• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Colorimetric sensors of divalent metals and/or oxidizing anions in drinking water, industrial water and/or food products. Cross-linked copolymers in the form of dense or porous membranes (films or films), as well as their application as colorimetric sensors of divalent metals and/or oxidative anions in aqueous media, such as in drinking and industrial water, as well as in food products. The present invention relates to the copolymers crosslinked by structures of formula I and to the processes for obtaining them. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2680718A1
    申请号:ES201730292
    申请日:2017-03-06
    公开日:2018-09-10
    发明作者:Saúl Vallejos Calzada；José Miguel GARCÍA PÉREZ；Félix GARCÍA GARCÍA；Felipe Serna Arenas；Miriam TRIGO LÓPEZ；Ana SANJUAN CORTÁZAR；Jose Antonio REGLERO RUIZ；Aranzazu MENDÍA JALÓN；Asunción MUÑOZ SANTAMARÍA；Blanca Sol PASCUAL PORTAL
    申请人:Universidad de Burgos；
    IPC主号:
    专利说明:

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    where R1 is a group H or C H3, and where X, Y and Z r represent the percentages of the monomers used, where Z represents between 0.1% to 10% of the total number of monomers, and where the proportion of X with respect to Y is from 1: 3 to 3: 1.
    The process for obtaining the crosslinked copolymers of the invention, described above, can be represented by the following Scheme 2:
    image7
    Scheme 2
    8


    where R1 is a group H or CH3, and where X, Y and Z are the percentages of the monomers used, where Z represents between 0.1% to 10% of the total number of monomers; and where the ratio of X to Y is 1 : 3 to 3: 1.
    5 In a preferred embodiment, the ratio of X to Y is 1: 1. In a preferred embodiment Z represents 0.25% of the total number of monomers.
    In another preferred embodiment X is 49.875%, Y is 49.875% and Z is 0.25%.
    An embodiment of the crosslinked copolymers of the invention relates to copolymers of formula (X):
    image8
    where R1 is a group H or CH3, and where X, Y and Z are the percentages of the monomers used, where Z represents between 0.1% to 10% of the total number of monomers; and where the ratio of X to Y is 1: 3 to 3: 1.
    In a preferred embodiment, the ratio of X to Y is 1: 1. In a preferred embodiment Z represents 0.25% of the total number of monomers. In another preferred embodiment X is 49.875%, Y is 49.875% and Z is 0.25%.
    For the purposes of the present invention the polymers are obtained by binding of monomers where the monomers comprise polymerizable groups. 25
    9


    For purposes of the present invention, non-limiting examples of polymerizable groups are the vinyl, methacrylate, acrylate, methacrylamide or acrylamide groups.
    image9
    (where R is H or an alkyl, alkenyl or aryl group).
    The monomers used in step (a) described in the present invention can be both commercial monomers and synthesis monomers.
    In a preferred embodiment of the invention, at least one of the monomers used in
    Step (a) independently selects from a group consisting of vinyl pyrrolidone, ethyl methacrylate, butyl acrylate, butyl methacrylate, methyl acrylate, styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methacrylate 2-ethoxyethyl, lauryl acrylate, lauryl methacrylate, vinyl acetate, methacrylic acid, methacrylic anhydride, acrylic acid, methacrylamide, 2-N methacrylate, N-dimethylaminoethyl.
    In a preferred embodiment of the invention, at least one of the monomers used in step (a) is vinyl pyrrolidone.
    In a preferred embodiment of the present invention, at least one of the monomers
    20 used in step (a) is methyl methacrylate. Monomers, referred to in the present invention, are called monomers used in step (a) that comprise an anchor group R2.
    10
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    In another preferred embodiment of the invention X is 49.875%, Y is 49.875% and Z is 0.25%.
    The cross-linked copolymers by structures of formula I described in the present invention, membranes, films, coatings and solid state materials obtained from them, are characterized by an ideal combination of mechanical properties both dry and swollen, that is, with water within the polymer network. This converts the crosslinked copolymers by structures of formula I of the present invention into materials suitable for the production of dense membranes that can be used, among other areas, in the detection of divalent metal cations, such as mercury (II) or
    10 copper (II), and / or oxidizing anions such as nitrites, in water and / or food products. That is, the crosslinked copolymers of the invention are colorimetric sensors of divalent metals and / or oxidizing anions, in water and / or food products.
    One embodiment relates to the use of crosslinked copolymers by structures of formula I in accordance with the present invention, in the detection and / or quantification of divalent metal cations in aqueous media or food products by at least one method independently selected from:
    -the use of the RGB parameters of a digital photograph; or 20 -the use of spectroscopic techniques.
    A preferred embodiment relates to the use of crosslinked copolymers by structures of formula I according to the present invention, where the divalent metal cation is mercury [Hg (II)]. In another preferred embodiment the metal is copper [Cu (II)].
    Another embodiment relates to the use of crosslinked copolymers by structures of formula I according to the present invention, in the detection and / or quantification of oxidizing anions in aqueous media or food products by at least one method independently selected from:
    30 -the use of the RGB parameters of a digital photograph; or -the use of spectroscopic techniques.
    18


    A preferred embodiment refers to the use of crosslinked copolymers by structures of formula I in accordance with the present invention, where the oxidizing anion detected and / or quantified is nitrite anion (NO2-) An embodiment of the invention also relates to The porous membranes obtained by chemical and / or physical foaming processes from the solid membranes described previously. As examples of the physical foaming process is the dissolution of high pressure gas (CO2 and / or N2), and as chemical foaming processes there are some non-limiting examples such as leaching from salts or mixtures of polymers or the use of Before being energetic endodermal chemicals that produce the cellular structure by heating and releasing the gas, and in general any foaming process that originates a porous structure within the solid membrane. DESCRIPTION OF THE FIGURES
    Figure 1. Characterization of N- (4-nitrophenyl) methacrylamide: (a) chemical structure; (b) infrared spectrum; (c) proton magnetic resonance (1 H NMR); (d) carbon magnetic resonance (13C NMR).
    Figure 2. Characterization of N- (4-aminophenyl) methacrylamide: (a) chemical structure; (b) infrared spectrum; (c) proton magnetic resonance (1 H NMR); (d) carbon magnetic resonance (13C NMR).
    Figure 3. Sensor membrane prepared according to Example 3 immersed in buffered water at pH = 2: adding between 0.002 to 10 mg / L of Hg (NO3) 2 · H2O to independent pieces of material. Figure 3A shows the effect on the disappearance of a band in the UV-visible spectrum. The graph in Figure 3B shows the relationship between the ppb of added mercury and the intensity of the green color at 650 nm, and the graph in Figure 3C shows the relationship between the logarithm of the ppb of added mercury and the intensity of the green color at 650 nm, as well as the adjustment to a polynomial of order 3.
    Figure 4. Sensor membranes prepared according to Example 3 after being submerged in solutions with different concentrations of mercury (samples 1 to 6, in which the gray scale corresponds to a color scale where the darkest gray corresponds to the green color and the lighter gray colors correspond to yellow colors), and the change
    19
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    权利要求:
    Claims (1)
    [1]
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    类似技术:
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    同族专利:
    公开号 | 公开日
    WO2018162396A1|2018-09-13|
    ES2680718B2|2019-01-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN101381426A|2008-10-17|2009-03-11|南京大学|Linking dithizone resin and preparation method thereof|
    CN103801271A|2014-01-22|2014-05-21|长安大学|Dithizone grafted chelating gel, preparation method thereof and method for treating mercury-containing wastewater|
    JPH08123026A|1994-10-28|1996-05-17|Fuji Photo Film Co Ltd|Photosensitive resin composition, color filter using same and its production|
    CN105348676A|2015-11-18|2016-02-24|扬州凯尔化工有限公司|Polyvinyl chloride membrane electrode for nitrite ion measurement|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201730292A|ES2680718B2|2017-03-06|2017-03-06|Colorimetric sensors for divalent metals and / or oxidizing anions in drinking water, industrial water and / or food products.|ES201730292A| ES2680718B2|2017-03-06|2017-03-06|Colorimetric sensors for divalent metals and / or oxidizing anions in drinking water, industrial water and / or food products.|
    PCT/EP2018/055317| WO2018162396A1|2017-03-06|2018-03-05|Colorimetric sensors of divalent metals and/or oxidising anions in drinking water, industrial water and/or food products|
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