JPS62205102A - Production of ion exchanger - Google Patents

Production of ion exchanger

Info

Publication number
JPS62205102A
JPS62205102A JP61047077A JP4707786A JPS62205102A JP S62205102 A JPS62205102 A JP S62205102A JP 61047077 A JP61047077 A JP 61047077A JP 4707786 A JP4707786 A JP 4707786A JP S62205102 A JPS62205102 A JP S62205102A
Authority
JP
Japan
Prior art keywords
carrier
ion exchanger
porous spherical
paraffin
group
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.)
Granted
Application number
JP61047077A
Other languages
Japanese (ja)
Other versions
JPH0518321B2 (en
Inventor
Harumi Miyajima
宮嶋 はるみ
Yoshinori Inoue
嘉則 井上
Hiroki Kumagai
熊谷 浩樹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yokogawa Electric Corp
Original Assignee
Yokogawa Electric Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yokogawa Electric Corp filed Critical Yokogawa Electric Corp
Priority to JP61047077A priority Critical patent/JPS62205102A/en
Publication of JPS62205102A publication Critical patent/JPS62205102A/en
Publication of JPH0518321B2 publication Critical patent/JPH0518321B2/ja
Granted legal-status Critical Current

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PURPOSE:To obtain an ion exchanger wherein a very small amount of an ion exchange group is introduced to only the surface of a hydrophilic carrier, by reacting a substance which is directly reacted with a glycidyl group introduced to a hydrophilic porous spherical carrier to become an ion exchange group with the glycidyl group. CONSTITUTION:For example, a monomer such as hydroxyalkyl, glycerin, etc. is polymerized in the presence of a crosslinking agent (e.g., divinylbenzene, ethylene glycol dimethacrylate, etc.) to give a hydrophilic porous spherical carrier, which is impregnated with paraffin, dispersed into an alkali solution and reacted with a glycidyl group-containing reagent (e.g. epichlorohydrin, alkylene diglycidyl ether, etc.) capable of reacting with a hydroxyl group in the present of a catalyst (e.g. alpha,alpha'-azobisisobutyronitrile, etc.) so that the glycidyl group is introduced into the carrier. The carrier is washed with a solvent, the paraffin in the carrier is washed way and then the glycidyl group is reacted with a substance (e.g. sodium nitrite, etc.) which is directly reacted with a glycidyl group and becomes an ion exchanger.

Description

【発明の詳細な説明】 〈産業上の利用分デf〉 本発明は、親水性担体の表面にのみ微量のイオン交換括
が導入これイオンクロマトグラフ用充填剤等で使用され
るイオン交換体を製造する方法に関する。
[Detailed Description of the Invention] <Industrial Application Def> The present invention introduces a trace amount of ion exchanger only on the surface of a hydrophilic carrier. Relating to a method of manufacturing.

く従来の技術〉 上述のようなイオン交換体は、イオンクロマトグラフ用
充填剤として使用される場合、低交換当量で且つ表面に
のみイオン交換基が導入されているものであることが望
ましい。このため、例えば外径0.01〜0.05μm
の超微細粒子でなるラテックス状イオン交@樹脂を担体
の表面に付着させたものがイオン交換体として利用され
ている。このようなラテックス型のイオン交換体は、担
体の表面にラテックス状イオン交換樹脂を安定的に保持
させることが困難であるという欠点があった。また、イ
オン交換体を充」ハしてなる分離カラムの分離性能がラ
テックス状イオン交換樹脂によって支配されるため、分
離カラムの分離性能の多手工化を図るにはラテックス状
イオン交換イS(脂も多種類必要となる欠点があった。
BACKGROUND ART When the above-mentioned ion exchanger is used as a packing material for ion chromatography, it is desirable that the ion exchanger has a low exchange equivalent and has ion exchange groups introduced only on the surface. For this reason, for example, an outer diameter of 0.01 to 0.05 μm
A latex-like ion exchange resin made of ultrafine particles is attached to the surface of a carrier and is used as an ion exchanger. Such latex-type ion exchangers have a drawback in that it is difficult to stably retain the latex-like ion exchange resin on the surface of the carrier. In addition, since the separation performance of a separation column filled with an ion exchanger is controlled by the latex ion exchange resin, it is necessary to use latex ion exchange resin (S) to increase the separation performance of the separation column. There was also a drawback that many types were required.

一方、多孔質な担体は透過性がよく究極的に上記分列カ
ラムの分離性能も高くなるため、イオンクロマトグラフ
用充填剤(011ち、イオン交換体)の担体として広く
使用されている。
On the other hand, porous carriers have good permeability and ultimately improve the separation performance of the separation column, so they are widely used as carriers for ion chromatography packing materials (011, ion exchangers).

このようなタイプのイオン交換体は、化学結合によって
イオン交換基が担体に導入されていて安定であるため、
JH体に種々のイオン交換基を容易に導入できる利点が
ある。
This type of ion exchanger is stable because the ion exchange group is introduced into the carrier through chemical bonding.
There is an advantage that various ion exchange groups can be easily introduced into the JH form.

然し乍ら、上記多孔質担体であっても表面にのみイオン
交換基を導入するのは困叉「であり、該担体の細孔内部
までイオン交換基が導入されてしまうという欠点があっ
た。このため、イオン交換体のイオン交換容量の調節が
回圧となるうえ、担体の細孔内へ試料が拡ntしたりす
る現象も生じ、こうしたイオン交換体を充填した分離カ
ラムの分離性能向上は殆んど期待できなくなっていた。
However, even with the above-mentioned porous carrier, it is difficult to introduce ion exchange groups only to the surface, and there is a drawback that the ion exchange groups are introduced into the pores of the carrier. In addition, adjustment of the ion exchange capacity of the ion exchanger becomes a rounding pressure, and a phenomenon such as the sample expanding into the pores of the carrier also occurs, so that the separation performance of a separation column packed with such an ion exchanger is hardly improved. I had lost all hope.

〈発明が解決しようとする問題点〉 本発明はかかる状況に比みてなされたものであり、その
目的は、イオンクロマトグラフ用充填剤として使用した
場合、分離カラムの性能が向上すると共に分離特性も容
易に変化させられるようなイオン交換体の製造方法を提
供することにある。
<Problems to be Solved by the Invention> The present invention has been made in consideration of such a situation, and its purpose is to improve the performance of a separation column and improve the separation characteristics when used as a packing material for ion chromatography. The object of the present invention is to provide a method for producing an ion exchanger that can be easily changed.

く問題点を解決するための手段〉 上述のような問題点を解決する本発明の特徴は、イオン
交換体の製造方法において、親水性の多孔性球状担体に
導入されるグリシシン基と直接的に反応してイオン交換
基となる物質とグリシシン基を反応させ、親水性1u体
の表面にのみ微量のイオン交換基が導入されるようにし
たことにある。
Means for Solving the Problems> The feature of the present invention that solves the problems described above is that in the method for producing an ion exchanger, the glycicin groups introduced into the hydrophilic porous spherical carrier and The reason is that a substance that reacts to become an ion exchange group is reacted with a glycicin group, so that a trace amount of an ion exchange group is introduced only onto the surface of the hydrophilic 1U body.

〈実施例〉 以下、本発明について図を用いて詳しく説明する。図は
本発明実施例を説明するフローチャートである。図にお
いて、最初、モノマーを架橋剤と一緒に重合させて1’
Jられる多孔性球状担体にパラフィンを含浸させること
が行なわれる。即ち、例えばグリセリンジメタクリレー
トでなる架橋剤と、例えば3−ヒドロキシプロピルメタ
クリレートのような千ツマ−と、例えばα、α°−7ゾ
ビスイソブチルニトリルのような重合触媒と、例えばク
ロルベンゼンおよびジエチルフタレートからなる混合物
を、一定の溶液(例えば、m合度500のポリビニアル
コールと塩化カリウJ\を脱イオン水に溶解した溶液)
に加え、高速攪拌しながら例えば65°Cに加温して懸
濁1合を行なわせる。このようにして生成した重合体粒
子を、濾別し温水浄洗してのちインプロパツールで洗浄
し、例えば粒径8〜12μmの上記多孔性球状担体を得
る。該担体をメタノール洗浄してのち、例えば80°C
で4時間乾燥し、その後、炭素数8〜20程度のパラフ
ィン(例えば、n−デカン)の中に入れ、例えば超音波
をかけて攪拌する。このようにして、上記多孔性球状担
体にパラフィンが含浸される。次に、上記多孔性球状担
体にグリシジル基を導入することが行なわれる。即ち、
グリシジル基を有し且つ水酸基と反応しろる試薬(例え
ば、1.4−ブタンジオールジグリシジルエーテル)と
水素化ホウ素ナトリウムを含むアルカリ性溶液(例えば
INのカセイソーダ)に、上記多孔性球状担体を加え、
例えば室温で5峙間攪拌しながら反1.iSさせる。そ
の後、メタノール、クロロホルム、およびメタノールの
順で洗浄することにより、未反応物と上記パラフィンを
洗い流して、グリシジル基が導入された多孔性球状担体
を?ソる。最後に、1を亥j1体のグリシジル基と直目
的に反15 してイオン交換4Bとなる物質(f+lI
えば、亜硫酸ナトリウム)を上記多孔性球状1[!体と
を反応させ、多孔性球状担体の表面に微量のイオン交換
基を導入する。即ち、グリシジル基が4人された多孔性
球状担体を、例えば亜硫酸ナトリウムが溶解された水溶
液中に分i!IL、、1促j′Fシながら例えば70°
Cで5117 t?jf反応させ、その後、脱イオン水
で洗浄して希塩酸中にl提清させて、表面に微量のイオ
ン交換基が導入された多孔性球状担体を生成・保存する
。因みに、このようにして得られた多孔性球状担体をイ
オンクロマトグラフ用分離カラ1、に充1(1シ、Li
’、Na’、NI1%、に’を含む試料を分析したとこ
ろ、これら全てのイオンが分析周期わずか5分で良好に
分離する結果が得られた。
<Example> Hereinafter, the present invention will be explained in detail using the drawings. The figure is a flowchart illustrating an embodiment of the present invention. In the figure, monomers are first polymerized together with a crosslinking agent to form 1'
The porous spherical carrier to be prepared is impregnated with paraffin. a crosslinking agent such as glycerol dimethacrylate, a polymer such as 3-hydroxypropyl methacrylate, a polymerization catalyst such as α,α°-7 bisisobutyl nitrile, and a combination of e.g. chlorobenzene and diethyl phthalate. A mixture consisting of a certain solution (for example, a solution of polyvinyl alcohol with a m content of 500 and potassium chloride
In addition, suspension is carried out by heating to, for example, 65°C while stirring at high speed. The polymer particles thus produced are separated by filtration, washed with hot water, and then washed with an impropat tool to obtain the porous spherical carrier having a particle size of, for example, 8 to 12 μm. After washing the carrier with methanol, for example, at 80°C
The sample is dried for 4 hours, and then placed in paraffin having about 8 to 20 carbon atoms (for example, n-decane) and stirred, for example, by applying ultrasonic waves. In this way, the porous spherical carrier is impregnated with paraffin. Next, glycidyl groups are introduced into the porous spherical carrier. That is,
Adding the porous spherical carrier to an alkaline solution (e.g. IN caustic soda) containing a reagent having a glycidyl group and reacting with a hydroxyl group (e.g. 1,4-butanediol diglycidyl ether) and sodium borohydride,
For example, while stirring for 5 minutes at room temperature, add 1. Let it be iS. Thereafter, by washing with methanol, chloroform, and methanol in this order, unreacted substances and the above paraffin are washed away, and the porous spherical carrier into which the glycidyl group has been introduced is removed. Soru. Finally, a substance (f + lI
For example, sodium sulfite) into the porous spherical 1 [! A minute amount of ion exchange group is introduced onto the surface of the porous spherical carrier. That is, a porous spherical carrier having four glycidyl groups is separated into an aqueous solution in which, for example, sodium sulfite is dissolved. IL,, for example, 70° while pressing 1
5117 t in C? jf reaction, and then washed with deionized water and dissolved in dilute hydrochloric acid to produce and preserve a porous spherical carrier having a trace amount of ion exchange group introduced onto its surface. Incidentally, the porous spherical carrier thus obtained was filled into 1 ion chromatographic separation column (1 column, Li
When a sample containing ', Na', 1% NI, and Ni' was analyzed, all of these ions were successfully separated in an analysis cycle of only 5 minutes.

尚、本発明は上述の実施例に限定されることなく種−?
の変形が可能であり、例えば、多孔(イL球状担体の表
面に微量のイオン交換基を導入する工程を次のように変
更してもよいものとする。即ち、ヒドロキシプロパンス
ルホン酸と3−フッ化ホウ4;ニーFルエ−テ]しをr
lむ11−シーオー什ン溶イrtQ l、二、上記テノ
リシシル括か導入J′Σれた多孔1′F球状世体?(加
え、例えば10°Cで6時間反j、シ、させろl:稈に
変り1したり、グリコール酸と水酪化ホウ素ナトリウム
を含む水溶Mi中に、J−1記グリシジルJλが導入さ
れた多孔性球状担体を加え、(!/1えば50゛Cで5
時間反応させる工程に変更してもよい。また、多孔性球
状担体にグリシジル基を導入する上述の工程も、市販の
相当試薬(例えば、口本石油株式会社製r (1号ソル
ベント1■」)の中に上記多孔性球状担体を分散、させ
、更に、エピクロルヒドリンを含む希カセイソーダ溶溶
を加え、例えば4 (1’Cで2時間だけ、1117、
1’l! l、ながら反応させる工程に変更してもよい
ものとする。
It should be noted that the present invention is not limited to the above-mentioned embodiments, but can be applied to other species.
For example, the step of introducing a small amount of ion exchange groups onto the surface of the porous spherical carrier may be changed as follows. Boron fluoride 4;
lm11-ShiOten melting rtQ l, 2, the above-mentioned tenorishicil bracket introduced J'Σ porous 1'F spherical world? (In addition, for example, let it incubate for 6 hours at 10°C. It turns into a culm, or the glycidyl Jλ described in J-1 is introduced into the aqueous Mi containing glycolic acid and sodium boroborohydride. Add a porous spherical carrier, (!/1 for example 5 at 50°C)
The process may be changed to a step of reacting for a period of time. The above-mentioned step of introducing glycidyl groups into the porous spherical carrier can also be carried out by dispersing the porous spherical carrier in a commercially available equivalent reagent (for example, R (No. 1 Solvent 1■) manufactured by Kuchimoto Sekiyu Co., Ltd.). Then add dilute caustic soda solution containing epichlorohydrin, for example 4 (1117 for 2 hours at 1'C,
1'l! However, the process may be changed to a step in which the reaction is carried out while reacting.

〈発明の効果〉 以上詳しく説明したような本発明によれば、親水性の多
孔性球状1目体の表面にのみi、?!!鑓のイオン交換
基が導入されるようなも一1成であるため、試オ)(被
測定体)は親水性担体の表面でだけイオン交換反応を起
こすようになる。従って、本発明によれば、前記従来例
のように担体の細孔内へ試本]が拡11々する現象が回
避でき、イオン交換体を充填した分離カラムの分離性能
が向上する利点がある。
<Effects of the Invention> According to the present invention as described in detail above, i, ? ! ! Since the ion-exchange group is introduced, the sample (analyte) undergoes an ion-exchange reaction only on the surface of the hydrophilic carrier. Therefore, according to the present invention, it is possible to avoid the phenomenon of the sample expanding into the pores of the carrier as in the conventional example, and there is an advantage that the separation performance of the separation column packed with the ion exchanger is improved. .

また、上記多孔性球状担体の表面に微量のイオン交換基
を導入する工程で反応試薬を変えるだけで、分列特性の
異なるイオン交換体を容易に製造できる利点もある。更
に、上記多孔性球状担体が親水性であるため、試料[1
コの疎水性物質によるイオン交換体(ひいては分蹟カラ
ム)の汚染が防止できる利点もある。
Another advantage is that ion exchangers with different sorting characteristics can be easily produced by simply changing the reaction reagent in the step of introducing a small amount of ion exchange groups onto the surface of the porous spherical carrier. Furthermore, since the porous spherical carrier is hydrophilic, sample [1
Another advantage is that contamination of the ion exchanger (and thus the fractionation column) by hydrophobic substances can be prevented.

【図面の簡単な説明】[Brief explanation of drawings]

図は本発明実JI8i例のイオン交換体製造方法を説明
するフローチャートである。
The figure is a flowchart illustrating a method for producing an ion exchanger according to the JI8i example of the present invention.

Claims (5)

【特許請求の範囲】[Claims] (1)下記(a)乃至(d)の工程により、親水性担体
の表面にのみ微量のイオン交換基を導入することを特徴
とするイオン交換体製造方法。 (a)モノマーを架橋剤と一緒に重合させて得られる親
水性の多孔性球状担体にパラフィンを含浸させる工程。 (b)前記パラフィンを含浸する多孔性球状担体をアル
カリ性溶液に分散させ、グリシジル基を有し水酸基と反
応しうる試薬と触媒存在下で反応させ、前記担体にグリ
シジル基を導入する工程。 (c)前記パラフィンを含浸する多孔性球状担体を溶媒
で洗浄して、前記パラフィンを洗い出す工程。 (d)前記グリシジル基と直接的に反応してイオン交換
基となる物質を前記多孔性球状担体に加えて反応させ、
該担体の表面に微量のイオン交換基を導入する工程。
(1) A method for producing an ion exchanger, which comprises introducing a trace amount of ion exchange groups only onto the surface of a hydrophilic carrier by the following steps (a) to (d). (a) A step of impregnating paraffin into a hydrophilic porous spherical carrier obtained by polymerizing a monomer together with a crosslinking agent. (b) A step of dispersing the paraffin-impregnated porous spherical carrier in an alkaline solution and reacting it with a reagent having a glycidyl group and capable of reacting with a hydroxyl group in the presence of a catalyst to introduce glycidyl groups into the carrier. (c) washing the paraffin-impregnated porous spherical carrier with a solvent to wash out the paraffin; (d) adding a substance that directly reacts with the glycidyl group to become an ion exchange group to the porous spherical carrier and causing the reaction;
A step of introducing a trace amount of ion exchange groups onto the surface of the carrier.
(2)前記モノマーは、ヒドロキシアルキル、グリセリ
ル、グリシジル、ポリエチレングリコール、メタクリル
酸メチル、およびビニルエーテルのいずれかでなる特許
請求範囲第(1)項記載のイオン交換体製造方法。
(2) The method for producing an ion exchanger according to claim (1), wherein the monomer is any one of hydroxyalkyl, glyceryl, glycidyl, polyethylene glycol, methyl methacrylate, and vinyl ether.
(3)前記架橋剤は、ジビニルベンゼン、エチレングリ
コールジメタクリレート、およびグリセリンジメタクリ
レートのいずれかでなる特許請求範囲(1)項記載のイ
オン交換体製造方法。
(3) The method for producing an ion exchanger according to claim (1), wherein the crosslinking agent is one of divinylbenzene, ethylene glycol dimethacrylate, and glycerin dimethacrylate.
(4)前記試薬は、エピクロロヒドリン若しくはアルキ
レンジグリシジルエーテルでなる特許請求範囲第(1)
項記載のイオン交換体製造方法。
(4) The reagent is epichlorohydrin or an alkylene diglycidyl ether according to claim (1).
The method for producing an ion exchanger described in Section 1.
(5)前記触媒は、α,α′−アゾビスイソブチルニト
リルでなる特許請求範囲第(1)〜第(4)項のいずれ
かに記載のイオン交換体製造方法。
(5) The method for producing an ion exchanger according to any one of claims (1) to (4), wherein the catalyst is α,α'-azobisisobutylnitrile.
JP61047077A 1986-03-04 1986-03-04 Production of ion exchanger Granted JPS62205102A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61047077A JPS62205102A (en) 1986-03-04 1986-03-04 Production of ion exchanger

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61047077A JPS62205102A (en) 1986-03-04 1986-03-04 Production of ion exchanger

Publications (2)

Publication Number Publication Date
JPS62205102A true JPS62205102A (en) 1987-09-09
JPH0518321B2 JPH0518321B2 (en) 1993-03-11

Family

ID=12765106

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61047077A Granted JPS62205102A (en) 1986-03-04 1986-03-04 Production of ion exchanger

Country Status (1)

Country Link
JP (1) JPS62205102A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007057526A (en) * 2005-07-26 2007-03-08 Showa Denko Kk Method for analyzing low-molecular-weight compound in sample containing water-soluble polymer and low-molecular-weight compound

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007057526A (en) * 2005-07-26 2007-03-08 Showa Denko Kk Method for analyzing low-molecular-weight compound in sample containing water-soluble polymer and low-molecular-weight compound

Also Published As

Publication number Publication date
JPH0518321B2 (en) 1993-03-11

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