WO2011040805A1 - Membrane de détection exempte de plastifiant pour capteurs chimiques - Google Patents

Membrane de détection exempte de plastifiant pour capteurs chimiques Download PDF

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Publication number
WO2011040805A1
WO2011040805A1 PCT/MY2010/000197 MY2010000197W WO2011040805A1 WO 2011040805 A1 WO2011040805 A1 WO 2011040805A1 MY 2010000197 W MY2010000197 W MY 2010000197W WO 2011040805 A1 WO2011040805 A1 WO 2011040805A1
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WO
WIPO (PCT)
Prior art keywords
monomer units
plasticizer
membrane
ion
copolymer
Prior art date
Application number
PCT/MY2010/000197
Other languages
English (en)
Inventor
Mohd Rais Ahmad
Sagir Alva
Original Assignee
Mimos Berhad
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mimos Berhad filed Critical Mimos Berhad
Publication of WO2011040805A1 publication Critical patent/WO2011040805A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes
    • G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component

Definitions

  • the present invention relates generally to a sensing membrane, more particularly to a plasticizer-free sensing . membrane for chemical sensors.
  • Ion-selective electrodes are the chemical sensors of longest history and probably the most frequent routine application. They have found widespread use in clinical laboratories and are ' being explored for numerous other applications. ISEs produce a measurable electrical change upon contact with a fluid sample containing target ions. Potentiometric detection based on ion-selective electrodes offers several advantages, such as speed and ease of preparation and procedures, simple instrumentation, relatively fast response, wide dynamic range, reasonable selectivity and low cost. Besides, they are also suitable for on-site analysis and, nowadays, are found to be applicable in the analysis of some biologically relevant ions, process control and environmental analysis.
  • the most common ion selective electrode construction requires an ion-selective membrane of polymeric type containing the ionophore.
  • polymeric type containing the ionophore Some typical examples are poly (vinyl chloride) or PVC. This is primarily due to its high tensile strength, chemical inertness and plasticizer compatibility.
  • PVC poly (vinyl chloride)
  • plasticizer for the purpose of softening the polymer. It could not be used without plasticizer.
  • plasticized PVC in ion- selective sensors
  • plasticizer leaching has prompted the issuance of a health warning on biomaterials . Therefore various efforts made to reduce or eliminate plasticizer content in such devices.
  • plasticizer is one of the principle factors directly affecting sensor lifetime and reduction in plasticizer may results in an increased membrane resistance and may decrease the solubility of the active sensing components within the membrane.
  • the photopolymerized acrylate membranes could be choice a alternative of sensing membranes. Because the photopolymerize acrylate membranes has many advantages, e.g. self plasticising, without the need of any external plasticiser and photocurable . The polymer also exhibits excellent adhesion on solid surfaces and this makes it very suitable for application in solid-state ion sensors.
  • Photopolymerization offers multiple advantages which include spatial and temporal control, solventless polymerizations, as well as compatibility with multiple solvents. Due to the multitude of advantages it offers, photopolymerization of acrylates has been used for a variety of applications including sensor material, biomaterial, dental material, contact lens and adhesive. Photoinitiated free radical polymerization of multifunctional monomers produces highly crosslinked networks with high thermal stability, mechanical strength and resistance to solvent absorption.
  • the copolymer membranes of the invention are fabricated from methyl methacrylate and tetrahydrofurfuryl acrylate monomers.
  • the disclosed copolymer exhibits excellent properties as a sensing membrane that includes clear and colorless appearance, good flexibility, not sticky, and good adhesion onto surface.
  • the polarity of this copolymer can be varied depend ratio between methyl methacrylate and tetrahydrofurfuryl acrylate, and thus can be used to variety sensors fabricated. Other objects of this invention will become apparent on the reading of this entire disclosure.
  • a copolymer membrane for use on an ion detective sensor as a sensing membrane, the membrane comprises a plasticizer-free copolymer including first monomer units of methyl methacrylate and second monomer units of tetrahydrofurfuryl acrylate, wherein the copolymer is mixed with sensing components and photocured under ultraviolet (UV) light.
  • UV ultraviolet
  • the sensing components comprise liphophilic salt, photoinitiator, ionophore and cross linker diacrylate.
  • a plasticizer-free ion detective sensor comprising sensing element for detecting chemical species, including a copolymer membrane enclosing the sensing element, the membrane providing high polarity and low impedance, the improvement comprising forming the membrane from first monomer units of methyl methacrylate and second monomer units of tetrahydrofurfuryl acrylate, wherein the copolymer is mixed with sensing components and photocured under ultraviolet (UV) light.
  • the ion detective sensor is a potentiometric chemical sensor based ion selective electrode (ISE) or an ion sensitive field effect transistor (ISFET) .
  • Figure 1 shows the structures of methyl methacrylate and tetrahydrofurfuryl acrylate
  • Figure 2 depicts the structures of photocured MT copolymer membrane of the present invention
  • Figure 3 illustrates the result of the response of magnesium ion selective electrode based on copolymer MT 28
  • Figure 4 illustrates the result of the response of potassium ion use generic cation selective electrode based on copolymer MT 28; and Figure 5 illustrates the result of the response of CI ion using generic anion selective electrode based on copolymer MT 28.
  • the present invention is directed to a plasticizer free ion detective sensor wherein the sensor provides copolymer membranes which are fabricated from methyl methacrylate (11) and tetrahydrofurfuryl acrylate (12) monomers as shown in Figure 1. It has been discovered that the use of such membranes provides many advantages including of good characteristics as a sensing membrane, provides fast and stable sensor response and thus an excellent choice for chemical sensor, ease of handling, economic benefits of low costs of the monomers and low impedance due to polar tetrahydrofurfuryl substituent and compatibility with sensor components .
  • MT membrane (13) a self-plasticising sensing membrane as shown in Figure 2.
  • MT membrane (13) a self-plasticising sensing membrane
  • particularly preferred is a specific volume ratio of the monomers such as 2 part of methyl methacrylate (11) and 8 part of tetrahydrofurfuryl acrylate (12), along with the rest of the sensing membrane components such as liphophilic salt, photoinitiator, ionophore and cross linker diacrylate are mixed together in the absence of plasticizer, and without the assistance of solvent, and photocured under UV light.
  • the ratio between the methyl methacrylate (11) and tetrahydrofurfuryl acrylate (12) can be varied to obtain different polarity of copolymer membrane to be used to variety sensors fabricated.
  • Another example of volume ratio of the monomers is 3 part of methyl methacrylate (11) and 7 part of tetrahydrofurfuryl acrylate (12) .
  • the inventive copolymer membranes- of the present invention may also be used in an ion sensitive field effect transistor (ISFET) . Therefore as will be appreciated by those skilled in the art, variations in the volume ratio of such monomers will be able to achieve the desired physical characteristics of the membranes .
  • ISFET ion sensitive field effect transistor
  • HEMA 2-hydroxylethyl methacrylate
  • DMPP 2-dimethoxyl-2- phenylacetopenone
  • MMA methyl methacrylate
  • THFA tetrahydrofurfuryl acrylate
  • HDDA 2- hexenedioldiacrylate
  • the homogenous cocktail was deposited on top of the freshly prepared and hydrated inner layer and photocured under UV radiation in UV-exposure apparatus under constant flow of nitrogen gas for approximately 3 minutes to form copolymer MT 28 as a sensing layer. Further, the magnesium ion selective electrode was tested versus a commercial Ag/AgCl double junction reference electrode. The results were shown in the following Table 1 and Figure 3.
  • HEMA 2-hydroxylethyl methacrylate
  • D PP 2-dimethoxyl-2- phenylacetopenone
  • the mixture was photocured under UV radiation in UV- exposure unit under constant flow of nitrogen gas for approximately 3 minutes.
  • the polymer film formed was then hydrated with 0.1 M of Potassium Chloride solution for approximately 10 minutes to form the inner layer of the sensor.
  • the copolymers exhibit excellent properties as a sensing membrane which includes good flexibility.
  • the capability to vary the composition of the copolymer to achieve certain specific properties is a key feature of this invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Biochemistry (AREA)
  • Polymers & Plastics (AREA)
  • Molecular Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une membrane copolymère (13) destinée à être utilisée sur un capteur de détection d'ions comme membrane de détection. Cette membrane contient un copolymère exempt de plastifiant contenant de premières unités monomères de méthacrylate de méthyle (11) et des deuxièmes unités monomères d'acrylate de tétrahydrofurfuryle (12), ledit copolymère étant mélangé à des composants de détection et photodurci sous une lumière ultraviolette (UV).
PCT/MY2010/000197 2009-10-02 2010-09-29 Membrane de détection exempte de plastifiant pour capteurs chimiques WO2011040805A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI20094140 2009-10-02
MYPI20094140 MY150724A (en) 2009-10-02 2009-10-02 Plasticizer-free sensing membrane for chemical sensors

Publications (1)

Publication Number Publication Date
WO2011040805A1 true WO2011040805A1 (fr) 2011-04-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/MY2010/000197 WO2011040805A1 (fr) 2009-10-02 2010-09-29 Membrane de détection exempte de plastifiant pour capteurs chimiques

Country Status (2)

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MY (1) MY150724A (fr)
WO (1) WO2011040805A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0479731A2 (fr) * 1990-10-02 1992-04-08 Centre Suisse D'electronique Et De Microtechnique S.A. Dispositif semi-conducteur comportant une membrane possédant une sensibilité sélective aux ions et procédé de réalisation de la membrane
WO2000054039A1 (fr) * 1999-03-10 2000-09-14 Elizabeth Anne Howlett Hall Matiere polymere selective
US20030217920A1 (en) * 2001-12-06 2003-11-27 Auburn University Plasticizer-free-ion-detective sensors

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0479731A2 (fr) * 1990-10-02 1992-04-08 Centre Suisse D'electronique Et De Microtechnique S.A. Dispositif semi-conducteur comportant une membrane possédant une sensibilité sélective aux ions et procédé de réalisation de la membrane
WO2000054039A1 (fr) * 1999-03-10 2000-09-14 Elizabeth Anne Howlett Hall Matiere polymere selective
US20030217920A1 (en) * 2001-12-06 2003-11-27 Auburn University Plasticizer-free-ion-detective sensors

Also Published As

Publication number Publication date
MY150724A (en) 2014-02-28

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