WO2015067908A1 - Use of a molecularly imprinted polymer for trapping iprodione in an aqueous medium - Google Patents

Use of a molecularly imprinted polymer for trapping iprodione in an aqueous medium Download PDF

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Publication number
WO2015067908A1
WO2015067908A1 PCT/FR2014/052857 FR2014052857W WO2015067908A1 WO 2015067908 A1 WO2015067908 A1 WO 2015067908A1 FR 2014052857 W FR2014052857 W FR 2014052857W WO 2015067908 A1 WO2015067908 A1 WO 2015067908A1
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Prior art keywords
iprodione
methacrylamide
use according
crosslinked polymer
aqueous medium
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PCT/FR2014/052857
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French (fr)
Inventor
Elias BOU-MAROUN
Manal BITAR
Philippe CAYOT
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Universite De Bourgogne
Institut National Superieur Des Sciences Agronomiques De L'alimentation Et De L'environnement
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Publication of WO2015067908A1 publication Critical patent/WO2015067908A1/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
    • C12H1/04—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material
    • C12H1/0416—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material
    • C12H1/0424—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material with the aid of a polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
    • B01D15/3852—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36 using imprinted phases or molecular recognition; using imprinted phases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides

Definitions

  • the invention relates to molecular imprinted polymers (MIPs) and their use for trapping iprodione in an aqueous medium.
  • MIPs molecular imprinted polymers
  • the field of use of the present invention relates in particular to the decontamination of wine, or the purification of water.
  • MIP Molecular imprinted polymers
  • They can in particular be used to trap specific chemical compounds.
  • US 2002/0012727 discloses the use of a crosslinked acrylic acid polymer for decaffeinating beverages.
  • Document US 2011/054132 describes the use of MIP-type polymers for trapping / absorbing mycotoxin-type molecules.
  • the copolymer comprising the monomers 2-vinylpiridine and 2-hydroxyethylmethacrylate, crosslinked with ethylene glycol dimethacrylate, seems to be particularly suitable for trapping ochratoxin in wine.
  • Baggiani et al. (Journal of Chromatography A, 2007, 1141, pages 158-164) have described the use of MIP polymers to extract pyrimethanil-type fungicides present in wine.
  • the MIP polymer used is based on methacrylic acid and ethylene dimethacrylate. It does not trap Iprodione fungicides.
  • MIP polymers can also be used to trap fungicides, for example. This problem is particularly redundant in the wine industry, and particularly concerns iprodione which is a fungicide commonly found in vines. The bunches of grapes, but also the runoff water may contain traces of iprodione that it would be desirable to eliminate. However, entrapment of iprodione in an aqueous medium can be difficult. Indeed, the iprodione molecules are generally trapped in cavities of the MIP polymer by formation of hydrogen bonds. It is these hydrogen bonds that generally create strong interactions between iprodione and the MIP polymer. However, in an aqueous medium, water and iprodione can create hydrogen bonds and are therefore in competition.
  • the Applicant has discovered that the use of a specific MIP polymer solves this problem, and allows to effectively remove iprodione, even in predominantly aqueous medium. This technical effect is obtained in particular thanks to the selectivity of the MIP implemented with respect to the iprodione with respect to the water molecules.
  • the present invention relates to the use of a molecular imprinted polymer for trapping specific organic molecules. It is more particularly to trap, in an aqueous medium, the iprodione which is a fungicide.
  • the present invention relates to the use of a methacrylamide-based molecular imprinted crosslinked polymer for trapping iprodione in an aqueous medium.
  • the methacrylamide-based molecular imprinted crosslinked polymer used is hereinafter referred to as poly (methacrylamide), or MIP-MAM.
  • molecular imprinted polymer is meant a polymer having a structure adapted to specific chemical compounds.
  • the molecular imprinted polymer comprises complementary cavities in shape, in size and in chemical functionality adapted to a specific molecule (target molecule) thus making it possible to trap it selectively, even in the presence of its counterparts in the same matrix.
  • aqueous medium is meant a liquid medium comprising at least 50% by volume of water. It may especially be a medium comprising ethanol such as wine for example. According to a preferred embodiment, the aqueous medium consists of 100% by volume of water. It may for example be fruit or vegetable wash water, runoff water ... Typically, this type of media is likely to include fungicides such as iprodione.
  • the polymer used in the present invention is advantageously a crosslinked homopolymer of methacrylamide. Its molecular weight is advantageously between 10,000 and 1,000,000 g / mol.
  • the molecular imprinting polymer used in the present invention comprises a number of N sites of interactions of between 400 and 1500, more advantageously still between 1000 and 1500 per gram of polymer. These interaction sites are all sites available to trap iprodione.
  • the imprinting factor, IF, of said molecular imprinting polymer is advantageously between 1 and 2.5, more preferably between 2 and 2.5.
  • the print factor is the MIP's ability to trap iprodione and differentiate itself from its unprinted "Non-Imprinted-Polymer" counterpart.
  • the molecular imprinted polymer comprises a molar amount of crosslinking agent greater than the amount of monomeric unit. More advantageously, it has a molar ratio between the monomers (monomeric units) and the crosslinking agent of between 0.1 and 0.5, more advantageously still between 0.2 and 0.5. In other words, the polymer comprises a number of moles of monomers advantageously between 0.1 and 0.5 times the number of moles of crosslinking agent.
  • the crosslinking agent is a polyfunctional chemical compound, that is to say a compound comprising groups capable of forming bonds between polymeric chains, as defined in the state of the art.
  • TRIM trimethylolpropane trimethacrylate, CAS number: 3290-92-4
  • EGDMA ethylene glycol dimethacrylate, CAS number: 97-90-5
  • the crosslinking agent is TRIM. It is preferentially EGDMA.
  • the polymer used in the present invention is a methacrylamide homopolymer (MAM) crosslinked with TRIM, the MAM / TRIM molar ratio being advantageously between 0.1 and 0.5.
  • the polymer used in the present invention is a homopolymer of methacrylamide (MAM) crosslinked with EGDMA, the molar ratio MAM / EGDMA being advantageously between 0.1 and 0.5.
  • 1 gram of polymer can be used to trap between 750 and 1500 micrograms of iprodione, more preferably between 1.4 and 1.5 milligrams of iprodione.
  • the Applicant considers that the entrapment of iprodione is favored by the formation of hydrogen bonds between iprodione and the crosslinked methacrylamide polymer. These hydrogen bonds make it possible to retain iprodione which is not very soluble in water. It is thus surprising to note that the entrapment of iprodione is possible in (essentially) aqueous medium and especially in water. Indeed, the majority of water is able to form hydrogen bonds that compete with the trapping of iprodione.
  • the polymer used can be prepared according to the conventional polymerization techniques forming part of the general knowledge of those skilled in the art. However, it is advantageously prepared by bulk polymerization or by precipitation polymerization.
  • the methacrylamide polymer is prepared by precipitation polymerization.
  • the crosslinked poly (methacrylamide) is prepared by dissolving the methacrylamide monomer, and at least one crosslinking agent in at least one solvent, advantageously a pore-forming solvent.
  • the polymerization solvent can in particular be chosen from the group comprising toluene, hexane, acetonitrile, dichromethane and their mixtures.
  • the concentration of monomer in the reaction medium is generally between 0.0005 to 0.1 g per ml of solvent, more advantageously still in the range of 0.001 to 0.01 g per ml of solvent.
  • the polymerization is carried out in the presence of at least one initiator. It may especially be a conventional free radical initiator such as for example 2,2-dimethoxy-2-phenylacetophenone (DMPAP) [CAS number 24650-42-8].
  • DMPAP 2,2-dimethoxy-2-phenylacetophenone
  • the polymer is advantageously prepared in the presence of the molecule to be entrapped, that is iprodione. Typically, 0.1 to 0.2 gram of iprodione is introduced into the reaction medium for 0.15 to 0.5 gram of methacrylamide monomer.
  • the polymer is prepared by precipitation polymerization of the methacrylamide monomer in an organic solvent, preferably toluene in the presence of iprodione and TRIM.
  • the polymer is advantageously washed to remove traces of iprodione possibly trapped.
  • the washing solvent is advantageously a protic solvent in which the iprodione is soluble but in which the polymer is insoluble. It is advantageously an alcohol, even more advantageously ethanol.
  • the polymer obtained after washing is essentially free of iprodione.
  • the resulting amount of iprodione is typically less than 1% by weight based on the weight of the polymer.
  • the polymer After washing, the polymer is advantageously dried. It can then be milled to form particles whose interaction sites are exposed, particularly when the polymer is obtained by bulk polymerization.
  • the polymer In order to facilitate the use of the polymer, it can be introduced into a solid phase extraction cartridge.
  • the cross-linked poly (methacrylamide) may be recycled by washing with a washing solvent such as that mentioned above, advantageously a protic wash solvent. This washing eliminates iprodione in order to reuse the polymer.
  • the present invention also relates to a method of treating an aqueous medium containing iprodione, wherein at least a portion of the iprodione is entrapped by immersing a cross-linked, molecular-fingerprint-based polymer. methacrylamide.
  • a cross-linked, molecular-fingerprint-based polymer methacrylamide.
  • all the iprodione present is trapped.
  • iprodione can be trapped by immersing one gram of a methacrylamide-based molecular fingerprint crosslinked polymer.
  • FIG. 1a illustrates the number of N-sites of interactions of the poly (methacrylamide) as a function of the crosslinking agent used, for a polymer obtained by mass polymerization.
  • FIG. 1b illustrates the number N of interactions of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by precipitation polymerization.
  • FIG. 2a illustrates the affinity constant K of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by bulk polymerization.
  • FIG. 2b illustrates the affinity constant K of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by precipitation polymerization.
  • FIG. 3a illustrates the impregnation factor IF of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by bulk polymerization.
  • FIG. 3b illustrates the impregnation factor IF of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by precipitation polymerization.
  • the imprinted molecule is iprodione.
  • the polymerization is carried out in toluene (pore-forming solvent), using 2,2-dimethyl-2-phenylacetophenone to initiate the radical polymerization reaction (under UV radiation), in a glass vial of 1.6 cm internal diameter.
  • the experimental protocol is as follows:
  • the reagents are placed in a bottle of 17 mm internal diameter and 10 ml volume. The mixture is subjected to magnetic stirring. After degassing by ultrasonication for 5 minutes, the flask is placed 10 cm from a UV lamp (366 nm) overnight. The polymerization results in a monolith or a precipitate (according to the proportions of the synthetic reagents).
  • the monolith obtained is transferred into a mortar to be ground into powder.
  • the precipitate does not need to be crushed.
  • Each MIP finally undergoes successive washings (7 washes) with ethanol.
  • the phase separation is carried out by centrifugation.
  • Drying is carried out in an oven at 70 ° C overnight.
  • the imprinted molecule is iprodione.
  • Table 3 Properties of Prepared MIP Polymers
  • TRIM trimethylolpropane trimethacrylate (CAS number: 3290-92-4)
  • EGDMA ethylene glycol dimethacrylate (CAS number: 97-90-5)
  • MAM methacrylamide (CAS number: 79-39-0)
  • N number of sites available to trap iprodione
  • IF print factor. This factor takes into account the printing capacity of each polymer. The higher the IF, the better the molecular impression.
  • MIP-3, MIP-4, MIP-7 and MIP-8 comprise an additional monomer, styrene.
  • these polymers have a lower printing factor than the crosslinked homopolymers of methacrylamide according to the invention (MIP- 1, MIP-2, MIP-5 and MIP-6).
  • crosslinked homopolymers of MIP-MAM methacrylamide make it possible to improve the entrapment of iprodione with respect to the copolymers of methacrylamide and styrene.
  • MIP-10 and MIP-11 do not include MAM monomer. They were obtained by precipitation polymerization. They have a significantly lower print factor than MIP-6. These results show that the presence of the monomer MAM improves the entrapment of iprodione.
  • Poly (acrylamide / EGDMA) (MIP-9) indeed has a printing factor equal to 1 while poly (MAM / EGDMA) (MIP-2) has a printing factor equal to 1.9. This difference is particularly remarkable with regard to the similarity of the acrylamide and methacrylamide monomers.
  • the MIPs obtained by precipitation polymerization have a higher print factor than that of MIP obtained from the same monomers but by mass polymerization. The polymerization method therefore probably has an influence on the structure of the MIP.

Abstract

The present invention relates to the use of a molecularly imprinted polymer for trapping specific organic molecules. It more particularly involves trapping, in an aqueous medium, iprodione which is a fungicide. More particularly, the present invention relates to the use of a methacrylamide-based, molecularly imprinted, crosslinked polymer for trapping iprodione in an aqueous medium.

Description

UTILISATION D'UN POLYMERE A EMPREINTES MOLECULAIRES POUR PIEGER L'IPRODIONE EN MILIEU AQUEUX  USE OF A MOLECULAR IMPRESSION POLYMER TO PIEGE IPRODIONE IN AQUEOUS MEDIUM
DOMAINE DE L'INVENTION FIELD OF THE INVENTION
L'invention concerne des polymères à empreintes moléculaires (MIP) et leur utilisation pour piéger l'iprodione en milieu aqueux. The invention relates to molecular imprinted polymers (MIPs) and their use for trapping iprodione in an aqueous medium.
Le domaine d'utilisation de la présente invention concerne notamment la décontamination du vin, ou la purification de l'eau. The field of use of the present invention relates in particular to the decontamination of wine, or the purification of water.
ETAT ANTERIEUR DE LA TECHNIQUE PRIOR STATE OF THE TECHNIQUE
Les polymères à empreintes moléculaires (MIP) présentent des propriétés de déformabilité leur permettant de reprendre leur forme initiale après avoir été soumis à des contraintes extérieures. Molecular imprinted polymers (MIP) have deformability properties allowing them to return to their original shape after being subjected to external stresses.
Ils peuvent notamment être utilisés pour piéger des composés chimiques spécifiques. They can in particular be used to trap specific chemical compounds.
Par exemple, le document US 2002/0012727 décrit l'utilisation d'un polymère d'acide acrylique réticulé pour décaféiner des boissons. Le document US 2011/054132 décrit l'utilisation de polymères de type MIP pour piéger/absorber des molécules de type mycotoxines. Le copolymère comprenant les monomères 2-vinylpirydine et 2- hydroxyéthylméthacrylate, réticulé avec de l'éthylène glycol diméthacrylate, semble être particulièrement adapté au piégeage de l'ochratoxine dans du vin. Baggiani et al. (Journal of Chromatography A, 2007, 1141, pages 158-164) ont décrit l'utilisation de polymères MIP pour extraire les fongicides de type pyriméthanil présents dans le vin. Le polymère MIP utilisé est à base d'acide méthacrylique et d'éthylène diméthacrylate. Il ne permet pas de piéger les fongicides de type iprodione. For example, US 2002/0012727 discloses the use of a crosslinked acrylic acid polymer for decaffeinating beverages. Document US 2011/054132 describes the use of MIP-type polymers for trapping / absorbing mycotoxin-type molecules. The copolymer comprising the monomers 2-vinylpiridine and 2-hydroxyethylmethacrylate, crosslinked with ethylene glycol dimethacrylate, seems to be particularly suitable for trapping ochratoxin in wine. Baggiani et al. (Journal of Chromatography A, 2007, 1141, pages 158-164) have described the use of MIP polymers to extract pyrimethanil-type fungicides present in wine. The MIP polymer used is based on methacrylic acid and ethylene dimethacrylate. It does not trap Iprodione fungicides.
Les polymères MIP peuvent également être utilisés pour piéger des fongicides par exemple. Cette problématique est particulièrement redondante dans l'industrie viticole, et concerne notamment l'iprodione qui est un fongicide couramment répandu sur les vignes. Les grappes de raisins, mais aussi les eaux de ruissèlement peuvent ainsi contenir des traces d'iprodione qu'il serait souhaitable d'éliminer. Or, le piégeage de l'iprodione en milieu aqueux peut s'avérer difficile. En effet, les molécules d'iprodione sont généralement piégées dans des cavités du polymère MIP par formation de liaisons hydrogène. Ce sont ces liaisons hydrogène qui créent généralement des interactions fortes entre l'iprodione et le polymère MIP. Or, en milieu aqueux, l'eau et l'iprodione peuvent créer des liaisons hydrogène et sont donc en compétition. MIP polymers can also be used to trap fungicides, for example. This problem is particularly redundant in the wine industry, and particularly concerns iprodione which is a fungicide commonly found in vines. The bunches of grapes, but also the runoff water may contain traces of iprodione that it would be desirable to eliminate. However, entrapment of iprodione in an aqueous medium can be difficult. Indeed, the iprodione molecules are generally trapped in cavities of the MIP polymer by formation of hydrogen bonds. It is these hydrogen bonds that generally create strong interactions between iprodione and the MIP polymer. However, in an aqueous medium, water and iprodione can create hydrogen bonds and are therefore in competition.
Le Demandeur a découvert que l'utilisation d'un polymère MIP spécifique permet de résoudre cette problématique, et permet d'éliminer efficacement l'iprodione, et ce même en milieu majoritairement aqueux. Cet effet technique est obtenu notamment grâce à la sélectivité du MIP mis en œuvre, vis-à-vis de l'iprodione par rapport aux molécules d'eau. The Applicant has discovered that the use of a specific MIP polymer solves this problem, and allows to effectively remove iprodione, even in predominantly aqueous medium. This technical effect is obtained in particular thanks to the selectivity of the MIP implemented with respect to the iprodione with respect to the water molecules.
EXPOSE DE L'INVENTION SUMMARY OF THE INVENTION
La présente invention concerne l'utilisation d'un polymère à empreintes moléculaires pour le piégeage de molécules organiques spécifiques. Il s'agit plus particulièrement de piéger, en milieu aqueux, l'iprodione qui est un fongicide. The present invention relates to the use of a molecular imprinted polymer for trapping specific organic molecules. It is more particularly to trap, in an aqueous medium, the iprodione which is a fungicide.
Plus particulièrement, la présente invention concerne l'utilisation d'un polymère réticulé à empreintes moléculaires à base de méthacrylamide pour piéger l'iprodione en milieu aqueux. More particularly, the present invention relates to the use of a methacrylamide-based molecular imprinted crosslinked polymer for trapping iprodione in an aqueous medium.
Le polymère réticulé à empreintes moléculaires à base de méthacrylamide mis en œuvre est ci-après désigné poly (méthacrylamide), ou MIP-MAM. The methacrylamide-based molecular imprinted crosslinked polymer used is hereinafter referred to as poly (methacrylamide), or MIP-MAM.
Par polymère à empreintes moléculaires, on entend un polymère présentant une structure adaptée à des composés chimiques spécifiques. En d'autres termes, le polymère à empreintes moléculaires comprend des cavités complémentaires en forme, en taille et en fonctionnalité chimique adaptés à une molécule spécifique (molécule cible) permettant ainsi de la piéger sélectivement, et ce même en présence de ses homologues dans la même matrice. By molecular imprinted polymer is meant a polymer having a structure adapted to specific chemical compounds. In other words, the molecular imprinted polymer comprises complementary cavities in shape, in size and in chemical functionality adapted to a specific molecule (target molecule) thus making it possible to trap it selectively, even in the presence of its counterparts in the same matrix.
Par « milieu aqueux », on entend un milieu liquide comprenant au moins 50% en volume, d'eau. Il peut notamment s'agir d'un milieu comprenant de l'éthanol tel que le vin par exemple. Selon un mode de réalisation préféré, le milieu aqueux est constitué par 100% en volume d'eau. Il peut par exemple s'agir de l'eau de lavage de fruits ou de légumes, de l'eau de ruissellement... Typiquement, ce type de milieux est susceptible de comprendre des fongicides tels que l'iprodione. Le polymère mis en œuvre dans la présente invention est avantageusement un homopolymère réticulé de méthacrylamide. Son poids moléculaire est avantageusement compris entre 10 000 et 1 000 000 g/mol. By "aqueous medium" is meant a liquid medium comprising at least 50% by volume of water. It may especially be a medium comprising ethanol such as wine for example. According to a preferred embodiment, the aqueous medium consists of 100% by volume of water. It may for example be fruit or vegetable wash water, runoff water ... Typically, this type of media is likely to include fungicides such as iprodione. The polymer used in the present invention is advantageously a crosslinked homopolymer of methacrylamide. Its molecular weight is advantageously between 10,000 and 1,000,000 g / mol.
Le méthacrylamide correspond au composé chimique de formule CH2=C(CH3)-C(=0)- NH2. Methacrylamide corresponds to the chemical compound of formula CH 2 = C (CH 3 ) -C (= O) -NH 2 .
De manière avantageuse, le polymère à empreintes moléculaires mis en œuvre dans la présente invention comprend un nombre de sites N d'interactions compris entre 400 et 1500, plus avantageusement encore, entre 1000 et 1500 par gramme de polymère. Ces sites d'interactions constituent autant de sites disponibles pour piéger l'iprodione. Advantageously, the molecular imprinting polymer used in the present invention comprises a number of N sites of interactions of between 400 and 1500, more advantageously still between 1000 and 1500 per gram of polymer. These interaction sites are all sites available to trap iprodione.
Le facteur d'impression, IF, dudit polymère à empreintes moléculaires est avantageusement compris entre 1 et 2.5, plus avantageusement entre 2 et 2.5. Le facteur d'impression correspond à la capacité du MIP à piéger l'iprodione et à se différencier de son homologue non imprimé NIP « Non-Imprinted-Polymer ». The imprinting factor, IF, of said molecular imprinting polymer is advantageously between 1 and 2.5, more preferably between 2 and 2.5. The print factor is the MIP's ability to trap iprodione and differentiate itself from its unprinted "Non-Imprinted-Polymer" counterpart.
De manière avantageuse, le polymère à empreintes moléculaires comprend une quantité molaire d'agent réticulant supérieure à la quantité d'unité monomérique. Plus avantageusement, il présente un rapport molaire entre les monomères (unités monomériques) et l'agent réticulant compris entre 0.1 et 0.5, plus avantageusement encore entre 0.2 et 0.5. En d'autres termes, le polymère comprend un nombre de moles de monomères avantageusement compris entre 0.1 et 0.5 fois le nombre de moles d'agent réticulant. Advantageously, the molecular imprinted polymer comprises a molar amount of crosslinking agent greater than the amount of monomeric unit. More advantageously, it has a molar ratio between the monomers (monomeric units) and the crosslinking agent of between 0.1 and 0.5, more advantageously still between 0.2 and 0.5. In other words, the polymer comprises a number of moles of monomers advantageously between 0.1 and 0.5 times the number of moles of crosslinking agent.
L'agent réticulant est un composé chimique polyfonctionnel, c'est-à-dire un composé comprenant des groupements aptes à former des liaisons entre chaînes polymériques, comme défini dans l'état de l'art. The crosslinking agent is a polyfunctional chemical compound, that is to say a compound comprising groups capable of forming bonds between polymeric chains, as defined in the state of the art.
Il s'agit avantageusement du TRIM (triméthylolpropane triméthacrylate ; numéro CAS : 3290-92-4) ou du EGDMA (éthylène glycol diméthacrylate ; numéro CAS : 97-90-5). Selon un mode de réalisation avantageux, l'agent réticulant est le TRIM. Il s'agit préférentiellement de l'EGDMA. It is advantageously TRIM (trimethylolpropane trimethacrylate, CAS number: 3290-92-4) or EGDMA (ethylene glycol dimethacrylate, CAS number: 97-90-5). According to an advantageous embodiment, the crosslinking agent is TRIM. It is preferentially EGDMA.
Selon un mode de réalisation avantageux, le polymère mis en œuvre dans la présente invention est un homopolymère de méthacrylamide (MAM) réticulé avec le TRIM, le rapport molaire MAM/TRIM étant avantageusement compris entre 0.1 et 0.5. Selon un autre mode de réalisation avantageux, le polymère mis en œuvre dans la présente invention est un homopolymère de méthacrylamide (MAM) réticulé avec le EGDMA, le rapport molaire MAM/EGDMA étant avantageusement compris entre 0.1 et 0.5. According to an advantageous embodiment, the polymer used in the present invention is a methacrylamide homopolymer (MAM) crosslinked with TRIM, the MAM / TRIM molar ratio being advantageously between 0.1 and 0.5. According to another advantageous embodiment, the polymer used in the present invention is a homopolymer of methacrylamide (MAM) crosslinked with EGDMA, the molar ratio MAM / EGDMA being advantageously between 0.1 and 0.5.
Typiquement, 1 gramme de polymère (le poly(méthacrylamide) réticulé) peut être utilisé pour piéger entre 750 et 1500 microgrammes d'iprodione, plus avantageusement entre 1,4 et 1,5 milligrammes d'iprodione. Typically, 1 gram of polymer (cross-linked poly (methacrylamide)) can be used to trap between 750 and 1500 micrograms of iprodione, more preferably between 1.4 and 1.5 milligrams of iprodione.
Sans émettre une quelconque hypothèse, le Demandeur considère que le piégeage de l'iprodione est favorisé par la formation de liaisons hydrogène entre l'iprodione et le polymère réticulé de méthacrylamide. Ces liaisons hydrogène permettent de retenir l'iprodione qui est peu soluble dans l'eau. Il est donc surprenant de constater que le piégeage de l'iprodione est possible dans un milieu (essentiellement) aqueux et notamment dans l'eau. En effet, l'eau majoritaire est apte à former des liaisons hydrogène qui concurrencent le piégeage de l'iprodione. Without making any assumption, the Applicant considers that the entrapment of iprodione is favored by the formation of hydrogen bonds between iprodione and the crosslinked methacrylamide polymer. These hydrogen bonds make it possible to retain iprodione which is not very soluble in water. It is thus surprising to note that the entrapment of iprodione is possible in (essentially) aqueous medium and especially in water. Indeed, the majority of water is able to form hydrogen bonds that compete with the trapping of iprodione.
Le polymère mis en œuvre peut être préparé selon les techniques de polymérisation conventionnelles faisant partie des connaissances générales de l'homme du métier. Cependant, il est avantageusement préparé par polymérisation en masse (bulk) ou par polymérisation par précipitation. The polymer used can be prepared according to the conventional polymerization techniques forming part of the general knowledge of those skilled in the art. However, it is advantageously prepared by bulk polymerization or by precipitation polymerization.
Selon un mode de réalisation préféré, le polymère de méthacrylamide est préparé par polymérisation par précipitation. According to a preferred embodiment, the methacrylamide polymer is prepared by precipitation polymerization.
Typiquement, le poly(méthacrylamide) réticulé est préparé par mise en solution du monomère méthacrylamide, et d'au moins un agent réticulant dans au moins un solvant, avantageusement un solvant porogène. Typically, the crosslinked poly (methacrylamide) is prepared by dissolving the methacrylamide monomer, and at least one crosslinking agent in at least one solvent, advantageously a pore-forming solvent.
Le solvant de polymérisation peut notamment être choisi dans le groupe comprenant le toluène, hexane, acétonitrile, dichrométhane et leurs mélanges. The polymerization solvent can in particular be chosen from the group comprising toluene, hexane, acetonitrile, dichromethane and their mixtures.
La concentration en monomère dans le milieu réactionnel est généralement comprise entre 0.0005 à 0.1 g par mL de solvant, plus avantageusement encore entre 0.001 et 0.01 g par mL de solvant. The concentration of monomer in the reaction medium is generally between 0.0005 to 0.1 g per ml of solvent, more advantageously still in the range of 0.001 to 0.01 g per ml of solvent.
L'homme du métier saura ajuster la quantité du solvant afin de favoriser la formation d'un précipité ou d'un monolithe au cours de la polymérisation. Typiquement, la polymérisation est mise en œuvre en présence d'au moins un initiateur. Il peut notamment s'agir d'un initiateur de radicaux libres conventionnel tel que par exemple 2,2-dimethoxy-2-phenylacetophenone (DMPAP) [CAS number 24650-42-8]. Those skilled in the art will be able to adjust the amount of the solvent to promote the formation of a precipitate or a monolith during the polymerization. Typically, the polymerization is carried out in the presence of at least one initiator. It may especially be a conventional free radical initiator such as for example 2,2-dimethoxy-2-phenylacetophenone (DMPAP) [CAS number 24650-42-8].
Le polymère est avantageusement préparé en présence de la molécule à piéger, c'est-à- dire l'iprodione. Typiquement, 0.1 à 0.2 gramme d'iprodione sont introduits dans le milieu réactionnel pour 0.15 à 0.5 gramme de monomère méthacrylamide. The polymer is advantageously prepared in the presence of the molecule to be entrapped, that is iprodione. Typically, 0.1 to 0.2 gram of iprodione is introduced into the reaction medium for 0.15 to 0.5 gram of methacrylamide monomer.
Selon un mode de réalisation préféré, le polymère est préparé par polymérisation par précipitation du monomère méthacrylamide dans un solvant organique, de préférence le toluène en présence d'iprodione et de TRIM. According to a preferred embodiment, the polymer is prepared by precipitation polymerization of the methacrylamide monomer in an organic solvent, preferably toluene in the presence of iprodione and TRIM.
Une fois formé, le polymère est avantageusement lavé pour éliminer les traces d'iprodione éventuellement piégées. Once formed, the polymer is advantageously washed to remove traces of iprodione possibly trapped.
Le solvant de lavage est avantageusement un solvant protique dans lequel l'iprodione est soluble mais dans lequel le polymère est insoluble. Il s'agit avantageusement d'un alcool, encore plus avantageusement de l'éthanol. The washing solvent is advantageously a protic solvent in which the iprodione is soluble but in which the polymer is insoluble. It is advantageously an alcohol, even more advantageously ethanol.
Le polymère obtenu à l'issue du lavage est essentiellement dépourvu d'iprodione. La quantité d'iprodione résultante est typiquement inférieure à 1% en masse par rapport à la masse du polymère. The polymer obtained after washing is essentially free of iprodione. The resulting amount of iprodione is typically less than 1% by weight based on the weight of the polymer.
Après lavage, le polymère est avantageusement séché. Il peut ensuite être broyé pour former des particules dont les sites d'interactions sont exposés, particulièrement lorsque le polymère est obtenu par polymérisation en masse. After washing, the polymer is advantageously dried. It can then be milled to form particles whose interaction sites are exposed, particularly when the polymer is obtained by bulk polymerization.
Afin de faciliter l'utilisation du polymère, il peut être introduit dans une cartouche d'extraction en phase solide. In order to facilitate the use of the polymer, it can be introduced into a solid phase extraction cartridge.
Après utilisation et éventuellement saturation à l'iprodione, le poly(méthacrylamide) réticulé peut être recyclé par lavage avec un solvant de lavage tel que celui mentionné ci- dessus, avantageusement un solvant de lavage protique. Ce lavage permet d'éliminer l'iprodione afin de pouvoir réutiliser le polymère. After use and optionally saturation with iprodione, the cross-linked poly (methacrylamide) may be recycled by washing with a washing solvent such as that mentioned above, advantageously a protic wash solvent. This washing eliminates iprodione in order to reuse the polymer.
La présente invention concerne également un procédé de traitement d'un milieu aqueux contenant de l'iprodione, selon lequel au moins une partie de l'iprodione est piégée par immersion d'un polymère réticulé à empreintes moléculaires et à base de méthacrylamide. De manière avantageuse, l'intégralité de l'iprodione présente est piégée. The present invention also relates to a method of treating an aqueous medium containing iprodione, wherein at least a portion of the iprodione is entrapped by immersing a cross-linked, molecular-fingerprint-based polymer. methacrylamide. Advantageously, all the iprodione present is trapped.
Typiquement, dans ce procédé, entre 0.75 et 2 milligrammes, voire entre 1,4 et 1,5 milligrammes, d'iprodione peuvent être piégés par immersion d'un gramme d'un polymère réticulé à empreintes moléculaires à base de méthacrylamide. Typically, in this process, between 0.75 and 2 milligrams, or even between 1.4 and 1.5 milligrams, iprodione can be trapped by immersing one gram of a methacrylamide-based molecular fingerprint crosslinked polymer.
L'invention et les avantages qui en découlent ressortiront mieux des figures et exemples suivants donnés afin d'illustrer l'invention et non de manière limitative. The invention and the advantages thereof will appear more clearly from the following figures and examples given to illustrate the invention and not in a limiting manner.
DESCRIPTION DES FIGURES DESCRIPTION OF THE FIGURES
La figure la) illustre le nombre de sites N d'interactions du poly(méthacrylamide) en fonction du réticulant mis en œuvre, pour un polymère obtenu par polymérisation en masse. FIG. 1a) illustrates the number of N-sites of interactions of the poly (methacrylamide) as a function of the crosslinking agent used, for a polymer obtained by mass polymerization.
La figure lb) illustre le nombre N d'interactions du poly(méthacrylamide) en fonction du réticulant mis en œuvre lors de sa préparation par polymérisation par précipitation. FIG. 1b) illustrates the number N of interactions of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by precipitation polymerization.
La figure 2a illustre la constante d'affinité K du poly(méthacrylamide) en fonction du réticulant mis en œuvre lors de sa préparation par polymérisation en masse. FIG. 2a illustrates the affinity constant K of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by bulk polymerization.
La figure 2b illustre la constante d'affinité K du poly(méthacrylamide) en fonction du réticulant mis en œuvre lors de sa préparation par polymérisation par précipitation. FIG. 2b illustrates the affinity constant K of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by precipitation polymerization.
La figure 3a) illustre le facteur d'imprégnation IF du poly(méthacrylamide) en fonction du réticulant mis en œuvre lors de sa préparation par polymérisation en masse. FIG. 3a) illustrates the impregnation factor IF of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by bulk polymerization.
La figure 3b) illustre le facteur d'imprégnation IF du poly(méthacrylamide) en fonction du réticulant mis en œuvre lors de sa préparation par polymérisation par précipitation. FIG. 3b) illustrates the impregnation factor IF of the poly (methacrylamide) as a function of the crosslinking agent used during its preparation by precipitation polymerization.
EXEMPLES DE REALISATION DE L'INVENTION EXAMPLES OF CARRYING OUT THE INVENTION
Plusieurs polymères à empreintes moléculaires ont été préparés, soit par polymérisation en masse, soit par polymérisation par précipitation (voir tableaux 1-3). Tableau 1 : Proportions des réactifs dans la synthèse par polymérisation en masse (Bulk) Several molecular imprinted polymers have been prepared, either by bulk polymerization or by precipitation polymerization (see Tables 1-3). Table 1: Proportions of Reagents in Bulk Polymerization Synthesis (Bulk)
Figure imgf000008_0001
Figure imgf000008_0001
La molécule empreinte est l'iprodione. The imprinted molecule is iprodione.
La polymérisation est réalisée dans le toluène (solvant porogène), en utilisant le 2,2diméthyl-2-phénylacétophénone pour initier la réaction radicalaire de polymérisation (sous rayonnement UV), dans un flacon en verre de 1,6 cm de diamètre interne. The polymerization is carried out in toluene (pore-forming solvent), using 2,2-dimethyl-2-phenylacetophenone to initiate the radical polymerization reaction (under UV radiation), in a glass vial of 1.6 cm internal diameter.
Le protocole expérimental est le suivant : The experimental protocol is as follows:
Les réactifs sont mis en présence dans un flacon de 17 mm de diamètre interne et 10 mL de volume. Le mélange est soumis à une agitation magnétique. Après dégazage par ultrasonication pendant 5 min, le flacon est placé à 10 cm d'une lampe à rayonnement UV (366nm) pendant une nuit. La polymérisation aboutit à un monolithe ou à un précipité (suivant les proportions des réactifs de synthèse).  The reagents are placed in a bottle of 17 mm internal diameter and 10 ml volume. The mixture is subjected to magnetic stirring. After degassing by ultrasonication for 5 minutes, the flask is placed 10 cm from a UV lamp (366 nm) overnight. The polymerization results in a monolith or a precipitate (according to the proportions of the synthetic reagents).
Dans le cas de la polymérisation en masse, le monolithe obtenu est transvasé dans un mortier pour être broyé en poudre. En revanche, le précipité n'a pas besoin d'être broyé. Chaque MIP subit enfin des lavages successifs (7 lavages) avec l'éthanol. In the case of bulk polymerization, the monolith obtained is transferred into a mortar to be ground into powder. On the other hand, the precipitate does not need to be crushed. Each MIP finally undergoes successive washings (7 washes) with ethanol.
2 g de polymère sont lavés avec 10 mL de solvant pendant 20 minutes à l'ultrason. 2 g of polymer are washed with 10 ml of solvent for 20 minutes with ultrasound.
La séparation des phases est réalisée par centrifugation. The phase separation is carried out by centrifugation.
Le séchage est réalisé dans une étuve à 70°C pendant une nuit. Drying is carried out in an oven at 70 ° C overnight.
Tableau 2 : Proportions des réactifs dans la synthèse par polymérisation par précipitation Table 2: Proportions of reagents in synthesis by precipitation polymerization
Figure imgf000008_0002
Figure imgf000008_0002
La molécule empreinte est l'iprodione. Tableau 3 : Propriétés des polymères MIP préparés The imprinted molecule is iprodione. Table 3: Properties of Prepared MIP Polymers
Figure imgf000009_0001
Figure imgf000009_0001
TRIM : triméthylolpropane triméthacrylate (numéro CAS : 3290-92-4) TRIM: trimethylolpropane trimethacrylate (CAS number: 3290-92-4)
EGDMA : éthylène glycol diméthacrylate (numéro CAS : 97-90-5) EGDMA: ethylene glycol dimethacrylate (CAS number: 97-90-5)
MAM : méthacrylamide (numéro CAS : 79-39-0) MAM: methacrylamide (CAS number: 79-39-0)
STY: styrène (numéro CAS : 100-42-5) STY: styrene (CAS number: 100-42-5)
Polymérisation M : polymérisation en masse (bulk) Polymerization M: mass polymerisation (bulk)
Polymérisation P : polymérisation par précipitation Polymerization P: precipitation polymerization
N : nombre de sites disponibles pour piéger l'iprodione N: number of sites available to trap iprodione
K : constance d'affinité K: constancy of affinity
IF : facteur d'impression. Ce facteur tient compte de la capacité d'impression de chaque polymère. Plus l'IF est élevé, plus l'impression moléculaire est réussie.  IF: print factor. This factor takes into account the printing capacity of each polymer. The higher the IF, the better the molecular impression.
IF = Kd (MIP)/Kd(NIP) IF = Kd (MIP) / Kd (NIP)
Kd coefficient de partage de l'iprodione entre le polymère et la solution de recapture (milieu aqueux : éthanol/eau ; 50/50 ; v/v) Essais de sorption d'une solution d'iprodione à 2.10"5 mol.L"1 par le MIP-6 : Kd partition coefficient of iprodione between the polymer and the recapture solution (aqueous medium: ethanol / water, 50/50, v / v) Sorption tests of a solution of iprodione at 2.10 "5 mol.L " 1 with MIP-6:
Figure imgf000010_0001
Figure imgf000010_0001
Ces essais montrent une meilleure interaction ΜΙΡ/iprodione dans l'eau par rapport au mélange eau/alcool (alcool = éthanol). These tests show a better interaction ΜΙΡ / iprodione in water compared to the mixture water / alcohol (alcohol = ethanol).
Les MIP-3, MIP-4, MIP-7 et MIP-8 comprennent un monomère additionnel, le styrène. Quelles que soient les conditions d'obtention (précipitation ou masse) ou la nature de l'agent réticulant (TRIM ou EGDMA), ces polymères présentent un facteur d'impression inférieur à celui des homopolymères réticulés de méthacrylamide selon l'invention (MIP- 1, MIP-2, MIP-5 et MIP-6). MIP-3, MIP-4, MIP-7 and MIP-8 comprise an additional monomer, styrene. Whatever the conditions for obtaining (precipitation or mass) or the nature of the crosslinking agent (TRIM or EGDMA), these polymers have a lower printing factor than the crosslinked homopolymers of methacrylamide according to the invention (MIP- 1, MIP-2, MIP-5 and MIP-6).
Ainsi, les homopolymères réticulés de méthacrylamide MIP-MAM permettent d'améliorer le piégeage de l'iprodione par rapport aux copolymères de méthacrylamide et de styrène. Thus, crosslinked homopolymers of MIP-MAM methacrylamide make it possible to improve the entrapment of iprodione with respect to the copolymers of methacrylamide and styrene.
Les MIP-10 et MIP-11 ne comprennent pas le monomère MAM. Ils ont été obtenus par polymérisation par précipitation. Ils présentent un facteur d'impression nettement inférieur à celui du MIP-6. Ces résultats montrent que la présence du monomère MAM permet d'améliorer le piégeage de l'iprodione. Le poly(acrylamide/EGDMA) (MIP-9) présente en effet un facteur d'impression égal à 1 alors que le poly(MAM/EGDMA) (MIP-2) présente un facteur d'impression égal à 1.9. Cette différence est particulièrement remarquable au regard de la similarité des monomères acrylamide et méthacrylamide. MIP-10 and MIP-11 do not include MAM monomer. They were obtained by precipitation polymerization. They have a significantly lower print factor than MIP-6. These results show that the presence of the monomer MAM improves the entrapment of iprodione. Poly (acrylamide / EGDMA) (MIP-9) indeed has a printing factor equal to 1 while poly (MAM / EGDMA) (MIP-2) has a printing factor equal to 1.9. This difference is particularly remarkable with regard to the similarity of the acrylamide and methacrylamide monomers.
En outre, la méthode de polymérisation peut également influencer signifîcativement la sélectivité des MIP. Ceci est particulièrement mis en évidence par la comparaison entre le MIP-2 (IF = 1 ,9) et le MIP-6 (IF = 2,4) ou entre le MIP-4 (IF = 1) et le MIP-8 (IF = 1.8). De manière générale, les MIP obtenus par polymérisation par précipitation présentent un facteur d'impression supérieur à celui de MIP obtenus à partir des mêmes monomères mais par polymérisation en masse. La méthode de polymérisation a donc probablement une influence sur la structure du MIP. In addition, the polymerization method can also significantly influence the selectivity of the MIPs. This is particularly highlighted by the comparison between MIP-2 (IF = 1, 9) and MIP-6 (IF = 2.4) or between MIP-4 (IF = 1) and MIP-8 ( IF = 1.8). In general, the MIPs obtained by precipitation polymerization have a higher print factor than that of MIP obtained from the same monomers but by mass polymerization. The polymerization method therefore probably has an influence on the structure of the MIP.

Claims

REVENDICATIONS
1. Utilisation d'un polymère réticulé à empreintes moléculaires à base de méthacrylamide pour piéger l'iprodione en milieu aqueux. 1. Use of a methacrylamide-based molecular fingerprint cross-linked polymer for entrapping iprodione in an aqueous medium.
2. Utilisation selon la revendication 1 , caractérisée en ce que le polymère réticulé à empreintes moléculaires est un homopolymère de méthacrylamide. 2. Use according to claim 1, characterized in that the crosslinked polymer molecular imprints is a homopolymer of methacrylamide.
3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que le polymère réticulé à empreintes moléculaires comprend un agent réticulant choisi dans le groupe comprenant TRIM et EGDMA. 3. Use according to claim 1 or 2, characterized in that the crosslinked polymer molecular imprints comprises a crosslinking agent selected from the group comprising TRIM and EGDMA.
4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que le polymère réticulé à empreintes moléculaires comprend un agent réticulant, le rapport molaire entre les unités monomériques et l'agent réticulant étant compris entre 0.1 et 0.5. 4. Use according to one of claims 1 to 3, characterized in that the crosslinked polymer molecular imprints comprises a crosslinking agent, the molar ratio between the monomer units and the crosslinking agent being between 0.1 and 0.5.
5. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce que polymère réticulé à empreintes moléculaires est un homopolymère de méthacrylamide réticulé avec le TRIM, le rapport molaire méthacrylamide/TRIM étant compris entre 0.1 et 0.5. 5. Use according to one of claims 1 to 4, characterized in that crosslinked polymer molecular imprints is a methacrylamide homopolymer crosslinked with the TRIM, the methacrylamide / TRIM molar ratio being between 0.1 and 0.5.
6. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce que polymère réticulé à empreintes moléculaires est un homopolymère de méthacrylamide réticulé avec le EGDMA, le rapport molaire méthacrylamide/EGDMA étant compris entre 0.1 et 0.5. 6. Use according to one of claims 1 to 4, characterized in that crosslinked polymer molecular imprints is a methacrylamide homopolymer crosslinked with EGDMA, the methacrylamide / EGDMA molar ratio being between 0.1 and 0.5.
7. Utilisation selon l'une des revendications 1 à 6, caractérisée en ce que le polymère réticulé à empreintes moléculaires est obtenu par polymérisation par précipitation. 7. Use according to one of claims 1 to 6, characterized in that the crosslinked polymer molecular imprints is obtained by precipitation polymerization.
8. Utilisation selon l'une des revendications 1 à 7, caractérisée en ce que le polymère réticulé à empreintes moléculaires est obtenu par polymérisation du méthacrylamide en présence d'iprodione et d'au moins un agent réticulant. 8. Use according to one of claims 1 to 7, characterized in that the crosslinked polymer molecular imprints is obtained by polymerization of methacrylamide in the presence of iprodione and at least one crosslinking agent.
9. Utilisation selon l'une des revendications 1 à 8, caractérisé en ce que le polymère réticulé à empreintes moléculaires est obtenu en présence d'un solvant porogène. 9. Use according to one of claims 1 to 8, characterized in that the crosslinked polymer molecular imprints is obtained in the presence of a pore-forming solvent.
10. Utilisation selon la revendication 1, caractérisé en ce que le polymère réticulé à empreintes moléculaires est obtenu par polymérisation par précipitation de méthacrylamide en présence de TRIM. 10. Use according to claim 1, characterized in that the crosslinked polymer with molecular imprints is obtained by precipitation polymerization of methacrylamide in the presence of TRIM.
11. Utilisation selon la revendication 1, caractérisé en ce que le polymère réticulé à empreintes moléculaires est obtenu par polymérisation par précipitation de méthacrylamide en présence de EGDMA. 11. Use according to claim 1, characterized in that the crosslinked polymer molecular imprints is obtained by precipitation polymerization of methacrylamide in the presence of EGDMA.
12. Utilisation selon l'une des revendications 1 à 11, caractérisé en ce que le milieu aqueux est l'eau. 12. Use according to one of claims 1 to 11, characterized in that the aqueous medium is water.
13. Utilisation selon l'une des revendications 1 à 11, caractérisé en ce que le milieu aqueux est du vin. 13. Use according to one of claims 1 to 11, characterized in that the aqueous medium is wine.
14. Procédé de traitement d'un milieu aqueux contenant de l'iprodione, selon lequel au moins une partie de l'iprodione est piégée par immersion d'un polymère réticulé à empreintes moléculaires à base de méthacrylamide. 14. A process for treating an aqueous medium containing iprodione, wherein at least a portion of the iprodione is entrapped by immersing a methacrylamide-based molecular imprinted crosslinked polymer.
15. Procédé selon la revendication 14, caractérisé en ce que 0.75 à 2 milligrammes de l'iprodione est piégée par immersion d' 1 gramme de polymère réticulé à empreintes moléculaires à base de méthacrylamide. 15. The method of claim 14, characterized in that 0.75 to 2 milligrams of iprodione is trapped by immersion of 1 gram of methacrylamide-based molecular fingerprint crosslinked polymer.
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