JP2006137889A - New polymer and plasticizer-free resin composition containing the same - Google Patents
New polymer and plasticizer-free resin composition containing the same Download PDFInfo
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- JP2006137889A JP2006137889A JP2004330130A JP2004330130A JP2006137889A JP 2006137889 A JP2006137889 A JP 2006137889A JP 2004330130 A JP2004330130 A JP 2004330130A JP 2004330130 A JP2004330130 A JP 2004330130A JP 2006137889 A JP2006137889 A JP 2006137889A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 33
- 150000002500 ions Chemical class 0.000 claims abstract description 31
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 22
- 239000002555 ionophore Substances 0.000 claims abstract description 21
- 230000000236 ionophoric effect Effects 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 125000004964 sulfoalkyl group Chemical group 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 239000000470 constituent Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004971 Cross linker Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical group CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910001414 potassium ion Inorganic materials 0.000 description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 230000002411 adverse Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 108010067973 Valinomycin Proteins 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CFPFMAGBHTVLCZ-UHFFFAOYSA-N (4-chlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(Cl)C=C1 CFPFMAGBHTVLCZ-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 208000019622 heart disease Diseases 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000005156 substituted alkylene group Chemical group 0.000 description 2
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 1
- AYMIQQNUNVNNNK-UHFFFAOYSA-N 6-nonan-5-yloxy-6-oxohexanoic acid Chemical compound CCCCC(CCCC)OC(=O)CCCCC(O)=O AYMIQQNUNVNNNK-UHFFFAOYSA-N 0.000 description 1
- 206010002383 Angina Pectoris Diseases 0.000 description 1
- -1 DD16C5 Chemical compound 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 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 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 206010003119 arrhythmia Diseases 0.000 description 1
- 230000006793 arrhythmia Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 208000010125 myocardial infarction Diseases 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000003308 potassium ionophore Substances 0.000 description 1
- PNOXUQIZPBURMT-UHFFFAOYSA-M potassium;3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [K+].CC(=C)C(=O)OCCCS([O-])(=O)=O PNOXUQIZPBURMT-UHFFFAOYSA-M 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、新規ポリマー及びそれを含む可塑剤フリー樹脂組成物に関する。本発明のポリマーは、可塑剤を含まなくても可塑性を有して加工容易であるので、例えば生体内で用いる電極等の部材として有用である。 The present invention relates to a novel polymer and a plasticizer-free resin composition containing the same. Since the polymer of the present invention has plasticity and can be easily processed without containing a plasticizer, it is useful as a member such as an electrode used in vivo.
生体内イオンバランスの欠如、特にナトリウム、カリウムイオンの相対的イオンバランスの不均衡は、高血圧や不整脈、特に心疾患患者においては狭心症及び心筋梗塞の原因となる。近年、心疾患患者に対して長期連続モニタリングが可能な、生体埋込み型の電解質センサが求められている。従来、イオン選択性電極としては、ポリ塩化ビニル(PVC)樹脂から成るマトリックスに、特定のイオンに選択的に応答するイオノフォアを含有させたものが用いられている。マトリックスとして用いられるPVCは、所望の形状及びサイズに加工するため、可塑剤を含んでいる。 Lack of in vivo ion balance, particularly relative ion balance imbalance of sodium and potassium ions, causes angina and myocardial infarction in patients with hypertension and arrhythmias, particularly heart disease. In recent years, there has been a demand for an implantable electrolyte sensor capable of long-term continuous monitoring for heart disease patients. Conventionally, as an ion selective electrode, an ionophore that selectively responds to specific ions is used in a matrix made of polyvinyl chloride (PVC) resin. PVC used as a matrix contains a plasticizer in order to be processed into a desired shape and size.
PVCをマトリックス樹脂とする従来のイオン選択性電極を、生体埋込み型の電解質センサとして用いると、PVC樹脂中に含まれる可塑剤が生体内に溶け出して生体に悪影響を与える可能性が懸念される。一方、PVCに可塑剤を含めなければ、イオン選択性電極として求められる形状及びサイズに成形、加工することが困難であり、また、イオノフォアの包括性を満足することも困難である。 If a conventional ion-selective electrode using PVC as a matrix resin is used as a biologically-embedded electrolyte sensor, there is a concern that the plasticizer contained in the PVC resin may dissolve into the living body and adversely affect the living body. . On the other hand, if the plasticizer is not included in the PVC, it is difficult to form and process into a shape and size required as an ion selective electrode, and it is also difficult to satisfy the comprehensiveness of the ionophore.
本発明の目的は、可塑剤を含まなくても可塑性、成形性に優れ、イオノフォアを含有するイオン選択性電極のマトリックス樹脂として利用可能な新規なポリマー、その製造方法及びそのイオン選択性電極のマトリックス樹脂としての用途を提供することである。 An object of the present invention is to provide a novel polymer which is excellent in plasticity and moldability without containing a plasticizer and can be used as a matrix resin of an ion selective electrode containing an ionophore, a production method thereof, and a matrix of the ion selective electrode It is to provide a use as a resin.
本願発明者らは、鋭意研究の結果、アルキル（メタ）アクリレートである主鎖構成成分と、アルキレンジ（メタ）アクリレートである架橋剤成分と、スルホアルキル（メタ）アクリレートである可塑性付与成分とを重合させることにより、可塑剤を用いなくても良好な可塑性、成形性を有し、イオノフォアを保持するイオン選択性電極用のマトリックス樹脂として利用可能なポリマーが得られることを見出し、本発明を完成した。 As a result of diligent research, the inventors of the present application have obtained a main chain constituent component that is an alkyl (meth) acrylate, a crosslinker component that is an alkylene di (meth) acrylate, and a plasticizer that is a sulfoalkyl (meth) acrylate. By polymerizing, it was found that a polymer that has good plasticity and moldability without using a plasticizer and can be used as a matrix resin for an ion-selective electrode that retains an ionophore was obtained, and the present invention was completed. did.
すなわち、本発明は、少なくとも１種のアルキル（メタ）アクリレートである主鎖構成成分と、少なくとも１種のアルキレンジ（メタ）アクリレートである架橋剤成分と、少なくとも１種のスルホアルキル（メタ）アクリレートである可塑性付与成分とを重合させて得られるポリマーを提供する。また、本発明は、少なくとも１種のアルキル（メタ）アクリレートである主鎖構成成分と、少なくとも１種のアルキレンジ（メタ）アクリレートである架橋剤成分と、少なくとも１種のスルホアルキル（メタ）アクリレートである可塑性付与成分とを重合させることを含むポリマーの製造方法を提供する。さらに、本発明は、上記本発明のポリマーをマトリックス成分として含み、可塑剤を実質的に含まない樹脂組成物を提供する。さらに、本発明は、上記本発明のポリマーをマトリックス成分とし、イオノフォアをさらに含むイオン選択性電極を提供する。 That is, the present invention relates to a main chain constituent component that is at least one alkyl (meth) acrylate, a crosslinking agent component that is at least one alkylene di (meth) acrylate, and at least one sulfoalkyl (meth) acrylate. There is provided a polymer obtained by polymerizing the plasticizing component. The present invention also provides a main chain constituent component that is at least one alkyl (meth) acrylate, a crosslinker component that is at least one alkylene di (meth) acrylate, and at least one sulfoalkyl (meth) acrylate. A method for producing a polymer comprising polymerizing a plasticizing component which is: Furthermore, this invention provides the resin composition which contains the polymer of the said invention as a matrix component, and does not contain a plasticizer substantially. Furthermore, the present invention provides an ion selective electrode comprising the above polymer of the present invention as a matrix component and further comprising an ionophore.
本発明により、可塑剤を含まなくても可塑性、成形性に優れ、イオノフォアを含有するイオン選択性電極のマトリックス樹脂として利用可能な新規なポリマーが初めて提供された。本発明のポリマーをマトリックス樹脂として用いたイオン選択性電極は、可塑剤を含まないので、生体埋込み型の電解質センサとして安全に用いることができる。 The present invention provides for the first time a novel polymer that is excellent in plasticity and moldability without using a plasticizer and can be used as a matrix resin for an ion selective electrode containing an ionophore. Since the ion selective electrode using the polymer of the present invention as a matrix resin does not contain a plasticizer, it can be safely used as a biologically embedded electrolyte sensor.
上記の通り、本発明のポリマーは、少なくとも１種のアルキル（メタ）アクリレートである主鎖構成成分と、少なくとも１種のアルキレンジ（メタ）アクリレートである架橋剤成分と、少なくとも１種のスルホアルキル（メタ）アクリレートである可塑性付与成分とを重合させて得られる。なお、本願明細書及び請求の範囲において「（メタ）アクリレート」は、メタクリレート及び／又はアクリレートを意味する。 As described above, the polymer of the present invention comprises a main chain component that is at least one alkyl (meth) acrylate, a cross-linking agent component that is at least one alkylene di (meth) acrylate, and at least one sulfoalkyl. It is obtained by polymerizing a plasticity-imparting component that is (meth) acrylate. In the present specification and claims, “(meth) acrylate” means methacrylate and / or acrylate.
本発明のポリマーにおいて、主鎖構成成分として用いられるアルキル（メタ）アクリレート中のアルキル基の炭素数は、特に限定されないが、通常、１〜３０であり、好ましくは６〜１３である。アルキル基は直鎖状でも分枝状でもよい。また、アルキル基は、置換基を含まないことが好ましいが、本発明の効果に悪影響を与えない範囲で、例えば、水酸基、アルコキシル基、アミノ基、ニトロ基、ハロゲン、カルボニル基、エーテル基（アルキル基中のメチレン基が-O-に置換）等の置換基を合計１個ないし数個含んでいてもよい。本願明細書及び請求の範囲において、そうでないことが文脈から明らかな場合を除き「アルキル」という語（後述する架橋剤成分及び可塑性付与成分についても同様）は、本発明の効果に悪影響を与えない上記のような「置換アルキル」をも包含する意味で用いられている。後述の「アルキレン」についても、同様に、本発明の効果に悪影響を与えない上記のような置換基を有する「置換アルキレン」をも包含する意味で用いている。主鎖構成成分は、単独成分であってもよいし、複数種類の成分を組み合わせて用いることもできる。主鎖構成成分の特に好ましい例として、下記構造式で表されるエチルヘキシルメタクリレート(EHMA)とドデシルメタクリレート(DDMA)との混合物（混合比率（モル比）は好ましくは1:0.5〜2、特に好ましくは1:1)を挙げることができる。 In the polymer of the present invention, the carbon number of the alkyl group in the alkyl (meth) acrylate used as the main chain constituent component is not particularly limited, but is usually 1 to 30, and preferably 6 to 13. The alkyl group may be linear or branched. In addition, the alkyl group preferably does not contain a substituent, but, for example, a hydroxyl group, an alkoxyl group, an amino group, a nitro group, a halogen, a carbonyl group, an ether group (alkyl group) can be used as long as the effects of the present invention are not adversely affected. 1 to several substituents in total, such as a methylene group in the group substituted by -O-. In the present specification and claims, unless otherwise clear from the context, the term “alkyl” (the same applies to the crosslinker component and the plasticizing component described later) does not adversely affect the effects of the present invention. The term “substituted alkyl” as used above is also used. Similarly, “alkylene” described later is also used to include “substituted alkylene” having the above-described substituents that do not adversely affect the effects of the present invention. The main chain constituent component may be a single component or a combination of a plurality of types of components. As a particularly preferred example of the main chain constituent, a mixture of ethylhexyl methacrylate (EHMA) and dodecyl methacrylate (DDMA) represented by the following structural formula (mixing ratio (molar ratio) is preferably 1: 0.5 to 2, particularly preferably 1: 1).
本発明のポリマーにおいて、架橋剤成分として用いられるアルキレンジ（メタ）アクリレート中のアルキレン基の炭素数は、特に限定されないが、通常、１〜２０であり、好ましくは４〜１０である。アルキレン基は直鎖状でも分枝状でもよく、また、上記のように本発明の効果に悪影響を与えない置換基を有する置換アルキレン基も「アルキレン基」に包含される。架橋剤成分は、単独成分であってもよいし、複数種類の成分を組み合わせて用いることもできる。架橋剤成分の特に好ましい例として、下記構造式で表されるヘキサンジオールジアクリレート(HDDA,ヘキシレンジアクリレート）、及びヘキサンジオールジメタクリレート(HDDMA, ヘキシレンジメタクリレート）を挙げることができる。架橋剤成分は、１分子中に不飽和二重結合を２個含むので、異なる２分子と付加重合することができ、その結果、この２分子を架橋することができる。 In the polymer of the present invention, the number of carbon atoms of the alkylene group in the alkylene di (meth) acrylate used as the crosslinking agent component is not particularly limited, but is usually 1 to 20, and preferably 4 to 10. The alkylene group may be linear or branched, and a substituted alkylene group having a substituent that does not adversely affect the effects of the present invention as described above is also included in the “alkylene group”. The crosslinking agent component may be a single component or a combination of a plurality of types of components. Particularly preferred examples of the crosslinking agent component include hexanediol diacrylate (HDDA, hexylene diacrylate) and hexanediol dimethacrylate (HDDMA, hexylene dimethacrylate) represented by the following structural formula. Since the crosslinking agent component contains two unsaturated double bonds in one molecule, it can undergo addition polymerization with two different molecules, and as a result, these two molecules can be crosslinked.
本発明のポリマーにおいて、可塑性付与成分として用いられるスルホアルキル（メタ）アクリレート中のアルキレン基の炭素数は、特に限定されないが、通常、１〜１０であり、好ましくは１〜５である。アルキレン基は直鎖状でも分枝状でもよく、また、上記のように本発明の効果に悪影響を与えない置換基を有する置換アルキレン基も「アルキレン基」に包含される。可塑性付与成分は、単独成分であってもよいし、複数種類の成分を組み合わせて用いることもできる。可塑性付与成分の特に好ましい例として、下記構造式で表される3-スルホプロピルメタクリレートカリウム塩(SPAK)を挙げることができる。 In the polymer of the present invention, the number of carbon atoms of the alkylene group in the sulfoalkyl (meth) acrylate used as the plasticity-imparting component is not particularly limited, but is usually 1 to 10, and preferably 1 to 5. The alkylene group may be linear or branched, and a substituted alkylene group having a substituent that does not adversely affect the effects of the present invention as described above is also included in the “alkylene group”. The plasticity-imparting component may be a single component or a combination of a plurality of types of components. As a particularly preferred example of the plasticizing component, 3-sulfopropyl methacrylate potassium salt (SPAK) represented by the following structural formula can be given.
上記した主鎖構成成分、架橋剤成分及び可塑性付与成分（各成分として複数の化合物が用いられる場合にはそれらの合計）の混合比率は、モル比で１００：１〜５：１〜１０が好ましく、１００：１〜３：１〜６がさらに好ましい。 The mixing ratio of the main chain constituent component, the cross-linking agent component, and the plasticity-imparting component (the total when a plurality of compounds are used as each component) is preferably 100: 1 to 5: 1-10 in terms of molar ratio. 100: 1 to 3: 1 to 6 are more preferable.
本発明のポリマーは、上記した主鎖構成成分、架橋剤成分及び可塑性付与成分を重合させることにより製造することができる。各成分はいずれも（メタ）アクリレートであるので、常法により容易に付加重合させることができる。すなわち、例えば、酢酸エチル、アセトニトリル、DMSO、メタノール、エタノールのような有機溶媒中に各成分を溶解し、2,2'-アゾビス(2-メチルプロピオニトリル)(AIBN)のような重合開始剤を添加し、通常30℃〜60℃、好ましくは40℃〜45℃の温度下で、通常2時間〜8時間、好ましくは4時間〜6時間反応させることにより製造することができる。反応開始時における、溶媒に対する主鎖構成成分の濃度は、特に限定されないが、通常、5mg/Lないし10mg/L程度である。反応後は、未反応のモノマーを除去するため、好ましくは超音波処理を行ないながら、例えばメタノールのような溶媒で洗浄する。 The polymer of the present invention can be produced by polymerizing the main chain constituent component, the crosslinking agent component and the plasticizing component. Since each component is (meth) acrylate, it can be easily subjected to addition polymerization by a conventional method. That is, for example, each component is dissolved in an organic solvent such as ethyl acetate, acetonitrile, DMSO, methanol, ethanol, and a polymerization initiator such as 2,2′-azobis (2-methylpropionitrile) (AIBN). And is usually reacted at a temperature of 30 ° C. to 60 ° C., preferably 40 ° C. to 45 ° C., usually for 2 hours to 8 hours, preferably 4 hours to 6 hours. The concentration of the main chain constituent component relative to the solvent at the start of the reaction is not particularly limited, but is usually about 5 mg / L to 10 mg / L. After the reaction, in order to remove the unreacted monomer, washing with a solvent such as methanol is preferably performed while performing ultrasonic treatment.
本発明のポリマーは、可塑剤を実質的に含まない樹脂組成物のマトリックス成分として用いることができる。例えば、イオノフォアを含有するイオン選択性電極を構成する樹脂組成物のマトリックス成分として用いることができるが、本発明のポリマーの用途は、イオン選択性電極用に限定されるものではなく、可塑剤を含むことなく良好な可塑性、成形性が求められる種々の樹脂組成物（例えば、生体埋め込み材料、ゴムホース等）に適用することができる。 The polymer of the present invention can be used as a matrix component of a resin composition substantially free of a plasticizer. For example, it can be used as a matrix component of a resin composition constituting an ion selective electrode containing an ionophore, but the use of the polymer of the present invention is not limited to an ion selective electrode, and a plasticizer is used. It can be applied to various resin compositions (for example, bio-embedded materials, rubber hoses, etc.) that require good plasticity and moldability without being included.
上記のとおり、本発明はまた、上記本発明のポリマーをマトリックス樹脂とし、イオノフォアを含んで成るイオン選択性電極をも提供する。含有するイオノフォアは、何ら限定されるものではなく、イオン選択性電極に用いられている公知のイオノフォアのいずれをも用いることができる。例えば、カリウムテトラキス(p-クロロフェニル）ボレート、DD16C5、ビス１−ブチルペンチルアジペイトのようなナトリウムイオン選択性イオノフォア、バリノマイシン、カリウムテトラキス(p-クロロフェニル）ボレートのようなカリウムイオン選択性イオノフォア等を例示することができるが、もちろんこれらに限定されるものではない。 As described above, the present invention also provides an ion-selective electrode comprising the polymer of the present invention as a matrix resin and comprising an ionophore. The ionophore to be contained is not limited at all, and any known ionophore used for an ion selective electrode can be used. Examples include potassium tetrakis (p-chlorophenyl) borate, DD16C5, sodium ion selective ionophores such as bis 1-butylpentyl adipate, valinomycin, potassium ion selective ionophores such as potassium tetrakis (p-chlorophenyl) borate, etc. Of course, it is not limited to these.
イオノフォアの含有量は、各イオノフォアの性質や測定濃度範囲等に応じて適宜選択されるが、本発明のポリマーに対し、通常、重量基準で１００：1〜4程度、好ましくは１００：2〜3程度である。 The content of the ionophore is appropriately selected according to the properties of each ionophore, the measurement concentration range, and the like, but is usually about 100: 1 to 4, preferably 100: 2 to 3 based on the weight of the polymer of the present invention. Degree.
イオノフォアを含有するイオン選択性電極用樹脂組成物は、上記した本発明のポリマーの重合工程を、イオノフォアの共存下において行なうことにより製造することができる。反応条件は上記と同様でよく、イオノフォアの添加量も、ポリマーに対する上記した重量比率が達成される量でよい。 The ion-selective electrode resin composition containing an ionophore can be produced by performing the above-described polymerization process of the polymer of the present invention in the presence of an ionophore. The reaction conditions may be the same as described above, and the ionophore may be added in such an amount that the above-mentioned weight ratio with respect to the polymer is achieved.
重合反応により得られた、イオノフォア含有樹脂組成物は、そのままでイオン選択性電極として利用可能であるが、通常、イオン選択性電極として好ましい形状、サイズに成形又は加工される。この工程は、通常、次のようにして行なわれる。イオン選択性ポリマーとして調合されたポリマーは、パンチャーを用いて2ｍｍ〜5ｍｍ程度の円形のフィルム状に加工され作用電極表面上へ、ホルダーを用いて固定される。 The ionophore-containing resin composition obtained by the polymerization reaction can be used as it is as an ion-selective electrode, but is usually molded or processed into a preferred shape and size as an ion-selective electrode. This step is usually performed as follows. The polymer prepared as an ion selective polymer is processed into a circular film of about 2 mm to 5 mm using a puncher and fixed on the surface of the working electrode using a holder.
本発明のイオン選択性電極は、従来のイオン選択性電極と全く同様にして用いることができる。本発明のイオン選択性電極は、可塑剤を含まないので、可塑剤の溶出を懸念する必要がない。従って、生体埋込み型のイオン選択性電極として用いるのに特に適している。もっとも、生体埋込み型に限定されるものではない。 The ion selective electrode of the present invention can be used in exactly the same manner as a conventional ion selective electrode. Since the ion selective electrode of the present invention does not contain a plasticizer, there is no need to worry about elution of the plasticizer. Therefore, it is particularly suitable for use as a biologically implanted ion selective electrode. However, it is not limited to the living body implant type.
以下、本発明を実施例に基づきより具体的に説明する。もっとも、本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.
実施例１ ポリマーの製造
EHMA 100mg、DDMA 100mg、HDDMA 4mg、SPAK 4mg、バリノマイシン（カリウムイオノフォア）6.5mgを１本のスクリュー管に測り取った。一方、AIBNを酢酸エチルに5mg/mlの濃度に溶解した。該AIBN溶液0.4mlを、上記のスクリュー管に入れ、パラフィルム（登録商標） で蓋をして、１５分間超音波処理した。スクリュー管を８０℃の水浴中に水平に固定し、約１１時間反応させた（水浴にかけた後、エバポレーターで１５〜２０分間引いた）。メタノール約2mlを加え、２０分間超音波処理をした後、中の溶液を捨てた。再度、メタノール約2mlを加え、２０分間超音波処理をした後、中の溶液を捨てた。次いで、６０℃の水浴中、エバポレーターにかけ、40〜50hPaの圧力で引いた。上記操作により、スクリュー管中に本発明のポリマーが得られた。得られたポリマーは、可塑性があって取り扱い性が良く、無臭であった。
Example 1 Production of Polymer
EHMA 100 mg, DDMA 100 mg,
実施例２ 電極の作製
実施例１で製造したポリマーからイオン選択性電極を作製した。これは具体的に次のようにして行なった。製造されたポリマーは、パンチャーで円形に加工され、2ｍｍ〜3ｍｍの形状を有する。続いて、ポリマーをコンディショニングするために、0.1M塩化カリウム溶液に４時間から１２時間程度浸漬する。その後、コンディショニングされたポリマーを作用電極へホルダーを用いて固定し、測定溶液中へ浸漬する。
Example 2 Production of Electrode An ion selective electrode was produced from the polymer produced in Example 1. This was specifically performed as follows. The produced polymer is processed into a circle by a puncher and has a shape of 2 mm to 3 mm. Subsequently, in order to condition the polymer, it is immersed in a 0.1 M potassium chloride solution for about 4 to 12 hours. Thereafter, the conditioned polymer is fixed to the working electrode using a holder and immersed in the measurement solution.
実施例３ カリウムイオンに対する応答
実施例２で作製した、カリウムイオン応答性イオン選択性電極を用い、濃度10-5〜10-1Mの塩化カリウム水溶液との応答性を調べた。これは具体的に次のようにして行なった。コンディショニングされたポリマーを固定した作用電極を参照電極とともに、所定濃度に調整された測定溶液に浸漬する。そのとき、濃度に応じた自然電位を測定することで選択的にポリマー内のバリノマイシンによって捕捉されたカリウム濃度が測定された。結果を図１に示す。
Example 3 Response to Potassium Ion Using the potassium ion-responsive ion-selective electrode prepared in Example 2, the responsiveness with a potassium chloride aqueous solution having a concentration of 10 −5 to 10 −1 M was examined. This was specifically performed as follows. The working electrode to which the conditioned polymer is fixed is immersed in a measurement solution adjusted to a predetermined concentration together with a reference electrode. At that time, the concentration of potassium selectively captured by valinomycin in the polymer was measured by measuring the natural potential according to the concentration. The results are shown in FIG.
図１は、横軸にカリウムイオン濃度の常用対数、縦軸に起電力／電圧(emf/mV)をプロットした図である。図１に示される通り、カリウムイオン濃度の対数に対してほぼ直線的にemf/mVが増加しており、このイオン選択性電極により、カリウムイオン濃度を正確に測定できることがわかる。 FIG. 1 is a graph plotting the common logarithm of potassium ion concentration on the horizontal axis and the electromotive force / voltage (emf / mV) on the vertical axis. As shown in FIG. 1, the emf / mV increases almost linearly with respect to the logarithm of the potassium ion concentration, and it can be seen that the potassium ion concentration can be accurately measured by this ion selective electrode.
Claims (11)
An ion selective electrode comprising the polymer according to any one of claims 1 to 6 as a matrix component and further comprising an ionophore.
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| CN112666770A (en) * | 2021-01-12 | 2021-04-16 | 浙江工业大学 | Electrochromic flexible device based on P (SPMA-MMA) hydrogel electrolyte and preparation method and application thereof |
| JP2022542470A (en) * | 2019-07-29 | 2022-10-03 | ローズマウント インコーポレイテッド | electrochemical sensor |
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| JP2022542470A (en) * | 2019-07-29 | 2022-10-03 | ローズマウント インコーポレイテッド | electrochemical sensor |
| JP7386317B2 (en) | 2019-07-29 | 2023-11-24 | ローズマウント インコーポレイテッド | electrochemical sensor |
| CN112666770A (en) * | 2021-01-12 | 2021-04-16 | 浙江工业大学 | Electrochromic flexible device based on P (SPMA-MMA) hydrogel electrolyte and preparation method and application thereof |
| CN112666770B (en) * | 2021-01-12 | 2022-09-23 | 浙江工业大学 | Electrochromic flexible device based on P (SPMA-MMA) hydrogel electrolyte and preparation method and application thereof |
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