polymer material used for the same |
| JP4717328B2 (en) * | 2003-03-05 | 2011-07-06 | 北越紀州製紙株式会社 | A filter medium for an air filter, which is a sheet-like fibrous structure having a function of adsorbing gas molecules |
-
2004
- 2004-12-24 JP JP2004373755A patent/JP4584703B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006175407A (en) | 2006-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Functionalized electrospun nanofibrous microfiltration membranes for removal of bacteria and viruses | |
| Huang et al. | Electrospun fibrous membranes for efficient heavy metal removal | |
| Han et al. | Homogeneous polyethersulfone hybrid membranes prepared with in-suit synthesized magnesium hydroxide nanoparticles by phase inversion method | |
| CN102908906B (en) | Preparation method and application of separation film with nano composite cortical layer | |
| Ulbricht et al. | Porous polypropylene membranes with different carboxyl polymer brush layers for reversible protein binding via surface-initiated graft copolymerization | |
| JP6237059B2 (en) | Molded body containing porous metal complex and filter using the same | |
| KR102922912B1 (en) | Preparation method of metal organic framework-cellulose nanofiber composite | |
| Zhou et al. | Preparation of electrospun silk fibroin/Cellulose Acetate blend nanofibers and their applications to heavy metal ions adsorption | |
| CN109126463A (en) | A kind of preparation method of the high-flux nanofiltration membrane of middle layer containing micropore | |
| JP2013154301A (en) | Adsorption sheet and adsorption element using the same | |
| KR101402604B1 (en) | Metal-Complexed carbon Menmbrane and method for preparing the same | |
| TW200932813A (en) | Cellulose porous membrane | |
| JP5482133B2 (en) | Activated carbon fiber | |
| WO2022038344A1 (en) | Membranes | |
| Rist et al. | Bio-based electrospun polyamide membrane–sustainable multipurpose filter membranes for microplastic filtration | |
| CN107287770A (en) | The method that method of electrostatic spinning prepares polyacid/polymer hybridisation nano fibrous membrane | |
| CN106824116A (en) | Beta cyclodextrin modification adsorbed film and preparation method thereof | |
| Taheran et al. | Development of adsorptive membranes by confinement of activated biochar into electrospun nanofibers | |
| CN111203199A (en) | Porous β -cyclodextrin cross-linked polymer nanofiber, preparation method thereof and application thereof in removing bisphenol organic pollutants in water body | |
| Kang et al. | Nanostructural engineering of electrospun poly (vinyl alcohol)/carbon nanotube mats into dense films for alcohol dehydration | |
| Berned‐Samatán et al. | Self‐supported single‐wall carbon nanotube buckypaper membranes applied to air and water filtration | |
| JP2019063757A (en) | Method for producing hollow fiber membrane adsorbent | |
| JP4584703B2 (en) | Sheet or polymer solid having molecular adsorption function, and production method thereof | |
| CN115006993A (en) | Catalytic oxidation formaldehyde-removing porous separation membrane and preparation method and application thereof | |
| JP5564220B2 (en) | Composite structure including three-dimensional structure and filter using the structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071116 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071116 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100416 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20100519 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100525 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100722 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100831 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100902 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4584703 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130910 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |