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    • 专利摘要:
    In a reference electrode for the potentiometric measurement of ion concentrations, comprising a swellable polymer body filled with at least one electrolyte salt and a second type, preferably of Ag / AgCl type, located in the polymer body, the polymer body is composed of hydrophobic prepolymer segments, which are crosslinked three-dimensionally by hydrophilic polymer chains are .
    公开号:AT520779A1
    申请号:T498/2017
    申请日:2017-12-21
    公开日:2019-07-15
    发明作者:
    申请人:Erba Tech Austria Gmbh；
    IPC主号:
    专利说明:


    Austrian
    Patent office (io) AT 520779 A1 2019-07-15 (12) Austrian patent application (21) Application number:
    (22) Filing date:
    (43) Published on:
    A 498/2017 21.12.2017 15.07.2019 (51) Int. CI .: G01N27 / 22 (2006.01)
    G01N 27/30 (2006.01)
    G01N 27/401 (2006.01)
    GO1N 27/403 (2006.01)
    AT 520779 A1 2019-07-15
    (56) Citations: (71) Patent applicants: EP 1956368 A1 Erba Technologies Austria GmbH EP3101414 A1 8020 Graz (AT) WO 2014091083 A1 US 6419809 B1 DE 10214035 A1 (74) Representative: EP 1124132 A1 Haffner and Keschmann Patentanwälte GmbH DE 102015118581 A1 1010 Vienna (AT)
    (54) Reference electrode for potentiometric measurement of ion concentrations (57) In the case of a reference electrode for potentiometric measurement of ion concentrations, comprising a swellable polymer body filled with at least one electrolyte salt and a second-type discharge element, preferably of the Ag / AgCI type, located in the polymer body from hydrophobic
    Prepolymer segments built up that are three-dimensionally cross-linked by hydrophilic polymer chains.
    Fig. 1 r r- r
    Summary:
    In the case of a reference electrode for the potentiometric measurement of ion concentrations, comprising a swellable polymer body filled with at least one electrolyte salt and a second-type deflecting element located in the polymer body, preferably of the Ag / AgCl type, the polymer body is made up of hydrophobic prepolymer segments which are three-dimensionally crosslinked by means of hydrophilic polymer chains are.
    Fig. 1
    1/40 r r r f
    The invention relates to a reference electrode for potentiometric measurement of ion concentrations, comprising a swellable polymer body filled with at least one electrolyte salt and a second-type discharge element, preferably of the Ag / AgCl type, located in the polymer body.
    A specific active electrode and a reference electrode, which are in contact with a sample, are used for the potentiometric measurement of ion concentrations with the aid of ion-sensitive electrodes. According to known laws, the potential difference between the electrodes of such an electrode pair is a measure of the sought ion concentration in the sample.
    In the case of reference electrodes of the second type, a reference system is provided with a discharge element made of a metal, which is provided with a coating of its sparingly soluble metal salt, the reference system being in contact with an electrolyte, the so-called internal electrolyte. Reference electrodes with a silver conductor element, which is provided with an AgCl coating, are widespread. KCl and / or NaCl is usually provided as the electrolyte salt. The electrochemical potential of an Ag / AgCl / KCl electrode depends on the temperature and the chloride ion activity. Provided that the electrolyte is saturated and thus the chloride ion activity is constant, the potential of the Ag / AgCl / KCl electrode is also constant at a defined temperature, so that such an electrode can be used as a reference electrode.
    The properties of such reference electrodes are determined in particular by the loss rate of the electrolyte
    2/40 f r r, which is caused by the leaching of the electrolyte upon contact with the sample. With such leaching of the electrolyte, potential fluctuations can occur at the reference electrode, which have a direct effect on the behavior of the working electrode and thus lead to measurement inaccuracies. Therefore, efforts are made to maintain a defined and constant chloride concentration in the electrolyte so that the reference electrode supplies a defined potential.
    In order to obtain potential-stable reference electrodes, the inner electrolyte space is usually connected to the aqueous sample via an ion-permeable diaphragm. In order to keep the liquid junction potential occurring at the junction between the diaphragm and the sample medium as low as possible, i.e. To create defined conditions in the diaphragm area with regard to mixing the sample with the internal electrolyte, a permanent electrolyte salt current is maintained which is maintained during the measurement and which is directed through the diaphragm from the internal electrolyte space to the sample. KCl is preferably used as the chloride component because the permeabilities for potassium and chloride ions are approximately the same when they pass from the diaphragm into the sample, which leads to a minimization of the mixing potential.
    Designs of reference electrodes in which the electrolyte solution is solidified by the addition of gel formers have already become known. Reference electrodes are also known, in which the electrolyte salt is introduced into a polymer and, together with the hardened polymers, the structural core of a robust one
    3/40
    Forms reference electrode, for whose function no additional diaphragm is required (EP 247535 A2).
    Solid-state reference electrodes have also become known which are particularly suitable for training in thick-film technology. With thick-film processes, miniaturized reference electrodes can be produced using only solid electrode components.
    For solid-state reference electrodes, where the
    Electrolyte salt is embedded in a polymer body, versions are also described in the literature in which an electrolyte salt reservoir is formed in the form of crystalline KCl, which is mixed with polymers that swell to a greater or lesser extent in aqueous media. The KC1 crystal suspension ensures a defined high chloride concentration in the polymer body. However, the fact that all alkali chlorides are so readily soluble in water is problematic that water is only available for sufficient swelling after the polymer body has completely dissolved. This fact is reflected in an extension of the so-called wet-up phase, that is the time it takes the polymer internal electrolyte to reach one
    Constant potential of the reference electrode is required.
    The invention therefore aims to improve a reference electrode of the type mentioned at the outset, in which a swellable polymer body is filled with at least one electrolyte salt, in such a way that the wet-up phase can be shortened. The invention further aims to improve the adhesive properties of the reference electrode
    4/40 r r on polymer substrates, e.g. to achieve better adhesion to an inner electrolyte housing or, in the case of thick-film applications, better adhesion to the sensor base. In addition, the invention aims to provide a reference electrode with a long-term potential stability.
    To achieve these objects, the invention essentially consists in a reference electrode of the type mentioned at the beginning in that the polymer body is constructed from hydrophobic prepolymer segments which are three-dimensionally cross-linked by hydrophilic polymer chains.
    To achieve the stated objects, the invention further provides a method for producing a polymer body for use as a reference electrode, comprising the steps:
    a) producing a mixture of hydrophobic prepolymer segments and hydrophilic and optionally hydrophobic monomers in order to obtain a prepolymer-monomer mixture,
    b) adding a solution of at least one electrolyte salt to the prepolymer-monomer mixture,
    c) mixing the electrolyte salt solution with the prepolymer / monomer mixture, the at least one electrolyte salt partially precipitating in microcrystalline form and partially remaining in the solution,
    d) polymerizing the monomers to give hydrophilic polymer chains which cross-link the prepolymer segments three-dimensionally, thereby obtaining the polymer body in which the at least one electrolyte salt is embedded.
    5/40
    According to the invention, a hydrophobic or non-polar prepolymer crosslinked by hydrophilic bridge elements is thus used in the reference electrode, which already contains the water anticipated to swell as a saturated solution of the electrolyte salt before curing, which has the consequence that the electrolyte-containing, crosslinked polymer has a greatly reduced wetup Phase and can be used immediately after aqueous equilibration of the transition layer between the polymer body and the sample liquid. Due to the degree of crosslinking and the added salt-water mixture, the swelling rate is preferably less than 5-20%. The salt current caused by diffusive processes from the internal electrolyte to the sample is greatly minimized, which ensures the long potential stability, and is in the order of magnitude of the measuring current required for the potential measurement.
    In the course of mixing the electrolyte salt solution with the prepolymer-monomer mixture, a large part of the electrolyte salt precipitates out in a microcrystalline manner and the remaining water or the still dissolved electrolyte salt, after curing with the 3D-crosslinked polymer, gives the internal electrolyte, in which the embedded microcrystalline electrolyte salt in accordance with the law of mass action the ion concentration necessary for the stable potential.
    Since, as corresponds to a preferred embodiment, the 3D cross-linked hydrated polymer body forms a molecular diaphragm for the at least one electrolyte salt to form a sample space surrounding the reference electrode, i.e. as a polymer body with a few nanometer-sized hydrophobic domains in a network of hydrophilic
    6/40
    Γ frr • rr r rtrrrr <ff .. ii «- r. · -.
    Bridging elements are embedded, the ion transfer at the interface to the sample medium is reduced to the bare minimum. In this microstructure, the ion diffusion from the polymer body is throttled into the solution, the salt ion reflux resulting from the diffusion from the inner electrolyte space being supposed to move in the area of the measuring current. Since the salt transfer into the sample solution to be measured is, for the above-mentioned reason, greatly reduced in comparison to an electrolyte boundary layer, as occurs in conventional KCl internal electrolyte sample transitions, the LiquidJunction potential component is significantly reduced.
    The good adhesion of the polymer body to one
    The polymer substrate results from a hydrophobic-hydrophobic interaction between the hydrophobic prepolymer segments and the polymer substrate.
    Reduced swelling in aqueous media and good adhesion to polymeric edge components is particularly important in thick-film applications for the mechanically stable bond between the inner electrolyte layer and one
    Polymer substrate, as used in planar sensor technology
    Application comes essential
    According to a preferred embodiment of the invention, it is provided that the at least one electrolyte salt is formed from KCl or NaCl or a mixture of KCl and NaCl and, if appropriate, additionally a long-chain quaternary
    Ammonium chloride, e.g. Methyltrioctylammonium chloride or methyltridodecylammonium chloride.
    7/40
    KCl has proven to be particularly advantageous due to the low liquid junction potential. In the case of a mixture of KCl with NaCl, it has been shown in the production process according to the invention that the influence of the liquid junction potential can be reduced even further by increasing the proportion of KCl in the alkali chloride solution added to the reference electrode according to the invention. Obviously, potassium chloride dissolves better in the hydrated hydrophilic polymer material than sodium chloride. While the former accumulates in the polymer body and thus dominates the ion reflux over the molecular diaphragm, the sodium chloride crystallizes more proportionally and thus forms the salt reservoir in the vicinity of the drainage element, in particular the silver / silver chloride drainage element. Long-chain quaternary ammonium chlorides (e.g. methyltrioctyl or methyltridodecyl ammonium chloride and other long-chain quaternary ammonium chlorides), which are added to the prepolymer-monomer mixture in addition to NaCl or dilute KCl solution, can also be used as the soil body determining the chloride concentration. Since these quaternary ammonium salts are only partially water-soluble, the potential stability and thus the reference electrode service life can be extended over time. The use of quaternary ammonium salts only has the disadvantage that there is chloride sensitivity until the polymeric internal electrolyte space has completely swelled, i.e. that the reference electrode acts as a chloride electrode throughout shortly after use; this effect weakens in the course of the hydration of the polymer body in the area of the power key and finally disappears.
    8/40 r r r f
    The at least one electrolyte salt, in particular alkali metal chloride, such as e.g. KCl and / or NaCl, both in microcrystalline form and in aqueous solution. The presence of finely divided alkali chloride and a hydrate phase, which is in thermodynamic equilibrium with a saturated alkali chloride solution, ensures that the silver-silver chloride electrode system only has a stable temperature-dependent potential over long periods of time (several months).
    With regard to the structure of the polymer body from hydrophobic prepolymer segments which are crosslinked by means of hydrophilic polymer chains, a preferred embodiment of the invention provides that the prepolymer segments comprise a hydrophobic prepolymer carrying vinyl groups, in particular a polymethyl methacrylate prepolymer carrying vinyl groups. The prepolymer preferably has an average molecular weight of 1,000 to 1,000,000 daltons, in particular 10,000 to 100,000 daltons.
    The hydrophilic polymer chains are preferably formed from hydrophilic monomers and optionally hydrophobic monomers, the hydrophilic monomers being selected from the group comprising hydrophilic ethers and
    Hydroxyl group-bearing (meth) acrylates, e.g.
    Hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (in particular with a number of ethylene oxide sequences per molecule from 3 to 10,000), polypropylene glycol di (meth) acrylates,
    Polyethylene glycol mono (meth) acrylates and
    Glycidyloxypropyl methacrylate and methacrylic acid,
    9/40
    Acrylic acid, maleic anhydride, acrylamides and
    Methacrylamides.
    The hydrophobic monomers are preferably selected from the group comprising methyl methacrylate,
    Hexamethyldi (meth) acrylate, methacrylates, acrylates of the lower alcohols, such as e.g. Propanol, isopropanol, butanol, isobutanol, tert. Butanol, pentanoie and hexanoie acrylates, diols and low to high molecular weight
    Fatty alcohols.
    (Meth) acrylate resins that can be used both as adhesives and as casting resins consist on the one hand of a vinyl-terminal (meth) acrylate prepolymer component, which is inherently non-polar, and of the methyl methacrylate monomer, which is used both as a solvent and acts as a reaction component for the prepolymer.
    Mostly radical polymerization using an organic peroxide or a photoinitiator results in a 3D-crosslinked acrylate resin glass with high impact strength, optimal optical properties and optimal resistance to solvents.
    In the case of such an “acrylic resin, the non-polar monomer (methyl methacrylate) is exchanged for hydrophilic to water-miscible monomers, such as e.g.
    Hydroxymethyl methacrylate (HEMA), hydroxypropyl methacrylate, diethylene glycol di (meth) acrylate,
    Polyethylene glycol di (meth) acrylate,
    Glycidyloxypropyl methacrylate and others , in the course of the crosslinking reaction based on radical polymerization, 3D-crosslinked polymer bodies are obtained that have optimal adhesive properties despite swelling in aqueous systems
    10/40 r r to polymers but also to glass. Adhesion to glass can be achieved on the one hand by adding small amounts of aminopropyl-triethoxysilane in a polyacrylate formulation modified with more hydrophilic monomers or by pretreating glass with aqueous aminopropyltriethoxysilane solutions, in both cases an amino functionalization of the glass surface is produced on which the Epoxy group of the
    Glycidyloxypropyl methacrylate binds covalently.
    The polymer swelling can preferably be adjusted by the choice of the hydrophilic monomer components or the monomer mixture and / or by the weight ratio of the monomer to the prepolymer component. In particular, the degree of swelling is achieved by selecting the
    Weight ratio of hydrophilic monomers to hydrophobic monomers.
    A preferred embodiment of the invention provides that the polymer body has a prepolymer segment content of 15 to 80% by weight, preferably between 25 to 70% by weight.
    The prepolymer-monomer mixture preferably comprises 6070% by weight of a vinyl group-bearing polymethyl methacrylate prepolymer and 30-40% by weight of methyl methacrylate. The methyl methacrylate can be substituted by hydrophilic (meth) acrylate esters by adding an amount of hydroxyethyl methacrylate or other hydrophilic monomers analogous to the methyl methacrylate content to the resin system and then using a Rotavapor at 80 to 100 ° C under vacuum (initially water jet vacuum, later oil pump vacuum) pulls off the methyl methacrylate. The
    The resulting product is highly viscous and has a shelf life of well over 3 years in the refrigerator.
    This product can be mixed with the methyl methacrylate-containing starting resin. In order to increase the hydrophilicity and also the swelling rate, the content of hydrophilic monomers can be increased by adding them.
    Compared to linear hydrophilic polymers that can be obtained by in situ polymerization of a monomer cocktail of hydrophilic to hydrophobic monomers, the 3D crosslinked polymer bodies of the invention are homogeneous and show a significantly lower swelling in water or in aqueous electrolytes. A major advantage of the polymers according to the invention is that monomer cocktails, the individual components of which have a very different polarity or hydrophilicity, tend to form at least two mutually incompatible polymer phases in the course of the polymerization, which in particular causes inhomogeneous polymer bodies with regard to water absorption. If hydrophilic polymer bridges are grafted onto a multiply vinyl-functionalized hydrophobic prepolymer ball, the effect of inhomogeneity due to the incompatibility is eliminated.
    By adding low molecular weight hydrophilic substances, e.g. Glycerin, diethylene to polyethylene glycol, the network formed during the polymerization can be expanded, which results in increased water absorption. Polyethylene glycol di (meth) acrylate requires the introduction of large cross-linking segments with a strong hydrophilic character. You choose as
    12/40 f r r c c f
    Crosslinking reaction a photo-initiated polymerization at room temperature, so you can anticipate the swelling by adding a few percent water or aqueous electrolyte solution.
    The addition of functional (meth) acrylate monomers, in particular monomers bearing amino groups or tetraalkylammonium groups, can be used in the polymer body to stabilize the chloride concentration (formation of a further chloride reservoir).
    According to a preferred embodiment of the invention, the hydrophilic polymer chains are additionally formed from monomers bearing quaternary ammonium groups, such as e.g. Trialkyl (meth) acryloylalkylammonium chloride, especially triethyl (meth) acryloylethylammonium chloride,
    Aminoalkyl (meth) acrylates, e.g.
    Dimethylaminoethyl (meth) acrylate, and their hydrochlorides. This causes the presence of an additional chloride reservoir.
    Furthermore, it can preferably be provided that the hydrophilic polymer chains are additionally formed from multi-terminally thiol-modified chain-like compounds of variable polarity, such as e.g. Polyoxyethylene dithiols or polyoxypropylene dithiols, which preferably photopolymerize with the vinyl groups of the prepolymer via a THIOL-ENE-CLICK reaction. This is an additional method of creating long chain hydrophilic
    Bridging segments, as can also be achieved by copolymerization with polyethylene glycol di (meth) acrylates. Through this networking with higher molecular weight hydrophilic
    Bridge formers achieve a coarse mesh in the
    13/40 r r r t
    Polymer composite and thus a possibility of modulating the ion mobility in the hydrophilic polymer.
    The polymer body preferably further contains
    Methacryloylalkoxysilyl compounds, e.g.
    Trialkoxysilylalkenyl (meth) acrylates. This causes the polymer body to be covalently bound to a silicate or oxidic substrate (e.g. glass surface or glass tube surface). Partial hydrolysis of the alkoxy groups of the trialkoxysilyl-bearing monomer component on the surface subsequently leads to condensation with the silanol or hydroxyl groups of the oxidic (e.g. glass) interface and thus to a (meth) acryloyl functionalization of the surface. These (meth) acryloyl groups crosslink with the terminal radical functions of the growing polymer chains generated in the course of the polymerization.
    It is particularly preferably provided that the polymer body is applied to a carrier using thick-film technology, in particular in a layer thickness of 10-50 pm. In this context, the
    Silver / silver chloride electrode is preferably arranged such that it is covered by the polymer body over a longer distance and the polymer body layer forms a current key with a layer thickness of approximately 10 to 50 pm toward the sample opening on the reference side, the ratio
    Current key volume to sample opening area is 100 to 500, preferably 200. This ensures that a constant salt concentration gradient results, on the one hand, from the NaCl excess in the polymer body between the sample-side mouth opening of the polymer body and the Ag / AgCl deflecting element
    14/40 above the silver / silver chloride discharge element and on the other hand by the mean electrolyte concentration of the sample media.
    fr re s / r r f. 1 i <t «f fr f r r r r r r i r tr r r r r re ·
    To apply the polymer body layer by means of
    To favor screen printing, it is preferably provided that the polymer body contains inorganic fillers, such as
    Contains silicates or inert oxides, the fillers preferably being contained in an amount of 30-70% by weight in the polymer body.
    Alternatively, the polymer body together with the deflecting element can be arranged in a tubular hollow form which has an opening, the polymer forming a 0.1 to 10 mm 2 , preferably 0.5 to 5 mm 2 window towards a sample.
    As already mentioned, the polymer body according to the invention can be produced using a method comprising the steps:
    a) producing a mixture of hydrophobic prepolymer segments and hydrophilic and optionally hydrophobic monomers in order to obtain a prepolymer-monomer mixture,
    b) adding a solution of at least one electrolyte salt to the prepolymer-monomer mixture,
    c) mixing the electrolyte salt solution with the prepolymer / monomer mixture, the at least one electrolyte salt partially precipitating in microcrystalline form and partially remaining in the solution,
    d) polymerizing the monomers to form hydrophilic polymer chains which cross-link the prepolymer segments three-dimensionally, as a result of which the
    15/40 r r r
    - r t- i '- r t t i ff' 't r i r r ι i r i i · r r r
    Polymer body is obtained in which the at least one electrolyte salt is embedded.
    In step b), an electrolyte salt solution with a saturation of 2-100%, preferably 10-100%, is preferably used.
    The electrolyte salt solution is preferably added in an amount of 5-25% by weight, preferably 5-10% by weight, based on the prepolymer-monomer mixture.
    Furthermore, it is preferably provided that the polymerization in step d) is carried out by means of a UV initiator, preferably selected from the group of the benzoin ethers or the substituted acetophenones, such as e.g. 2,2Dimethoxy-2phenyl-acetophenone (benzil dimethyl ketal).
    In order to facilitate the application of a layer of the polymer body in thick-film technology, a mixing with at least one inorganic filler, such as e.g. with silicates or inert oxides, the at least one filler preferably being added in an amount of 30-70% by weight, based on the total amount. The mixture of the electrolyte salt solution with the prepolymer-monomer mixture obtained in step c) is preferably applied in the form of a layer to a support by means of screen printing via a discharge element, and step d) is then carried out in order to obtain a polymer body layer. Furthermore, the procedure is preferably such that an insulating layer, in particular a UV-curing insulating lacquer layer, is applied to the polymer body layer, the
    Isolierschicht has an exemption that
    16/40
    Γ f
    The diaphragm window functions, via which a sample can be brought into contact with the polymer body layer, the deflection element preferably being arranged at a distance of> 1 mm, preferably approximately 3 millimeters, from the diaphragm window.
    The invention is explained in more detail below with reference to exemplary embodiments shown in the drawing. 1 shows an enlarged schematic illustration of a polymer body of the reference electrode according to the invention, FIG. 2 shows a schematic illustration of the processes in the reference electrode according to the invention in the area of the conductor element and in the sample contact area,
    3 shows a pH stick electrode with a reference electrode arrangement according to the invention, FIG. 4 shows the potential profile of a pH electrode with a reference electrode according to the invention over time, FIG. 5 shows the profile of the potential difference in an arrangement according to FIG. 3 over time using an Ag / AgCl Reference electrode with IM KCl electrolyte and FIG. 6 a schematic illustration of a thick-film sensor with ISE membrane spot and reference electrode according to the invention.
    1 shows the polymer body according to the invention. The nonpolar, hydrophobic prepolymer segments 1 in the form of balls are marked as circles. The
    Prepolymer segments adhere to non-polar or weakly polar surfaces 2 by means of a hydrophobic-hydrophobic interaction. The prepolymer segments 1 are cross-linked to one another via hydrophilic polymer sequences 3 forming chains and networks. Between these are water of hydration, free water and the ions of the alkali chlorides of the electrolyte salt, where ,, M (+)
    17/40
    Salt cations, ,, X (-) salt anions and „> v water molecules.
    In Fig. 2, the left part is schematically
    Functionality of the alkali metal chloride crystals in
    Shown near the surface of the silver / silver chloride derivation element. The discharge element 4 consists of a silver core 5, which is provided with a silver chloride coating 6. The surrounding environment of the salt crystals thus results in a defined chloride activity on the discharge element 4 and thus also the resulting constant silver / silver (I) potential. The right part of FIG. 2 shows the transition between the polymer body 7 and the sample liquid 8 with the hydrophobic prepolymer domains 1 which restrict the salt ion diffusion.
    The invention is further illustrated below with the aid of
    Exemplary embodiments for producing the reference electrode are shown.
    EXAMPLE 1:
    Example 1 relates to a pH sensor in a 2-bar measuring chain in combination with an Ag / AgCl reference electrode, the cylindrical polymer body of which is arranged in a glass tube.
    Production of the polymer body:
    Parts by weight of acrylic resin with 35%
    Hydroxyethyl acrylate content was mixed with 2.5 parts by weight of hydroxyethyl methacrylate and mixed with 7% by weight of saturated sodium chloride solution with stirring. The turbidity that occurs is due to the NaCl precipitation in the
    18/40 r r '
    Mixture caused. Finally, 0.2 part by weight of the photoinitiator 2,2-dimethoxy-2-acetophenone was added. This mixture was placed in a glass tube 9 tapered towards the sample space {Fig. 3 - length: 3 cm,
    Diameter: 3 mm, diameter at the taper: 2 mm) filled, the tapered opening 11 with a Parafilm film (a stretchy, whitish translucent
    Closure film, made from about 50:50 paraffin wax and
    Polyolefin) was sealed to prevent the mixture from flowing out. After placing an electrochemically chlorinated silver rod serving as a discharge element 5 in the middle part of the tube 9 (the distance from the lower end of the chlorinated silver rod 5 to the sample opening was approx. 0.5-0.7 cm), the tube content became LW-UV -Light hardened (LW-UV,
    2000 watts, 60 sec).
    The reference electrode thus obtained was against the
    Derivation closed and bound to a pH glass electrode 10. After swelling in a pH7 Sörensen buffer with 0.1 mol / L NaCl background, i.e. After swelling and stabilization of the reference electrode potential, the following tests were carried out over a period of 12 months.
    Measuring arrangements:
    A.) pH function graphs depending on the NaCl content of salted Sörensen buffers (basis = m / 15 prim / sec.
    Phosphate) Measured values against the pH values of the test solutions determined with a combination electrode from WTW. The shift in the pH measurement functions, which is influenced by the salinity, provides information about the mixing potential resulting from the combination electrode.
    19/40 f
    B.) Measurement of the reference potential against a silver-silver chloride reference electrode separated by a power key with a 1.0 molar KC1 internal electrolyte. Monitoring the potential difference between the two electrodes over a period of 7 months.
    Results:
    The investigations have shown that when the m / 15 molar Sörensen buffers are salted, the pH curve in the range between pH5 and ph6 by a maximum of 0.02 pH units, between pH6 and pH7 by a maximum of 0.06 and at pH8 by +/- 0.0 pH units shifted to higher pH values (see Fig. 4, which shows the potential curve of a pH electrode with a reference electrode according to the invention in two measuring media: Sörensen buffer (m / 15 prim / sec.P) once without and once plus 0.1M NaCl). 4 shows the following values:
    pH without NaCl[mV] 0, IM NaCl[mV] 5 85 83 6 130 128 7 180 177 8th 220 220
    The long-term measurements have shown that the initial potential difference between the reference electrode according to the invention in the formulation defined above and an external reference electrode with 1 molar KC1 solution as internal electrolyte changes from 18.0 +/- 0.3 mV to 17.5 + / 0.3 mV according to FIG. 6 monthly use and changed to 16.5 +/- 0.3 mV after almost 8 months (see Fig. 5). After one
    20/40
    Year running time, the potential difference is reduced to 1415 mV.
    EXAMPLE 2:
    Example 2 relates to a thick film pH sensor including a reference electrode system in a thick film version.
    Construction:
    A silver-silver chloride sheet 13, about 1 millimeter wide and several centimeters long, screen-printed on a polymer support 12, acted as the base sensor on the reference electrode side. According to FIG. 6, a 3D cross-linkable prepolymer according to the invention, covering the silver-silver chloride sheet to about 2-3 centimeters, was used. Formulation 16 with the following composition applied.
    Formulation: 10 parts by weight of acrylate-prepolymer-HEMA mixture (7: 3) were mixed with a further 10 parts by weight of HEMA and 10 parts by weight of a microcrystalline
    Alumosilikates, 1 part of saturated sodium chloride solution and 0.4 parts of analog photoinitiator mixed.
    After application of formulation 16, curing was carried out in LW-UV at 1000 watt lamp output and this layer composite was also overprinted with an insulating lacquer system 14 which cured under UV light, the structure of the insulating lacquer layer 14 being chosen such that an approximately 15 mm window 15 on the Reference electrode intermediate layer was positioned so that a distance to the silver-silver chloride web 13 of more than 2 millimeters was realized. The reference electrode is after 2-3
    21/40 hour swelling of the resulting polymer body 16 in a physiological standby buffer system ready for measurement (see FIG. 6). Furthermore, the insulating lacquer layer 14 has, at least for each ion-selective electrode, a further window 19, adapted to the size and position of the ion-selective sensor layer 17. The ion-selective electrode, consisting of the ion-selective sensor layer 17 and the diverting element 18, is likewise applied to the polymer carrier 12 and, with the exception of the window 19 which is exposed, is covered by the insulating lacquer layer 14.
    Measurements:
    Measuring arrangement: pH value measurement when combining the
    Thick film reference electrode with the thick film pH electrode 17; Sörensen buffers (m / 15 phosphate buffers) were measured with and without salting with 0.1 or 0.2 mol / liter sodium chloride. Furthermore, the potential stability of the thick film reference electrode was checked over a period of 2 weeks.
    Results:
    The measurements have shown that in the pH range between 6.5 and 8.0 the pH function in the case of salts with 0.1 mol / liter is around 0.02 pH units and in the case of salts with 0.2 mol / liter NaCl shifts by 0.04-0.05 pH units.
    The potential of the reference electrode remains stable for several weeks at about 15 mV compared to an external reference system once the wetup (swelling phase) is complete.
    22/40 / - 22
    Claims:
    1. Reference electrode for potentiometric measurement of ion concentrations, comprising a swellable polymer body filled with at least one electrolyte salt and a second-type deflecting element located in the polymer body, preferably of the Ag / AgCl type, characterized in that the polymer body is made up of hydrophobic prepolymer segments which are formed by hydrophilic Polymer chains are cross-linked three-dimensionally.
    2. Reference electrode according to claim 1, characterized in that the at least one electrolyte salt of KCl or NaCl or a mixture of KCl and NaCl is formed and optionally additionally a long-chain quaternary ammonium chloride, such as e.g. Methyltrioctylammonium chloride or methyltridodecylammonium chloride.
    3. Reference electrode according to claim 1 or 2, characterized in that the at least one electrolyte salt is present both in microcrystalline form and in aqueous solution.
    4. Reference electrode according to claim 1, 2 or 3, characterized in that the polymer body is a diaphragm for the at least one electrolyte salt
    Forms reference electrode surrounding sample space.
    5. Reference electrode according to one of claims 1 to 4, characterized in that the prepolymer segments comprise a vinyl group-bearing hydrophobic prepolymer, in particular a vinyl group-bearing polymethyl methacrylate prepolymer.
    23/40 r t
    6. Reference electrode according to one of claims 1 to 5, characterized in that the hydrophilic polymer chains are formed from hydrophilic monomers and optionally hydrophobic monomers, the hydrophilic monomers being selected from the group comprising hydrophilic ether and hydroxyl group-bearing (meth) acrylates , such as
    Hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (in particular with a number of ethylene oxide sequences per molecule from 3 to 10,000), polypropylene glycol di (meth) acrylates,
    Polyethylene glycol mono (meth) acrylates and
    Glycidyloxypropyl methacrylate and methacrylic acid,
    Acrylic acid, maleic anhydride, acrylamides and
    Methacrylamides.
    7. Reference electrode according to claim 6, characterized in that the hydrophobic monomers are selected from the group comprising methyl methacrylate, hexamethyldi (meth) acrylate, methacrylates, acrylates of the lower alcohols, such as e.g. Propanol, isopropanol, butanol, isobutanol, tert. Butanol, pentanoie and hexanoie acrylates, diols and low to high molecular weight fatty alcohols.
    8. Reference electrode according to claim 6 or 7, characterized in that the hydrophilic polymer chains are additionally formed from monomers bearing quaternary ammonium groups, such as e.g.
    Trialkyl (meth) acryloylalkylammonium chloride, especially triethyl (meth) acryloylethylammonium chloride,
    24/40 for r.
    Aminoalkyl {meth) acrylates, e.g.
    Dimethylaminoethyl (meth) acrylate, and their hydrochlorides.
    9. Reference electrode according to claim 6, 7 or 8, characterized in that the hydrophilic polymer chains are additionally formed from multi-terminally thiol-modified chain-shaped compounds of variable polarity, such as e.g. Polyoxyethylene dithiols or polyoxypropylene dithiols, which preferably photopolymerize with the vinyl groups of the prepolymer via a THIOL-ENE-CLICK reaction.
    10. Reference electrode according to one of claims 1 to 9, characterized in that the polymer body methacryloylalkoxysilyl compounds, such as. Contains trialkoxysilylalkenyl (meth) acrylates.
    11. Reference electrode according to one of claims 1 to 10, characterized in that the polymer body has a content of prepolymer segments of 15 to 80 wt .-%, preferably between 25 to 70 wt .-%.
    12. Reference electrode according to one of claims 1 to 11, characterized in that the polymer body in thick-film technology, in particular in a layer thickness of 10-50 pm, is applied to a carrier.
    13. Reference electrode according to one of claims 1 to 12, characterized in that the polymer body inorganic fillers, such as. Contains silicates or inert oxides, the fillers preferably being contained in an amount of 30-70% by weight in the polymer body.
    25/40
    14. Reference electrode according to one of claims 1 to 12, characterized in that the polymer body together with the deflection element is arranged in a tubular hollow shape which has an opening, the polymer against a sample 0.1 to 10 mm 2 , preferably 0, 5 to 5 mm 2 large window forms.
    15. A method for producing a polymer body for use for a reference electrode according to one of claims 1 to 14, comprising the steps:
    a) producing a mixture of hydrophobic prepolymer segments and hydrophilic and optionally hydrophobic monomers in order to obtain a prepolymer-monomer mixture,
    b) adding a solution of at least one electrolyte salt to the prepolymer-monomer mixture,
    c) mixing the electrolyte salt solution with the prepolymer / monomer mixture, the at least one electrolyte salt partially precipitating in microcrystalline form and partially remaining in the solution,
    d) polymerizing the monomers to give hydrophilic polymer chains which cross-link the prepolymer segments three-dimensionally, thereby obtaining the polymer body in which the at least one electrolyte salt is embedded.
    16. The method according to claim 15, characterized in that an electrolyte salt solution with a saturation of 2-100%, preferably 10-100% is used in step b).
    17. The method according to claim 15 or 16, characterized in that the electrolyte salt solution in one
    26/40 r.
    Amount of 5-25 wt .-%, preferably 5-10 wt .-%, based on the prepolymer-monomer mixture is added.
    18. The method according to claim 15, 16 or 17, characterized in that the polymerization according to step d) is carried out by means of a UV initiator, preferably selected from the group of benzoin ethers or substituted acetophenones, such as e.g. 2,2-dimethoxy2phenyl acetophenone (benzil dimethyl ketal).
    19. The method according to any one of claims 15 to 18, characterized in that in step c) further mixing with at least one inorganic filler, such as. with silicates or inert oxides, the at least one filler preferably being added in an amount of 30-70% by weight, based on the total amount.
    20. The method according to any one of claims 15 to 19, characterized in that the mixture of the electrolyte salt solution obtained in step c) with the prepolymer-monomer mixture in the form of a layer by means of screen printing over a
    Discharge element is applied to a carrier and then step d) is carried out to a
    Obtain polymer body layer.
    21. The method according to claim 20, characterized in that an insulating layer, in particular a UV-curing insulating lacquer layer, is applied to the polymer body layer, the insulating layer having an exemption which functions as a diaphragm window, via which a sample contacts the polymer body layer can be brought, the deflecting element preferably in
    27/40 for a distance of> 1 mm, preferably about 3 millimeters from the diaphragm window.
    Vienna, December 21, 2017
    Applicant
    28/40
    49055
    Fig. 1
    29/40
    49055
    e.g. ß Y -Lz V 7 771
    VJeiCi a ~ hJ-A
    CT
    Fig. 2 /
    z ο θ Pn 0 cP P <) Q
    OOQpr
    Hoörvrfc
    30/40
    Γ Γ
    49055
    Fig. 3
    31/40
    49055 f.
    250 potential (mV) versus pH
    Fig. 4
    32/40 <
    r · r r r '
    49055 deltaU (mV)
    Deployment time in months
    Fig. 5
    33/40
    Γ ί
    49055
    Fig. 6
    34/40 Austrian
    Patent office
    Research report on A 498/2017
    Classification of the subject of the application according to IPC:G01N 27/22 (2006.01); G01N 27/30 (2006.01); G01N 27/401 (2006.01); G01N 27/403 (2006.01) Classification of the application according to CPC:G01N 27/22 (2013.01); G01N 27/30 (2013.01); G01N 27/301 (2013.01); G01N 27/401 (2013.01);G01N 27/403 (2013.01) Researched test substance (classification):G01N Consulted online database:EPODOC; WPIAP; TXTnn; GOOGLE; NPL This search report was compiled on claims 1-21 filed on December 21, 2017. Category*) Title of the publication:Country code, publication number, document type (applicant), publication date, text or figure if necessary Concerningclaim XYYYYAAA EP 1956368 Al (HAMILTON BONADUZ AG) August 13, 2008 (August 13, 2008)Entire document. In particular paragraphs [0025], [0054] - [0073]and Figure 1.EP 3101414 Al (KK PILOT CORP, HORIBA LTD) December 07, 2016 (December 07, 2016)Paragraphs [0042] - [0046]WO 2014091083 Al (BO AKADEMI) June 19, 2014 (June 19, 2014)Page 8, line 30 - Page 9, line 20.US 6419809 Bl (SUZUKI HIROAKI, KARUBE ISAO) July 16, 2002 (July 16, 2002)Column 7, line 22 - column 8, line 55. In particular figures6A and 6B.DE 10214035 Al (METTLER TOLEDO GMBH) October 09, 2003 (October 09, 2003)Entire document.EP 1124132 Al (HAMILTON BONADUZ AG) August 16, 2001 (August 16, 2001)Entire document.DE 102015118581 Al (ENDRESS + HAUSER CONDUCTA GMBH + CO KG)May 04, 2017 (May 4, 2017)Entire document. 1-7, 9,11, 13-17,19th8, 12, 18, 20, 218th18th12, 20, 211-211-211-21 Date of completion of the search: "... . Examiner:02.10.2018 from Ί LEHNER Johanna *> Categories of the listed documents: A publication that defines the general state of the art.X Publication of particular importance: the application P document that is of importance (categories X or Y), but aftersubject cannot be published as new or published on the priority date of the registration solely on the basis of this publication.inventive activity can be considered based. E Document of particular importance (Category X) from whichY Publication of importance: the subject of the application may not result in an "older right" (earlier filing date, howeverNovelty would be considered as based on inventive step, if the republished, protection is possible in AustriaMake publication with one or more other publications).is associated with this category and this connection for & publication which is a member of the same patent family.is obvious to a specialist.
    35/40 ·· ·· ·· ···· ···· ····· ·· · • · · · ··· · ··· ······ · · • · ··· · · · ·
    49055 re: Austrian patent application A 498/2017, G 01 N
    Erba Technologies Austria GmbH in Graz (Austria)
    Claims:
    1. Reference electrode for potentiometric measurement of ion concentrations, comprising one with at least one
    权利要求:
    Claims (19)
    [1]
    Electrolyte salt-filled swellable polymer body and a second-type discharge element (4) located in the polymer body, preferably of the Ag / AgCl type, the polymer body being made up of hydrophobic prepolymer segments (1) which are three-dimensionally cross-linked by hydrophilic polymer chains (3) , that the
    Prepolymer segments (1) comprise a vinyl group-bearing hydrophobic prepolymer in the form of a vinyl group-bearing polymethyl methacrylate prepolymer and that the hydrophilic polymer chains (3) are formed from hydrophilic monomers and optionally hydrophobic monomers, the hydrophilic monomers being selected from the group comprising hydrophilic ether and hydroxyl group-bearing (meth) acrylates, such as Hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (in particular with a number of ethylene oxide sequences per molecule from 3 to 10,000), polypropylene glycol di (meth) acrylates, polyethylene glycol mono (meth) acrylates and glycidyloxypropyl methacrylate, as well as methacrylic acid, acrylic acid, maleic anhydride, acrylamides and methacrylamides.
    [2]
    2. Reference electrode according to claim 1, characterized in that the at least one electrolyte salt of KCl or NaCl or a mixture of KCl and NaCl is formed
    36/40 [LAST CLAIMS) ·· • · · • · · • · · • · · ···· ···· ···· • · · · · • ··· · ··· • · · · · • · · · · · is and possibly also a long-chain quaternary ammonium chloride, such as Methyltrioctylammonium chloride or methyltridodecylammonium chloride.
    [3]
    3. Reference electrode according to claim 1 or 2, characterized in that the at least one electrolyte salt is present both in microcrystalline form and in aqueous solution.
    [4]
    4. Reference electrode according to claim 1, 2 or 3, characterized in that the polymer body forms a diaphragm for the at least one electrolyte salt to form a sample space surrounding the reference electrode.
    [5]
    5. Reference electrode according to one of claims 1 to 4, characterized in that the hydrophobic monomers are selected from the group comprising methyl methacrylate, hexamethyldi (meth) acrylate, methacrylates, acrylates of the lower alcohols, such as e.g. Propanol, isopropanol, butanol, isobutanol, tert. Butanol, pentanoie and hexanoie acrylates, diols and low to high molecular weight fatty alcohols.
    [6]
    6. Reference electrode according to one of claims 1 to 5, characterized in that the hydrophilic polymer chains (3) are additionally formed from quaternary ammonium-bearing monomers, such as e.g.
    Trialkyl (meth) acryloylalkylammonium chloride, especially triethyl (meth) acryloylethylammonium chloride,
    Aminoalkyl (meth) acrylates, e.g.
    Dimethylaminoethyl (meth) acrylate, and their hydrochlorides.
    [7]
    7. Reference electrode according to one of claims 1 to 6, characterized in that the hydrophilic polymer chains
    37/40 [LAST CLAIMS ^ ·· ···· ···· ·· · ··· • ··· • · · • · · · are additionally formed from multi-terminally thiol-modified chain-like compounds of variable polarity, such as e.g. Polyoxyethylene dithiols or polyoxypropylene dithiols, which preferably photopolymerize with the vinyl groups of the prepolymer via a THIOL-ENE-CLICK reaction.
    [8]
    8. Reference electrode according to one of claims 1 to 7, characterized in that the polymer body methacryloylalkoxysilyl compounds, such as e.g. Contains trialkoxysilylalkenyl (meth) acrylates.
    [9]
    9. Reference electrode according to one of claims 1 to 8, characterized in that the polymer body has a content of prepolymer segments of 15 to 80 wt .-%, preferably between 25 to 70 wt .-%.
    [10]
    10. Reference electrode according to one of claims 1 to 9, characterized in that the polymer body in thick-film technology, in particular in a layer thickness of 10-50 pm, is applied to a carrier.
    [11]
    11. Reference electrode according to one of claims 1 to 10, characterized in that the polymer body inorganic fillers, such as. Contains silicates or inert oxides, the fillers preferably being contained in an amount of 30-70% by weight in the polymer body.
    [12]
    12. Reference electrode according to one of claims 1 to 11, characterized in that the polymer body together with the deflecting element is arranged in a tubular hollow shape which has an opening, the polymer against a sample 0.1 to 10 mm 2 , preferably 0, 5 to 5 mm 2 large window forms.
    38/40 [LAST CLAIMS) ·· • · · • · · • · · • · · ···· ········ • · · · · • ··· · ··· • · · · · • · · · · · ·
    [13]
    13. A method for producing a polymer body for use for a reference electrode according to one of claims 1 to 12, comprising the steps:
    a) making a mixture of hydrophobic
    Prepolymer segments and hydrophilic and possibly hydrophobic monomers in order to obtain a prepolymer-monomer mixture,
    b) adding a solution of at least one electrolyte salt to the prepolymer-monomer mixture,
    c) mixing the electrolyte salt solution with the prepolymer / monomer mixture, the at least one electrolyte salt partially precipitating in microcrystalline form and partially remaining in the solution,
    d) polymerizing the monomers to give hydrophilic polymer chains which cross-link the prepolymer segments three-dimensionally, thereby obtaining the polymer body in which the at least one electrolyte salt is embedded.
    [14]
    14. The method according to claim 13, characterized in that in step b) an electrolyte salt solution with a saturation of 2-100%, preferably 10-100% is used.
    [15]
    15. The method according to claim 13 or 14, characterized in that the electrolyte salt solution in an amount of 5-25 wt .-%, preferably 5-10 wt .-%, based on the prepolymer-monomer mixture is added.
    [16]
    16. The method according to claim 13, 14 or 15, characterized in that the polymerization according to step d) is carried out by means of a UV initiator, preferably selected from the group of benzoin ethers or substituted acetophenones, such as e.g. 2,2-dimethoxy-2phenyl-acetophenone (benzil dimethyl ketal).
    39/40 (LAST CLAIMS) ·· ···· ···· • · · · · • ··· · ··· • · · · · • · · · · · ·· ·· • · · • · · • · · · • · ·
    [17]
    17. The method according to any one of claims 13 to 16, characterized in that in step c) further mixing with at least one inorganic filler, such as. with silicates or inert oxides, the at least one filler preferably being added in an amount of 30-70% by weight, based on the total amount.
    [18]
    18. The method according to any one of claims 13 to 17, characterized in that the mixture of the electrolyte salt solution obtained in step c) with the prepolymer-monomer mixture in the form of a layer is applied to a carrier by means of screen printing via a discharge element and then step d) is performed to obtain a polymer body layer.
    [19]
    19. The method according to claim 18, characterized in that an insulating layer, in particular a UV-curing insulating lacquer layer, is applied to the polymer body layer, the insulating layer having an exemption which functions as a diaphragm window, via which a sample contacts the polymer body layer can be brought, wherein the deflection element is preferably arranged at a distance of> 1 mm, preferably about 3 millimeters from the diaphragm window.
    Vienna, applicant on December 6, 2018
    40/40 [LAST CLAIMS ^
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    AT520779B1|2020-03-15|
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    WO2019118993A1|2019-06-27|
    CN111919112A|2020-11-10|
    EP3729067B1|2021-11-03|
    EP3729067A1|2020-10-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US6419809B1|1999-06-24|2002-07-16|Katayanagi Institute|Miniature reference electrode|
    EP1124132A1|2000-02-10|2001-08-16|Hamilton Bonaduz AG|Polymerelectrolyte|
    DE10214035A1|2002-03-27|2003-10-09|Mettler Toledo Gmbh|Polymer electrolyte, half cell for electrochemical measurements and their use|
    EP1956368A1|2007-02-08|2008-08-13|Hamilton Bonaduz AG|Nano hybrid gels as polymer electrolytes|
    WO2014091083A1|2012-12-14|2014-06-19|Åbo Akademi|A reference electrode and an arrangement for an electrochemical measurement|
    EP3101414A1|2014-01-31|2016-12-07|Kabushiki Kaisha Pilot Corporation|Internal liquid for comparison electrode, comparison electrode, and glass electrode|
    DE102015118581A1|2015-10-30|2017-05-04|Endress+Hauser Conducta Gmbh+Co. Kg|Ion-selective potentiometric measuring chain|
    US4434249A|1982-06-28|1984-02-28|Electrochemical Technology Corp.|Method of preparing acrylic ion-transfer membranes|
    DE102012102321A1|2012-03-20|2013-09-26|NMI Naturwissenschaftliches und Medizinisches Institut an der Universität Tübingen|Miniaturized ion-selective electrode of the second kind|EP3809128A4|2018-06-14|2021-07-14|NOK Corporation|Method for producing silver-silver chloride electrode|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA498/2017A|AT520779B1|2017-12-21|2017-12-21|Reference electrode for potentiometric measurement of ion concentrations|ATA498/2017A| AT520779B1|2017-12-21|2017-12-21|Reference electrode for potentiometric measurement of ion concentrations|
    US16/771,159| US20210172895A1|2017-12-21|2018-12-20|Reference electrode for the potentiometric measurement of ion concentrations|
    PCT/AT2018/000098| WO2019118993A1|2017-12-21|2018-12-20|Reference electrode for potentiometric measurement of ion concentrations|
    CN201880081745.1A| CN111919112A|2017-12-21|2018-12-20|Reference electrode for potentiometric measurement of ion concentration|
    EP18839800.2A| EP3729067B1|2017-12-21|2018-12-20|Reference electrode for potentiometric measurement of ion concentrations|
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