JP2012030197A - Zwitterionic polymer molecule mixed fibrous adsorbing material - Google Patents
Zwitterionic polymer molecule mixed fibrous adsorbing material Download PDFInfo
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- JP2012030197A JP2012030197A JP2010173959A JP2010173959A JP2012030197A JP 2012030197 A JP2012030197 A JP 2012030197A JP 2010173959 A JP2010173959 A JP 2010173959A JP 2010173959 A JP2010173959 A JP 2010173959A JP 2012030197 A JP2012030197 A JP 2012030197A
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- water
- zwitterionic polymer
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- adsorbent
- mixed
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- 239000007924 injection Substances 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
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- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- FZLUWDXMHJPGBS-UHFFFAOYSA-N n-(3-aminopropyl)prop-2-enamide Chemical compound NCCCNC(=O)C=C FZLUWDXMHJPGBS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- HGASFNYMVGEKTF-UHFFFAOYSA-N octan-1-ol;hydrate Chemical compound O.CCCCCCCCO HGASFNYMVGEKTF-UHFFFAOYSA-N 0.000 description 1
- BJRNKVDFDLYUGJ-UHFFFAOYSA-N p-hydroxyphenyl beta-D-alloside Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
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- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- NGFMICBWJRZIBI-UJPOAAIJSA-N salicin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1CO NGFMICBWJRZIBI-UJPOAAIJSA-N 0.000 description 1
- 229940120668 salicin Drugs 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HNFOAHXBHLWKNF-UHFFFAOYSA-M sodium;2-bromoethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCBr HNFOAHXBHLWKNF-UHFFFAOYSA-M 0.000 description 1
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- 239000012086 standard solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- DRTQHJPVMGBUCF-UHFFFAOYSA-N uracil arabinoside Natural products OC1C(O)C(CO)OC1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-UHFFFAOYSA-N 0.000 description 1
- 229940045145 uridine Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/30—Partition chromatography
- B01D15/305—Hydrophilic interaction chromatography [HILIC]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/364—Amphoteric or zwitterionic ion-exchanger
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明は、有機化合物や金属などの吸着除去を行うための吸着材において、環境、食品、工業製品などの試料中から吸着除去対象物である極性化合物や金属を吸着除去するための繊維状吸着材に関するものである。 The present invention relates to an adsorbent for adsorbing and removing organic compounds, metals and the like, and a fibrous adsorption for adsorbing and removing polar compounds and metals, which are objects of adsorption and removal, from samples such as the environment, food, and industrial products. It relates to materials.
現在、数万〜１０万種類にも及ぶとされる化学物質が年間数億トンもの規模で生産されているが、これらによる環境汚染と共に、ヒトや生態系への悪影響も懸念されている。化学物質の中には、環境中で分解されにくく、生物体内に蓄積しやすく、ヒトに有害な影響を及ぼすおそれがあるものがある。例えば、主に殺虫剤として使用されていたＤＤＴ、ドリン剤、クロルデン類などの塩素系農薬、電気機器類の絶縁油や工業用熱媒体として広く使われていたＰＣＢｓなどは、その毒性は勿論であるが環境での難分解性からＰＯＰｓ（Ｐｅｒｓｉｓｔｅｎｔ Ｏｒｇａｎｉｃ Ｐｏｌｌｕｔａｎｔｓ：残留性有機汚染物質）としてその製造および使用が禁止されている。これらの化学物質の環境中における初期濃度は低いが、長期にわたり環境中に滞留している間に、固体物質の表面や、生体内濃縮などによって高濃度化し、生態系に重篤な影響を与える恐れがある。このような問題から、近年においては、生分解性が高く、蓄積性の低い化合物への置き換えが行われており、農薬では蓄積性が低いとされる親水性のものが多用されるようになってきている。 Currently, several tens of thousands to 100,000 kinds of chemical substances are produced on the scale of several hundred million tons per year. In addition to environmental pollution caused by these substances, there are concerns about adverse effects on humans and ecosystems. Some chemical substances are difficult to be decomposed in the environment, easily accumulate in living organisms, and may have harmful effects on humans. For example, DDT, drins, chlordens and other chlorinated pesticides that were mainly used as insecticides, insulating oils for electrical equipment, and PCBs that are widely used as industrial heat media are not to mention their toxicity. However, its production and use are prohibited as POPs (Persistent Organic Pollutants) because of its persistent nature in the environment. Although the initial concentration of these chemical substances in the environment is low, while they remain in the environment for a long period of time, the concentration of these substances increases due to the surface of solid substances and in vivo concentration, etc., and seriously affects the ecosystem. There is a fear. Due to such problems, in recent years, replacement with a compound having high biodegradability and low accumulation has been carried out, and in agricultural chemicals, hydrophilic substances that are considered to have low accumulation have come to be used frequently. It is coming.
化学物質の除去には溶媒抽出や共沈などの種々の方法が用いられているが、操作性や環境負荷を考慮すると、固体の吸着材を用いるのが有利である。有機化合物の吸着除去には、古くから活性炭やポリスチレンゲルなどの吸着材が使用されてきた。これらの吸着材は高い疎水性を示し、多くの有機化合物を吸着することが可能である。特に、疎水性の高い芳香族有機化合物はこれらの吸着材と親和性が高く、水試料中からほぼ完全に除去することが可能である。しかしながら、これらの吸着材では疎水性相互作用に基づき有機化合物の吸着を行うため、親水基を有する極性化合物に対する吸着能力は低く、極性化合物の吸着材としては必ずしも有効であるとはいえない。 Various methods such as solvent extraction and coprecipitation are used to remove chemical substances, but it is advantageous to use a solid adsorbent in consideration of operability and environmental load. For adsorbing and removing organic compounds, adsorbents such as activated carbon and polystyrene gel have been used for a long time. These adsorbents exhibit high hydrophobicity and can adsorb many organic compounds. In particular, aromatic organic compounds with high hydrophobicity have a high affinity with these adsorbents and can be almost completely removed from water samples. However, since these adsorbents adsorb organic compounds based on hydrophobic interaction, they have low adsorbability for polar compounds having hydrophilic groups, and are not necessarily effective as polar compound adsorbents.
極性化合物の吸着材としては、古くから、活性白土、ゼオライト、シリカゲル、アルミナなどが知られている。これらは、油脂製品や非水系溶媒中に存在する極性化合物の吸着除去に有効であり、食品や化学製品の精製などに使用されている。しかしながら、水や極性溶媒中では溶媒そのものが吸着するため、極性化合物に対する吸着能は極度に低下してしまうという問題がある。 As an adsorbent for polar compounds, activated clay, zeolite, silica gel, alumina and the like have been known for a long time. These are effective for adsorption and removal of polar compounds present in oil and fat products and non-aqueous solvents, and are used for purification of foods and chemical products. However, since the solvent itself is adsorbed in water or a polar solvent, there is a problem that the adsorptivity for polar compounds is extremely lowered.
近年、極性化合物の分離分析手法として親水性相互作用液体クロマトグラフィー（Ｈｙｄｒｏｐｈｉｌｉｃ−Ｉｎｔｅｒａｃｔｉｏｎ Ｌｉｑｕｉｄ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：ＨＩＬＩＣ）が注目を浴びている（非特許文献１）。この分離系は親水性の官能基を有する極性固定相とアセトニトリル−水混合溶媒などの極性移動相とにより構成され、極性固定相への溶質の親和性を利用して極性化合物の相互分離を行うものである。この分離機構は親水性相互作用（Ｈｙｄｒｏｐｈｉｌｉｃ−Ｉｎｔｅｒａｃｔｉｏｎ）と呼ばれており、吸着材の親水基に基づく極性や水素結合などの相互作用や、吸着材に保持された水相への分配などの複合的な相互作用である。この親水性相互作用を利用できれば、疎水性吸着材では困難な極性化合物の吸着・除去が容易となる。親水性相互作用に用いられる吸着材としては、アミノ基、アミド基、ジオール基などを結合したシリカゲルが知られているが、これらの極性化合物に対する本質的な親和性は必ずしも高くはない。極性化合物に対する親和性を高める手段として、Ｚｗｉｔｔｅｒ−ｉｏｎ（ツビッターイオン：分子内に酸性基と塩基性基の両方を含む両性電解質）性分子を結合させた両性イオン交換型の吸着材が特許文献１に開示されている。この吸着材を用いることで、穏和な条件でタンパク質やペプチドを高い回収率で分離することが可能であるとされている。 In recent years, hydrophilic-interaction liquid chromatography (HILIC) has attracted attention as a method for separating and analyzing polar compounds (Non-patent Document 1). This separation system is composed of a polar stationary phase having a hydrophilic functional group and a polar mobile phase such as an acetonitrile-water mixed solvent. The separation of polar compounds is performed using the affinity of the solute to the polar stationary phase. Is. This separation mechanism is called hydrophilic interaction (Hydrophilic-Interaction), which is a combination of interactions such as polarity and hydrogen bonding based on the hydrophilic group of the adsorbent, and distribution to the aqueous phase retained by the adsorbent. Interaction. If this hydrophilic interaction can be utilized, it becomes easy to adsorb and remove polar compounds, which is difficult with a hydrophobic adsorbent. As an adsorbent used for hydrophilic interaction, silica gel bonded with an amino group, an amide group, a diol group or the like is known, but the essential affinity for these polar compounds is not necessarily high. Zwitter-ion (Zubitter ion: an amphoteric electrolyte containing both acidic and basic groups in the molecule) as a means to increase the affinity for polar compounds is an amphoteric ion-exchange adsorbent that is a patent document. 1 is disclosed. By using this adsorbent, it is said that proteins and peptides can be separated at a high recovery rate under mild conditions.
特許文献１と同様のＺｗｉｔｔｅｒ−ｉｏｎ性分子であるスルホベタイン基を導入した吸着材を用いて固相抽出法により水溶性の高い極性化合物の抽出を行った報告もある（非特許文献２、非特許文献３）。この報告において、被検化合物である極性化合物は極性有機溶媒に溶解された後、この吸着材が充填された固相抽出カートリッジに負荷され、この吸着材に吸着される。吸着された極性化合物は、水または塩水溶液により速やかに溶出され、高い回収率を得ることができるとされる。この報告によれば、アンチカオトロピック性（水の構造を安定化させる力）の第四級アンモニウム基とスルホ基を分子内にもつスルホベタイン基の高い水和力によって吸着材表面に水和層が形成され、この水和層に効率的に極性化合物が抽出されることとなる。この文献では、親水性相互作用を発現するとされる市販の固相抽出剤との比較において、スルホベタイン型固相抽出剤は種々の極性化合物に対して最も高い回収率を示すとしている。このように、親水性相互作用は、極性化合物の吸着・除去には簡便かつ効率のよい手段であると共に、溶出液に水または塩水溶液を用いるという環境負荷も少ない方法である。しかしながら、両性イオンは分子内で自己中和しているとされるものの、実際の使用条件下ではイオン性官能基に対イオンが結合してしまい正または負の荷電を帯びてしまうと考えられる。そのため、非特許文献２や非特許文献３のような第四級アンモニウム基とスルホ基を有するＺｗｉｔｔｅｒ−ｉｏｎ性分子を用いる場合には、強いイオン交換相互作用が発現すると考えられる。実際、非特許文献２に示されている結果では、イオン性を有する化合物が特徴的な保持をしており、イオン交換相互作用またはイオン排除相互作用が加味された相互作用により抽出分離が行われていると判断される。 There is also a report of extraction of a highly water-soluble polar compound by a solid phase extraction method using an adsorbent into which a sulfobetaine group, which is a Zwitter-ion molecule as in Patent Document 1, is introduced (Non-Patent Document 2, Non-Patent Document 2, Patent Document 3). In this report, a polar compound as a test compound is dissolved in a polar organic solvent, loaded onto a solid-phase extraction cartridge filled with the adsorbent, and adsorbed on the adsorbent. The adsorbed polar compound is rapidly eluted with water or an aqueous salt solution, and a high recovery rate can be obtained. According to this report, the hydration layer is formed on the surface of the adsorbent due to the high hydration power of the sulfobetaine group having quaternary ammonium groups and sulfo groups in the molecule, which has antichaotropic properties (the ability to stabilize the structure of water). As a result, polar compounds are efficiently extracted into this hydrated layer. In this document, the sulfobetaine-type solid-phase extractant shows the highest recovery rate for various polar compounds in comparison with a commercially available solid-phase extractant that expresses a hydrophilic interaction. Thus, the hydrophilic interaction is a simple and efficient means for adsorption / removal of polar compounds, and is a method with less environmental load using water or a salt solution as an eluent. However, although the zwitterion is considered to be self-neutralized in the molecule, it is considered that the counter ion binds to the ionic functional group under the actual use conditions and is positively or negatively charged. For this reason, when a Zwitter-ion molecule having a quaternary ammonium group and a sulfo group as in Non-Patent Document 2 and Non-Patent Document 3 is used, it is considered that a strong ion exchange interaction appears. In fact, according to the results shown in Non-Patent Document 2, a compound having ionicity has a characteristic retention, and extraction and separation are performed by an interaction including an ion exchange interaction or an ion exclusion interaction. It is judged that
両性イオン交換体に関しては、前記親水性相互作用型吸着材の他にも既に幾つかの開示がある。特許文献２および特許文献３には、膜形成ポリマーに両性イオン交換体粉末を混合後、キャスティングなどの方法により成膜するという、両性イオン交換膜の製造方法が開示されている。本両性イオン交換膜の用途は透析や脱塩を主としたものであるため、膜形成ポリマーとしては、非水溶性の耐薬品性の高いポリスルホン、アクリル、ポリアミド、ポリイミド、ポリアミドイミド、ポリウレタン、フッ素樹脂、シリコーン樹脂などを用いるとしている。親水性相互作用を吸着機構として用いるには、高い含水率・保水率の吸着材が必要となるため、母材自身の親水性・保水性も重要となる。しかしながら、これらの膜形成ポリマーの親水性は決して高くはなく、特許文献２の両性イオン交換繊維を混合した両性イオン交換膜の含水率は３９％程度、特許文献３の無機両性イオン交換体を混合した両性イオン交換膜では３０％以下と決して高いものではない。 Regarding the amphoteric ion exchanger, there are already some disclosures in addition to the hydrophilic interaction type adsorbent. Patent Document 2 and Patent Document 3 disclose a method for producing an amphoteric ion exchange membrane in which an amphoteric ion exchanger powder is mixed with a membrane-forming polymer and then formed by a method such as casting. Since this amphoteric ion exchange membrane is mainly used for dialysis and desalting, the membrane-forming polymer is water-insoluble and highly chemically resistant polysulfone, acrylic, polyamide, polyimide, polyamideimide, polyurethane, fluorine Resin, silicone resin, etc. are used. In order to use hydrophilic interaction as an adsorption mechanism, an adsorbent having a high water content and water retention rate is required, and thus the hydrophilicity and water retention of the base material itself are also important. However, the hydrophilicity of these membrane-forming polymers is never high. The water content of the amphoteric ion exchange membrane mixed with the amphoteric ion exchange fiber of Patent Document 2 is about 39%, and the inorganic amphoteric ion exchanger of Patent Document 3 is mixed. In the amphoteric ion exchange membrane, it is not as high as 30% or less.
特許文献４には、陰イオン性グラフトポリマーと陽イオン性グラフトポリマーを混合溶解後、キャスティングなどの方法により成膜するという、両性イオン交換膜の製造方法が開示されている。本両性イオン交換体の用途もイオン透過膜、機能性分離膜などであり、水への溶解を防ぐために陰イオンポリマーまたは陽イオンポリマーの合成時に疎水性モノマーを混合している。特許文献４では、含水率相当の物性値を膨潤度として表記しているが、酸性溶液中では１００〜１５０％、アルカリ溶液中では２００〜３５０％と多くの水を含むことができるとされている。しかしながら、ｐＨ６では３５％以下であり、中性領域で親水性相互作用を発現させることが難しい。特許文献４では官能基が両性イオン交換体ではないため、陰イオンポリマーまたは陽イオンポリマーそれぞれのイオン化が促進されるｐＨ領域でのみ高い含水率を示したものと考えられる。 Patent Document 4 discloses a method for producing an amphoteric ion exchange membrane in which an anionic graft polymer and a cationic graft polymer are mixed and dissolved, and then formed into a film by a method such as casting. This amphoteric ion exchanger is also used for ion permeable membranes, functional separation membranes, etc., and hydrophobic monomers are mixed during the synthesis of an anionic polymer or a cationic polymer in order to prevent dissolution in water. In Patent Document 4, the physical property value corresponding to the moisture content is expressed as the degree of swelling, but it is said that it can contain a large amount of water as 100 to 150% in an acidic solution and 200 to 350% in an alkaline solution. Yes. However, at pH 6, it is 35% or less, and it is difficult to express hydrophilic interaction in the neutral region. In Patent Document 4, since the functional group is not an amphoteric ion exchanger, it is considered that a high water content was exhibited only in a pH region where ionization of each of the anionic polymer or the cationic polymer was promoted.
一方、繊維状の両性イオン交換体の開示もある。特許文献５には、陽イオン交換体微粒子をポリビニルアルコールと混合紡糸した後、アセタール化し、その後アミノ化して陰イオン交換基を導入するという両イオン交換繊維の製造方法が開示されている。この方法により得られる繊維の含水率に関しては開示されていないが、繊維母材がポリビニルアルコールであるため比較的高い値を示すものと推定される。しかしながら、陰イオン交換基と陽イオン交換基が同一分子内に存在しているものではないため、前記特許文献４の両性イオン交換膜と同様に、含水率のｐＨ依存性が極端に大きいものと推定される。 On the other hand, there is also disclosure of a fibrous zwitterion exchanger. Patent Document 5 discloses a method for producing an anion exchange fiber in which cation exchanger fine particles are mixed and spun with polyvinyl alcohol, acetalized, and then aminated to introduce an anion exchange group. Although the moisture content of the fiber obtained by this method is not disclosed, it is presumed that it shows a relatively high value because the fiber base material is polyvinyl alcohol. However, since the anion exchange group and the cation exchange group are not present in the same molecule, like the amphoteric ion exchange membrane of Patent Document 4, the pH dependency of the water content is extremely large. Presumed.
Ｚｗｉｔｔｅｒ−ｉｏｎ性分子を官能基として導入した両性イオン交換体に関する開示としては、特許文献１の他に特許文献６がある。特許文献６にはクロロメチル化した架橋ポリスチレンゲルにＮ，Ｎ−ジメチルベタインを導入した両性イオン交換樹脂の製造方法および無機塩類の分離法が開示されている。この開示においても基材樹脂は撥水性のポリスチレンであるため、含水率は４０％と低く、親水性相互作用を発現することは困難である。また、陰イオン交換基は第四級アンモニウム基であるため、陰イオン交換性は高いものと推定される。しかし、陽イオン交換基はカルボン酸型であるため、先述のスルホベタイン型のスルホ基に比べ陽イオン交換性を低く抑えることができるという利点をもっている。 Patent Document 6 in addition to Patent Document 1 discloses disclosure relating to an amphoteric ion exchanger in which a Zwitter-ion molecule is introduced as a functional group. Patent Document 6 discloses a method for producing an amphoteric ion exchange resin in which N, N-dimethylbetaine is introduced into a chloromethylated crosslinked polystyrene gel and a method for separating inorganic salts. Also in this disclosure, since the base resin is water-repellent polystyrene, the water content is as low as 40%, and it is difficult to develop a hydrophilic interaction. Moreover, since an anion exchange group is a quaternary ammonium group, it is estimated that anion exchange property is high. However, since the cation exchange group is a carboxylic acid type, it has an advantage that the cation exchange property can be suppressed lower than the sulfobetaine type sulfo group described above.
ところで、有害化学物質の吸着除去においては、有害重金属もその対象となる。金属の吸着に両性イオン交換体を用いる利点としては、金属陽イオンは陽イオン交換相互作用によって、陰イオンとして存在する金属オキソ酸は陰イオン交換相互作用によって吸着可能となると考えられる。従って、上述したような両性イオン交換体は重金属の吸着にも利用可能である。しかし、一般的な被処理溶液中には高濃度の塩類や有機物が含まれており、イオン交換相互作用による重金属除去が困難な場合も多く、上述のような両性イオン交換体での重金属除去は難しいものと推定される。このような夾雑物を多く含む溶液中の重金属処理には、キレート樹脂を利用した技術が開示（特許文献７ないし特許文献９）されており、単なる両性イオン交換体ではなく、キレート形成能を付与した吸着材が必要となる。 By the way, harmful heavy metals are also subject to adsorption and removal of harmful chemical substances. As an advantage of using an amphoteric ion exchanger for metal adsorption, it is considered that a metal cation can be adsorbed by a cation exchange interaction, and a metal oxo acid present as an anion can be adsorbed by an anion exchange interaction. Therefore, the amphoteric ion exchanger as described above can also be used for adsorption of heavy metals. However, the general solution to be treated contains high-concentration salts and organic substances, and it is often difficult to remove heavy metals by ion exchange interaction. Heavy metal removal by the amphoteric ion exchanger as described above is not possible. Presumed to be difficult. For such heavy metal treatment in a solution containing a large amount of impurities, a technique using a chelate resin has been disclosed (Patent Document 7 to Patent Document 9), and not a simple amphoteric ion exchanger but a chelate forming ability. Adsorbed material is required.
本発明は、上記の問題点を鑑みてなされたもので、環境、食品、工業製品などの夾雑成分を多量に含む試料中の極性化合物や重金属類の吸着除去において使用される、親水性相互作用とキレート形成能とを発現する繊維状吸着材を提供することを目的とする。 The present invention has been made in view of the above problems, and is a hydrophilic interaction used in adsorption removal of polar compounds and heavy metals in a sample containing a large amount of contaminating components such as the environment, food, and industrial products. It aims at providing the fibrous adsorbent which expresses chelate formation ability.
本発明の発明者が鋭意研究を行った結果、分子内に側鎖にアルキレン基を介して結合したアミノ基、あるいは環状のイミノ基、およびカルボキシル基を多数有する水溶性の両性イオン性高分子を親水性の高い繊維原料に混合し、湿式紡糸法により混合紡糸することにより、親水性相互作用によって極性化合物を効率よく吸着でき、かつキレート形成能により重金属を吸着することが可能な繊維状の吸着材が得られることを見いだした。 As a result of intensive studies by the inventor of the present invention, a water-soluble zwitterionic polymer having a large number of amino groups or cyclic imino groups and carboxyl groups bonded to the side chain via an alkylene group in the molecule has been obtained. Mixing with fiber material with high hydrophilicity and mixing spinning by wet spinning method, it is possible to adsorb polar compounds efficiently by hydrophilic interaction and to adsorb heavy metals by chelating ability I found that I could get the material.
本発明において、親水性の高い繊維原料に混合される、前記水溶性の両性イオン性高分子は、アリルアミン−マレイン酸共重合体またはジアリルアミン−マレイン酸共重合体が最も好ましい。 In the present invention, the water-soluble zwitterionic polymer mixed with the highly hydrophilic fiber raw material is most preferably an allylamine-maleic acid copolymer or a diallylamine-maleic acid copolymer.
本発明において、前記水溶性の両性イオン性高分子が混合される親水性の高い繊維原料は、セルロースまたはポリビニルアルコールである。 In the present invention, the highly hydrophilic fiber raw material mixed with the water-soluble zwitterionic polymer is cellulose or polyvinyl alcohol.
本発明においては、両性イオン性高分子が混合された繊維状の吸着材は、（ａ）前記水溶性の両性イオン性高分子を準備する、（ｂ）前記水溶性の両性イオン性高分子を繊維原料に混合する、（ｃ）両性イオン性高分子混合繊維原料を湿式紡糸法により混合紡糸する、という工程により製造される。 In the present invention, the fibrous adsorbent mixed with the zwitterionic polymer is (a) preparing the water-soluble zwitterionic polymer, (b) preparing the water-soluble zwitterionic polymer. It is manufactured by a process of mixing with a fiber raw material, and (c) mixing and spinning a zwitterionic polymer mixed fiber raw material by a wet spinning method.
本発明によれば、分子内にアミノ基あるいはイミノ基と共にカルボキシル基を多数有する水溶性の両性イオン性高分子を親水性の繊維原料に混合後、湿式紡糸法により混合紡糸することにより、極性化合物および重金属の吸着に適した繊維状の吸着材を容易に得ることが可能である。本発明の吸着材は、極性有機溶媒を用いた環境や食品などの試料の予備抽出液から親水性相互作用によって極性化合物を吸着することが可能であると共に、錯形成能も同時に発現するため、環境や食品などの試料中の極性化合物と重金属の吸着除去に好適な吸着材となりうる。 According to the present invention, a polar compound is obtained by mixing a water-soluble zwitterionic polymer having a number of carboxyl groups together with amino groups or imino groups in a molecule into a hydrophilic fiber raw material, and then mixing and spinning by a wet spinning method. In addition, a fibrous adsorbent suitable for heavy metal adsorption can be easily obtained. The adsorbent of the present invention is capable of adsorbing polar compounds by hydrophilic interaction from a pre-extraction solution of a sample such as an environment or food using a polar organic solvent, and at the same time exhibits complex forming ability, It can be an adsorbent suitable for adsorption and removal of polar compounds and heavy metals in samples such as the environment and food.
本発明では、水溶性の両性イオン性高分子として分子内に側鎖としてアルキレン基を介して結合したアミノ基、あるいは環状のイミノ基、およびカルボキシル基を多数有する水溶性の両性イオン性高分子を親水性の高い繊維原料に混合し、湿式紡糸法により混合紡糸することにより、極性化合物と重金属の吸着に適した繊維状の吸着材を製造する。 In the present invention, a water-soluble zwitterionic polymer having a large number of amino groups or cyclic imino groups and carboxyl groups bonded to each other through an alkylene group as a side chain as a water-soluble zwitterionic polymer. A fibrous adsorbent suitable for adsorption of polar compounds and heavy metals is produced by mixing with a highly hydrophilic fiber raw material and mixing and spinning by a wet spinning method.
本発明において繊維原料に混合される水溶性の両性イオン性高分子は、高分子中にアミノ基あるいは環状のイミノ基とカルボキシル基を有する両性イオン性高分子である。アミノ基あるいはイミノ基は陰イオン交換性の官能基であり、カルボキシル基は陽イオン交換性の官能基である。これら陰イオン性官能基および陽イオン性官能基の水和能（主として水分子の電気双極子と溶質粒子の電荷との静電気的作用および水素結合により水分子を引きつける力）により吸着材表面に水和層を形成させて親水性相互作用を発現させる。陰イオン性官能基または陽イオン性官能基としては、第四級アンモニウム基ならびにスルホ基を用いても水和層を形成させることができる。水和層の形成という点だけに着目すれば、第四級アンモニウム基ならびにスルホ基を用いるほうが有利ではあるが、これらはイオン性が高くイオン交換相互作用が強く発現してしまう。イオン性化合物の過剰吸着による吸着特性の変化を抑えるためには、弱イオン性のアミノ基あるいはイミノ基、カルボキシル基を用いる必要がある。これらの弱イオン性の官能基としては多様な形態のものが存在しうるが、本発明におけるアミノ基は高分子主鎖にアルキレン鎖を介して結合したアミノ基であることが好ましい。また、本発明におけるイミノ基は、ポリエチレンイミンのような主鎖中に存在するものではなく、環状のイミノ基構造をもつものである。さらに、この環状のイミノ基は、高分子の主鎖にアルキレン基を介して結合したものでもよいし、式（２）に示すような構造の環状イミノ基の一部が高分子の主鎖を形成していてもよい。一方、カルボキシル基は主鎖に直結したものでも、アルキレン基を介して結合したものでもよい。 The water-soluble zwitterionic polymer mixed with the fiber raw material in the present invention is a zwitterionic polymer having an amino group or a cyclic imino group and a carboxyl group in the polymer. The amino group or imino group is an anion exchange functional group, and the carboxyl group is a cation exchange functional group. Water is adsorbed on the adsorbent surface by the hydration ability of these anionic and cationic functional groups (mainly the electrostatic action between the electric dipoles of water molecules and the charge of the solute particles and the ability to attract water molecules by hydrogen bonding). A sum layer is formed to develop a hydrophilic interaction. As the anionic functional group or the cationic functional group, a hydrated layer can also be formed by using a quaternary ammonium group and a sulfo group. If attention is paid only to the formation of a hydrated layer, it is advantageous to use a quaternary ammonium group and a sulfo group, but these are highly ionic and strongly express ion exchange interaction. In order to suppress changes in adsorption characteristics due to excessive adsorption of ionic compounds, it is necessary to use weakly ionic amino groups, imino groups, or carboxyl groups. These weak ionic functional groups may have various forms, but the amino group in the present invention is preferably an amino group bonded to the polymer main chain via an alkylene chain. In addition, the imino group in the present invention does not exist in the main chain like polyethyleneimine, but has a cyclic imino group structure. Further, the cyclic imino group may be bonded to the main chain of the polymer via an alkylene group, or a part of the cyclic imino group having a structure as shown in the formula (2) may be bonded to the main chain of the polymer. It may be formed. On the other hand, the carboxyl group may be directly bonded to the main chain or may be bonded via an alkylene group.
高分子中にアルキレン基を介して結合したアミノ基、あるいは環状のイミノ基と共にカルボキシル基を有する水溶性の両性イオン性高分子は、このような形態のアミノ基あるいはイミノ基を有するあるいは後処理によりこのような形態のアミノ基あるいはイミノ基を導入可能なモノマーと、カルボキシル基を有するあるいは後処理によりカルボキシル基を導入可能なモノマーとの共重合により合成される。本発明の目的である親水性相互作用を発現させるためには、得られる共重合体のアミノ基あるいはイミノ基とカルボキシル基がＺｗｉｔｔｅｒ−ｉｏｎ性分子のように近傍に配置されていることが好ましい。つまり、ブロック共重合体やグラフト共重合体ではなく、ランダム共重合体、理想的には交互共重合体であることが好ましい。 A water-soluble zwitterionic polymer having an amino group bonded via an alkylene group in a polymer or a carboxyl group together with a cyclic imino group has an amino group or an imino group in such a form or is subjected to post-treatment. It is synthesized by copolymerization of a monomer capable of introducing such an amino group or imino group and a monomer having a carboxyl group or capable of introducing a carboxyl group by post-treatment. In order to express the hydrophilic interaction which is the object of the present invention, it is preferable that the amino group or imino group and carboxyl group of the obtained copolymer are arranged in the vicinity like a Zwitter-ion molecule. That is, it is preferably a random copolymer, ideally an alternating copolymer, not a block copolymer or a graft copolymer.
上記のような形態をもつ、アミノ基とカルボキシル基とを有する両性イオン性高分子の一つの形態としては、アミノアルキル（メタ）アクリレートあるいはアミノアルキルアクリルアミドと（メタ）アクリル酸との共重合により得ることができる。この場合、（メタ）アクリル酸の代わりに（メタ）アクリル酸のアルキルエステルを用いて得られる共重合体のアルキルエステル部分を加水分解することにより同様の両性イオン性高分子を得ることもできる。また、アミノアルキル（メタ）アクリレートあるいはアミノアルキルアクリルアミドの代わりに、グリシジル（メタ）アクリレートと（メタ）アクリル酸との共重合体のグリシジル基にアンモニアを反応させたものも使用することが可能である。この場合にも、（メタ）アクリル酸の代わりに（メタ）アクリル酸のアルキルエステルを用いることが可能であるが、アンモニアとの反応後に、アルキルエステル部分を加水分解することにより本発明において使用可能な両性イオン性高分子を得ることができる。アミノアルキル（メタ）アクリレートあるいはアミノアルキルアクリルアミドとしては、アミノエチルアクリレート、アミノエチルメタクリレート、アミノプロピルアクリルアミドなどがあげられる。また、（メタ）アクリル酸のアルキルエステルとしては、メチルメタクリレート、メチルアクリレート、エチルメタクリレート、エチルアクリレートなどがあげられる。一方、環状のイミノ基とカルボキシル基とを有する水溶性の両性イオン性高分子としては、上記アミノアルキル（メタ）アクリレートあるいはアミノアルキルアクリルアミドの代わりに、ピロリジル基、ピペリジル基、ピペラジル基などをエステル部にもつ（メタ）アクリル酸系モノマーを用いれば得ることが可能である。当然のことであるが、（メタ）アクリル酸系モノマーの代わりに（メタ）アリル系モノマーを用いても同様の両性イオン性高分子を得ることも可能である。一般に、これらの共重合体はランダム共重合体であるが、より好ましい形態である交互共重合体とするためには、カルボキシル基生成のためのモノマーとして無水マレイン酸を用いるのがよい。アミノ基あるいはイミノ基を有するモノマーとしては上述のモノマーを用い、無水マレイン酸と共重合させた後、無水マレイン酸を加水分解してジカルボン酸とすればよい。 One form of the zwitterionic polymer having an amino group and a carboxyl group having the above-described form is obtained by copolymerization of aminoalkyl (meth) acrylate or aminoalkylacrylamide and (meth) acrylic acid. be able to. In this case, the same zwitterionic polymer can be obtained by hydrolyzing the alkyl ester portion of the copolymer obtained by using an alkyl ester of (meth) acrylic acid instead of (meth) acrylic acid. Moreover, what made ammonia react with the glycidyl group of the copolymer of glycidyl (meth) acrylate and (meth) acrylic acid instead of aminoalkyl (meth) acrylate or aminoalkylacrylamide can also be used. . In this case as well, an alkyl ester of (meth) acrylic acid can be used instead of (meth) acrylic acid, but it can be used in the present invention by hydrolyzing the alkyl ester moiety after reaction with ammonia. Zwitterionic polymer can be obtained. Examples of aminoalkyl (meth) acrylate or aminoalkylacrylamide include aminoethyl acrylate, aminoethyl methacrylate, and aminopropyl acrylamide. Examples of the alkyl ester of (meth) acrylic acid include methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate. On the other hand, as a water-soluble zwitterionic polymer having a cyclic imino group and a carboxyl group, a pyrrolidyl group, a piperidyl group, a piperazyl group, or the like can be used instead of the aminoalkyl (meth) acrylate or aminoalkylacrylamide. It can be obtained by using a (meth) acrylic acid monomer. Of course, the same zwitterionic polymer can be obtained by using a (meth) allyl monomer instead of the (meth) acrylic acid monomer. In general, these copolymers are random copolymers, but maleic anhydride is preferably used as a monomer for generating a carboxyl group in order to obtain an alternating copolymer in a more preferable form. As the monomer having an amino group or imino group, the above-described monomer may be used, and after copolymerization with maleic anhydride, maleic anhydride may be hydrolyzed to dicarboxylic acid.
本発明における高分子中にアルキレン基を介して結合したアミノ基、あるいは環状のイミノ基と共にカルボキシル基を有する水溶性の両性イオン性高分子としては、交互共重合であること、水溶性、さらには入手の容易さを考えると、下記式（１）に示されるアリルアミン−マレイン酸共重合体または下記式（２）に示されるジアリルアミン−マレイン酸共重合体を用いるのが好ましい。なお、本発明においては、これら共重合体単独または混合して使用してもよい。 The water-soluble zwitterionic polymer having an amino group bonded via an alkylene group or a cyclic imino group and a carboxyl group in the polymer of the present invention includes alternating copolymerization, water-solubility, Considering availability, it is preferable to use an allylamine-maleic acid copolymer represented by the following formula (1) or a diallylamine-maleic acid copolymer represented by the following formula (2). In the present invention, these copolymers may be used alone or in combination.
（ここで、ｎおよびｍは正の整数を示す。）
(Here, n and m are positive integers.)
（ここで、ｎおよびｍは正の整数を示す。）
(Here, n and m are positive integers.)
これらの両性イオン性高分子は、例えば、ジアリルアミンまたはアリルアミンと無水マレイン酸との共重合により得られる共重合体を加水分解することにより得ることができる。ジアリルアミンまたはアリルアミンと無水マレイン酸との組成比（式（１）および式（２）におけるｎ：ｍ）は交互共重合型高分子であるためおおむね１：１である。これらの両性イオン性高分子の分子量を正確に求めることは難しいが、本発明においてはおおよその平均分子量として５，０００〜１００，０００のものが用いられる。これらの両性イオン性高分子は水溶性であり、それぞれのイオン性基の周りに多数の水分子が水和することによって高い保水性を示す。親水性相互作用においては両性イオン性高分子のイオン性基も極性化合物の抽出に有効に寄与することができるが、イオン交換相互作用またはイオン排除相互作用が強く発現することは好ましくはない。そのため、弱陽イオン性および弱陰イオン性の官能基を有する上記式（１）または上記式（２）の両性イオン性高分子を用いることが好ましい。 These zwitterionic polymers can be obtained, for example, by hydrolyzing a diallylamine or a copolymer obtained by copolymerization of allylamine and maleic anhydride. The composition ratio of diallylamine or allylamine and maleic anhydride (n: m in formula (1) and formula (2)) is approximately 1: 1 because it is an alternating copolymer type polymer. Although it is difficult to accurately determine the molecular weights of these zwitterionic polymers, those having an average molecular weight of 5,000 to 100,000 are used in the present invention. These zwitterionic polymers are water-soluble, and exhibit high water retention when a large number of water molecules are hydrated around each ionic group. In the hydrophilic interaction, the ionic group of the zwitterionic polymer can also contribute effectively to the extraction of the polar compound, but it is not preferable that the ion exchange interaction or the ion exclusion interaction is strongly expressed. Therefore, it is preferable to use the zwitterionic polymer of the above formula (1) or the above formula (2) having a weak cationic and weak anionic functional group.
本発明において、両性イオン性高分子が混合された繊維状の吸着材は、前記水溶性の両性イオン性高分子を繊維原料溶液に混合後、湿式紡糸法により混合紡糸して得られる。本発明においては、親水性相互作用を明確に発現させるため、前記水溶性の両性イオン性高分子を混合する繊維母材にも親水性を示すものが使用される。高い親水性を示す繊維母材としては、セルロース（レーヨン）、ポリビニルアルコール（ビニロン）があげられる。これらの繊維母材は高い保水性を有しており、この高い保水性は親水性相互作用の起源となる水和層の形成に貢献することができる。また、これらの繊維は湿式混合紡糸によって製造することが可能であるということも本発明において有効である。前記水溶性の両性イオン性高分子の合成においては、カルボキシル基生成のために加水分解操作を行う必要がある。つまり、水溶性の両性イオン性高分子は水溶液として得られるため、煩雑な脱水操作を行うことなく、湿式紡糸用の繊維原料溶液に混合するだけで容易に混合紡糸が可能となる。 In the present invention, the fibrous adsorbent mixed with the zwitterionic polymer is obtained by mixing the water-soluble zwitterionic polymer into the fiber raw material solution and then mixing and spinning by a wet spinning method. In the present invention, in order to express the hydrophilic interaction clearly, the fiber base material into which the water-soluble zwitterionic polymer is mixed is also used which exhibits hydrophilicity. Examples of the fiber base material exhibiting high hydrophilicity include cellulose (rayon) and polyvinyl alcohol (vinylon). These fiber base materials have high water retention, and this high water retention can contribute to the formation of a hydrated layer that is the origin of hydrophilic interaction. It is also effective in the present invention that these fibers can be produced by wet mixing spinning. In the synthesis of the water-soluble zwitterionic polymer, it is necessary to perform a hydrolysis operation to generate a carboxyl group. That is, since the water-soluble zwitterionic polymer is obtained as an aqueous solution, it can be easily mixed and spun by simply mixing it with the fiber raw material solution for wet spinning without performing a complicated dehydration operation.
本発明の繊維状吸着材は、セルロースあるいはポリビニルアルコールと湿式紡糸法により混合紡糸される。これら繊維との湿式混合紡糸は公知の方法により行うことが可能である。公知のビスコース法を用いてセルロースと混合紡糸する手順を次に示す。すなわち、（ｉ）水溶性の両性イオン性高分子を準備する、（ｉｉ）公知の方法により製造されたセルロースビスコースを準備する、（ｉｉｉ）水溶性の両性イオン性高分子とセルロースビスコースとを混合する、（ｉｖ）この混合溶液を紡糸ノズルから押し出し、（ｖ）希硫酸を主剤とした凝固浴中で再生させる、（ｖｉ）紡糸された繊維を洗浄・乾燥させるという工程により製造される。湿式混合紡糸においては再生条件が問題となるが、公知の再生条件で混合紡糸することが可能である。すなわち、水溶性の両性イオン性高分子混合セルロースビスコースを、紡糸ノズルから、硫酸８０〜１２０ｇ／Ｌおよび硫酸ソーダ５０〜３６０ｇ／Ｌを主成分として含有する凝固液（液温４０〜５０oＣ）中に押し出せばよい。ビスコース法以外のセルロースの製造方法、例えば、銅アンモニア法によっても同様の繊維状吸着材を得ることも可能であるが、セルロース中に混合される両性イオン性高分子に銅が吸着されてしまうという問題が生じる。銅が吸着してしまうと、増粘・凝集が生じて紡糸性が低下するだけでなく、紡糸後に銅を除去するための更なる洗浄工程が必要となる。従って、本発明の繊維状吸着材の製造においてはビスコース法を用いることが好ましい。 The fibrous adsorbent of the present invention is mixed and spun with cellulose or polyvinyl alcohol by a wet spinning method. Wet mixing spinning with these fibers can be performed by a known method. The procedure for mixing and spinning with cellulose using a known viscose method is shown below. That is, (i) preparing a water-soluble zwitterionic polymer, (ii) preparing cellulose viscose produced by a known method, (iii) a water-soluble zwitterionic polymer and cellulose viscose (Iv) The mixed solution is extruded from a spinning nozzle, (v) is regenerated in a coagulation bath containing dilute sulfuric acid as a main component, and (vi) the spun fiber is washed and dried. . Regeneration conditions are a problem in wet mixed spinning, but mixed spinning can be performed under known regeneration conditions. That is, a water-soluble zwitterionic polymer mixed cellulose viscose is fed from a spinning nozzle into a coagulating liquid (liquid temperature 40 to 50 ° C.) containing 80 to 120 g / L sulfuric acid and 50 to 360 g / L sulfuric acid as main components. Extrude into It is also possible to obtain a similar fibrous adsorbent by a cellulose production method other than the viscose method, for example, the copper ammonia method, but copper is adsorbed by the zwitterionic polymer mixed in the cellulose. The problem arises. If copper is adsorbed, thickening and agglomeration occur and spinnability is lowered, and a further washing step for removing copper after spinning is required. Therefore, it is preferable to use the viscose method in the production of the fibrous adsorbent of the present invention.
水溶性の両性イオン性高分子は粉体として紡糸工程で投入することも可能であるが、水溶性の両性イオン性高分子合成工程や繊維原料溶液への溶解性、さらには紡糸工程の作業性から、水溶液として繊維原料溶液に混合するのが好ましい。水溶液中における水溶性の両性イオン性高分子の濃度は、特に規定されるものではないが、紡糸工程を考慮すると５〜５０重量％のものが用いられる。水溶性の両性イオン性高分子溶液の添加方法としては、従来公知の任意の方法を採用しうるが、水系溶液をインジェクションポンプによって、定量的且つ連続的に添加するのが好ましい。 The water-soluble zwitterionic polymer can be added as a powder in the spinning process, but it is soluble in the water-soluble zwitterionic polymer synthesis process, fiber raw material solution, and workability of the spinning process. Therefore, it is preferable to mix the fiber raw material solution as an aqueous solution. The concentration of the water-soluble zwitterionic polymer in the aqueous solution is not particularly limited, but 5 to 50% by weight is used in consideration of the spinning process. As a method for adding the water-soluble zwitterionic polymer solution, any conventionally known method can be adopted, but it is preferable to add the aqueous solution quantitatively and continuously by an injection pump.
本発明において繊維原料溶液に混合される両性イオン性高分子の比率は、繊維母材に対して２〜４０重量％であることが望ましい。混合比率が低い場合には吸着能が低くなるため、吸着材としては適さない。混合比率が高い場合には、理論上吸着量の高い繊維が得られるが、繊維原料溶液に混合時に繊維原料の増粘・凝集が生じる、繊維の再生が不十分な繊維となる、などの問題が生じる恐れがある。したがって、少なくとも上記の範囲で混合する必要があり、好ましくは５〜３０重量％の混合比率で混合される。 In the present invention, the ratio of the zwitterionic polymer mixed in the fiber raw material solution is preferably 2 to 40% by weight with respect to the fiber base material. When the mixing ratio is low, the adsorptive capacity becomes low, so it is not suitable as an adsorbent. When the mixing ratio is high, fibers with a high adsorption amount can be obtained theoretically, but there are problems such as thickening and aggregation of the fiber raw material when mixing in the fiber raw material solution, and insufficient fiber regeneration. May occur. Therefore, it is necessary to mix at least within the above-mentioned range, and it is preferably mixed at a mixing ratio of 5 to 30% by weight.
本発明に係わる繊維状吸着材の形状には格別の制限はなく、長繊維のモノフィラメント、マルチフィラメント、短繊維の紡績糸でもよいが、単繊維径に関しては１〜５０μｍ、好ましくは５〜３０μｍであるほうが被処理溶液との接触効率を向上させることができる。このような繊維状の吸着材を使用すれば、長繊維または紡績糸状の吸着材を適切な密度に充填した充填塔に被処理溶液を通液させる、あるいは、被処理溶液に短繊維状の吸着材を添加・攪拌して濾過処理を行うという簡単な方法で、迅速に吸着除去を行うことができる。当然のことであるが、本発明の繊維は、織布、編物、不織布などの布帛に加工することが容易であるため、これらの布帛を利用した多種多彩な形状の吸着材を製造することができる。また、混合紡糸後、乾燥工程を経ずに、３〜２０ｍｍに裁断した湿潤した短繊維とし、必要に応じて、パルプおよび適切なバインダと混合後、公知の抄紙法によって抄紙すれば、吸着能をもつた紙状の吸着材フィルタを作成することも可能である。
つぎに実施例によって本発明を説明するが、この実施例によって本発明を何ら限定するものではない。
The shape of the fibrous adsorbent according to the present invention is not particularly limited, and may be monofilament, multifilament, and short fiber spun yarn of long fibers, but the single fiber diameter is 1 to 50 μm, preferably 5 to 30 μm. In some cases, the contact efficiency with the solution to be treated can be improved. If such a fibrous adsorbent is used, the solution to be treated is passed through a packed tower packed with a long fiber or spun yarn adsorbent at an appropriate density, or a short fiber adsorbed to the solution to be treated. Adsorption and removal can be quickly performed by a simple method of adding and stirring the material and performing a filtration treatment. As a matter of course, the fibers of the present invention can be easily processed into fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics. Therefore, it is possible to produce various kinds of adsorbents using these fabrics. it can. In addition, after mixing and spinning, without passing through a drying step, it becomes a wet short fiber cut to 3 to 20 mm, and if necessary, after mixing with pulp and an appropriate binder and making paper by a known paper making method, the adsorptive capacity It is also possible to create a paper-like adsorbent filter with a.
Next, the present invention will be described with reference to examples, but the present invention is not limited to the examples.
（１） 両性イオン性高分子混合繊維状吸着材の製造
ジアリルアミン−マレイン酸共重合体（日東紡績社製ＰＡＳ−４１０Ｃ、濃度４０％）１００ｍＬを、公知の方法により得られたセルロースビスコース（セルロース濃度：９％、アルカリ濃度：４．５％、粘度：５０秒［落球法］）５，０００ｍＬ中に溶解した。均一に混合後、減圧脱泡し、公知のビスコース繊維の製造方法に準じた湿式紡糸法によって両性イオン性高分子混合繊維を製造した。この時の再生凝固浴の組成は、硫酸：９０ｇ／Ｌ、硫酸亜鉛：１２ｇ／Ｌ、硫酸ナトリウム：３５０ｇ／Ｌとした。また、紡糸条件は、紡速：６０ｍ／ｓｅｃ、延伸：６０％とした。このようにして、２．０ｄｔｅｘの繊維を得た。得られた繊維は、裁断して長さ５１ｍｍの短繊維とした。混合された両性イオン性高分子の量を求めるため、Ｐｅｒｋｉｎ Ｅｌｍｅｒ ２４００ Ｓｅｒｉｅｓ ＩＩ ＣＨＮＳ／Ｏ Ｅｌｅｍｅｎｔａｌ Ａｎａｌｙｚｅｒで測定したところ、窒素量は０．４３Ｎ％であった。
(1) Manufacture of amphoteric ionic polymer mixed fibrous adsorbent Cellulose viscose (cellulose) obtained by 100 ml of diallylamine-maleic acid copolymer (Nittobo PAS-410C, concentration 40%) by a known method Concentration: 9%, alkali concentration: 4.5%, viscosity: 50 seconds [falling ball method]) dissolved in 5,000 mL. After uniform mixing, the mixture was degassed under reduced pressure, and a zwitterionic polymer mixed fiber was produced by a wet spinning method in accordance with a known viscose fiber production method. The composition of the regeneration coagulation bath at this time was sulfuric acid: 90 g / L, zinc sulfate: 12 g / L, and sodium sulfate: 350 g / L. The spinning conditions were spinning speed: 60 m / sec and stretching: 60%. In this way, 2.0 dtex fibers were obtained. The obtained fiber was cut into a short fiber having a length of 51 mm. In order to determine the amount of the mixed zwitterionic polymer, the amount of nitrogen was 0.43 N% as measured by Perkin Elmer 2400 Series II CHNS / O Elemental Analyzer.
（２） 両性イオン性高分子混合繊維状吸着材の不織布化
前記（１）で得たジアリルアミン−マレイン酸共重合体混合繊維５００ｇをローラーカード機（大和機工製、ＳＣ−３６０Ｄ）に通して開繊した。ついで、このウエッブをニードルパンチ機（大和機工製、ＮＬ３８０）に通して交絡して、目付量１４４０ｇ／ｍ２、厚さ約１０ｍｍの不織布とした。
(2) Making a zwitterionic polymer mixed fibrous adsorbent into a non-woven fabric 500 g of the diallylamine-maleic acid copolymer mixed fiber obtained in the above (1) is passed through a roller card machine (SC-360D, manufactured by Yamato Kiko) and opened It was fine. Subsequently, the web was passed through a needle punch machine (NL380, manufactured by Yamato Kiko Co., Ltd.) to form a nonwoven fabric having a basis weight of 1440 g / m 2 and a thickness of about 10 mm.
スルホベタイン型吸着材の合成
比較例として、非特許文献２および非特許文献３に記載のスルホベタイン型吸着材を合成した。合成方法は非特許文献２および非特許文献３を参考に行った。すなわち、グリシジルメタクリレート５０ｇ、Ｎ，Ｎ−ジメチルアクリルアミド１０ｇ、エチレンジメタクリレート４０ｇ、酢酸ブチル４０ｇ、２−メチルブタノール６０ｇの混合溶液に２，２’−アゾビスイソブチロニトリル１ｇを溶解した混合溶液を、０．２％ポリビニルアルコール（重合度５００）水溶液１、０００ｍＬ中に加え、攪拌機を用いて攪拌羽根を２５０ｒｐｍで回転させ、油層を分散した。その後、分散液（懸濁液）を加温し、７０℃で７時間重合反応を行った。生成した共重合体粒子を濾取し、水、メタノールの順で洗浄した。一日風乾後、分級を行い、４５〜９０μｍの親水性基材樹脂３５ｇを得た。この親水性基材樹脂の平均粒子径をＢｅｃｋｍａｎ Ｃｏｕｌｔｅｒ Ｍｕｌｔｉｓｉｚｅｒ ３ Ｃｏｕｌｔｅｒ Ｃｏｕｎｔｅｒで測定したところ、平均粒子径は６４μｍであった。また、比表面積と平均細孔径をＢｅｃｋｍａｎ Ｃｏｕｌｔｅｒ ＳＡ３１００ Ｓｕｒｆａｃｅ Ａｒｅａ Ａｎａｌｙｚｅｒで測定したところ、比表面積は８４ｍ２／ｇ、平均細孔径は１５．６ｎｍであった。ついで、２−ブロモエタンスルホン酸ナトリウムの１０重量％水溶液１００ｍＬに３０％ジメチルアミン水溶液１５ｍＬを加え、室温で２０時間反応させた。その後、陽イオン交換樹脂（Ｄｏｗｅｘ ＡＧ５０−Ｘ４、Ｂｉｏ−Ｒａｄ Ｌａｂｏｒａｔｏｒｉｅｓ）および陰イオン交換樹脂（Ｄｏｗｅｘ ＡＧ１−Ｘ８、Ｂｉｏ−Ｒａｄ Ｌａｂｏｒａｔｏｒｉｅｓ）を充填したクロマト管に通液し、過剰のジメチルアミンなどの不純物を除去し、Ｎ，Ｎ−ジメチルエタンスルホン酸水溶液を得た。その後、再結晶により得られた結晶を４０℃の真空乾燥機中で乾燥させた。親水性基材樹脂を０．１Ｍの塩酸でクロロヒドリン型に変換した親水性基材樹脂１ｇに、上記方法により得られたＮ，Ｎ−ジメチルエタンスルホン酸１．５ｇおよび水酸化ナトリウム水溶液（ｐＨ１２．５）２０ｍＬを加え、４０℃で７時間攪拌しながら反応させた。反応終了後、水、メタノールの順で洗浄し、乾燥させ、比較対象のスルホベタイン型吸着材を得た。
As synthesis comparative examples of sulfobetaine-type adsorbents, the sulfobetaine-type adsorbents described in Non-Patent Document 2 and Non-Patent Document 3 were synthesized. The synthesis method was performed with reference to Non-Patent Document 2 and Non-Patent Document 3. That is, a mixed solution in which 1 g of 2,2′-azobisisobutyronitrile was dissolved in a mixed solution of 50 g of glycidyl methacrylate, 10 g of N, N-dimethylacrylamide, 40 g of ethylene dimethacrylate, 40 g of butyl acetate and 60 g of 2-methylbutanol. , 0.2% polyvinyl alcohol (polymerization degree 500) aqueous solution was added to 1,000 mL, and the stirring blade was rotated at 250 rpm using a stirrer to disperse the oil layer. Thereafter, the dispersion (suspension) was heated, and a polymerization reaction was carried out at 70 ° C. for 7 hours. The produced copolymer particles were collected by filtration and washed with water and methanol in this order. After air drying for one day, classification was performed to obtain 35 g of a hydrophilic base resin having a thickness of 45 to 90 μm. When the average particle size of the hydrophilic base resin was measured with a Beckman Coulter Multisizer 3 Coulter Counter, the average particle size was 64 μm. Moreover, when the specific surface area and average pore diameter were measured by Beckman Coulter SA3100 Surface Area Analyzer, the specific surface area was 84 m 2 / g and the average pore diameter was 15.6 nm. Next, 15 mL of a 30% dimethylamine aqueous solution was added to 100 mL of a 10 wt% aqueous solution of sodium 2-bromoethanesulfonate and allowed to react at room temperature for 20 hours. Thereafter, the solution was passed through a chromatographic tube filled with a cation exchange resin (Dowex AG50-X4, Bio-Rad Laboratories) and an anion exchange resin (Dowex AG1-X8, Bio-Rad Laboratories), and impurities such as excess dimethylamine. Then, N, N-dimethylethanesulfonic acid aqueous solution was obtained. Thereafter, the crystals obtained by recrystallization were dried in a vacuum dryer at 40 ° C. To 1 g of the hydrophilic base resin obtained by converting the hydrophilic base resin into a chlorohydrin type with 0.1 M hydrochloric acid, 1.5 g of N, N-dimethylethanesulfonic acid obtained by the above method and a sodium hydroxide aqueous solution (pH 12.2. 5) 20mL was added and it was made to react, stirring at 40 degreeC for 7 hours. After completion of the reaction, water and methanol were washed in this order and dried to obtain a comparative sulfobetaine adsorbent.
保水量の評価
前記実施例（２）で得られた両性イオン性高分子混合繊維状吸着材の不織布を５０oＣの真空乾燥機内で１０時間乾燥後、直径１３ｍｍの円筒状に打ち抜き、内径１２．７ｍｍの注射筒型固相抽出用カートリッジに図１に示すように１枚を充填し、評価用カートリッジとした。評価用カートリッジに０．１Ｍ ＮａＯＨ ３ｍＬを通液した後、中性になるまで純水を通液し、さらに純水１０ｍＬで満たし１時間静置し、十分に保水させた。カートリッジを減圧マニュホールドで１０分間吸引し、過剰な水分を落とし、重量を測定した。さらに、その評価用カートリッジにアセトニトリル３ｍＬを５ｍＬ／ｍｉｎで通液した後、１０分間吸引を継続し、重量を測定した。それらの評価用カートリッジを５０℃、１５時間真空乾燥させた後計量し、純水およびアセトニトリルを通液させたときの重量との差より保水量を求めた。保水量の比較として、実施例（２）と同様の方法で不織布としたレギュラーレーヨン（オーミケンシ社製、商品名：ホープ、１．７ｄｔｅｘ）、および比較例のスルホベタイン型吸着材、さらに強陽イオン交換樹脂（Ｂｉｏ−Ｒａｄ Ｌａｂｏｒａｔｏｒｉｅｓ、ＡＧ５０Ｗ−Ｘ８、２００〜４００ｍｅｓｈ）と強陰イオン交換樹脂（Ｂｉｏ−Ｒａｄ Ｌａｂｏｒａｔｏｒｉｅｓ、ＡＧ １−Ｘ８、２００〜４００ｍｅｓｈ）を用いた。尚、比較例のスルホベタイン型樹脂、強陽イオン交換樹脂および強陰イオン交換樹脂の評価用カートリッジへの充填量は０．２５ｇとした。評価結果を表１に示す。水含浸後の保水量の比較において、本発明の両性イオン性高分子混合繊維は非常に高い保水性を示した。本試験においてアセトニトリル通液を行っているが、アセトニトリルを通液することにより過剰の水を洗い出すと共に、水溶性の高いアセトニトリルによって水の構造を破壊するためである。したがって、アセトニトリル通液後の値は、吸着材に強固に水和している水の量を示していると考えられる。ただし、陰イオン交換樹脂および陽イオン交換樹脂の基材樹脂はポリスチレンゲルであるため、本評価試験の１０分間吸引ではアセトニトリルを完全に除去できていない可能性がある。そのため、湿潤重量が大きくなり、保水量が高くなっている恐れがある。このような可能性があるにもかかわらず、アセトニトリル通液後の値は、本発明の両性イオン性高分子混合繊維が最も高い値を示している。これらの結果から、本発明の両性イオン性高分子混合繊維は保水性が高く、親水性相互作用の発現に有効な吸着材であることが判った。
Evaluation of water retention amount The zwitterionic polymer mixed fibrous adsorbent nonwoven fabric obtained in Example (2) was dried in a 50 ° C vacuum dryer for 10 hours, then punched into a cylindrical shape having a diameter of 13 mm, and an inner diameter of 12.7 mm. As shown in FIG. 1, one syringe cylinder type solid phase extraction cartridge was filled into a cartridge for evaluation. After passing 3 mL of 0.1M NaOH through the cartridge for evaluation, pure water was passed until neutrality, and further filled with 10 mL of pure water and allowed to stand for 1 hour to sufficiently retain water. The cartridge was sucked with a vacuum manifold for 10 minutes to remove excess moisture, and the weight was measured. Further, after passing 3 mL of acetonitrile through the evaluation cartridge at 5 mL / min, suction was continued for 10 minutes and the weight was measured. These cartridges for evaluation were vacuum-dried at 50 ° C. for 15 hours and then weighed, and the water retention amount was determined from the difference from the weight when pure water and acetonitrile were passed. As a comparison of the amount of water retention, regular rayon (trade name: Hope, 1.7 dtex, manufactured by Omikenshi Co., Ltd.) made into a nonwoven fabric by the same method as in Example (2), the sulfobetaine type adsorbent of Comparative Example, and a strong cation Exchange resin (Bio-Rad Laboratories, AG50W-X8, 200 to 400 mesh) and strong anion exchange resin (Bio-Rad Laboratories, AG 1-X8, 200 to 400 mesh) were used. The amount of the sulfobetaine type resin, the strong cation exchange resin and the strong anion exchange resin of the comparative example filled in the evaluation cartridge was 0.25 g. The evaluation results are shown in Table 1. In comparison of the water retention amount after water impregnation, the zwitterionic polymer mixed fiber of the present invention showed very high water retention. In this test, acetonitrile is passed through, in order to wash out excess water by passing acetonitrile and destroy the structure of water with highly water-soluble acetonitrile. Therefore, the value after passing acetonitrile is considered to indicate the amount of water strongly hydrated by the adsorbent. However, since the base resin of the anion exchange resin and the cation exchange resin is a polystyrene gel, acetonitrile may not be completely removed by suction for 10 minutes in this evaluation test. Therefore, there is a possibility that the wet weight is increased and the water retention amount is increased. Despite this possibility, the value after passing through acetonitrile shows the highest value for the zwitterionic polymer mixed fiber of the present invention. From these results, it was found that the zwitterionic polymer mixed fiber of the present invention has high water retention and is an effective adsorbent for the expression of hydrophilic interaction.
固相抽出法による金属吸着量の評価
前記実施例（２）で得られた両性イオン性高分子混合繊維不織布を６０oＣの真空乾燥機内で３時間乾燥後、評価試験１と同様に内径１２．７ｍｍの注射筒型固相抽出用カートリッジに図１に示すように１枚を充填し、評価用カートリッジとした。この評価用カートリッジに、アセトニトリル、純水、３Ｍ硝酸、純水および０．１Ｍ酢酸アンモニウム緩衝液（ｐＨ５）の順で、それぞれ１０ｍＬずつ通液して、充填された両性イオン性高分子混合繊維不織布のコンディショニングを行った。その後、０．０１Ｍ酢酸アンモニウム緩衝液（ｐＨ５）で調整された０．０１Ｍ硫酸銅溶液３ｍＬをゆっくり通液し、充填された両性イオン性高分子混合繊維不織布を銅で飽和させた。その後、純水１０ｍＬ、０．００５Ｍの硝酸５ｍＬで過剰の銅を洗浄後、両性イオン性高分子混合繊維不織布に吸着された銅を３Ｍ硝酸３ｍＬで溶出させた。溶出液を１０ｍＬに定容後、吸光光度計で８０５ｎｍにおける銅の吸光度を測定し、両性イオン性高分子混合繊維不織布における銅吸着量を求めた。その結果、銅の吸着量は、０．２９ｍｍｏｌ Ｃｕ／ｇであり、十分な吸着能をもつことが判った。ついで、同様にコンディショニングした評価用カートリッジに０．０１Ｍ酢酸アンモニウム緩衝液（ｐＨ５）／メタノール＝１／４で調整された０．００２Ｍ硫酸銅溶液１０ｍＬをゆっくり通液して、同様の金属吸着量評価を行った。その結果、銅の吸着量は、０．２８ｍｍｏｌ Ｃｕ／ｇであり、メタノール共存下でも十分な吸着能をもつことが判った。
Evaluation of metal adsorption amount by solid-phase extraction method The zwitterionic polymer mixed fiber nonwoven fabric obtained in Example (2) was dried for 3 hours in a 60 ° C. vacuum dryer, and the inner diameter was 12.7 mm as in Evaluation Test 1. As shown in FIG. 1, one syringe cylinder type solid phase extraction cartridge was filled into a cartridge for evaluation. 10 mL each of acetonitrile, pure water, 3M nitric acid, pure water, and 0.1M ammonium acetate buffer (pH 5) were passed through the cartridge for evaluation, and filled with the zwitterionic polymer mixed fiber nonwoven fabric. Was conditioned. Thereafter, 3 mL of 0.01 M copper sulfate solution adjusted with 0.01 M ammonium acetate buffer (pH 5) was slowly passed through to saturate the filled zwitterionic polymer mixed fiber nonwoven fabric with copper. Thereafter, excess copper was washed with 10 mL of pure water and 5 mL of 0.005M nitric acid, and then the copper adsorbed on the zwitterionic polymer mixed fiber nonwoven fabric was eluted with 3 mL of 3M nitric acid. The volume of the eluate was adjusted to 10 mL, and the absorbance of copper at 805 nm was measured with an absorptiometer to determine the amount of copper adsorbed on the zwitterionic polymer mixed fiber nonwoven fabric. As a result, the amount of copper adsorbed was 0.29 mmol Cu / g, and it was found that the adsorbing capacity was sufficient. Next, 10 mL of a 0.002 M copper sulfate solution adjusted to 0.01 M ammonium acetate buffer (pH 5) / methanol = 1/4 was slowly passed through the evaluation cartridge similarly prepared, and the same metal adsorption amount evaluation was performed. Went. As a result, the amount of copper adsorbed was 0.28 mmol Cu / g, and it was found that the adsorbing ability was sufficient even in the presence of methanol.
固相抽出法による極性化合物の抽出回収率比較試験
前記実施例（２）で得られた両性イオン性高分子混合繊維不織布を、評価試験１と同様の固相抽出用カートリッジに充填し、評価用カートリッジとした。同様に、評価試験１のレギュラーレーヨン不織布と比較例により合成したスルホベタイン型吸着材も同様の方法で評価用カートリッジとした。この評価用カートリッジに、アセトニトリル１０ｍＬ、純水２０ｍＬ、アセトニトリル−水（９：１）１０ｍＬを順に通液して、カートリッジのコンディショニングを行った。その後、表２に示す被検化合物をアセトニトリル−水（９：１）で溶解した溶液（濃度：各１ｐｐｍ）１０ｍＬを通液し、被検化合物を各吸着材で抽出した。表２において、ｌｏｇ Ｐｏ／ｗはオクタノール／水分配係数であり、この値が小さいものほど水に分配しやすい化合物であることを意味する。その後、アセトニトリル５ｍＬで洗浄後、純水１０ｍＬを用いて各吸着材に抽出された被検化合物を溶出させた。各溶出液を、紫外可視分光光度計を用いて測定し、得られた吸光度と吸着処理を行わない被検試料標準溶液の吸光度から、各吸着材における抽出回収率を求めた。表２は、被検化合物とその溶解度と水−オクタノール分配比（ｌｏｇ Ｐｏ／ｗ）を示す。また、被検化合物の化学構造を式３−式９に示す。
Extraction recovery comparison test of polar compounds by solid phase extraction method The zwitterionic polymer mixed fiber nonwoven fabric obtained in the above Example (2) was filled in the same solid phase extraction cartridge as in Evaluation Test 1 for evaluation. A cartridge was used. Similarly, the regular rayon nonwoven fabric of Evaluation Test 1 and the sulfobetaine-type adsorbent synthesized by the comparative example were also used as evaluation cartridges in the same manner. The cartridge was conditioned by sequentially passing 10 mL of acetonitrile, 20 mL of pure water, and 10 mL of acetonitrile-water (9: 1) through the cartridge for evaluation. Thereafter, 10 mL of a solution (concentration: 1 ppm each) in which the test compound shown in Table 2 was dissolved in acetonitrile-water (9: 1) was passed, and the test compound was extracted with each adsorbent. In Table 2, log Po / w is an octanol / water partition coefficient, and the smaller this value, the easier it is to partition into water. Thereafter, after washing with 5 mL of acetonitrile, the test compound extracted to each adsorbent was eluted using 10 mL of pure water. Each eluate was measured using an ultraviolet-visible spectrophotometer, and the extraction recovery rate in each adsorbent was determined from the obtained absorbance and the absorbance of the test sample standard solution not subjected to the adsorption treatment. Table 2 shows the test compounds, their solubility, and the water-octanol partition ratio (log P o / w ). The chemical structure of the test compound is shown in Formula 3 to Formula 9.
３種の吸着材における抽出回収率を図２に示す。図２で明白なように、本発明の両性イオン性高分子混合繊維不織布ではすべての化合物に対して９０％以上の回収率を示したが、レギュラーレーヨンの回収率は低く、すべての化合物で５０％を超えることはなかった。このことからも、両性イオン性高分子を混合させることで親水性相互作用を明確に発現させることができ、極性化合物を高度に抽出回収できることが判った。また、非特許文献２において明確な親水性相互作用を発現するとされている比較例のスルホベタイン型吸着材では、ウラシル、アデノシン、ウリジン、アセフェートに対して高い選択性を示したが、配糖体であるサリシンおよびアルブチンに対する選択性は低く、本発明の両性イオン性高分子混合繊維不織布に比べてかなり低い回収率となった。このことからも、本発明の両性イオン性高分子混合繊維状吸着材が明確な親水性相互作用を発現していることが判る。 The extraction recovery rates for the three adsorbents are shown in FIG. As apparent from FIG. 2, the zwitterionic polymer mixed fiber nonwoven fabric of the present invention showed a recovery rate of 90% or more for all compounds, but the recovery rate of regular rayon was low, and 50% for all compounds. % Did not exceed. This also indicates that the hydrophilic interaction can be clearly expressed by mixing the zwitterionic polymer, and the polar compound can be highly extracted and recovered. In addition, the sulfobetaine-type adsorbent of Comparative Example, which is said to express a clear hydrophilic interaction in Non-Patent Document 2, showed high selectivity for uracil, adenosine, uridine, and acephate. The selectivity for salicin and arbutin was low, and the recovery rate was considerably lower than that of the zwitterionic polymer mixed fiber nonwoven fabric of the present invention. This also shows that the zwitterionic polymer mixed fibrous adsorbent of the present invention expresses a clear hydrophilic interaction.
オクタン中の極性化合物の吸着特性の評価
実施例（２）で得られた両性イオン性高分子混合繊維不織布を、評価試験１と同様の固相抽出用カートリッジに充填し、評価用カートリッジとした。この評価用カートリッジを用いてオクタン中に添加した極性化合物の吸着率を調べた。この評価用カートリッジに、アセトニトリル１０ｍＬ、純水２０ｍＬ、アセトン１０ｍＬを順に通液して、カートリッジのコンディショニングを行った。コンディショニング後の評価カートリッジをアスピレータで２０分間吸引し、不織布に残ったアセトンを除去した。その後、カテコール、安息香酸およびベンジルアミンのオクタン溶液（濃度：各１ｐｐｍ）１０ｍＬを通液し、被検化合物を各吸着材で抽出した。元のオクタン溶液と不織布通過液を、紫外可視分光光度計を用いて測定し、その吸光度差から吸着率を求めた。カテコール、安息香酸およびベンジルアミンの測定波長は、それぞれ２８０ｎｍ、２３０ｎｍおよび２８０ｎｍとした。各極性化合物(カテコール、安息香酸およびベンジルアミン)の吸着率は、それぞれ９２．２％、９７．９％および９７．２％となり、本発明の両性イオン性高分子混合繊維状吸着材は無極性溶媒中の極性化合物の吸着除去にも利用可能であることが判った。
Evaluation of Adsorption Characteristics of Polar Compound in Octane The zwitterionic polymer mixed fiber nonwoven fabric obtained in Example (2) was filled in the same solid phase extraction cartridge as in Evaluation Test 1 to obtain an evaluation cartridge. Using this evaluation cartridge, the adsorption rate of the polar compound added in octane was examined. The cartridge was conditioned by sequentially passing 10 mL of acetonitrile, 20 mL of pure water, and 10 mL of acetone through the cartridge for evaluation. The evaluation cartridge after conditioning was sucked with an aspirator for 20 minutes to remove acetone remaining on the nonwoven fabric. Thereafter, 10 mL of an octane solution (concentration: 1 ppm each) of catechol, benzoic acid and benzylamine was passed through, and the test compound was extracted with each adsorbent. The original octane solution and the nonwoven fabric passing solution were measured using an ultraviolet-visible spectrophotometer, and the adsorption rate was determined from the difference in absorbance. The measurement wavelengths of catechol, benzoic acid and benzylamine were 280 nm, 230 nm and 280 nm, respectively. The adsorption rate of each polar compound (catechol, benzoic acid and benzylamine) was 92.2%, 97.9% and 97.2%, respectively, and the zwitterionic polymer mixed fibrous adsorbent of the present invention was nonpolar. It was found that it can also be used for adsorption removal of polar compounds in the solvent.
金属吸着特性の評価
実施例（２）で得られた両性イオン性高分子混合繊維不織布を、評価試験１と同様の固相抽出用カートリッジに充填し、評価用カートリッジとした。この評価用カートリッジを用いて種々のｐＨにおける金属の吸着特性を調べた。評価用カートリッジは、評価試験２と同様のコンディショニングを行った後、ｐＨ２〜９に調整したカルシウム（Ｃａ）、カドミウム（Ｃｄ）、コバルト（Ｃｏ）、三価クロム（Ｃｒ）、銅（Ｃｕ）、鉄（Ｆｅ）、マンガン（Ｍｎ）、モリブデン（Ｍｏ）、ニッケル（Ｎｉ）、鉛（Ｐｂ）、チタン（Ｔｉ）および亜鉛（Ｚｎ）の１２元素混合溶液を通液し、吸着させた。その後、両性イオン性高分子混合繊維不織布を純水２０ｍＬで洗浄し、３Ｍ硝酸１０ｍＬで溶出させ、ＩＣＰ発光分析装置を用いて溶液中濃度を測定し、吸着回収率を求めた。結果を図３（図３ａないし図３ｌを含む。）に示す。オキソ酸を形成して陰イオンとして存在しているモリブデン（Ｍｏ）を除き、ｐＨ５以上で高い吸着回収率が得られた。この吸着特性は一般的に使用されるイミノ二酢酸型キレート樹脂の吸着特性と似ているが、イミノ二酢酸型キレート樹脂に対する錯形成速度が非常に遅いとされる三価クロム（Ｃｒ）も高度に吸着できることが判った。一方、陰イオンとして存在するモリブデン（Ｍｏ）は酸性領域でのみ吸着しており、この挙動もイミノ二酢酸型キレート樹脂と類似であった。ここでの試験は、一回のみの通液吸着試験であり、本発明の両性イオン性高分子混合繊維状吸着材の吸着速度が早く、通液吸着処理においても高度に重金属を除去できることが分かる。
Evaluation of metal adsorption characteristics The amphoteric ionic polymer mixed fiber nonwoven fabric obtained in Example (2) was filled in the same solid phase extraction cartridge as in Evaluation Test 1 to obtain an evaluation cartridge. Using this evaluation cartridge, the adsorption characteristics of metals at various pH values were examined. After performing the same conditioning as the evaluation test 2, the evaluation cartridge was adjusted to pH 2 to 9 (calcium (Ca), cadmium (Cd), cobalt (Co), trivalent chromium (Cr), copper (Cu), A 12-element mixed solution of iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb), titanium (Ti) and zinc (Zn) was passed through and adsorbed. Thereafter, the zwitterionic polymer mixed fiber nonwoven fabric was washed with 20 mL of pure water and eluted with 10 mL of 3M nitric acid, and the concentration in the solution was measured using an ICP emission spectrometer to determine the adsorption recovery rate. The results are shown in FIG. 3 (including FIGS. 3a to 3l). Excepting molybdenum (Mo) which is present as an anion by forming oxo acid, a high adsorption recovery rate was obtained at pH 5 or higher. This adsorption characteristic is similar to that of commonly used iminodiacetic acid-type chelating resins, but trivalent chromium (Cr), which is considered to have a very slow complex formation rate for iminodiacetic acid-type chelating resins, is also highly advanced. It was found that it can be adsorbed. On the other hand, molybdenum (Mo) present as an anion was adsorbed only in the acidic region, and this behavior was similar to that of iminodiacetic acid type chelate resin. The test here is a one-time liquid adsorption test, and the adsorption rate of the zwitterionic polymer mixed fibrous adsorbent of the present invention is high, and it can be seen that heavy metals can be highly removed even in the liquid adsorption process. .
本発明によれば、水溶性の両性イオン性高分子として、その高分子中に側鎖としてアルキレン基を介して結合したアミノ基、あるいは環状のイミノ基、およびカルボキシル基を有する水溶性の両性イオン性高分子を、繊維原料溶液に混合後、湿式混合紡糸を行うという簡便な方法で、親水性相互作用により極性化合物を吸着し、かつ金属類をも吸着可能な繊維状の吸着材を製造することができる。また、無極性溶媒中の極性化合物の吸着材としても使用可能である。本発明の両性イオン性高分子を混合した繊維状吸着材は、広範囲な試料中の極性化合物と金属の吸着除去に使用することができる。本発明の両性イオン性高分子混合繊維状吸着材は柔軟性に富み、織布、編物、不織布などの布帛に容易に加工することが可能であるため、これらの布帛を利用することで極性化合物や重金属の吸着性に優れた、排水や用水、さらには種々の工業製品中の極性化合物と重金属の除去用の吸着性フィルタを得ることができる。また、短繊維としてパルプおよび適切なバインダと混合後、抄紙すれば親水性相互作用およびキレート形成能を発現する紙状の吸着材フィルタを作成することも可能である。さらに、本発明の両性イオン性高分子混合繊維状吸着材は、工業的な水処理だけでなく、化学物質分析のための前処理用吸着材としても利用可能である。 According to the present invention, as a water-soluble zwitterionic polymer, a water-soluble zwitterion having an amino group or a cyclic imino group and a carboxyl group bonded to the polymer through an alkylene group as a side chain. A fibrous adsorbent capable of adsorbing polar compounds by hydrophilic interaction and adsorbing metals by a simple method of mixing wet polymers with fiber raw material solution followed by wet mixing spinning be able to. It can also be used as an adsorbent for polar compounds in nonpolar solvents. The fibrous adsorbent mixed with the zwitterionic polymer of the present invention can be used for adsorption removal of polar compounds and metals in a wide range of samples. Since the zwitterionic polymer mixed fibrous adsorbent of the present invention is rich in flexibility and can be easily processed into fabrics such as woven fabrics, knitted fabrics and nonwoven fabrics, polar compounds can be obtained by using these fabrics. Further, it is possible to obtain an adsorptive filter for removing polar compounds and heavy metals in waste water and water, and various industrial products, which are excellent in adsorptivity of heavy metals and heavy metals. Moreover, it is also possible to produce a paper-like adsorbent filter that exhibits hydrophilic interaction and chelate-forming ability by making paper after mixing with pulp and an appropriate binder as short fibers. Furthermore, the zwitterionic polymer mixed fibrous adsorbent of the present invention can be used not only as an industrial water treatment but also as a pretreatment adsorbent for chemical substance analysis.
１：両性イオン性高分子混合繊維状吸着材（不織布）
２：固相抽出カートリッジ
３：上部フリット
４：下部フリット
1: Zwitterionic polymer mixed fibrous adsorbent (nonwoven fabric)
2: Solid phase extraction cartridge 3: Upper frit 4: Lower frit
Claims (4)
The method for producing a fibrous adsorbent according to any one of claims 1 to 3, wherein the water-soluble zwitterionic polymer is mixed with a fiber raw material and then mixed and spun by a wet spinning method.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109289812A (en) * | 2018-11-12 | 2019-02-01 | 南京林业大学 | A kind of preparation method of the paper base adsorbent based on wood fibre |
| WO2022039112A1 (en) * | 2020-08-20 | 2022-02-24 | 昭和電工マテリアルズ株式会社 | Absorbent particles, base particles, packed column and method for recovering rare earth elements |
| CN115770626A (en) * | 2022-11-22 | 2023-03-10 | 河南科高辐射化工科技有限公司 | Amphoteric ion exchange fiber and preparation method and application thereof |
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| CN109289812A (en) * | 2018-11-12 | 2019-02-01 | 南京林业大学 | A kind of preparation method of the paper base adsorbent based on wood fibre |
| CN109289812B (en) * | 2018-11-12 | 2021-03-23 | 南京林业大学 | Preparation method of paper-based adsorbent based on wood fiber |
| WO2022039112A1 (en) * | 2020-08-20 | 2022-02-24 | 昭和電工マテリアルズ株式会社 | Absorbent particles, base particles, packed column and method for recovering rare earth elements |
| CN115770626A (en) * | 2022-11-22 | 2023-03-10 | 河南科高辐射化工科技有限公司 | Amphoteric ion exchange fiber and preparation method and application thereof |
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