JPH04143650A - Polymer membrane for ion selective electrode and method for measuring concentration of anion - Google Patents
Polymer membrane for ion selective electrode and method for measuring concentration of anionInfo
- Publication number
- JPH04143650A JPH04143650A JP2267411A JP26741190A JPH04143650A JP H04143650 A JPH04143650 A JP H04143650A JP 2267411 A JP2267411 A JP 2267411A JP 26741190 A JP26741190 A JP 26741190A JP H04143650 A JPH04143650 A JP H04143650A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- polymer membrane
- electrode
- selective
- selective electrode
- 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.)
- Pending
Links
- 150000002500 ions Chemical class 0.000 title claims abstract description 63
- 229920005597 polymer membrane Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims description 30
- 150000001450 anions Chemical class 0.000 title claims description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 17
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000011002 quantification Methods 0.000 abstract 1
- 239000003945 anionic surfactant Substances 0.000 description 26
- -1 ethylhexyl Chemical group 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- 238000003918 potentiometric titration Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000011088 calibration curve Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- JRLISGAUAJZAGL-UHFFFAOYSA-M tridodecyl(methyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC JRLISGAUAJZAGL-UHFFFAOYSA-M 0.000 description 2
- NBQXYAJLUDQSNV-UHFFFAOYSA-N 1-[(4-methylphenyl)methyl]-5-oxopyrrolidine-3-carboxylic acid Chemical compound C1=CC(C)=CC=C1CN1C(=O)CC(C(O)=O)C1 NBQXYAJLUDQSNV-UHFFFAOYSA-N 0.000 description 1
- YOJKKXRJMXIKSR-UHFFFAOYSA-N 1-nitro-2-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1 YOJKKXRJMXIKSR-UHFFFAOYSA-N 0.000 description 1
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LPKZGAGGBDTXOZ-UHFFFAOYSA-N [1-nitro-8-(8-nitro-8-phenyloctoxy)octyl]benzene Chemical compound C=1C=CC=CC=1C([N+](=O)[O-])CCCCCCCOCCCCCCCC([N+]([O-])=O)C1=CC=CC=C1 LPKZGAGGBDTXOZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- NGOVNSCURCOLBI-UHFFFAOYSA-N azanium;octadecyl sulfate Chemical class N.CCCCCCCCCCCCCCCCCCOS(O)(=O)=O NGOVNSCURCOLBI-UHFFFAOYSA-N 0.000 description 1
- CSNHNGDROQRZKT-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CSNHNGDROQRZKT-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- HHECSPXBQJHZAF-UHFFFAOYSA-N dihexyl hexanedioate Chemical compound CCCCCCOC(=O)CCCCC(=O)OCCCCCC HHECSPXBQJHZAF-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- LQHDVHUTTATERF-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium dodecyl benzenesulfonate Chemical compound C1(=CC=CC=C1)S(=O)(=O)OCCCCCCCCCCCC.C(CCCCCCCCCCCCCCCCC)[N+](C)(C)CCCCCCCCCCCCCCCCCC LQHDVHUTTATERF-UHFFFAOYSA-N 0.000 description 1
- MSSPASWTWTZPQU-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC MSSPASWTWTZPQU-UHFFFAOYSA-M 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WFYYNXUVAKJFAV-UHFFFAOYSA-N methyl(tridecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCC[NH2+]C WFYYNXUVAKJFAV-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-K nitrilotriacetate(3-) Chemical compound [O-]C(=O)CN(CC([O-])=O)CC([O-])=O MGFYIUFZLHCRTH-UHFFFAOYSA-K 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 229960000776 sodium tetradecyl sulfate Drugs 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- AYFACLKQYVTXNS-UHFFFAOYSA-M sodium;tetradecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCS([O-])(=O)=O AYFACLKQYVTXNS-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GHYAHFJIQRUUFA-UHFFFAOYSA-N tetradec-1-ene-1-sulfonic acid Chemical compound CCCCCCCCCCCCC=CS(O)(=O)=O GHYAHFJIQRUUFA-UHFFFAOYSA-N 0.000 description 1
- NWOKSKQOENPYPP-UHFFFAOYSA-M tetraoctadecylazanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC NWOKSKQOENPYPP-UHFFFAOYSA-M 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229940006302 tripolyphosphate ion Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、イオン選択性電極用高分子膜およびこれを用
いた陰イオン濃度の測定方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polymer membrane for an ion-selective electrode and a method for measuring anion concentration using the same.
更に詳しくは、本発明はポリ塩化ビニル、可塑剤および
特定の第四級アンモニウム塩からなるポリ塩化ビニル組
成物を用いた、簡単でかつ高精度で陰イオン濃度を選択
的に測定することができ、長期間の使用にも耐えるイオ
ン選択性電極用高分子膜、およびこれを用いた陰イオン
濃度の測定方法に関する。More specifically, the present invention makes it possible to selectively measure anion concentration simply and with high accuracy using a polyvinyl chloride composition consisting of polyvinyl chloride, a plasticizer, and a specific quaternary ammonium salt. , relates to a polymer membrane for ion-selective electrodes that can withstand long-term use, and a method for measuring anion concentration using the same.
［従来の技術］
陰イオン濃度の測定法、例えば陰イオン界面活性剤溶液
の濃度を測定する方法としては、クロロホルムを抽出溶
媒およびメチレンブルーを指示薬として標準陽イオン界
面活性剤溶液で分相滴定する方法［ネイチャー、１６０
，７９５ （１９４７）やその改良法である逆滴定法［
油化学、９．１２４（１９６０）］が用いられている。[Prior Art] A method for measuring anion concentration, for example, a method for measuring the concentration of an anionic surfactant solution, is a method of phase separation titration with a standard cationic surfactant solution using chloroform as an extraction solvent and methylene blue as an indicator. [Nature, 160
, 795 (1947) and its improved method, the back titration method [
Oil Chemistry, 9.124 (1960)] is used.
また、陰イオン界面活性剤の希薄溶液の濃度を測定する
方法としては、メチレンブルーとの錯塩をクロロホルム
で抽出し、吸光度を測定する方法［アナリスト（Ａｎａ
ｌｙｓｔｌ 、 ８ユ、２８６ （１９６２）］、陽イ
オン界面活性剤に感応する液膜型イオン電極を指示電極
として用い電位差滴定法で陰イオン界面活性剤濃度を定
量する方法［日本化学会誌、１０．１４４２ （１９８
０）］などがある。In addition, as a method for measuring the concentration of a dilute solution of an anionic surfactant, there is a method in which a complex salt with methylene blue is extracted with chloroform and the absorbance is measured [Analyst (Analyst)
lystl, 8U, 286 (1962)], a method for quantifying anionic surfactant concentration by potentiometric titration using a liquid film type ion electrode sensitive to cationic surfactants as an indicator electrode [Journal of the Chemical Society of Japan, 10. 1442 (198
0)].
また、第四級アンモニウム塩のクロライド型よりなる塩
化物イオン選択性応答物質をエポキシ樹脂とポリ塩化ビ
ニルに保持させた塩化物イオン選択性電極用膜も提案さ
れているＣ特開平２４０１８４号公報）。In addition, a membrane for a chloride ion selective electrode in which a chloride ion selective response substance consisting of a chloride type of quaternary ammonium salt is held in an epoxy resin and polyvinyl chloride has also been proposed (C JP-A-240184). .
［発明が解決しようとする課題］
しかしながら、前記分相滴定法や吸光光度法は、いずれ
も手動的な方法であるため操作に熟練を要し、また分析
に長時間を要する欠点があった。[Problems to be Solved by the Invention] However, the phase separation titration method and the spectrophotometry method are both manual methods, so they require skill in operation and have the disadvantage that analysis requires a long time.
また前記液膜型イオン電極を指示電極として用い、電位
差滴定法で陰イオン界面活性剤濃度を定量する方法は、
陰イオン界面活性剤が電極の感応物質である陽イオン界
面活性剤を溶かすため、長期間使用すると電位が不安定
となり測定の際大きな誤差を生じるという問題点があっ
た。Furthermore, a method for quantifying the anionic surfactant concentration by potentiometric titration using the liquid film type ion electrode as an indicator electrode is as follows:
Since the anionic surfactant dissolves the cationic surfactant, which is the sensitive substance of the electrode, there was a problem in that when used for a long period of time, the potential became unstable and a large error occurred during measurement.
更に第四級アンモニウム塩のクロライド型を用いた塩化
物イオン選択性電極用膜は、陰イオン界面活性剤に対し
ては感度が低く、長時間使用すると電位が不安定となり
、測定の際大きな誤差を生じるという問題点があった。Furthermore, membranes for chloride ion-selective electrodes that use the chloride type of quaternary ammonium salts have low sensitivity to anionic surfactants, and the potential becomes unstable when used for long periods of time, resulting in large errors in measurement. There was a problem in that it caused
本発明の発明者らはポリ塩化ビニル、可塑剤および特定
の第４級アンモニウム塩からなるポリ塩化ビニル組成物
をイオン選択性膜として用いることにより、上記の問題
点が解決されることを見出した。The inventors of the present invention have found that the above problems can be solved by using a polyvinyl chloride composition consisting of polyvinyl chloride, a plasticizer, and a specific quaternary ammonium salt as an ion-selective membrane. .
従って本発明の目的は、陰イオンの濃度を短時間に高精
度で定量でき長期間使用しても安定なイオン選択性電極
用高分子膜、およびそれを用いた陰イオン濃度の測定方
法を提供することにある。Therefore, an object of the present invention is to provide a polymer membrane for an ion-selective electrode that can quantify the concentration of anions with high precision in a short time and is stable even after long-term use, and a method for measuring anion concentrations using the same. It's about doing.
［課題を解決するための手段］
本発明は、
（ａｌポリ塩化ビニル２４ないし３０重量％、（ｂｌ可
塑剤７５ないし６４重量％および（ｃｌ下紀−数式
％式％
Ｃ式中Ｒ１およびＲ２はそれぞれ独立で炭素数１２ない
し１８のアルキル基、Ｒ３ＪよびＲ４はそれぞれ独立で
炭素数１ないし１８のアルキル基、ＡはＲ″’０３Ｏ３
−ｆＲ’は炭素数１０ないし１８の直鎖アルキル基）ま
たはＲ’Ｃ，Ｈ４５Ｏ，−ｆＲ’は炭素数１０ないし１
３の直鎖アルキル基）を示す）で表わされる第四級アン
モニウム塩ｌないし６重量％
からなることを特徴とするイオン選択性電極用高分子膜
、および前記イオン選択性電極用高分子膜を用いた陰イ
オン濃度の測定方法である。[Means for Solving the Problems] The present invention provides (al polyvinyl chloride 24 to 30% by weight, (bl plasticizer 75 to 64% by weight) and (cl lower formula % formula % C where R1 and R2 are Each independently represents an alkyl group having 12 to 18 carbon atoms, R3J and R4 each independently represents an alkyl group having 1 to 18 carbon atoms, A is R″'03O3
-fR' is a straight chain alkyl group having 10 to 18 carbon atoms) or R'C, H45O, -fR' is a straight chain alkyl group having 10 to 18 carbon atoms)
A polymer membrane for an ion-selective electrode characterized by comprising 1 to 6% by weight of a quaternary ammonium salt represented by This is the method used to measure anion concentration.
本発明で用いることのできるポリ塩化ビニル（ａ）は市
販のポリ塩化ビニルのいずれをも用いることができるが
、数平均重合度３００〜３０００のものが好ましく、さ
らに好ましくは数平均重合度１０００〜２０００のもの
である。数平均重合度が３００未満の時は膜の機械的強
度が弱く。As the polyvinyl chloride (a) that can be used in the present invention, any commercially available polyvinyl chloride can be used, but those having a number average degree of polymerization of 300 to 3000 are preferable, and more preferably those having a number average degree of polymerization of 1000 to 3000. 2000. When the number average degree of polymerization is less than 300, the mechanical strength of the membrane is weak.
３０００を超えるとイオン選択性が低下するので好まし
くない、ポリ塩化ビニルの数平均重合度は粘度法による
分子量の測定によって求めることができる。The number average degree of polymerization of polyvinyl chloride, which is undesirable if it exceeds 3000 because the ion selectivity decreases, can be determined by measuring the molecular weight using a viscosity method.
本発明で用いることのできる可塑剤（ｂ）・は、０ニト
ロフエニルオクチルエーテル、リン酸トリブチル、リン
酸トリー２−エチルヘキシル、フタル酸ジメチル、フタ
ル酸ジエチル、フタル酸ジヘブチル、フタル酸ジ−ｎ−
オクチル、フタル酸ジー２−エチルヘキシル、フタル酸
ブチルベンジル、オレイン酸ブチル、アジピン酸ジブチ
ル、アジピン酸ジ−ｎ−ヘキシル、アジピン酸ジー２−
エチルヘキシル、セバシン酸ジブチル、ジェチレングリ
コールジベンゾエート、ブチルフタリルブチルクリコレ
ート、２−ニトロビフェニルおよび塩素化ビフェニルな
どを例示することができる。Plasticizers (b) that can be used in the present invention include O-nitrophenyl octyl ether, tributyl phosphate, tri-2-ethylhexyl phosphate, dimethyl phthalate, diethyl phthalate, diheptyl phthalate, and di-n phthalate. −
Octyl, di-2-ethylhexyl phthalate, butylbenzyl phthalate, butyl oleate, dibutyl adipate, di-n-hexyl adipate, di-2-adipate
Examples include ethylhexyl, dibutyl sebacate, diethylene glycol dibenzoate, butylphthalyl butyl cricolate, 2-nitrobiphenyl, and chlorinated biphenyls.
本発明で用いることのできる第四級アンモニウム塩ｆｃ
ｌは、下記−数式
％式％
であられされるもので、式中４個のアルキル基の中の少
なくとも２個のアルキル基は炭素数１２ないし１８の高
級アルキル基であり、その他のアルキル基は炭素数１な
いし１８の低級ないし高級アルキル基から選択すること
ができる。すなわち式中Ｒ１およびＲ２はそれぞれ独立
で炭素数１２ないし１８のアルキル基、Ｒ３およびＲ４
はそれぞれ独立で炭素数１ないし１８のアルキル基を表
わすが、原料の入手および合成の容易さを考慮すると、
Ｒ３およびＲ４はＣＨ，または炭素数１２ないし１８の
アルキル基が好適である。Quaternary ammonium salt fc that can be used in the present invention
l is expressed by the following formula - % formula %, where at least two of the four alkyl groups are higher alkyl groups having 12 to 18 carbon atoms, and the other alkyl groups are It can be selected from lower to higher alkyl groups having 1 to 18 carbon atoms. That is, in the formula, R1 and R2 are each independently an alkyl group having 12 to 18 carbon atoms, R3 and R4
Each independently represents an alkyl group having 1 to 18 carbon atoms, but considering the ease of obtaining raw materials and synthesis,
R3 and R4 are preferably CH or an alkyl group having 12 to 18 carbon atoms.
このような第４級アンモニウム塩としては、メチルトリ
デシルアンモニウムドデシル硫酸塩、テトラオクタデシ
ルアンモニウムドデシル硫酸塩、ジメチルジオクタデシ
ルアンモニウムドデシル硫酸塩、メチルトリテトラデシ
ルアンモニウムドデシル硫酸塩、メチルトリドデシルア
ンモニウムヘキサデシル硫酸塩、テトラオクタデシルア
ンモニウムヘキサデシル硫酸塩、ジメチルジオクタデシ
ルアンモニウムヘキサデシル硫酸塩、メチルトリテトラ
デシルアンモニウムヘキサデシル硫酸塩、メチルトリド
デシルアンモニウムオクタデシル硫酸塩、テトラオクタ
デシルアンモニウムオクタデシル硫酸塩、ジメチルジオ
クタデシルアンモニウムオクタデシル硫酸塩、メチルト
リテトラデシルアンモニウムオクタデシル硫酸塩、メチ
ルトリデシルアンモニウムドデシルベンゼンスルホン酸
塩、テトラオクタデシルアンモニウムドデシルベンゼン
スルホン酸塩、ジメチルジオクタデシルアンモニウムド
デシルベンゼンスルホン酸塩およびメチルトリテトラデ
シルアンモニウムドデシルベンゼンスルホン酸塩などを
例示することができる。Such quaternary ammonium salts include methyltridecylammonium dodecyl sulfate, tetraoctadecyl ammonium dodecyl sulfate, dimethyldioctadecyl ammonium dodecyl sulfate, methyltridetradecylammonium dodecyl sulfate, and methyltridecylammonium hexadecyl sulfate. Salt, Tetraoctadecyl ammonium hexadecyl sulfate, Dimethyldioctadecyl ammonium hexadecyl sulfate, Methyl tritetradecylammonium hexadecyl sulfate, Methyl tridodecyl ammonium octadecyl sulfate, Tetraoctadecyl ammonium octadecyl sulfate, Dimethyl diotadecyl ammonium octadecyl sulfate salts, methyltritetradecylammonium octadecyl sulfate, methyltridecylammonium dodecylbenzenesulfonate, tetraoctadecylammonium dodecylbenzenesulfonate, dimethyldioctadecylammonium dodecylbenzenesulfonate and methyltridetradecylammonium dodecylbenzenesulfonate For example,
上記−数式で示される本発明の第四級アンモニウム塩を
用いることにより、長時間使用しても安定で寿命の長い
高分子膜を得ることができる。By using the quaternary ammonium salt of the present invention represented by the above formula, it is possible to obtain a polymer membrane that is stable and has a long life even when used for a long time.
イオン選択性電極用高分子膜は以下の方法で作成するこ
とができる。A polymer membrane for an ion-selective electrode can be created by the following method.
ポリ塩化ビニル２４ないし３０重量％、可塑剤７５な・
いし６４重量％および第四級アンモニウム塩１ないし６
重量％からなる混合物を２０〜１００倍量（重量基準）
の有機溶媒に溶解する。この溶液をガラス板上においた
内径２０〜４０ｍｍのガラスリング中に入れ、溶媒を蒸
発し、イオン選択性電極用高分子膜を得る。24 to 30% by weight of polyvinyl chloride, 75% of plasticizer.
64% by weight of I and 1 to 6 quaternary ammonium salts
20 to 100 times the amount of the mixture consisting of % by weight (based on weight)
Soluble in organic solvent. This solution is placed in a glass ring having an inner diameter of 20 to 40 mm placed on a glass plate, and the solvent is evaporated to obtain a polymer membrane for an ion-selective electrode.
組成物中のポリ塩化ビニルが２４重量％未満では、得ら
れた高分子膜が柔らかく、３０重量％を超えると得られ
た高分子膜が硬くなるので好ましくない、可塑剤が、７
５重量％を超えるかまたは６４重量％未満では高分子膜
の形成が困難となり好ましくない。第四級アンモニウム
塩が１重量％未満では、高分子膜を電極に取り付けた時
、陰イオンに対する感度が悪く、６重量％を超えて添加
しても感度は向上しない。If the polyvinyl chloride content in the composition is less than 24% by weight, the obtained polymer film will be soft, and if it exceeds 30% by weight, the obtained polymer film will become hard, which is undesirable.
If it exceeds 5% by weight or less than 64% by weight, it becomes difficult to form a polymer film, which is not preferable. If the quaternary ammonium salt is less than 1% by weight, the sensitivity to anions will be poor when the polymer membrane is attached to the electrode, and if it is added in an amount exceeding 6% by weight, the sensitivity will not improve.
イオン泗択性電極用高分子膜製造の際の有機溶媒として
は、テトラヒドロフランなどを使用することができる。Tetrahydrofuran or the like can be used as an organic solvent when producing a polymer membrane for an ion-selective electrode.
本発明のイオン選択性電極用高分子膜は、市販の液膜型
電極の先端に取り付けて使用することができる。The polymer membrane for an ion-selective electrode of the present invention can be used by being attached to the tip of a commercially available liquid film type electrode.
電極は適当な参照電極、内部液との組み合わせによって
電池を構成し、エレクトロメータを用いて、膜電位の測
定を行う。例えば内部参照電極として ｌＡｇｌＡｇ（
：ＩＩ系、外部参照電極としてカロメル電極を用い、下
記のような電池系を構成して膜電位を測定する。A battery is constructed by combining the electrode with a suitable reference electrode and an internal solution, and the membrane potential is measured using an electrometer. For example, lAglAg (
: II system, using a calomel electrode as an external reference electrode, constructing the following battery system and measuring membrane potential.
一一一イオン選択性電極−−−」
また、
前記イオン選択性電極の内部液には０．０５〜１．Ｑ
＠ｍｏｌ／ｎの直鎖アルキルベンゼンスルホン酸水溶
液と０．０５〜１．０＋ｓｍｏｌ／βの塩化カリウム水
溶液との混合物などを用いることができる。1-11 Ion-selective electrode ---" Also, the internal liquid of the ion-selective electrode contains 0.05 to 1. Q
A mixture of a linear alkylbenzenesulfonic acid aqueous solution of @mol/n and a potassium chloride aqueous solution of 0.05 to 1.0+smol/β can be used.
本発明による陰イオン界面活性剤の濃度の測定は、直接
検量線法および電位差滴定法により行なうことができる
。The concentration of anionic surfactants according to the present invention can be measured by direct calibration curve method and potentiometric titration method.
直接検量線法は、あらかじめｌｏ−３〜１０ｍｏｌ／ｊ
２の既知濃度の陰イオン界面活性剤溶液を前記の電極で
測定し、陰イオンの濃度と起電力との関係から検量線を
作成しておき、その検量線から未知濃度の陰イオン界面
活性剤溶液の濃度を求めることができる。In the direct calibration curve method, lo-3 to 10 mol/j
Measure the anionic surfactant solution with a known concentration in step 2 using the above electrode, create a calibration curve from the relationship between the anion concentration and the electromotive force, and use the calibration curve to measure the anionic surfactant solution with an unknown concentration. The concentration of the solution can be determined.
電位差滴定法は、未知濃度の陰イオン界面活性剤溶液に
、前記電極を指示電極として用い、既知濃度の第四級ア
ンモニウム塩溶液で電位差滴定をして求めることができ
る。In the potentiometric titration method, the anionic surfactant solution of unknown concentration can be determined by potentiometric titration with a quaternary ammonium salt solution of known concentration using the electrode as an indicator electrode.
［実施例］ 参考例および実施例により本発明を説明する。[Example] The present invention will be explained by reference examples and examples.
まず、参考例により第四級アンモニウム塩の製造法を説
明する。First, a method for producing a quaternary ammonium salt will be explained using a reference example.
翌２だ引上
メチルトリドデシルアンモニウムイオダイド（２０ａ＋
ｍｏｌ／ １２１のエチルエーテル溶液５０ＩＩＩ２と
ドデシル硫酸ナトリウム（３０＋ｕ＋ｏｌ／ Ｉ２）の
水溶液５０１けを分液ロートに入れ十分に振とうした０
分液後、エーテル相を水で２回洗浄し、無水硫酸ナトリ
ウムで乾燥後、エーテルを留去してメチルトリドデシル
アンモニウムドデシル硫酸塩を得た。The next 2 days, pull up methyltridodecylammonium iodide (20a+
Put 50 ml/121 ethyl ether solution and 501 ml aqueous solution of sodium dodecyl sulfate (30+u+ol/I2) into a separating funnel and shake thoroughly.
After separation, the ether phase was washed twice with water, dried over anhydrous sodium sulfate, and then the ether was distilled off to obtain methyltridodecylammonium dodecyl sulfate.
１１．１
参考例１のメチルトリドデシルアンモニウムイオダイド
をテトラオクタデシルアンモニウムイオダイドに代えて
テトラオクタデシルアンモニウムドデシル硫酸塩を製造
した。11.1 Tetraoctadecyl ammonium dodecyl sulfate was produced by replacing methyltridecylammonium iodide in Reference Example 1 with tetraoctadecyl ammonium iodide.
１λ！旦
参考例１のメチルトリドデシルアンモニウムイオダイド
をジメチルジオクタデシルアンモニウムイオダイドに代
えてジメチルジオクタデシルアンモニウムドデシル硫酸
塩を製造した。1λ! First, dimethyldioctadecylammonium dodecyl sulfate was prepared by replacing methyltridodecylammonium iodide in Reference Example 1 with dimethyldioctadecylammonium iodide.
１互１４
参考例１のメチルトリドデシルアンモニウムイオダイド
をメチルトリテトラデシルアンモニウムイオダイドに代
えてメチルトリテトラデシルアンモニウムドデシル硫酸
塩を製造した。1/14 Methyltridetradecylammonium dodecyl sulfate was produced by replacing methyltridetradecylammonium iodide in Reference Example 1 with methyltritetradecylammonium iodide.
ＵＬｆ！ＬＬ（イオン選択性電極用高分子膜の作成）次
に上記参考例１〜４で得られた各種第４級アンモニウム
塩を、重合度の異なる各種ポリ塩化ビニルおよび可塑剤
と配合し、かつ第４級アンモニウム塩の配合量を変え、
各種イオン選択性電極用高分子膜を作成した。ULf! LL (Preparation of polymer membrane for ion-selective electrode) Next, various quaternary ammonium salts obtained in Reference Examples 1 to 4 above were blended with various polyvinyl chlorides having different degrees of polymerization and a plasticizer, and By changing the amount of quaternary ammonium salt,
We created polymer membranes for various ion-selective electrodes.
夫五丘上二］）
ポリ塩化ビニル（数平均重合度１３００） ５２．２＋
ｗｇと０−ニトロフェニルオクチルエーテル１２６．０
ｍｇと、参考例１で得られたメチルトリドデシルアンモ
ニウムドデシル硫酸塩１．８ｍｇとを４■βのテトラヒ
ドロフランに溶解した。この溶液をガラス板上においた
内径３０■■のガラスリング中に入れて温媒を蒸発し、
イオン選択性電極用高分子膜を得た。Polyvinyl chloride (number average degree of polymerization 1300) 52.2+
wg and 0-nitrophenyl octyl ether 126.0
mg and 1.8 mg of methyltridodecylammonium dodecyl sulfate obtained in Reference Example 1 were dissolved in 4.beta. of tetrahydrofuran. This solution was placed in a glass ring with an inner diameter of 30 mm placed on a glass plate, and the hot medium was evaporated.
A polymer membrane for an ion-selective electrode was obtained.
例１−２〜４） 実施例１− ｆｌ）において、メチル
トリドデシルアンモニウムドデシル硫酸塩の代わりに、
第１表２載の参考例２〜４で得られた各種第４級アンモ
ニウムを用いてイオン選択性電極用高分子膜を作成した
。Examples 1-2 to 4) In Example 1-fl), instead of methyltridodecylammonium dodecyl sulfate,
Polymer membranes for ion-selective electrodes were prepared using various quaternary ammoniums obtained in Reference Examples 2 to 4 listed in Table 1.
夾五興上二卦）
ポリ塩化ビニル（平均重合度１２００１５２．２Ｂと０
−ニトロフェニルオクチルエーテル１２４．２ｍｇと参
考例１で得られたメチルトリドデシルアンモニウムドデ
シル硫酸塩３．６Ｂとを４■βのテトラヒドロフランに
溶解した。この溶液から実施例１〜ｆｉｌ と同じ方法
でイオン選択性電極用高分子膜を得た。Polyvinyl chloride (average degree of polymerization 1200152.2B and 0
-124.2 mg of nitrophenyl octyl ether and 3.6 B of methyltridodecylammonium dodecyl sulfate obtained in Reference Example 1 were dissolved in 4.beta. of tetrahydrofuran. A polymer membrane for an ion-selective electrode was obtained from this solution in the same manner as in Examples 1 to fil.
夫直鳳上二卦）
ポリ塩化ビニル（平均重合度１５００１５２．２ｍｇと
０−ニトロフェニルオクチルエーテル１２０Ｊ−ｇと参
考例１で得られたメチルトリドデシルアンモニウムドデ
シル硫酸塩７．２Ｂとを４■βのテトラヒドロフランに
溶解した。この溶液から実施例１−＋１１と同じ方法で
イオン選択性電極用高分子膜を得た。4 ■β A polymer membrane for an ion-selective electrode was obtained from this solution in the same manner as in Example 1-+11.
実施例で得られた各種イオン選択性電極用高分子膜の構
成成分および組成を第１表に示した。Table 1 shows the constituent components and compositions of various polymer membranes for ion-selective electrodes obtained in Examples.
以下余白
７（イオン選択性電極の作成）
支直興に］）
フィリップス社製ｌＳ−５６１型の電極ポデーに実施例
１− ｆｉｌで作成したイオン選択性電極用高分子膜を
それぞれ取り付け、また、内部液に０．１ ｍｍｏｌ／
ｉのドデシルベンゼンスルホン酸水溶液（ＬＡＳ）と０
．１ｉｎ＋ｏｌ／Ｉ２の塩化カリウム水溶液を用いイオ
ン選択性電極を作成した。Below is blank 7 (Creation of ion-selective electrode) To Naoki Shinobu]) The polymer membranes for ion-selective electrodes prepared in Example 1-fil were attached to the electrode pods of the Philips IS-561 type, and 0.1 mmol/in internal solution
i of dodecylbenzenesulfonic acid aqueous solution (LAS) and 0
．． An ion-selective electrode was prepared using a 1 in+ol/I2 potassium chloride aqueous solution.
実１１１Ｚ二」２）
実施例２− ＋１１において、イオン選択性電極用高分
子膜を実施例１− ＋２１で得たイオン選択性高分子膜
に代えてイオン選択性電極を作成した。2) In Example 2-+11, an ion-selective electrode was prepared by replacing the polymer membrane for the ion-selective electrode with the ion-selective polymer membrane obtained in Example 1-+21.
実ｕ ３１
実施例２− ＋１１においてイオン選択性電極用高分子
膜を実施例１− （３１で得たイオン選択性高分子膜に
代えてイオン選択性電極を作成した。Actual u 31 Example 2- In +11, an ion-selective electrode was created by replacing the polymer membrane for an ion-selective electrode with the ion-selective polymer membrane obtained in Example 1- (31).
叉Ｕ二」４）
実施例２− （１）においてイオン選択性電極用高分子
膜を実施例１− （４）で得たイオン選択性高分子膜に
代えてイオン選択性電極を作成した。4) In Example 2-(1), an ion-selective electrode was created by replacing the polymer membrane for the ion-selective electrode with the ion-selective polymer membrane obtained in Example 1-(4).
実１１引１５ ）
実施例２− ｉｌ＋ においてイオン選択性電極用高分
子膜を実施例１− （５１で得たイオン選択性高分子膜
に代えてイオン選択性電極を作成した。Example 11-15) An ion-selective electrode was prepared by replacing the polymer membrane for an ion-selective electrode in Example 2-il+ with the ion-selective polymer membrane obtained in Example 1-(51).
実ｆｉｌｌスニ」６）
フィリップス社製ｌＳ−５６１型の電極ボデーに実施例
１− ＋１１ で作成したイオン選択性電極用高分子膜
をそれぞれ取り付け、また、内部液に０１ｍｍｏｌ／Ｉ
２の炭素数１０から１３のアルキルベンゼンスルホン酸
水溶液とＯ，１ｍｍｏｌ／ｆｆの塩化カリウム水溶液を
用いイオン選択性電極を作成した。6) The polymer membrane for ion-selective electrodes prepared in Example 1-+11 was attached to the electrode body of the Philips IS-561 type, and the internal liquid was filled with 01 mmol/I.
An ion-selective electrode was prepared using an aqueous solution of an alkylbenzenesulfonic acid having 10 to 13 carbon atoms and an aqueous solution of O, 1 mmol/ff potassium chloride.
実１１１Ａ：」７１
実施例２− （６１においてイオン選択性電極用高分子
膜を実施例１− ＋６１ で得たイオン選択性高分子膜
に代えてイオン選択性電極を作成した。Example 111A: 71 Example 2- (In 61, an ion-selective electrode was created by replacing the polymer membrane for an ion-selective electrode with the ion-selective polymer membrane obtained in Example 1-+61.
７（イオン選択性の測定）
実施例２− ｆｉｌ、 ｆ６）および（７）で作成した
３種類のイオン選択性電極で、■ドデシルスルホン酸ナ
トリウム、■テトラデシルスルホン酸ナトリウム、■ド
テシル硫酸ナトリウム、■テトラデシル硫酸ナトリウム
、■α−テトラデセンスルホン酸ナトリウム、■Ｃ１〜
Ｃ１６α−オレフィンスルホン酸ナトリウム、■ポリオ
キシエチレンドデシルエーテル硫酸ナトリウム（エチレ
ンオキサイド付加モル数”＝３）、■ラウリン酸ナトリ
ウムに対する選択係数を求めた。7 (Measurement of ion selectivity) Using the three types of ion-selective electrodes prepared in Example 2-fil, f6) and (7), ■ sodium dodecyl sulfonate, ■ sodium tetradecyl sulfonate, ■ sodium dodecyl sulfate, ■Sodium tetradecyl sulfate, ■Sodium α-tetradecene sulfonate, ■C1~
Selectivity coefficients for sodium C16α-olefin sulfonate, (1) sodium polyoxyethylene dodecyl ether sulfate (number of moles of ethylene oxide added = 3), and (2) sodium laurate were determined.
選択係数はＪＩＳ ＫＯ１２２ｒイオン電極方法通則」
に従って求めた。すなわち、前記の３種類の電極を用い
て、１０−３ｍｏｌ／Ｉ２のドデシルベンゼンスルホン
酸ナトリウム溶液の電位差（Ｅ ＬＡ、）と１０ｍｏｌ
／Ｉ２（ドデシルベンゼンスルホン酸ナトリウム溶液と
同濃度）の前記８種類の陰イオンの電位差（ＥＸＩをそ
れぞれ２０℃で測定した。次に、得られた電位差から次
式によって選択係数を算出した。結果を第２表に示した
。The selection coefficient is based on JIS KO122r ion electrode method general rules.
I asked for it according to. That is, using the three types of electrodes described above, the potential difference (E LA, ) of 10-3 mol/I2 sodium dodecylbenzenesulfonate solution and 10 mol/I2
/I2 (same concentration as sodium dodecylbenzenesulfonate solution) potential difference (EXI) of the eight types of anions was measured at 20°C.Next, the selection coefficient was calculated from the obtained potential difference using the following formula.Results are shown in Table 2.
ｏｇＫ
ここに、
Ｋ ９選択係数
Ｅ、 測定した陰イオン溶液による電位差Ｅ、Ａ、：
ＬＡＳ溶液による電位差
Ｃ，，、：ＬＡＳの濃度（ｍｏｌ／β）ｚｘ、測定した
陰イオンのイオン価
Ｚ ＬＡＷ： Ｌ Ａ Ｓのイオン価
Ｒ：気体定数（８，３１４Ｊ・Ｋ−”ｍｏｌ−’）Ｔ
：測定溶液の絶対温度（Ｋ）
Ｆ ：ファラデ一定数［９６４８５ｆｃ： クーロン）
１以下余白
第２表
１血奥Ａ
実施例２− ｆｌ）、 ｆｌ）、 ｉ３＋ および（４
）で作成した４種類の電極で、■塩素イオン、■硫酸イ
オン、■炭酸イオン、■過塩素酸イオン、■トリポリリ
ン酸イオン、■ｐ−１−ルエンスルホン酸イオン、■ｍ
−キシレンスルホン酸イオン、■エチレンジアミン四酢
酸イオン、■ニトリロトリ酢酸イオンに対する選択係数
を求めた。ogK where, K 9 selection coefficient E, potential difference due to the measured anion solution E, A,:
Potential difference due to LAS solution C,...: LAS concentration (mol/β) zx, measured anion valence Z LAW: LAS ion valence R: gas constant (8,314 J·K-"mol-' )T
: Absolute temperature of measurement solution (K) F : Faraday constant [96485fc: Coulombs]
1 or less margin Table 2 1 Blood depth A Example 2 - fl), fl), i3+ and (4
), four types of electrodes were prepared: ■chloride ion, ■sulfate ion, ■carbonate ion, ■perchlorate ion, ■tripolyphosphate ion, ■p-1-luenesulfonate ion, ■m
The selectivity coefficients for -xylene sulfonate ion, (1) ethylenediaminetetraacetate ion, and (2) nitrilotriacetate ion were determined.
選択係数の求め方は、実施例３と同様に行った。結果を
第３表に示した。The selection coefficient was determined in the same manner as in Example 3. The results are shown in Table 3.
第２表および第３表から明らかなように、本発明のイオ
ン選択性電極用高分子膜は、無機陰イオン、その他第３
表に示した各種の陰イオン類に較べ、第２表記載の陰イ
オン界面活性剤に対して、はるかに大きい選択特性を有
する。このことから本発明の高分子膜は陰イオン界面活
性剤の濃度を選択的に定量できる優れたイオン選択性電
極用高分子膜であることがわかる。As is clear from Tables 2 and 3, the polymer membrane for ion-selective electrodes of the present invention can contain inorganic anions, other tertiary ions, etc.
Compared to the various anions shown in the table, it has much greater selectivity for the anionic surfactants listed in Table 2. This shows that the polymer membrane of the present invention is an excellent polymer membrane for ion-selective electrodes that can selectively quantify the concentration of anionic surfactants.
以下余白
第３表
実施例５
実施例２− ｆｌ）、（２）および（７）の３種類のイ
オン選択性電極を用いて、１０−”−１０−７ｍｏｌ／
ｇ、のドデシルベンゼンスルホン酸ナトリウム水溶液の
起電力を測定した。結果を第１図に示す。Below is a margin Table 3 Example 5 Example 2- Using three types of ion selective electrodes fl), (2) and (7), 10-”-10-7 mol/
The electromotive force of the sodium dodecylbenzenesulfonate aqueous solution of g. The results are shown in Figure 1.
第１図から明らかなように、この電極は１０〜１０−’
ｍｏｌ／ｆ２の濃度範囲のドデシルベンゼンスルホン酸
ナトリウムにＮｅｒｎｓｔ対応（濃度の対数と起電力が
比例）することが判明した。As is clear from FIG.
It was found that there is Nernst correspondence (the logarithm of the concentration and the electromotive force are proportional) to sodium dodecylbenzenesulfonate in the concentration range of mol/f2.
ここに得られた濃度の対数−起電力の検量線から、直線
検量線法により陰イオン界面活性剤の濃度を測定するこ
とができる。The concentration of the anionic surfactant can be measured by the linear calibration curve method from the logarithm of concentration--electromotive force calibration curve obtained here.
Ｍ（直接検量線法による陰イオン界面活性剤濃度の測定
）
第４表に示した配合組成の洗剤を実施例２の実験１で作
成したイオン選択性電極を用いて、実施例３で作成した
検量線から陰イオン界面活性剤の濃度を測定した。結果
を第５表に示した。M (Measurement of anionic surfactant concentration by direct calibration curve method) A detergent having the composition shown in Table 4 was prepared in Example 3 using the ion-selective electrode prepared in Experiment 1 of Example 2. The concentration of anionic surfactant was measured from the calibration curve. The results are shown in Table 5.
以下余白
第４表
？光査１１の自己合組成
Ｍ（電位差滴定法による陰イオン界面活性剤濃度の測定
）
実施例２− ＋１１で作成したイオン選択性電極を用い
、第４表に示した配合組成の溶剤をＩ ｍｍｏｌ／ｐの
テトラデシルジメチルベンジルアンモニウムブロマイド
で電位差滴定をして陰イオン界面活性剤の濃度を測定し
た。結果を第５表に示した。Margin table 4 below? Self-combined composition M of light scan 11 (Measurement of anionic surfactant concentration by potentiometric titration) Using the ion-selective electrode prepared in Example 2-+11, I mmol of the solvent having the composition shown in Table 4 was used. The concentration of anionic surfactant was determined by potentiometric titration with /p of tetradecyldimethylbenzyl ammonium bromide. The results are shown in Table 5.
比較例１ （吸光光度法による陰イオン界面活性剤濃度
の測定）
第４表に示した配合組成の洗剤水溶液を分液漏斗にとり
、メチレンブルー溶液を加え、陰イオン界面活性剤をメ
チレンブルーとの錯体を生成させた。これをクロロホル
ムで抽出して６５０ｎｍにおける吸光度から陰イオン界
面活性剤の濃度を測定した。結果を第５表に示した。Comparative Example 1 (Measurement of anionic surfactant concentration by spectrophotometry) A detergent aqueous solution having the composition shown in Table 4 was placed in a separating funnel, and a methylene blue solution was added to form a complex of anionic surfactant with methylene blue. generated. This was extracted with chloroform and the concentration of the anionic surfactant was measured from the absorbance at 650 nm. The results are shown in Table 5.
比較例２（従来の電位差滴定法による陰イオン界面活性
剤濃度の測定）
第４表に示した配合組成の洗剤の陰イオン界面活性剤の
濃度を、従来の電位差滴定法で測定した。結果を第５表
に示した。Comparative Example 2 (Measurement of anionic surfactant concentration by conventional potentiometric titration method) The concentration of anionic surfactant in detergents having the formulation shown in Table 4 was measured by conventional potentiometric titration method. The results are shown in Table 5.
第５表に示されたとおり、本発明によるイオン選択性電
極用高分子膜を用いた陰イオン界面活性剤濃度の測定方
法は、直接検量線法、電位差滴定法のいずれを用いても
従来法と同等の精度で分析結果が得られ、しかも従来法
よりはるかに簡便、迅速に行なうことができる。As shown in Table 5, the method for measuring anionic surfactant concentration using the polymer membrane for ion-selective electrodes according to the present invention can be performed using either the direct calibration curve method or the potentiometric titration method. Analytical results can be obtained with accuracy equivalent to that of conventional methods, and it is much simpler and faster than conventional methods.
７（イオン選択性電極の寿命）
実施例２− （２）、 ２− ＋３１．２− ｆ４）、
及び２− ＋５１で作成したイオン選択性電極をそれぞ
れ用いて１０−’■ｏｌ／βのドデシルベンゼンスルホ
ン酸溶液に対する起電力を６ケ月間連続的に測定した。7 (Life span of ion selective electrode) Example 2- (2), 2- +31.2- f4),
Using the ion-selective electrodes prepared in 2- and 2-+51, the electromotive force against a 10-' ol/β dodecylbenzenesulfonic acid solution was continuously measured for 6 months.
１日、１０日、１ケ月、３ケ月及び６ケ月目の起電力を
第６表に示した。Table 6 shows the electromotive forces on the 1st, 10th, 1st, 3rd, and 6th months.
比較±ユ
実施例２− （２）の電極の高分子膜を特開平２−４０
１８４号公報に開示された高分子膜において、第四級ア
ンモニウム塩としてトリオクチルメチルアンモニウムク
ロライドを用いた電極を用いて１０−’ｍｏｌ、＃！の
ドデシルベンゼンスルホン酸溶液に対する起電力を６ケ
月間連続的に測定した。Comparison±U Example 2- (2) The polymer membrane of the electrode was prepared using JP-A-2-40
In the polymer membrane disclosed in Publication No. 184, 10-'mol, #! The electromotive force against a dodecylbenzenesulfonic acid solution was continuously measured for 6 months.
１日、１０日、１ケ月、３ケ月及び６ケ月目の起電力を
第６表に示した、
第６表から明らかなように、第四級アンモニウム塩分子
中に炭素数１２ないし１８の高級アルキル基を１個しか
有しない比較例３のイオン選択性高分子膜を用いた電極
は６ケ月経過後、起電力が大きく低下しているのに対し
、上記の高級アルキル基を少なくとも２個以上有する本
発明の高分子膜を使用した電極は、６ケ月経過後でも起
電力低下は僅かであり、長期間の使用に耐えるイオン選
択性電極用高分子膜であることが認められる。The electromotive forces at the 1st, 10th, 1st, 3rd, and 6th months are shown in Table 6. The electromotive force of the electrode using the ion-selective polymer membrane of Comparative Example 3, which has only one alkyl group, decreased significantly after 6 months; The electrode using the polymer membrane of the present invention has a slight decrease in electromotive force even after 6 months, and it is recognized that the polymer membrane for ion-selective electrodes can withstand long-term use.
以下余白
［発明の効果］
本発明のイオン選択性電極用高分子膜は、陰イオン界面
活性剤に対して高感度で、長期間使用しても安定である
６また、本発明の陰イオン界面活性剤濃度の測定方法は
、操作が簡便であり、短時間に高精度で陰イオン界面活
性剤の濃度を測定することができる。The following margins [Effects of the Invention] The polymer membrane for an ion-selective electrode of the present invention is highly sensitive to anionic surfactants and is stable even when used for a long period of time. The method for measuring the active agent concentration is easy to operate, and the anionic surfactant concentration can be measured with high precision in a short time.
第１図は本発明のイオン選択性電極用高分子膜を用いた
時の陰イオン界面活性剤の濃度と起電力の関係を示すグ
ラフである。
○ 実施例２− ［１）の電極
・ 実施例２− ｆ２１の電極
△ 実施例２− （７）の電極
第
図
度 （
しり（ｒ １ｌ−Ａｂｌ ＋
手続補正書
平成３年ＩＯ月１６日FIG. 1 is a graph showing the relationship between the concentration of anionic surfactant and the electromotive force when the polymer membrane for an ion-selective electrode of the present invention is used. ○ Example 2 - Electrode of [1] Example 2 - Electrode of f21 △ Example 2 - Electrode number of (7)
Claims (1)
ないし１８のアルキル基、Ｒ＾３およびＲ＾４はそれぞ
れ独立で炭素数１ないし１８のアルキル基、Ａ＾−はＲ
＾５ＯＳＯ＿３＾−（Ｒ＾５は炭素数１０ないし１８の
直鎖アルキル基）またはＲ＾６Ｃ＿６Ｈ＿４ＳＯ＿３＾
−（Ｒ＾６は炭素数１０ないし１３の直鎖アルキル基）
を示す） で表わされる第四級アンモニウム塩１ないし６重量％ からなることを特徴とするイオン選択性電極用高分子膜
。 ２、請求項１記載のイオン選択性電極用高分子膜を装着
したイオン選択性電極を用い、膜電位を測定することを
特徴とする陰イオン濃度の測定方法。[Claims] 1. (a) 24 to 30% by weight of polyvinyl chloride, (b) 75 to 64% by weight of plasticizer, and (c) the following general formula▲There are numerical formulas, chemical formulas, tables, etc.▼ (in the formula R^1 and R^2 each independently have 12 carbon atoms
R^3 and R^4 are each independently an alkyl group having 1 to 18 carbon atoms, A^- is R
^5OSO_3^- (R^5 is a straight chain alkyl group having 10 to 18 carbon atoms) or R^6C_6H_4SO_3^
-(R^6 is a straight chain alkyl group having 10 to 13 carbon atoms)
A polymer membrane for an ion-selective electrode, comprising 1 to 6% by weight of a quaternary ammonium salt represented by: 2. A method for measuring anion concentration, comprising measuring membrane potential using an ion-selective electrode equipped with the polymer membrane for ion-selective electrodes according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2267411A JPH04143650A (en) | 1990-10-04 | 1990-10-04 | Polymer membrane for ion selective electrode and method for measuring concentration of anion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2267411A JPH04143650A (en) | 1990-10-04 | 1990-10-04 | Polymer membrane for ion selective electrode and method for measuring concentration of anion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04143650A true JPH04143650A (en) | 1992-05-18 |
Family
ID=17444476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2267411A Pending JPH04143650A (en) | 1990-10-04 | 1990-10-04 | Polymer membrane for ion selective electrode and method for measuring concentration of anion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04143650A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571396A (en) * | 1993-07-12 | 1996-11-05 | Dade International Inc. | Fluid analysis system and sensing electrode, electrode assembly, and sensing module components |
| JP2001281203A (en) * | 2000-03-31 | 2001-10-10 | Society For Techno-Innovation Of Agriculture Forestry & Fisheries | Molecular film for taste inspection |
| ES2362078A1 (en) * | 2009-12-11 | 2011-06-28 | Consejo Superior De Investigaciones Cientificas (Csic) | Complex tripolifosfato-tensioactive cati¿nico as ion¿foro in selective electrodes and its applications. (Machine-translation by Google Translate, not legally binding) |
| CN102539500A (en) * | 2010-12-31 | 2012-07-04 | 中国科学院烟台海岸带研究所 | Sensor based on asymmetric polymer film as well as detection method and applications thereof |
-
1990
- 1990-10-04 JP JP2267411A patent/JPH04143650A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571396A (en) * | 1993-07-12 | 1996-11-05 | Dade International Inc. | Fluid analysis system and sensing electrode, electrode assembly, and sensing module components |
| JP2001281203A (en) * | 2000-03-31 | 2001-10-10 | Society For Techno-Innovation Of Agriculture Forestry & Fisheries | Molecular film for taste inspection |
| JP4520577B2 (en) * | 2000-03-31 | 2010-08-04 | 株式会社インテリジェントセンサーテクノロジー | Molecular membrane for taste inspection |
| ES2362078A1 (en) * | 2009-12-11 | 2011-06-28 | Consejo Superior De Investigaciones Cientificas (Csic) | Complex tripolifosfato-tensioactive cati¿nico as ion¿foro in selective electrodes and its applications. (Machine-translation by Google Translate, not legally binding) |
| CN102539500A (en) * | 2010-12-31 | 2012-07-04 | 中国科学院烟台海岸带研究所 | Sensor based on asymmetric polymer film as well as detection method and applications thereof |
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