JPH021534B2 - - Google Patents
Info
- Publication number
- JPH021534B2 JPH021534B2 JP56096600A JP9660081A JPH021534B2 JP H021534 B2 JPH021534 B2 JP H021534B2 JP 56096600 A JP56096600 A JP 56096600A JP 9660081 A JP9660081 A JP 9660081A JP H021534 B2 JPH021534 B2 JP H021534B2
- Authority
- JP
- Japan
- Prior art keywords
- ion exchange
- exchange resin
- ion
- resin
- type
- 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 - Lifetime
Links
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 41
- 238000005342 ion exchange Methods 0.000 claims description 40
- 239000003456 ion exchange resin Substances 0.000 claims description 28
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 28
- 239000003957 anion exchange resin Substances 0.000 claims description 26
- 239000003729 cation exchange resin Substances 0.000 claims description 23
- 239000000057 synthetic resin Substances 0.000 claims description 16
- 229920003002 synthetic resin Polymers 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 229940023913 cation exchange resins Drugs 0.000 claims description 4
- 238000000926 separation method Methods 0.000 description 39
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 27
- 239000003480 eluent Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 16
- 150000001450 anions Chemical class 0.000 description 15
- 150000001768 cations Chemical class 0.000 description 15
- 239000011734 sodium Substances 0.000 description 13
- -1 (S 2 O 2- 3 ) Chemical class 0.000 description 12
- 238000011088 calibration curve Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000872 buffer Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 7
- 229920001429 chelating resin Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 238000007613 slurry method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000012799 strong cation exchange Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
本発明は液体中の陰イオンおよび/または陽イ
オンを高速液体クロマトグラフにより、感度良く
迅速に分析することが出来るイオン交換樹脂組成
物に関する。
従来、溶液中の陰イオンまたは陽イオンを高速
液体クロマトグラフにより分析する方法に用いら
れるイオン交換樹脂組成物としては、ザ・ダウ・
ケミカル・カンパニー社のものなどが知られてい
る。これは粒径の異なる陰、陽2種類のイオン交
換樹脂から成り、そのうちの一方は陰イオン交換
樹脂、他方は陽イオン交換樹脂であるイオン交換
組成物(特開昭50−77290)である。
しかしながら、この公知のイオン交換樹脂組成
物は、陰イオンを分析するときは、大きい粒子を
陽イオン交換樹脂とし、小さい粒子を陰イオン交
換樹脂で構成しなければならない。そしてこのよ
うに構成して得た組成物で逆に陽イオンを分析す
るには、測定に極めて長時間を要し、実質的に用
いることはできない。
一方反対に陽イオンを分析するときには、大き
い粒子を陰イオン交換樹脂とし、小さい粒子を陽
イオン交換樹脂で構成しなければならず、そして
このように構成して得られた樹脂組成物では陰イ
オンを分析しようとしても、この場合は測定に極
めて長時間を要し、実際的には用いることは出来
ない。
そして、また前記組成物以外の従来のイオン交
換樹脂組成物はイオンの溶出に甚しく時間がかか
るという欠点を有しているのである。
これらの欠点を解決する方法として、分離カラ
ムを小型で容積の小さいものに変換する試みがな
されたこともあるが、この変換に伴つて、分離圧
が上昇し、その圧力上昇のため、イオンクロマト
グラフイー装置におけるガラス製分離カラム、該
カラムに充填されたイオン交換樹脂およびテフロ
ンチユーブなどがしばしば破損することがあつ
た。従つて、従来のイオン交換樹脂を用いる場合
は、分離カラムを小型のものと切換えて使用する
ことは出来ず、分析に長時間かかることを余義な
くされた。
そこで、本発明者らは、このような現状に鑑み
高速液体クロマトグラフにより、液体中の陰イオ
ンおよび/または陽イオンを迅速に分析すること
が出来、且つイオンの種類によつてその都度、組
み合せ樹脂の粒径を変えたりする必要の無いイオ
ン交換樹脂組成物を得るため、種々検討を重ねた
結果、有効表面上に親水基を有しイオン交換基を
有しない微粒子の不溶性合成樹脂基質を必須構成
要件とし、この基質にさらにこれとほぼ同一の粒
径を有する陰イオン交換樹脂および/または陽イ
オン交換樹脂を混合した組成物が、分析しようと
するイオンの種類によつてその都度、組み合せ樹
脂の粒径を変える様なことをしなくても、液体中
の陰イオンおよび/または陽イオンを高感度で迅
速に分析可能とすることを見出し、この発見に基
いて本発明を完成した。
即ち、本発明は、有効表面上にイオン交換基を
有する微粒子の不溶性合成樹脂基質と、有効表面
上に親水基を有しイオン交換基を有しない微粒子
の不溶性合成樹脂基質とを混合してなるイオン交
換樹脂組成物である。
以下、本発明を詳細に説明する。
本発明において用いられる、有効表面上にイオ
ン交換基を有する、微粒子の不溶性合成樹脂基質
としては、陰イオン交換樹脂および陽イオン交換
樹脂が挙げられる。
陰イオン交換樹脂としては、粒径が2〜50ミク
ロン、好ましくは5〜25ミクロンの、公知の陰イ
オン交換樹脂が挙げられ、例えば、三菱化成工業
社製「強塩基性アニオン交換樹脂MCI GEL
CA04S(母体樹脂;スチレンジビニルベンゼン共
重合体、イオン交換基の種類;−N+(CH3)3、イ
オン交換容量;1.1meq/ml、粒径;11μm、使用
時の置換形;OH-タイプ、架橋度;4%)」、「同
MCI GEL CA06S(母体樹脂;スチレンジビニル
ベンゼン共重合体、イオン交換基の種類;−N+
(CH3)3、イオン交換容量;1.2meq/ml、粒径;
11μm、使用時の置換形;OH-タイプ、架橋度;
6%)」、同社製「ハイポーラス型強塩基性アニオ
ン交換樹脂MCI GEL CDR−10(母体樹脂;スチ
レンジビニルベンゼン共重合体、イオン交換基の
種類;−N+(CH3)3、イオン交換容量;0.3meq/
ml、粒径;7〜8μm、使用時の置換形;OH-タ
イプ)」、日立製作所社製「日立ゲル#3011−N
(母体樹脂;スチレンジビニルベンゼン共重合体、
イオン交換基の種類;−N+(CH3)3、イオン交換
容量;約0.7meq/ml、粒径;10μm、使用時の置
換形;OH-タイプ)」、東洋曹達工業社製「強ア
ニオン交換ゲルIEX−220SA(母体樹脂;スチレ
ンジビニルベンゼン共重合体、イオン交換基の種
類;−N+(CH3)3、イオン交換容量;3.7meq/ml
以上、粒径;10μm、使用時の置換形;OH-タイ
プ)」、同社製「シリカ系強アニオン交換ゲルIEX
−260SA SIL(母体樹脂;ポーラスシリカ、イオ
ン交換基の種類;−N+(CH3)2CH2C6H5、イオン
交換容量;0.5meq/g以上、粒径;10μm、使用
時の置換形;OH-タイプ)」、およびバイオラツ
ド社製「イオン交換樹脂Aminex A−29(母体樹
脂;スチレンジビニルベンゼン共重合体、イオン
交換基の種類;−N+(CH3)3、イオン交換容量;
1.4meq/ml、粒径;5〜8μm、使用時の置換
形;OH-タイプ、架橋度;8%)」などが挙げら
れる。
次に、陽イオン交換樹脂としては粒径が2〜50
ミクロン、好ましくは5〜25ミクロンの公知の陽
イオン交換樹脂が挙げられ、例えば、三菱化成工
業社製「強酸性カチオン交換樹脂MCI GEL
CK08S(母体樹脂;スチレンジビニルベンゼン共
重合体、イオン交換基の種類;−SO3 -、イオン
交換容量;1.5meq/ml以上、粒径;11μm、使用
時の置換形;H+タイプ、架橋度;8%)」、日立
製作所社製「日立ゲル#3011−S(母体樹脂;ス
チレンジビニルベンゼン共重合体、イオン交換基
の種類;−SO3 -、イオン交換容量;約4.0meq/
ml、粒径;10μm、使用時の置換形;H+タイ
プ)」、東洋曹達工業社製「強カチオン交換ゲル
IEX−210SC(母体樹脂;スチレンジビニルベン
ゼン共重合体、イオン交換基の種類;−SO3 -、
イオン交換容量;4.2meq/g以上、粒径10μm、
使用時の置換形;H+タイプ)」およびバイオラツ
ド社製「イオン交換樹脂Aminex A−8(母体樹
脂;スチレンジビニルベンゼン共重合体、イオン
交換基の種類;−SO3 -、イオン交換容量;
2.0meq/ml、粒径;5〜8μm、使用時の置換
形;H+タイプ、架橋度;10%)」などが挙げられ
る。
また有効表面上に親水基を有しイオン交換基を
有しない微粒子の不溶性合成樹脂基質としては、
粒径が2〜50ミクロン、好ましくは5〜25ミクロ
ンのポリマーゲルの有効表面上にOH基などの、
イオン交換基でない親水基を導入したもので、例
えば日立製作所社製「日立ゲル#3011−O(母体
樹脂;スチレンジビニルベンゼン共重合体、親水
基の種類;−CH2OH、導入量;約0.8mmol/
ml、粒径;11〜13μm)」および三菱化成工業社
製「分離用樹脂 TAQP−2(母体樹脂;アクリ
ル系樹脂、親水基の種類;−OH、粒径;10μ
m)」、および「同TAQP−3(母体樹脂;アクリ
ル系樹脂、親水基の種類;−OH、粒径;10μ
m)」などが挙げられる。
上記有効表面上に親水基を有しイオン交換基を
有しない不溶性合成樹脂(以下これを親水性分離
樹脂と略記する)と混合すべき陰イオン交換樹脂
および/または陽イオン交換樹脂の選択は分析す
るイオンの種類により異なる。
即ちフツ素イオン(以下F-と略記する)、塩素
イオン(Cl-)、リン酸イオン(PO3- 4)、硝酸イオ
ン(NO3 -)、硫酸イオン(SO2 4 -)およびチオ硫
酸イオン(S2O2- 3)など陰イオンを分析しようと
する場合は陰イオン交換樹脂を選択して使用す
る。反対にナトリウムイオン(Na+)、アンモニ
ウムイオン(NH4 +)、マグネシウムイオン
(Mg2+)およびカルシウムイオン(Ca2+)など、
陽イオンを分析しようとする場合は陽イオン交換
樹脂を選択して使用する。
陽イオン交換樹脂と陰イオン交換樹脂の両方を
使用したカラムでは、同一カラムで溶離液を変え
ることにより陰イオンまたは陽イオンの分析がで
きる。
また陰イオン交換樹脂および/または陽イオン
交換樹脂と、親水性分離樹脂との混合割合は、分
析すべきイオンの種類または溶出時間(リテンシ
ヨンタイム)によつて決定するのが好ましいが、
通常は重量比で1:0.1〜200、好ましくは1:1
〜120である。即ち、前者に対する後者の割合が
200よりも多い場合は溶離液の拡散が多くなつて
分離が悪くなり精度も低くなる。反対に0.1より
も少ないときは溶出時間が長くなる欠点を有し、
この欠点を改めるためには分離カラムを小型で容
積の小さいものに切変え、且つ分離圧を強大にし
なければならないという不都合が生じる。分離圧
を強大に保つことは分離カラム(ガラス製)、充
填剤およびテフロンチユーブが破損する危険を伴
う。
陰イオン交換樹脂および/または陽イオン交換
樹脂と、親水性分離樹脂との混合割合の好適な具
体例を示すと、F-、PO3- 4、Cl-、SO2- 4のような
陰イオンの場合は、1:1〜20が特に好ましく、
S2O2- 3のように溶出時間が非常に長いイオンの場
合は1:80〜120が特に好ましい。Na+、K+、
NH4 +、Mg2+およびCa2+のような陽イオンの場
合は1:1〜10が特に好ましい。陰イオンあるい
は陽イオンを同一カラムで溶離液を変えて測定す
る場合は各々の樹脂を1:1〜5で混合するのが
特に好ましい。
混合方法は、陰イオン交換樹脂と親水性分離樹
脂との混合、または陽イオン交換樹脂と親水性分
離樹脂との混合はいずれの場合も、常法で良く、
例えばそれぞれを秤量したあとビーカーに入れ水
または溶離液を加え、ガラス棒で撹拌し、さらに
超音波洗滌器にて均一に混合することが好まし
い。
陰イオン交換樹脂、陽イオン交換樹脂および親
水性分離樹脂との3者を混合するときは、先ず陰
イオン交換樹脂と親水性分離樹脂とを上述の如き
方法にて混合し、次いで陽イオン交換樹脂と親水
性分離樹脂とを同様に混合し、最後に両混合物を
混ぜ稀薄アルカリ溶液または溶離液を使用し、ガ
ラス棒で撹拌したあと、超音波洗滌器によつて均
一に混合する。
このようにして本発明のイオン交換樹脂組成物
が得られる。
本発明のイオン交換樹脂組成物を用いて溶液中
の陰イオンおよび/または陽イオンを高速液体ク
ロマトグラフにより分析するには第1図に示す如
き、市販の液体クロマトグラフイー用部分と電気
伝導度計を組み合せた装置が挙げられる。
即ち、溶離液収納槽1、送液ポンプ2、圧力計
3、サンプラー4、分離カラム5、バツフアー除
去カラム6および流体測定用フローセル7をこの
順序でチユーブで連通し、且つ該フローセルには
電気伝導度計8および記録計9が関連せしめられ
ている装置が挙げられる。尚バツフアー除去カラ
ム6とは、分析しようとする陽イオンまたは陰イ
オンとは逆の電価を有する溶離液中のイオンを除
去するカラムである。このバツフアー除去カラム
6の使用により、極めて低いバツクグラウンドで
試料イオンの直接検出ができる特徴を有する。
次に本装置を構成する高速液体クロマトグラフ
イー用部品の具体例を第1表に示す。
The present invention relates to an ion exchange resin composition that allows anions and/or cations in a liquid to be analyzed quickly and sensitively by high performance liquid chromatography. Conventionally, as an ion exchange resin composition used in a method of analyzing anions or cations in a solution by high performance liquid chromatography, The Dow Co., Ltd.
Chemical Company's products are well known. This is an ion exchange composition (Japanese Patent Application Laid-Open No. 77290/1983) consisting of two types of ion exchange resins, an anion exchange resin and a cation exchange resin with different particle sizes, one of which is an anion exchange resin and the other a cation exchange resin. However, in this known ion exchange resin composition, when anions are analyzed, the large particles must be composed of a cation exchange resin and the small particles must be composed of an anion exchange resin. On the other hand, in order to analyze cations using the composition obtained in this manner, the measurement requires an extremely long time and cannot be practically used. On the other hand, when analyzing cations, the large particles must be made of an anion exchange resin and the small particles must be made of a cation exchange resin, and the resin composition obtained by constructing in this way has anion exchange resins. Even if an attempt is made to analyze this, the measurement would take an extremely long time in this case, making it practically unusable. Furthermore, conventional ion exchange resin compositions other than the above-mentioned compositions have the disadvantage that it takes an extremely long time for ion elution. As a way to solve these drawbacks, attempts have been made to convert the separation column to a smaller, smaller-volume one, but with this conversion, the separation pressure increases, and because of this pressure increase, ion chromatography The glass separation column, the ion exchange resin packed in the column, the Teflon tube, etc. in the GRAPHIE apparatus were often damaged. Therefore, when conventional ion exchange resins are used, it is not possible to replace the separation column with a smaller one, and the analysis is forced to take a long time. Therefore, in view of the current situation, the present inventors have discovered that high-performance liquid chromatography can quickly analyze anions and/or cations in a liquid, and can also be used in combinations depending on the type of ions. In order to obtain an ion exchange resin composition that does not require changing the particle size of the resin, we have conducted various studies and found that a microparticle insoluble synthetic resin matrix with hydrophilic groups on the effective surface and no ion exchange groups is essential. A composition in which this substrate is further mixed with an anion exchange resin and/or a cation exchange resin having approximately the same particle size as the substrate is used depending on the type of ion to be analyzed. It was discovered that anions and/or cations in a liquid can be analyzed quickly and with high sensitivity without changing the particle size of the liquid, and based on this discovery, the present invention was completed. That is, the present invention is made by mixing a fine particle insoluble synthetic resin matrix having an ion exchange group on its effective surface with a fine particle insoluble synthetic resin matrix having a hydrophilic group on its effective surface and no ion exchange group. It is an ion exchange resin composition. The present invention will be explained in detail below. The particulate insoluble synthetic resin matrix having ion exchange groups on its effective surface used in the present invention includes anion exchange resins and cation exchange resins. Examples of the anion exchange resin include known anion exchange resins having a particle size of 2 to 50 microns, preferably 5 to 25 microns, such as "strongly basic anion exchange resin MCI GEL" manufactured by Mitsubishi Chemical Industries, Ltd.
CA04S (base resin: styrene divinylbenzene copolymer, type of ion exchange group: −N + (CH 3 ) 3 , ion exchange capacity: 1.1 meq/ml, particle size: 11 μm, substituted form when used: OH - type , degree of crosslinking; 4%)", "same
MCI GEL CA06S (base resin: styrene divinylbenzene copolymer, type of ion exchange group: −N +
(CH 3 ) 3 , ion exchange capacity; 1.2 meq/ml, particle size;
11μm, substituted form when used; OH -type , degree of crosslinking;
6%)", the company's "high porous strong basic anion exchange resin MCI GEL CDR-10 (base resin: styrene divinylbenzene copolymer, type of ion exchange group: -N + (CH 3 ) 3 , ion exchange Capacity: 0.3meq/
ml, particle size: 7 to 8 μm, substitution form when used: OH - type), Hitachi Gel #3011-N, manufactured by Hitachi, Ltd.
(Base resin: styrene divinylbenzene copolymer,
Type of ion exchange group: −N + (CH 3 ) 3 , ion exchange capacity: approximately 0.7 meq/ml, particle size: 10 μm, substituted form during use: OH - type), Toyo Soda Kogyo Co., Ltd. “Strong anion Exchange gel IEX-220SA (base resin: styrene divinylbenzene copolymer, type of ion exchange group: -N + (CH 3 ) 3 , ion exchange capacity: 3.7meq/ml
Particle size: 10 μm, substitution form when used: OH - type), silica-based strong anion exchange gel IEX manufactured by the company
-260SA SIL (base resin: porous silica, type of ion exchange group: -N + (CH 3 ) 2 CH 2 C 6 H 5 , ion exchange capacity: 0.5 meq/g or more, particle size: 10 μm, replacement during use OH - type)” and Bio-Rad’s ion exchange resin Aminex A-29 (base resin: styrene divinylbenzene copolymer, type of ion exchange group: −N + (CH 3 ) 3 , ion exchange capacity;
1.4 meq/ml, particle size: 5 to 8 μm, substituted form when used: OH - type, degree of crosslinking: 8%). Next, as a cation exchange resin, the particle size is 2 to 50.
Known cation exchange resins having a particle size of 5 to 25 microns, preferably 5 to 25 microns, can be mentioned, for example, “Strongly acidic cation exchange resin MCI GEL” manufactured by Mitsubishi Chemical
CK08S (base resin: styrene divinylbenzene copolymer, type of ion exchange group: -SO 3 - , ion exchange capacity: 1.5 meq/ml or more, particle size: 11 μm, substitution type when used: H + type, degree of crosslinking ; 8%)", Hitachi Gel #3011-S (base resin: styrene divinylbenzene copolymer, type of ion exchange group: -SO 3 - , ion exchange capacity: approximately 4.0meq/
ml, particle size: 10μm, substitution form when used: H + type), Toyo Soda Kogyo Co., Ltd., "Strong cation exchange gel"
IEX-210SC (base resin; styrene divinylbenzene copolymer, type of ion exchange group; -SO 3 - ,
Ion exchange capacity: 4.2meq/g or more, particle size 10μm,
Substituted form when used: H + type) and Bio-Rad's ion exchange resin Aminex A-8 (base resin: styrene divinylbenzene copolymer, type of ion exchange group: -SO 3 - , ion exchange capacity;
2.0 meq/ml, particle size: 5 to 8 μm, substituted form when used: H + type, degree of crosslinking: 10%). In addition, fine particle insoluble synthetic resin substrates having hydrophilic groups and no ion exchange groups on their effective surfaces include:
on the effective surface of the polymer gel with a particle size of 2 to 50 microns, preferably 5 to 25 microns, such as OH groups.
Hydrophilic groups that are not ion exchange groups are introduced, such as Hitachi Gel #3011-O (base resin: styrene divinylbenzene copolymer, type of hydrophilic group: -CH 2 OH, amount introduced: approximately 0.8 mmol/
ml, particle size: 11 to 13 μm) and Separation Resin TAQP-2 (base resin: acrylic resin, type of hydrophilic group: -OH, particle size: 10 μm) manufactured by Mitsubishi Chemical Industries, Ltd.
m)", and "TAQP-3 (base resin; acrylic resin, type of hydrophilic group: -OH, particle size: 10μ
m)" etc. The selection of anion exchange resin and/or cation exchange resin to be mixed with the above-mentioned insoluble synthetic resin that has hydrophilic groups on the effective surface and does not have ion exchange groups (hereinafter abbreviated as hydrophilic separation resin) is determined by analysis. It varies depending on the type of ion. Namely, fluorine ion (hereinafter abbreviated as F - ), chloride ion (Cl - ), phosphate ion (PO 3- 4 ), nitrate ion (NO 3 - ), sulfate ion (SO 2 4 - ), and thiosulfate ion. When attempting to analyze anions such as (S 2 O 2- 3 ), an anion exchange resin is selected and used. On the contrary, sodium ions (Na + ), ammonium ions (NH 4 + ), magnesium ions (Mg 2+ ), and calcium ions (Ca 2+ ), etc.
When attempting to analyze cations, select and use a cation exchange resin. With columns that use both cation exchange resins and anion exchange resins, anions or cations can be analyzed using the same column by changing the eluent. The mixing ratio of the anion exchange resin and/or cation exchange resin and the hydrophilic separation resin is preferably determined depending on the type of ion to be analyzed or the elution time (retention time).
Usually 1:0.1-200 in weight ratio, preferably 1:1
~120. In other words, the ratio of the latter to the former is
If the number is more than 200, the eluent will diffuse more, resulting in poor separation and lower accuracy. On the other hand, when it is less than 0.1, it has the disadvantage that the elution time becomes longer.
In order to overcome this drawback, it is necessary to change the separation column to a smaller one with a smaller volume and to increase the separation pressure, which is an inconvenience. Maintaining a high separation pressure carries the risk of damaging the separation column (made of glass), packing material, and Teflon tube. Preferred specific examples of the mixing ratio of anion exchange resin and/or cation exchange resin and hydrophilic separation resin include anions such as F - , PO 3- 4 , Cl - , SO 2- 4 In the case of 1:1 to 20 is particularly preferable,
In the case of an ion with a very long elution time such as S 2 O 2-3 , a ratio of 1:80 to 120 is particularly preferable. Na + , K + ,
For cations such as NH 4 + , Mg 2+ and Ca 2+ 1:1 to 10 is particularly preferred. When anions or cations are measured using the same column using different eluents, it is particularly preferable to mix each resin at a ratio of 1:1 to 5. The mixing method may be any conventional method for mixing an anion exchange resin and a hydrophilic separation resin, or for mixing a cation exchange resin and a hydrophilic separation resin.
For example, it is preferable to weigh each component, put it in a beaker, add water or an eluent, stir it with a glass rod, and further mix it uniformly with an ultrasonic cleaner. When mixing an anion exchange resin, a cation exchange resin, and a hydrophilic separation resin, first mix the anion exchange resin and the hydrophilic separation resin in the manner described above, and then mix the cation exchange resin and the hydrophilic separation resin. and a hydrophilic separation resin in the same manner, and finally, both mixtures are mixed using a dilute alkaline solution or eluent, stirred with a glass rod, and then mixed uniformly with an ultrasonic cleaner. In this way, the ion exchange resin composition of the present invention is obtained. In order to analyze anions and/or cations in a solution by high performance liquid chromatography using the ion exchange resin composition of the present invention, a commercially available liquid chromatography part as shown in FIG. An example is a device that combines a meter. That is, an eluent storage tank 1, a liquid feeding pump 2, a pressure gauge 3, a sampler 4, a separation column 5, a buffer removal column 6, and a fluid measurement flow cell 7 are connected in this order through a tube, and the flow cell is connected to an electrical conductor. An example is a device in which a meter 8 and a recorder 9 are associated. The buffer removal column 6 is a column that removes ions in the eluent having a charge opposite to that of the cations or anions to be analyzed. By using this buffer removal column 6, sample ions can be directly detected with extremely low background. Next, Table 1 shows specific examples of high performance liquid chromatography components that constitute this apparatus.
【表】
本発明によつて得られるイオン交換樹脂組成物
はF-、Cl-、PO3- 4、NO- 3、SO2- 4およびS2O2- 3な
どの陰イオンおよび/またはNa+、K+、NH4 +、
Mg2+およびCa2+などの陽イオンを非常に感度良
く、しかも迅速に分離することができる。
また、本発明のイオン交換樹脂組成物は分析す
るイオンの種類によつてその都度、組み合せ樹脂
の粒径を変えたりする必要が無い特徴を有する。
また、本発明のイオン交換樹脂組成物を用いるこ
とによつて、溶離液の送液ポンプ圧を下げるか、
または分離カラムを小型で小容量の分離カラムに
変えることが出来る。
以下、実施例および応用例を示して本発明をさ
らに詳細に説明する。
実施例 1
陰イオン交換樹脂(MCI GEL CDR−10、三
菱化成工業社製)60mgと、有効表面上に親水基を
有しイオン交換基を有しない微粒子の不溶性合成
樹脂基質(日立ゲル#3011−0、日立製作所社
製)1000mgとをそれぞれ秤量し、ビーカーに入れ
た後水を加え、ガラス棒で撹拌し、さらに超音波
洗滌器にて均一に混和し、本発明のイオン交換樹
脂組成物を得た。
実施例 2
陰イオン交換樹脂(MCI GEL CA04S、三菱
化成工業社製)60mgと、有効表面上に親水基を有
しイオン交換基を有しない微粒子の不溶性合成樹
脂基質(日立ゲル#3011−0、日立製作所社製)
600mgとをそれぞれ秤量し、ビーカーに入れたあ
と水を加え、ガラス棒で撹拌し、さらに超音波洗
滌器にて均一に混和し、本発明のイオン交換樹脂
組成物を得た。
実施例 3
陽イオン交換樹脂(MCI GEL CK08S、三菱
化成工業社製)150mgと、有効表面上に親水基を
有しイオン交換基を有しない微粒子の不溶性合成
樹脂基質(日立ゲル#3011−0、日立製作所社
製)1500mgとをそれぞれ秤量し、ビーカーに入れ
たあと水を加え、ガラス棒で撹拌し、さらに超音
波洗滌器にて均一に混和し、本発明のイオン交換
樹脂組成物を得た。
実施例 4
陰イオン交換樹脂(MCI GEL CA04G、三菱
化成工業社製)150mgと、有効表面上に親水基を
有しイオン交換基を有しない微粒子の不溶性合成
樹脂(日立ゲル#3011−0、日立製作所社製)
750mgとをそれぞれ秤量し、ビーカーに入れた後
水を加え、ガラス棒で撹拌し、さらに超音波洗滌
器にて均一に混和した。
また陽イオン交換樹脂(MCI GEL CK08S、
三菱化成工業社製)150mgと、有効表面上に親水
基を有しイオン交換基を有しない微粒子の不溶性
合成樹脂(日立ゲル#3011−0、日立製作所社
製)750mgとをそれぞれ秤量し、ビーカーに入れ
た後水を加え、ガラス棒で撹拌し、さらに超音波
洗滌器にて均一に混和した。
次いで、両混和物をビーカーにとり、0.1規定
水酸化ナトリウムを少量加え、ガラス棒で撹拌し
たあと、超音波洗滌器によつて均一に混和し、本
発明のイオン交換樹脂組成物を得た。
応用例 1
第1図の高速液体クロマトグラフイー装置にお
いて、各部品をそれぞれ第1表の実験装置1に記
載の如く設け、分離カラム5には実施例1で調製
したイオン交換樹脂組成物を、バツフアー除去カ
ラム6には陽イオン交換樹脂(アンバーライト
CG−120Type、ロームアンドハース社製)を
それぞれスラリー法で充填した。溶離液
(0.003M NaHCO3と0.0024MNa2CO3の含有液)
を溶離液収納槽1に収納し、送液ポンプ2の流速
を1.88ml/分で送液した。室温を17〜23℃とし、
電気伝導度計を10μ、そして記録計を1Vで測定
した。
次に下記の要領にて、F-、Cl-、PO3- 4および
SO2- 4を含むサンプルを調製し、これをサンプラ
ー4で30μ採取して分離カラム5に注入し、各
イオンが分離されたクロマトグラムを求めた結
果、第3図が得られた。
記
F-: 2.17μg/30μ
Cl-: 5.07〃
PO3- 4: 12.95〃
SO2- 4: 16.38〃
この結果から、本発明の組成物はF-、Cl-、
PO3- 4およびSO2- 4などの陰イオンをよく分離検出
し得ることが判る。
次に本装置のフツ素イオン(F-)に対する感
度を求めるため検量線を作成した。標準物質とし
て特級のNaFを用いた。空気乾燥器中で乾燥し
たNaF42.5mgを蒸留水に溶解し50mlとし標準溶液
とした。この標準溶液をマイクロシリンジで一定
量を採取し、分離カラム5に注入し、出力を記録
計で記録し、ピーク高さ(cm)と注入量(μg)
から検量線を求めた。このフツ素イオンに対する
検量線は第2図に示す如きであつて原点を通る直
線が得られた。
この結果より、本発明のイオン交換樹脂組成物
は、溶液中のフツ素イオンを定量的に感度良く分
析できることが判る。
また、Cl-、PO3- 4、NO3 -およびSO2- 4に対する
感度を求めるために、それぞれ上記F-の場合と
同様にして、標準溶液としてNaCl58.6mg/50ml
(蒸留水)、NaH2PO4・2H2O156.0mg/50ml
(〃)、NaNO384.9mg/50ml(〃)および
Na2SO4142.0mg/50ml(〃)を調製し、この標準
溶液をマイクロシリンジで一定量採取し、分離カ
ラム5に注入し、出力を記録計で記録し、ピーク
高さ(cm)と注入量(μg)とから検量線を作成
した。その結果、F-の場合と同様に、Cl-、
PO3- 4、NO3 -およびSO2- 4に対する検量線もそれ
ぞれ原点を通る直線が得られ、本発明のイオン交
換樹脂組成物は溶液中の各種陰イオンを定量的に
感度良く分析できることが判る。
応用例 2
第1図の高速液体クロマトグラフイー装置にお
いて、各部品をそれぞれ第1表の実験装置2に記
載の如く設け、分離カラム5には実施例2で調製
したイオン交換樹脂組成物を、バツフアー除去カ
ラム6には陽イオン交換樹脂(アンバーライト
CG−120Type、ロームアンドハース社製)を
それぞれスラリー法で充填した。溶離液
(0.003MNaHCO3と0.0024MNa2CO3との含有液)
を溶離液収納槽1に収納し、送液ポンプ2の流速
を1.92ml/分で送液した。室温を17〜23℃とし、
電気伝導度を15μ、そして貴録計を5mVで測
定した。
次に下記の要領にてフツ素イオン(F-)、塩素
イオン(Cl-)、リン酸イオン(PO3- 4)、硝酸イオ
ン(NO3 -)および硫酸イオン(SO2- 4)を含むサ
ンプルを調製し、これをサンプラー4で40μ採
取して分離カラム5に注入し、各イオンが分離さ
れたクロマトグラムを求めた結果、第4図が得ら
れた。
記
F-: 1.56μg/40μ
Cl-: 3.64〃
PO3- 4: 17.4 〃
NO3 -: 12.7 〃
SO2- 4: 17.6 〃
応用例 3
第1図の高速液体クロマトグラフイー装置にお
いて、各部品をそれぞれ第1表の実験装置4に記
載の如く設け、分離カラム5には実施例3で調製
したイオン交換樹脂組成物を、バツフアー除去カ
ラム6には、陰イオン交換樹脂(アンバーライト
CG−400Type、ロームアンドハース社製)を
それぞれスラリー法で充填した。そして溶離液
(0.005MHNO3溶液)を溶離液収納槽1に収納
し、送液ポンプ2の流速を2.49ml/分で送液し
た。室温を17〜23℃とし、電気伝導度計を10μ
、そして記録計を1Vで測定した。
次に下記の要領にてナトリウムイオン(Na+)、
カリウムイオン(K+)およびアンモニウムイオ
ン(NH4 +)を含むサンプルを調製し、これをサ
ンプラーで50μ採取して分離カラムに注入し、
各イオンが分離されたクロマトグラムを求めたと
ころ、第5図に示す如き結果が得られた。
記
Na+: 9.2μg/50μ
K+: 23.4〃
NH4 +: 9.0〃
この結果から、本発明組成物はNa+、K+およ
びNH4 +などの陽イオンを良く分離検出し得るこ
とが判る。
次に本装置のNa+、K+およびNH4 +に対する感
度を求めるため検量線を作成した。それぞれ標準
溶液としてNa2SO4142.04mg/50ml(蒸留水)、
K2SO4174.27mg/50ml(〃)および
(NH4)2SO4132.14mg/50ml(〃)を調製し、こ
の標準溶液をマイクロシリンジで一定量採取し、
分離カラムに注入し、出力を記録計で記録し、ピ
ーク高さと注入量とから検量線を作成した結果、
それぞれ原点を通る直線が得られた。
これらの結果から本発明の組成物は溶液中の
Na+、K+およびNH4 +を定量的に感度良く分析で
きることが判る。
応用例 4
第1図の高速液体クロマトグラフイー装置にお
いて、各部品をそれぞれ第1表の実験装置4に記
載の如く設け、分離カラムには実施例3で調製し
たイオン交換樹脂組成物を、除去カラムには陰イ
オン交換樹脂(アンバーライトCG−400TyPe、
ロームアンドハース社製)をそれぞれスラリー法
で充填した。そして溶離液〔0.005MHNO3、
0.001Mパラ・フエニレンジアミン硫酸塩(P−
phenylene−diamine sulphate)〕を溶離収納槽
1に収納し、送液ポンプ2の流速を1.54ml/分で
送液した。室温を17〜23℃とし、電気伝導度計を
10μ、そして記録計を1Vで測定した。
次に下記の要領にてMg2+およびCa2+を含むサ
ンプルを調製し、これをサンプラーで50μ採取
して分離カラム5に注入し、各イオンが分離され
たクロマトグラムを求めたところ第6図に示す如
き結果が得られた。
記
Mg2+: 9.7μg/50μ
Ca2+: 24.0〃
次に本装置のCa2+およびMg2+に対する感度を
求めるため検量線を作成した。それぞれの標準溶
液としてCaCl2110.0mg/50ml(蒸留水)および
MgSO4120.3mg/50mlを調製し、この標準溶液を
マイクロシリンジで一定量採取し、分離カラムに
注入し、出力を記録計で記録し、ピーク高さと注
入量とから、検量線を作成した結果、それぞれ原
点を通る直線が得られた。
これらの結果から、本発明の組成物は溶液中の
Ca2+およびMg2+を定量的に感度良く分析できる
ことが判る。
応用例 5
第1図の高速液体クロマトグラフイー装置にお
いて各部品をそれぞれ第1表の実験装置3に記載
の如く設け、分離カラム5には実施例4で調製し
たイオン交換樹脂組成物を、バツフアー除去カラ
ム6には陽イオン交換樹脂(アンバーライトCG
−120Type、ロームアンドハース社製)をそれ
ぞれスラリー法で充填した。溶離液
(0.003MNaHCO3と0.0024MNa2CO3とを含む溶
液)を溶離液収納槽1に収納し、送液ポンプ2の
流速を2.52ml/分で送液した。室温を17〜23℃と
し、電気伝導度を15μ、そして貴録計を5mV
で測定した。
そして下記の要領にてF-、Cl-、PO3- 4、NO3 -
およびSO2- 4を含むサンプルを調製し、これをサ
ンプラーで50μ採取して分離カラムに注入し、
それぞれが分離されたクロマトグラムを求めたと
ころ第7図に示す如き結果が得られた。
記
F-: 1.95μg/50μ
Cl-: 4.54〃
PO3- 4: 21.8 〃
NO3 -: 15.9 〃
SO2- 4: 22.0 〃
次に本応用例5において、バツフアー除去カラ
ムに陰イオン交換樹脂(アンバーライトCG−
400Type、ロームアンドハース社製)を充填
し、溶離液を0.005MHNO3と0.001Mパラ・フエ
ニレンジアミン硫酸塩の含有液とし、送液ポンプ
の流速を2.61ml/分とし、電気伝導度計をクロマ
テツク社製CD−Aを用い電気伝導度を10μと
し、そして記録計を1Vで測定する以外は、本応
用例5と全く同じ装置条件(分離カラム内の充填
樹脂は変えない)で行つた。
そして、下記の要領でNa+、K+およびNH4 +を
含むサンプルを調製し、これをサンプラーで50μ
採取して分離カラムに注入し、各イオンが分離
されたクロマトグラムを求めたところ、第8図に
示す如き結果が得られた。
記
Na+: 9.2μg/50μ
K+: 23.4〃
NH4 +: 9.0〃
以上、2つの試験結果から、本発明のイオン交
換樹脂組成物は陰イオンばかりでなく陽イオンの
分析にも使用できることが判る。[Table] The ion exchange resin composition obtained according to the present invention contains anions such as F - , Cl - , PO 3- 4 , NO - 3 , SO 2- 4 and S 2 O 2- 3 and/or Na + , K + , NH 4 + ,
Cations such as Mg 2+ and Ca 2+ can be separated very sensitively and rapidly. Furthermore, the ion exchange resin composition of the present invention has a feature that there is no need to change the particle size of the combined resin each time depending on the type of ion to be analyzed.
Furthermore, by using the ion exchange resin composition of the present invention, the pressure of the eluent pump may be lowered or
Alternatively, the separation column can be changed to a smaller, smaller capacity separation column. Hereinafter, the present invention will be explained in more detail by showing examples and application examples. Example 1 60 mg of anion exchange resin (MCI GEL CDR-10, manufactured by Mitsubishi Chemical Industries, Ltd.) and a fine particle insoluble synthetic resin substrate (Hitachi Gel #3011-) that has hydrophilic groups on its effective surface and no ion exchange groups. 0, manufactured by Hitachi, Ltd.), put them in a beaker, add water, stir with a glass rod, and mix uniformly with an ultrasonic cleaner to prepare the ion exchange resin composition of the present invention. Obtained. Example 2 60 mg of anion exchange resin (MCI GEL CA04S, manufactured by Mitsubishi Chemical Industries, Ltd.) and a fine particle insoluble synthetic resin substrate (Hitachi Gel #3011-0, which has hydrophilic groups on the effective surface and no ion exchange groups) Manufactured by Hitachi, Ltd.)
600 mg of each was weighed out, placed in a beaker, water was added, stirred with a glass rod, and mixed uniformly using an ultrasonic washer to obtain the ion exchange resin composition of the present invention. Example 3 150 mg of a cation exchange resin (MCI GEL CK08S, manufactured by Mitsubishi Chemical Industries, Ltd.) and a fine particle insoluble synthetic resin substrate (Hitachi Gel #3011-0, which has a hydrophilic group on its effective surface and no ion exchange group) (manufactured by Hitachi, Ltd.) were weighed out, placed in a beaker, added with water, stirred with a glass rod, and mixed uniformly in an ultrasonic cleaner to obtain the ion exchange resin composition of the present invention. . Example 4 150 mg of anion exchange resin (MCI GEL CA04G, manufactured by Mitsubishi Chemical Industries, Ltd.) and a fine particle insoluble synthetic resin (Hitachi GEL #3011-0, Hitachi GEL #3011-0, which has hydrophilic groups on the effective surface and no ion exchange groups) Manufactured by Seisakushosha)
750 mg of each was weighed out, placed in a beaker, water was added, stirred with a glass rod, and mixed uniformly with an ultrasonic cleaner. In addition, cation exchange resin (MCI GEL CK08S,
Weighed 150 mg (manufactured by Mitsubishi Chemical Industries, Ltd.) and 750 mg of a fine particle insoluble synthetic resin (Hitachi Gel #3011-0, manufactured by Hitachi, Ltd.) that has hydrophilic groups on its effective surface and does not have ion exchange groups, and placed them in a beaker. After adding water, the mixture was stirred with a glass rod and mixed uniformly using an ultrasonic cleaner. Next, both mixtures were placed in a beaker, a small amount of 0.1N sodium hydroxide was added thereto, and after stirring with a glass rod, the mixture was uniformly mixed using an ultrasonic washer to obtain the ion exchange resin composition of the present invention. Application Example 1 In the high performance liquid chromatography apparatus shown in FIG. 1, each part was installed as described in Experimental apparatus 1 in Table 1, and the ion exchange resin composition prepared in Example 1 was placed in the separation column 5. Buffer removal column 6 contains a cation exchange resin (Amberlite).
CG-120Type (manufactured by Rohm and Haas) were each filled using a slurry method. Eluent (solution containing 0.003M NaHCO3 and 0.0024MNa2CO3 )
was stored in the eluent storage tank 1, and the liquid was fed by the liquid feeding pump 2 at a flow rate of 1.88 ml/min. The room temperature is 17-23℃,
The conductivity was measured at 10μ and the recorder at 1V. Next, F - , Cl - , PO 3- 4 and
A sample containing SO 2-4 was prepared, 30μ of this was sampled with sampler 4, and injected into separation column 5. A chromatogram in which each ion was separated was obtained, and as a result, the result shown in FIG . 3 was obtained. F - : 2.17μg/30μ Cl - : 5.07〃 PO 3- 4 : 12.95〃 SO 2- 4 : 16.38〃 From these results, the composition of the present invention has F - , Cl - ,
It can be seen that anions such as PO 3- 4 and SO 2- 4 can be well separated and detected. Next, a calibration curve was created to determine the sensitivity of this device to fluorine ions (F - ). Special grade NaF was used as a standard material. 2.5 mg of NaF dried in an air dryer was dissolved in distilled water to make 50 ml and used as a standard solution. Collect a certain amount of this standard solution with a microsyringe, inject it into the separation column 5, record the output with a recorder, and calculate the peak height (cm) and injection amount (μg).
A calibration curve was obtained from The calibration curve for this fluorine ion was as shown in FIG. 2, and a straight line passing through the origin was obtained. This result shows that the ion exchange resin composition of the present invention can quantitatively and sensitively analyze fluorine ions in a solution. In addition, in order to determine the sensitivity to Cl - , PO 3- 4 , NO 3 - and SO 2- 4 , NaCl 58.6 mg/50 ml was used as a standard solution in the same manner as in the case of F - above.
(distilled water), NaH 2 PO 4・2H 2 O 156.0mg/50ml
(〃), NaNO 3 84.9mg/50ml (〃) and
Prepare 142.0 mg/50 ml (〃) of Na 2 SO 4 , collect a certain amount of this standard solution with a microsyringe, inject into separation column 5, record the output with a recorder, and calculate the peak height (cm) and injection. A calibration curve was created from the amount (μg). As a result, as in the case of F - , Cl - ,
The calibration curves for PO 3- 4 , NO 3 - and SO 2- 4 were also straight lines passing through the origin, indicating that the ion exchange resin composition of the present invention can quantitatively and sensitively analyze various anions in a solution. I understand. Application Example 2 In the high performance liquid chromatography apparatus shown in FIG. 1, each part was installed as described in Experimental Apparatus 2 in Table 1, and the ion exchange resin composition prepared in Example 2 was placed in the separation column 5. Buffer removal column 6 contains a cation exchange resin (Amberlite).
CG-120Type (manufactured by Rohm and Haas) were each filled using a slurry method. Eluent (solution containing 0.003MNaHCO3 and 0.0024MNa 2 CO 3 )
was stored in the eluent storage tank 1, and the liquid was fed by the liquid feeding pump 2 at a flow rate of 1.92 ml/min. The room temperature is 17-23℃,
The electrical conductivity was measured at 15 μ and a Kiyoku meter at 5 mV. Next, fluorine ions (F - ), chloride ions (Cl - ), phosphate ions (PO 3- 4 ), nitrate ions (NO 3 - ), and sulfate ions (SO 2- 4 ) are added as follows. A sample was prepared, 40μ of it was collected using a sampler 4, and the sample was injected into a separation column 5. A chromatogram in which each ion was separated was obtained, and as a result, the result shown in FIG. 4 was obtained. Note F - : 1.56μg/40μ Cl - : 3.64〃 PO 3- 4 : 17.4〃 NO 3 - : 12.7〃 SO 2- 4 : 17.6 〃 Application example 3 In the high performance liquid chromatography apparatus shown in Figure 1, each part were prepared as described in Experimental apparatus 4 in Table 1, the separation column 5 contained the ion exchange resin composition prepared in Example 3, and the buffer removal column 6 contained the anion exchange resin (Amberlite).
CG-400Type (manufactured by Rohm and Haas) were each filled using a slurry method. Then, the eluent (0.005MHNO 3 solution) was stored in the eluent storage tank 1, and the liquid was fed by the liquid feeding pump 2 at a flow rate of 2.49 ml/min. Set the room temperature to 17-23℃ and measure the electrical conductivity meter at 10μ.
, and the recorder was measured at 1V. Next, sodium ions (Na + ),
A sample containing potassium ions (K + ) and ammonium ions (NH 4 + ) is prepared, 50μ of this is collected with a sampler and injected into a separation column.
When a chromatogram in which each ion was separated was obtained, the results shown in FIG. 5 were obtained. Na + : 9.2 μg/50 μ K + : 23.4〃 NH 4 + : 9.0〃 From these results, it can be seen that the composition of the present invention can well separate and detect cations such as Na + , K + and NH 4 + . . Next, a calibration curve was created to determine the sensitivity of this device to Na + , K + and NH 4 + . Na 2 SO 4 142.04 mg/50 ml (distilled water) as standard solutions, respectively.
Prepare K 2 SO 4 174.27 mg/50 ml (〃) and (NH 4 ) 2 SO 4 132.14 mg/50 ml (〃), collect a certain amount of this standard solution with a microsyringe,
Injected into a separation column, recorded the output with a recorder, and created a calibration curve from the peak height and injection volume.
A straight line passing through the origin was obtained. From these results, the composition of the present invention shows that
It can be seen that Na + , K + and NH 4 + can be quantitatively analyzed with good sensitivity. Application Example 4 In the high performance liquid chromatography apparatus shown in Figure 1, each part was installed as described in Experimental Apparatus 4 in Table 1, and the ion exchange resin composition prepared in Example 3 was removed from the separation column. The column contains anion exchange resin (Amberlite CG-400TyPe,
(manufactured by Rohm and Haas) by a slurry method. and eluent [0.005MHNO 3 ,
0.001M para-phenylenediamine sulfate (P-
phenylene-diamine sulphate)] was stored in the elution storage tank 1, and the liquid was fed by the liquid feeding pump 2 at a flow rate of 1.54 ml/min. Set the room temperature to 17 to 23℃ and measure the electrical conductivity.
10μ, and the recorder was measured at 1V. Next, a sample containing Mg 2+ and Ca 2+ was prepared as described below, 50μ of this was sampled with a sampler, and injected into separation column 5, and a chromatogram in which each ion was separated was obtained. The results shown in the figure were obtained. Note: Mg 2+ : 9.7 μg/50 μ Ca 2+ : 24.0 Next, a calibration curve was created to determine the sensitivity of this device to Ca 2+ and Mg 2+ . CaCl 2 110.0 mg/50 ml (distilled water) and
120.3 mg/50 ml of MgSO 4 was prepared, a certain amount of this standard solution was collected with a microsyringe, injected into a separation column, the output was recorded with a recorder, and a calibration curve was created from the peak height and injection volume. , a straight line passing through the origin was obtained. From these results, the composition of the present invention has a
It can be seen that Ca 2+ and Mg 2+ can be quantitatively analyzed with good sensitivity. Application Example 5 In the high performance liquid chromatography apparatus shown in FIG. Removal column 6 contains cation exchange resin (Amberlite CG
-120Type, manufactured by Rohm and Haas) were each filled using the slurry method. The eluent (a solution containing 0.003 MNaHCO 3 and 0.0024 MNa 2 CO 3 ) was stored in the eluent storage tank 1, and the liquid was fed by the liquid feed pump 2 at a flow rate of 2.52 ml/min. The room temperature is 17-23℃, the electrical conductivity is 15μ, and the meter is 5mV.
It was measured with Then, in the following manner, F - , Cl - , PO 3- 4 , NO 3 -
Prepare a sample containing SO 2- 4 , collect 50μ with a sampler and inject it into a separation column,
When chromatograms were obtained in which each of the components was separated, the results shown in FIG. 7 were obtained. Note F - : 1.95μg/50μ Cl - : 4.54〃 PO 3- 4 : 21.8〃 NO 3 - : 15.9〃 SO 2- 4 : 22.0〃 Next, in this application example 5, an anion exchange resin ( Amber light CG-
400Type, manufactured by Rohm and Haas), the eluent was a solution containing 0.005MHNO 3 and 0.001M para-phenylenediamine sulfate, the flow rate of the liquid pump was 2.61 ml/min, and an electrical conductivity meter was used. The test was carried out under the same equipment conditions as Application Example 5 (the resin packed in the separation column was not changed), except that the electrical conductivity was set to 10 μ using CD-A manufactured by Chromatec, and the recorder was used for measurement at 1 V. Then, prepare a sample containing Na + , K + and NH 4 + as described below, and add 50μ of this using a sampler.
When the sample was collected and injected into a separation column, and a chromatogram in which each ion was separated was obtained, the results shown in FIG. 8 were obtained. Na + : 9.2 μg/50 μ K + : 23.4〃 NH 4 + : 9.0〃 From the above two test results, it can be concluded that the ion exchange resin composition of the present invention can be used for the analysis of not only anions but also cations. I understand.
第1図は本発明の応用例に使用する高速液体ク
ロマトグラフイー装置の概略説明図、第2図はフ
ツ素イオン(F-)の検量線を示す図そして第3
〜8図は各種イオンの分離パターンを示すイオン
クロマトグラムを示す図である。
1……溶離液収納槽、2……送液ポンプ、3…
…圧力計、4……サンプラー、5……分離カラ
ム、6……バツフアー除去カラム、7……フロー
セル、8……電気伝導度計、9……記録計。イ…
…F-、ロ……Cl-、ハ……PO4 3-、ニ……NO3 -、
ホ……SO4 2-、ヘ……Na+、ト……NH4 +、チ…
…K+、リ……Mg2+、ヌ……Ca2+。
Figure 1 is a schematic illustration of a high-performance liquid chromatography apparatus used in an application example of the present invention, Figure 2 is a diagram showing a calibration curve for fluorine ion (F - ), and Figure 3 is a diagram showing a calibration curve for fluorine ions (F - ).
Figures 8 to 8 are diagrams showing ion chromatograms showing separation patterns of various ions. 1...Eluent storage tank, 2...Liquid pump, 3...
... Pressure gauge, 4 ... Sampler, 5 ... Separation column, 6 ... Buffer removal column, 7 ... Flow cell, 8 ... Electrical conductivity meter, 9 ... Recorder. stomach…
...F - , B...Cl - , H...PO 4 3- , Ni...NO 3 - ,
Ho...SO 4 2- , He...Na + , To...NH 4 + , Chi...
…K + , Li…Mg 2+ , Nu…Ca 2+ .
Claims (1)
不溶性合成樹脂基質と、有効表面上に親水基を有
しイオン交換基を有しない微粒子の不溶性合成樹
脂基質とを混合してなるイオン交換樹脂組成物。 2 有効表面上にイオン交換基を有する微粒子の
不溶性合成樹脂基質が、陰イオン交換樹脂および
陽イオン交換樹脂から選ばれた少なくとも1つで
ある特許請求の範囲第1項記載の組成物。 3 有効表面上にイオン交換基を有する微粒子の
不溶性合成樹脂基質と、有効表面上に親水基を有
しイオン交換基を有しない微粒子の不溶性合成樹
脂基質との混合割合が1:0.1〜200である特許請
求の範囲第1項記載の組成物。[Scope of Claims] 1. A fine particle insoluble synthetic resin matrix having an ion exchange group on its effective surface and a fine particle insoluble synthetic resin matrix having a hydrophilic group on its effective surface and no ion exchange group are mixed. An ion exchange resin composition. 2. The composition according to claim 1, wherein the fine particle insoluble synthetic resin matrix having ion exchange groups on its effective surface is at least one selected from anion exchange resins and cation exchange resins. 3 The mixing ratio of the fine particle insoluble synthetic resin substrate having an ion exchange group on the effective surface and the fine particle insoluble synthetic resin substrate having a hydrophilic group on the effective surface and no ion exchange group is 1:0.1 to 200. A composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56096600A JPS58253A (en) | 1981-06-24 | 1981-06-24 | Composition for ion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56096600A JPS58253A (en) | 1981-06-24 | 1981-06-24 | Composition for ion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58253A JPS58253A (en) | 1983-01-05 |
| JPH021534B2 true JPH021534B2 (en) | 1990-01-11 |
Family
ID=14169363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56096600A Granted JPS58253A (en) | 1981-06-24 | 1981-06-24 | Composition for ion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58253A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60102978A (en) * | 1983-11-11 | 1985-06-07 | Nippon Light Metal Co Ltd | Blank member having hydrophilic film |
| JPS61182849U (en) * | 1985-05-02 | 1986-11-14 | ||
| JPS6460222A (en) * | 1987-08-27 | 1989-03-07 | Nec Corp | Carrier relay signal noise detection |
| JP2838208B2 (en) * | 1988-03-29 | 1998-12-16 | 東レ・ダウコーニング・シリコーン株式会社 | Transparent flame-retardant silicone rubber composition |
| JPH02174516A (en) * | 1988-12-23 | 1990-07-05 | Nec Corp | Demodulation of carrier relay signal |
| JP5409213B2 (en) * | 2009-09-04 | 2014-02-05 | 学校法人中部大学 | Cation analysis |
-
1981
- 1981-06-24 JP JP56096600A patent/JPS58253A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58253A (en) | 1983-01-05 |
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