BRPI1011169B1 - POROUS POLYMERIC SEPARATION MATERIAL, METHOD FOR PREPARING A POLYMERIC SEPARATION MATERIAL AND A FOOD OR FOOD PESTICIDE SEPARATION METHOD - Google Patents

Description

(54) Title: POROUS POLYMERIC SEPARATION MATERIAL, METHOD OF PREPARING A POLYMERIC SEPARATION MATERIAL AND SEPARATION METHOD OF A PESTICIDE FROM A FOOD OR FOOD PRODUCT (51) lnt.CI .: B01J 20/26; B01J 20/22; B01J 20/28; C08J 9/36; A23L 5/20; B01D 15/00 (30) Unionist Priority: 19/05/2009 SE 0900673-5 (73) Holder (s): BIOTAGE AB (72) Inventor (s): STIG JÕNSSON; ECEVIT YILMAZ; SANJA KRONAUER (85) National Phase Start Date: 11/21/2011

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POROUS POLYMERIC SEPARATION MATERIAL, METHOD OF PREPARING A POLYMERIC SEPARATION MATERIAL AND SEPARATION METHOD OF

A PESTICIDE IN A FOOD OR FOOD PRODUCT

Technical Field of the Invention

The present invention relates to the design, preparation and use of new resins comprising one or more metal complexes. These new resins are selective for one or more analytes / targets that are not satisfactorily separated by conventional chromatographic materials.

Prior Art

In the area of separation materials, there is a family of resins that contain metal binders. Most of these are aimed at protein separation. Examples of conventional commercial resins are Sephadex (GE Healthcare), Biogel (BioRad) and Toyopearl (Tosoh). These conventional resins generally have a low degree of crosslinking and a flexible support structure, and comprise large pores. Large pores are optimized for analytes such as proteins, but none of said conventional materials offers a satisfactory solution for certain types of small molecules.

Conventional chelate materials that have been developed for small molecules, such as Purolite® chelating resins, are conventionally used for the separation of small molecules that interact with metal ions. Said materials lead to poor separations, low selectivity and unsatisfactory resolutions for certain areas of application. Other metal chelate resins, such as Dowex 50WX8, Amberlite (R) CG50, Amberlite (R) IR-120, Amberlyst (R) 15, although widely used, do not always perform satisfactorily when used for demanding separations, such as pesticides and others

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2/44 environmental contaminants present in low concentrations in complex matrices. The use of cation exchangers loaded with silver for purification and separation of small unsaturated molecules, for example, fatty acids, pheromones and heterocycles containing polyaromatic sulfur has been described and such resins have been used in column chromatography systems for analytical and preparative purposes. Within the food industry it is generally a requirement that the raw materials of the food, components or products are not contaminated by metals during processing. Several studies described in the literature have shown that pesticide hydrolysis reactions can be catalyzed by metals in an aqueous environment. However, hydrolysis does not completely solve the problem of pesticide removal, as it does not remove the hydrolysis products that are formed.

Ridvan Say in Anal. Chim. Acta 579 (2006) 74-80 discloses molecularly labeled polymers prepared using paraoxane or paration as a model and methacryloyl20 antipyrine-gadolinium chelate as a monomer.

The removal of pesticides from food is a major focus in the food industry and there is growing public concern about the level of pesticide residues in food. US5558893 discloses a method of distilling contaminated citrus oils that can be used for the preparation of citrus oils, which are essentially free of pesticides. However, distillation generally has an adverse effect on the flavor of citrus oils, since several volatile compounds that impart flavor and flavor are simultaneously removed.

The removal and adsorption of fungicides and herbicides in

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3/44 aqueous solution of modified activated carbon is used for the purification of pharmaceutical oils, pesticides and refineries as disclosed in Separation and Purification Technology, Vol. 52, 3rd edition, January

2007, Pages 403-415.

Pesticides are not only a problem in citrus oils, but are present in many other essential oils (for example, palm oil). Consequently, there is a need for materials and methods to selectively remove, extract, separate and / or analyze pesticides from food and feed products, such as essential oils.

Summary of the Invention

An object of the present invention is to provide a porous separation material 15 for selective extraction and / or separation of pesticides.

An object of the present invention is achieved by a porous polymeric separation material characterized by containing pores in the mesoporous region; with an area of

The surface above 50 m ² / g of material and a pore volume between 0.2 and 1.2 ml / g of material, as determined by BET analysis, and the material comprises one or more functional group (s) attached (s) to one or more metal ion (s) selected from the group consisting of Cu ⁺ ,

Ag ⁺ , Pd ⁺ , Cu ²⁺ or Zn ²⁺ .

In one aspect, the porous polymeric separation material is a copolymer of divinylbenzene and styrene substituted with one or more functional group (s) selected from the group consisting of sulfonic acid and carboxylic acid; or a divinylbenzene copolymer and a

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4/44 polymerizable tertiary alkylamine.

An object of the present invention is obtained by a method of preparing a porous polymeric separation material, providing a functional monomer, a crosslinking monomer, optionally an initiator and a porogen;

polymerizing;

obtaining a porous polymeric material;

contacting said porous polymeric material with one or more metal ions selected from the group consisting of Cu ⁺ , Ag ⁺ , Pd ²⁺ , Cu ²⁺ or Zn ²⁺ ; and obtaining a porous polymeric separation material.

An object is in an aspect achieved by the method above, in which the functional monomer is selected from the group consisting of vinylbenzenesulfonic acid, such as 4-vinylbenzenesulfonic acid; vinylbenzyliminodiacetic acid, such as 4-vinylbenzyliminodiacetic acid; polymerizable tertiary alkyl amine derivatives; or a combination or salts thereof; and / or the crosslinked monomer is selected from divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or any combination thereof.

An object of the present invention is achieved by a method of separating a pesticide from a food product or feed by contacting the food or feed with a porous polymeric separation material according to the invention.

In one aspect, the method of separating a pesticide from a food product or feed also includes forming a ternary complex between the polymeric separation material

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Porous 5/44 and the pesticide; collect the purified food product or feed; and eluting said pesticide.

Detailed Description of Preferred Modalities

The present invention relates to a porous polymeric separation material (resin). The resin is a porous polymeric material and, consequently, is not a gel-shaped material.

Resins are specifically useful in separating pesticides. Resins are selective for one or more target molecule (s) and allow retention, separation, extraction and / or analysis, such as chromatographic analysis of target compounds that are not satisfactorily separated by conventional methods or materials. The target molecule is a pesticide.

The present invention relates to a porous polymeric separation material characterized by containing pores in the mesoporous region; with a surface area above 50 m ² / g and a pore volume between 0.2 and 1.2 ml / g of material, as determined by BET analysis and the material comprises one or more linked functional group (s) ( s) to one or more metal ion (s) selected from the group consisting of Cu ⁺ , Ag ⁺ , Pd ²⁺ , Cu ²⁺ or Zn ²⁺ .

In one embodiment, said metal ion is selected from Ag ⁺ and Pd ²⁺ . In one embodiment, said metal ion is Ag ⁺ . It is possible to use two or more different metal ions selected from Cu ⁺ , Ag ⁺ , Pd ²⁺ , Cu ²⁺ or Zn ²⁺ in a resin of the invention.

The surface area of the porous material is in a modality> 50 m ² / g of material.

The surface area of the porous separation material 30 is in a mode> 300 m ² / g of material, as between

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300 and 700 m ² / g of material; in one embodiment, the pore surface area is> 400 m ² / g of material, as between 400 and 700 m ² / g of material.

The porous polymeric separation material is prepared 5 having a degree of crosslink density above 20% by weight, based on the% by weight of the added crosslinked monomer.

The resin of the invention has a pore volume between 0.2 and 1.2 ml of material / g. In one embodiment, the pore volume is between 0.2 and 0.9 ml / g, such as 0.3 to 0.9 ml / g of material and 0.4 to 0.8 ml / g of material. In certain respects, the different ranges disclosed result in preferred resins.

The pores of the material are in the mesoporous region.

Mesoporous means pores with diameters between 2 and 50 nm. In one embodiment, the pores in the mesoporous region have a porous surface area> 50 m ² / g of material determined by BET analysis. The porous surface area is in a modality> 300 m ² / g of material, such as between 300 and 700 m ² / g of material; in one embodiment, the pore surface area is> 400 m ² / g of material, as between 400 and 700 m ² / g of material.

In one embodiment, the resin has a capacity between 0.2 and 1.0 mmol / g of material. Capacity is determined by separating the metal ion from the resin by ion exchange, for example, by washing with a suitable solvent, such as an aqueous sodium nitrate solution or aqueous nitric acid solution and anhydrous methylamine. A more specific description of the procedure is disclosed in Example 6.

In one embodiment, the capacity is 0.3 to 0.8 mmol / g

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Ί / 4Λ of material and, in one embodiment, the capacity is 0.35 to 0.6 mmol / g of material.

The resin is a copolymer of divinylbenzene and styrene substituted with one or more functional group (s) selected from the group consisting of sulfonic acid and carboxylic acid; or a copolymer of divinylbenzene and a polymerizable tertiary alkylamine.

A metal complex is a binary complex between a functional group attached to a polymeric support attached, for example, coordinated to a metal ion. The resin comprises one or more functional group (s) selected from the group consisting of sulfonic acid, carboxylic acid and tertiary alkylamine.

Tertiary alkylamines are tertiary amines defined by NR ^ -R ² ] ^ ³ , where R ¹ is a polymerizable group, such as a vinyl group, a vinyl benzyl group, etc., R ² and R ³ are independently selected from each other. heteroaryl C1-6 alkyl and C1-6 aminoalkyl, optionally substituted by a straight or branched C1-6 alkyl.

Heteroaryl means an aryl group comprising one or more nitrogen atoms.

functional group is generally introduced by the functional monomer and suitable functional monomers are, for example, vinylbenzenesulfonic acid, such as 425 vinylbenzenesulfonic acid; vinylbenzyliminodiacetic acid, such as 4-vinylbenzyliminodiacetic acid; polymerizable derivatives of tertiary alkylamines, such as amino acids, bipyridyl, terpiridyl and pyridyl. In some embodiments, vinylbenzenesulfonic acid, such as 430 vinylbenzenesulfonic acid is preferred.

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Crosslinking monomers can be selected from divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or any hydrophobic monomer or combination thereof. In some embodiments, divinylbenzene or combinations of divinylbenzene and other crosslinking monomers are preferred.

In one embodiment, it is preferable to use vinylbenzenesulfonic acid, such as vinylbenzenesulfonic acid 410, as the functional monomer, and divinylbenzene or combinations of divinylbenzene and other crosslinking monomers as the crosslinking monomer.

Primers can be selected from an azo initiator, such as 2,2'-azobis (2-methylpropionitrile) (AIBN) or 2,2'-azobis (2,4-dimethylvaleronitrile) (ABDV) or a peroxide initiator such as benzoyl peroxide or tert-butyl peroxide or any other radical initiator. Polymerization can be initiated thermally or by irradiation with UV light.

In addition, the metal ion in the binary complex is able to coordinate a third species (target molecule, that is, pesticide), which results in a ternary complex. The term chelate is reserved for complexes in which the metal ion is attached to two or more atoms in the chelator, for example, iminodiacetic acid, but within the context of the present application, also sulfonic acid complexes are included. The stability of the binary or ternary complexes is stoichiometrically directed and the bonds are reversible, that is, the addition of a target molecule with high equilibrium constant for the reaction will release a

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9/44 target molecule that is weakly bound. The retention of a given species in the adsorbent is related to the stability of the ternary complex.

degree of crosslinking of the porous polymeric separation material is dependent on the amount of the crosslinking monomer used during polymerization.

Consequently, the crosslinking density refers to the% by weight of the crosslinking agent in the prepolymerization mixture (functional monomer, crosslinking agent, optionally initiator). The degree of crosslinking of the polymeric separation material is above 20% by weight of the crosslinking monomer.

The materials of the invention are characterized by having a large surface area and pore volume as discussed above. In addition, resins are highly reticulated polymeric networks, resulting in a rigid structure. The rigid structure of the resins according to the invention allows good thermomechanical properties and the materials can therefore withstand severe experimental conditions.

The polymeric material forms a strong binary complex between the metal and the functional monomer in order to minimize metal leakage into the food matrix. In addition, the ternary metal complex (functional monomer, metal, and complex species) needs to be strong enough to trap the species, for example, the pesticide molecule in the immobilized support. The understanding of complex stability (Chem. Rev. 1989, 89, 1875-1914) is based on the principle of hard / soft acids and hard / soft bases. According to this concept, a soft base, such as sulfur in

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10/44 organothiophosphate, interacts more strongly with a soft acid, such as silver, compared to hard acids.

Examples of metals acting as soft acids are Cu ⁺ , Ag ⁺ , Pd ² , Pt ²⁺ and the border acids Fe ²⁺ , Cu ²⁺ , Zn ²⁺ .

If the stability constant between the functional group and the metal is low, the result may be that a binary complex between the metal and the species migrates and flows with elution (leakage). The amount of metal can be properly determined using atomic absorption spectroscopy (AAS). The stability constants for binary complexes with silver are, for example, (logK): sulfonic - Ag = 5.6 (stability constant between the sulfonic group and silver ions), iminodiacetic - Ag = 4.3 (stability constant between the sulfonic group and the silver ion) and for the thiol - Ag = 13.6 (stability constant between the sulfonic group and the silver ion) (Martell, AE; Smith, RM Critical Stability Constants; Plenum: New York, 1989) . The ternary complex can be broken by the addition of molecules that compete with metal coordination (generally referred to in the literature as ligand exchange chromatography), which result in the successive release of the absorbed species depending on their relative stability constants. In some cases, the quantitative release of the metal is preferable, for example, for the regeneration of the column which, in addition to the metal, also completely releases the absorbed species. This can be achieved by adding an acid (for example, diluted HNO3 or aqueous sodium nitrate). The porous polymeric separation material (resin) of the invention is obtained by providing a functional monomer, a monomer of

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11/44 crosslinking, optionally a initiator and a porogen; polymerizing; obtaining a porous polymeric material; contacting said porous polymeric material with one or more metal ion (s) selected from the group consisting of Cu ⁺ ,

Ag ⁺ , Pd ²⁺ , Cu ²⁺ or Zn ²⁺ , and obtaining a porous polymeric separation material. In one embodiment, the functional monomer is selected from the group consisting of vinylbenzenesulfonic acid, such as 4vinylbenzenesulfonic acid; vinylbenzyliminodiacetic acid, such as 4-vinylbenzyliminodiacetic acid; polymerizable derivatives of tertiary alkylamines; or a combination of salts thereof; and / or the crosslinking monomer is selected from divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or any combination thereof.

In one embodiment, the porous polymeric separation material is prepared by suspension polymerization.

The functional group is generally introduced by the functional monomer, and suitable functional monomers are, for example, vinylbenzenesulfonic acid, such as 4vinylbenzenesulfonic acid; vinylbenzyliminodiacetic acid, such as 4-vinylbenzyliminodiacetic acid; polymerizable derivatives of tertiary alkylamines, such as amino acids, bipyridyl, terpiridyl and pyridyl. In some embodiments, vinylbenzenesulfonic acids, such as 4-vinylbenzenesulfonic acid, are preferred.

Crosslinking monomers can be selected from divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or any other hydrophobic monomer or any combination thereof. In

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12/44 some embodiments, divinylbenzene or combinations of divinylbenzene and other crosslinking monomers are preferred.

In some embodiments, it is preferable to use 5 vinylbenzenesulfonic acid, such as 4-vinylbenzenesulfonic acid as the functional monomer and divinylbenzene or combinations of divinylbenzene and other crosslinking monomers as the crosslinking monomer.

Primers can be selected from the azo primer, 10 as 2,2'-azobis (2-methylpropionitrile) (AIBN) or 2,2'azobis (2,4-dimethylvaleronitrile) (ABDV) or a peroxide initiator, such as peroxide benzoyl or tert-butyl peroxide or any other radical initiator. Polymerization can be initiated thermally or by irradiation with UV light. Suitable porogens are known to the skilled person, non-limiting examples being chloroform, toluene, benzyl alcohol, n-octanol, ethyl acetate and methyl isobutyl ketone or mixtures thereof.

The present invention relates to a porous polymeric separation material that can be adjusted to selectively bind to pesticides. In one embodiment of the present invention, the pesticide is selected from organophosphate or organothiophosphate pesticides.

Pesticides are a diverse group of chemicals comprising, for example, organophosphates, organothiophosphates; and aryl groups containing heteroatoms selected from nitrogen and sulfur, such as prochlorosis.

In one embodiment of the present invention, the pesticide is selected from organophosphorates and / or organothiophosphates.

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Organophosphates are esters of phosphoric acid and non-limiting examples of them are paration, eton, malation, methylparation, chlorpyrifos, diazinone, dichlorvos, fosmet, tetrachlorvinfos, fention, pyridapention, pyrimiphosmethyl and azinfosmetil.

One embodiment of the present invention relates to a porous polymeric separation material and / or a method of separating a pesticide from food products or feed, such as essential oils, for example, citric oil. Conventional extraction, chromatographic separation and / or distillation methods and materials, therefore, do not allow satisfactory removal of certain pesticides. In some embodiments, the present invention relates to methods for separating organophosphates and / or organothiophosphates from essential oils, such as citrus oils. In said methods, the resin of the invention is used to obtain food or feed products essentially free of pesticides, in particular organophosphate and / or organothiophosphate pesticides.

Essentially it means that the product may contain small amounts or impurities of pesticides, but that most of the pesticides are removed.

One embodiment concerns a method of separating a pesticide from a food product or feed in contact with the food product or feed with a porous polymeric separation material according to the present invention. In one embodiment, the method further comprises forming a ternary complex between the porous polymeric separation material and the pesticide; collect the purified food product or feed; and eluting said pesticide.

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14/44 porous polymeric separation material can be used as an adsorbent in separation and / or extraction processes.

A pesticide is a substance or mixture of 5 substances used to kill a pest. Pesticides include algaecides, avicides, bactericides, fungicides, herbicides, insecticides, acaricides, molluscicides, nematicides, rodenticides and virucides. Pesticides can be synthetic or biological pesticides. Non-limiting examples of pesticides are organophosphates or organothiophosphates; or any combination of these.

Essential oils are volatile, usually concentrated, plant essences, and can be found in a variety of plant parts including, but not limited to, roots (such as vetiver); leaves (as in the tea tree), flowers (as in rose); citrus fruits (as in bergamot) and seeds (as in cumin). Citrus oils, including citrus oils, sweet orange, lemon, bergamot, mandarin, lemon, mandarin and grapefruit, or any combination thereof, are examples of essential oils. The essential oils used in the invention may be mixtures of oils and may contain other constituents known to the skilled person, such as impurities (other than pesticides), flavoring agent and / or other additives.

A solvent that can be used according to the invention for the removal of pesticides can be selected from the following groups: alkanes, ketones, ethers, esters, with cyclohexane, pentane alkanes being more suitable.

One embodiment of the invention relates to a material of

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15/44 porous polymeric separation, as described in one or more of the aforementioned modalities used in the separation of pesticides, such as pesticides containing organophosphates and / or organothiophosphates from food products or feed, as essential oils. In one embodiment, the essential oil is selected from citrus oil. Consequently, the resin can be used in the methods of separating pesticides from the matrices, such as food or feed products.

Separation or separating is understood to include extraction, removal, retention, trapping, chromatography, etc.

One embodiment of the present invention relates to the separation and / or purification of a pesticide from a food product or feed, in which a pesticide comes into contact with a porous polymeric separation material, as described in one or more of the above mentioned modalities .

According to the invention, the metallic ion, for example, silver, can after each step of binding pesticides to the

20 material separation porous polymer, be released through the addition of an acid (e.g. HNO3) or base (per example, methylamine anhydrous). Pesticides linked are, So, released. THE silver remains in solution and the

extracted complexes can be separated by solvent extraction.

The material of the invention is characterized as a metal complex supported on resin. The morphology of the resin divided into two categories, namely, macroporous or gel type. Gel resins have an endless amorphous reticulated network, without any fine structure. These

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16/44 resins have a low degree of crosslinking, typically 4 to 8%, but usually have a high functional capacity in terms of, for example, exchange capacity. An example of this is Dowex 50WX8. This material is a strong cationic resin widely used in fine chemistry and pharmaceutical column separations. Dowex 50WX8 is cross-linked with 8% divinylbenzene with benzenesulfonic acid functionality. Dowex 50WX8 is a gel type with little or no porosity according to the BET analysis and with a high exchange capacity. The resin of the invention was compared before and after functionalization with a metal ion, example 7, and Dowex 50WX8, a resin with high functional capacity, example 9.

From the comparative examples, as in example 7, a difference between a porous polymeric separation material of the invention and a non-functionalized polymer is that the breaking point (the point at which the target compounds begin to move through a polymer because they are not retained by it) is reached for the non-functionalized polymer shortly after loading the first portions of limonene, the main solvent component of many citrus oils.

From the comparative example, example 9, the breaking point is reached by gel-like material, just after loading the first portion of citrus oil, in contrast to the porous polymeric material of the invention.

Macroporous resins, unlike gel resins, have a well-developed permanent porous structure, even in the dry state. These resins generally have a high degree of crosslinking,> 10%. These materials have areas of

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17/44 elevated surfaces in the dry state (usually ranging from 50 to 1000 m ² / g measured by N2 BET). The large surface area is associated with a well-developed macroporous network, with good accessibility by small molecules. It is known, for example, from chromatography, that the large surface area retains small molecules, for example, pesticides, better than materials with a small surface area, due to the greater molecular interaction area of the support and the eluent. The pore volume influences the kinetics of the interaction. The authors speculate that the gel-like material, despite having greater exchange capacity, has weakened interaction strength and, consequently, less ability and retention capacity of small molecules that interact.

The capacity of the resin is within this context for a macroporous resin with a high surface area (non-polar), also depending on the accessibility of small molecules to a highly polar metal complex. The metal bonding capacity of the resin is measured by removing the metal complex, for example, by determining ionic and quantitative concentration of the bound metal ions in the resin, see example 6. In the context of chromatographic performance, the metal resin shows good performance ability to bind small molecules with high stability constants, while small molecules with smaller stability constants will be partially eluted (chromatographic effects) and, consequently, have less performance capacity than metal resin. The chromatographic effects can be more or less pronounced in the

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18/44 different matrix (example 7 and example 8). In examples 10 and 13, different pesticides were tested to establish the applicability of the invention (not restricted to the examples) and it shows that the resin has good ability to bind to pesticides with structurally diverse formulas.

In chromatographic applications, the matrix mixture is in contact with the resin and slowly passes through a column, resulting in the separation of the constituents of the matrix depending on the equilibrium distribution of each compound between the stationary and mobile phases.

In batch mode, the matrix mixture is in contact with the resin contained within a porous pouch made of fabric or other material (tea bag). The bag is then immersed in the mixture of the matrix, solution or conditioned medium for an appropriate period, after which it is removed as a tea bag. In addition, batch mode can be performed without using a pouch, and then the resin is suspended in the matrix mixture. The advantage of the method is that it provides easy separation of the adsorbent and a simplified process. The method can be used for pesticides with affinity for the resin.

The enclosed examples clearly show that the porous polymeric separation material according to the invention works in removing pesticides from matrices, as an essential oil. Examples 14 and 15 show that the resins of the invention, prepared in different particle sizes, are efficient in removing pesticides. Consequently, the material is successful in achieving one of the objectives of the invention, namely, the removal of a pesticide from an essential oil.

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All examples 7, 8, 9, 17 and 18 show that the polymers of the invention can be treated with a metal in order to obtain a porous polymeric separation material according to the invention. The examples reveal that the materials effectively remove pesticides, such as etion, malation and paration of essential oils.

In an embodiment of the present invention, it is possible to minimize and / or eliminate the chromatographic effects during the extraction of pesticides using resins of the invention, increasing the height of the bed of material in the extraction column.

If the matrix containing the pesticides is of a complex constitution, the separation performance may be affected. In an embodiment of the present invention, the undesirable effects of the matrix are minimized and / or avoided as the matrix is diluted with certain organic solvents or limonene. For example, citrus / lemon oil diluted with cyclohexane and / or limonene improves the bonding of pesticides to the resin compared to undiluted citrus / lemon oil. This allows for a better separation of pesticides by the resin of the invention.

In an embodiment of the present invention, the separation of matrices having high value constituents (fragrances, flavors and coloring agents that are characteristic matrix compounds that add value to the flavor product) is improved. Said components can complicate the separation, since these can bind to the resin. It has surprisingly been found that the selectivity of the separation can be improved by introducing washing steps after loading the

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20/44 matrix containing pesticides with various organic solvents, such as heptane and / or limonene. In this way, the application area for pesticide extraction can be extended to more complex matrices.

The resin of the invention can be applied to analytical problems using this in a sample treatment step before analysis. In addition, it is possible to adapt this method for large-scale and industrial purposes.

The resin of the invention can be used in batch mode or 10 in chromatography.

Wherever a range is present, each individual number within the range is meant as well as each possible sub-range within the range, for example, the range from 0 to 50 comprises sub-ranges from 2 to 10, 25, 1 to 25, 5 and from 5 to 40, etc.

Wherever one or more is used in the present invention, it is intended to include one or more, two or more, three or more, etc.

Examples

Example 1

Water (100 mL) and tributylamine (7.4 g, 0.04 mol), followed by sulfuric acid (4.0 g, 0.04 mol) and then sodium salt of 4-vinylbenzenesulfonic acid (8.4 g , 0.04 mol) were added to a flask under stirring. Toluene (55 mL) was added and the two-phase system was shaken vigorously for 0.5 h, at pH = 1. The phases were easily separated and the toluene phase used without purification in the next step. The sample was concentrated for NMR analysis. NMR (CDCI3, 500MHz) δΗ

1.38 (t, 9H), 3.09-3.26 (m, 18H), 5.30 (d, 1H), 5.81 (d,

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1Η), 6, 64-6, 76 (m, 1H), 7.38-7.47 (m, 2H), 7.81-7.90 (m,

2H), 10.2-10.5 (bs, 1H).

Polyvinyl alcohol (PVA) (Celvol 523) was dissolved in water (400 mL) at 90 ° C to form a 2% by weight solution, cooled to room temperature and then added to a suspension reactor. 80% technical grade divinylbenzene (26 g, 0.2 mol) was added to the toluene solution prepared from the 4-vinyl benzene sulfonic acid tributylamine salt (from example 1). The initiator, ABDV (V65, 2,2'-azobis (2,4-dimethylvaleronitrile) (0.6 g) was added to the toluene solution and nitrogen was bubbled through the solution. The PVA solution was loaded into the reactor followed by monomer solution.

The two-phase mixture was stirred for a few minutes and the temperature was raised to 50 ° C and, after 4 to 6 h, raised to 65 ° C. The process was maintained overnight. The polymer was filtered using 20 pm sieves and carefully washed with water. The polymer was washed with 1M H2SO4 for 0.5 h, and was then washed with about 400 ml of water. The polymer was then washed in a soxhlet with ethanol overnight, and dried to produce 28.4 g of polymer (83% yield). The particle size was determined to be 20 to 130 pm, and sieved through a 20 to 90 pm filter, before loading with metal. The titration of a fluidized polymer sample with water with 1 M NaOH and phenolphthalein as an indicator shows 0.36 mmol of sulfonic acid / g of dry polymer.

Properties of the porous hydrophobic polymeric separation material (BET analysis):

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Average particle size (D [4.3]): 61 μΜ

Surface area: 602 m ² / g

Pore volume: 0.88 mL

Average pore diameter: 58.2 Å.

Signal value dV / dlog (D) of the 120 Á pore graph. desorption:

Example 2 - Comparative example

Dowex 50WX8-400 resin (5 g) was fluidized in H2SO4

5% (1M) for 1 h and then washed with water (400 ml), pH 5, followed by methanol (100 ml). Titration of a sample of the polymer suspended in water with 1 M NaOH and phenolphthalein as an indicator shows 2.3 mmol of sulfonic acid / g of polymer. The resin was loaded with silver in the same way as example 5a.

Example 3 - Synthesis of resin with iminodiacetic acid functionality.

Iminodiacetic acid (4g, 30mmol) was dissolved in aqueous methanol (60ml, 1: 1) and sodium hydroxide (2g, 50mmol) was added. The solution was heated to 60 ° C and 4-vinylbenzyl chloride (5.4 g, 35 mmol) was added slowly. After half the amount of chloride was added, an additional 2g of sodium hydroxide was added followed by the addition of the remaining chloride. After 0.5 h at 60 ° C, the solution was cooled and washed with diethyl ether. The aqueous phase was acidified with conc. until pH 2.5, the crude product was removed by filtration and purified by recrystallization from aqueous methanol. Yield

36%.

Preparation of porous polymeric separation material.

Water (200 mL) and 4-vinylbenzyliminodiacetic acid

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23/44 (10.0 g, 0.04 mol), followed by tri-n-octylamine (14.0 g, 0.04 mol) and then toluene (50 mL) and benzyl alcohol (10 mL) were added to a bottle and shaken vigorously for 0.5 h. The phases were easily separated and the organic phase was used without purification in the next step.

Polyvinyl alcohol (PVA) (Celvol 523) was dissolved in water (400 mL) at 90 ° C to form a 2% by weight solution, cooled to room temperature and then added to a suspension reactor. 80% technical grade divinylbenzene (26 g, 0.2 mol) was added to the prepared solution of 4-vinylbenzyliminodiacetic trioctylamino salt (from the example above). Initiator, ABDV (V65, 2,2'-azobis (2,4dimethylvaleronitrile) (0.6 g) was added to the toluene solution and nitrogen was bubbled through the solution. The PVA solution was charged into the reactor, followed by the monomer.

The two-phase mixture was stirred for a few minutes and the temperature was raised to 50 ° C, and after 4 to 6 h, raised to 65 ° C. The process was maintained overnight. The polymer was filtered using 20 pm sieves and carefully washed with water. The polymer was washed with 1 M H2SO4 for 0.5 hour, and then washed with about 400 ml of water. The polymer was then washed in a soxhlet with ethanol overnight and dried. The particle size was determined to be 20 to 130 pm.

The material was loaded with silver in the same way as in example 1.

The silver release shows a dry resin with 0.21 mmol Ag / g.

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Example 4 - Synthesis of Bis (2-pyridylmethyl) -4-vinyl benzylamine

2-Picolyl hydrochloride (4.1 g, 25 mmol) and 4-vinyl benzylamine (1.6, 12 mmol) were dissolved in water (30 mL) and heated to 60 ° C. To this solution, aqueous sodium hydroxide (10 ml, 5M) was added over a period of 0.5 h and then stirred for an additional hour. The cooled solution was extracted with dichloromethane and the extract was dried and the solvent evaporated. The product was obtained as a brown viscous oil (3.4 g, 84%).

Preparation of porous polymeric separation material. Polyvinyl alcohol (PVA) (Celvol 523) was dissolved in water (400 mL) at 90 ° C to form a 2% by weight solution, cooled to room temperature and then added to a suspension reactor. 80% technical grade divinylbenzene (26 g, 0.2 mol) was added to the prepared solution of bis (2-pyridylmethyl) -4-vinylbenzylamine (0.02 mol) (from the example above). Initiator, ABDV (V65, 2,2'-azobis (2,4dimethylvaleronitrile) (0.6 g) was added to the toluene solution and nitrogen was bubbled through the solution. The PVA solution was charged into the reactor followed by the monomer solution .

The two-phase mixture was stirred for a few minutes and the temperature was raised to 50 ° C and, after 4 to 6 h, raised to 65 ° C. The process was maintained overnight. The polymer was filtered using 20 pm sieves and carefully washed with water. The polymer was washed with about 400 ml of water, followed by 100 ml of methanol. The polymer was then washed in a soxhlet with ethanol overnight, and dried. The particle size was

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25/44 determined to be from 40 to 130 pm.

The material was loaded with silver in the same way as in example 1.

Example 5 - Loading of the porous polymer separation material with various metal ions.

Example 5a - Loading with Ag ⁺ .

g of dry polymer, prepared as described in example 1, were suspended with 20 ml of MeOH. After 1 h

AgNÜ3 (1.0 g, 6 mmol) dissolved in 2 ml of water was added. After 1 h, the polymer was washed with 20 ml of methanol, 50 ml of water and 50 ml of methanol and dried. Theoretical

0.36 x 169, 9 = 61.2 mg AgNO3 per gram of polymer.

Example 5b - Loading with Ag ⁺ .

g of dry polymer from example 1 were fluidized in 30 ml of methanol. After 5 min the resin was washed with water. The resin was then suspended in 40 ml of water and poured into a flash column (internal diameter of 20 mm). 1.5 g of silver nitrate dissolved in 100 ml of water (acidified with 1 drop of HNO3) was slowly passed through the column (approximately 6 to 8 h). The material was washed with distilled water (100 ml), followed by methanol (100 ml) and then dried in a vacuum oven.

Example 5c - Loading with Cu ²⁺ g of dry polymer from example 1 were suspended in 30 ml of methanol. After 5 min the resin was washed with water. The resin was then suspended in 40 ml of water and poured into a flash column (internal diameter of 20 mm). CUCI2 (1.4 g, 10 mmol) was resolved in 100 ml of water (pH 5). It was slowly passed through the column (approximately 6 to 8 h). The material was washed with water

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26/44 distilled (100 ml), followed by methanol (100 ml) and then dried in a vacuum oven.

The sample (2.4 g) was treated with 2M HCI (30 ml) for 1 h. The greenish water was evaporated to dryness.

157 mg of CuClz / 2.4 g of resin = 65.4 mg of CuCl2 (0.49 mmol) / g of resin.

Example 5d - Loading with Cu ⁺ g of dry polymer, from example 1, were suspended in 30 ml of aqueous acetonitrile (15:85). After 5 min, the resin was poured into a fiash column (internal diameter 20 mm). Copper (I) chloride CuCl (2.0 g, 20 mmol) was dissolved in 100 mL of aqueous acetonitrile (15:85), under nitrogen and left to stand before adding to the column. The metal solution was slowly passed through the column (approximately 6 to 8 h). The material was washed with distilled water (30 ml), followed by methanol (30 ml) and then dried in a vacuum oven.

A sample was treated with 2M HCI (30 ml) for 1 h. The wash water was evaporated to dryness, a green solid residue. 144.6 mg / 2.1 g resin = 69 mg (0.70 mmol resin / g).

Example 5e - Loading with Pd ²⁺

1.0 g of dry polymer, prepared as disclosed in example 1 (until loading), was fluidized in 3 ml of methanol. After 5 min the resin was washed with water. The resin was then fluidized in 4 ml of water and poured on a fiash column (internal diameter of 10 mm). PdC12 (0.6 g, 3 mmol) was dissolved in 10 mL of water (pH 5), was slowly passed through the column (approximately 6 to 8

H) . The material was washed with distilled water (10 mL),

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27/44 followed by methanol (10 mL) and then dried in a vacuum oven.

Example 5e - Loading with Zn ²⁺ g of dry polymer from example 1 were suspended in 530 ml of methanol. After 5 min the resin was washed with water. The resin was then fluidized in 40 ml of water and poured into a flash column (20 mm internal diameter). ZnCl2 (2.0 g, 15 mmol) was dissolved in 100 ml of water (pH 5), was slowly passed through the column (approximately 6 to 8 h). The material was washed with distilled water (10 ml) followed by methanol (100 ml) and then dried in a vacuum oven.

In some of the aforementioned examples the resin (s) is / are washed again and such additional washing steps may, for example, include washing with ethyl acetate, heptane, acetonitrile and cyclohexane. The need for the washing step and the washing solvent are within the ability of the skilled person to determine.

Example 6 - Dissociation of metal

a) 0.5 g of resin prepared according to the example

5a was washed with 5 mL of MeNH ₂ 33% in EtOH (ethanol) + 5 mL MeOH (methanol) in 0.5 h. 0 eluent has been evaporated, about 20 mg of brown residue. The residue was dissolved in 50 g in water + 2 drops of HNO3 cone. and the

amount of silver was determined by atomic absorption spectrometry (ASA) to be 67 mg AgNCb / g resin; or

b) 1.0 g of dry resin prepared according to example 5b was placed in a filter funnel. 20 ml of a 0.5 M aqueous sodium nitrate solution was slowly

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28/44 through the funnel (approximately 0.5 to 1 h). Approximately 2 ml of a 1 M sodium chloride solution was added to the eluted nitrate solution. The resulting silver chloride was allowed to precipitate for 4 h and was then collected, washed and dried at 130 ° C for 1 h. Gravimetric analysis of the collected solid shows 51.0 mg.

Example 7 - Limonene Loading Test,

Comparison between the resin of the invention and non-functionalized polymer

Standard / Loading solution: Paration, malation and etion in limonene, 25 pg / mL

Internal standard solution: pyrene in ethyl acetate, 50 pg / mL

200 mg of:

Polymer prepared according to Example 5A, treated with silver

DVB sulfonic acid polymer (NFP, non-functionalized polymer, prepared according to Example 1, but without the final metal treatment).

were packaged separately in 3 mL SPE cartridges (two per material).

mL of the standard solution was loaded 10 times on each SPE column and 10 fractions were collected per column. 50 pL of internal standard was added to each collector glass tube and solvent was evaporated before GC-MS analysis in order to increase the concentration levels of the samples. The result can be seen in Table 1. Where the numbers in the first column refer to 1 mL aliquots added in respectively 5 consecutive steps in the respective polymer.

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Table 1.

% of pesticides not retained by limonene Etion Malation Paration Polymer charge 1 0 0 3 Load 2 0 0 3 Load 3 0 0 0 Load 4 0 0 0 Load 5 0 0 0 Load 6 0 0 0 Load 7 0 0 0 Load 8 0 0 0 Load 9 0 0 0 Load 10 0 0 1 NFP Load 1 0 0 0 Load 2 19 35 76 Load 3 41 77 118 Load 4 61 89 105 Load 5 77 74 128

The results of the example clearly show that the polymeric separation material according to the invention, example 5a, efficiently removes (0% not retained) pesticides from limonene, while the same material without metal treatment (NFP) does not retain pesticides as much efficient.

Example 8 - Standard Lemon Oil Loading Test / Loading Solution: paration, malation and etion in lemon oil, 25 pg / mL

Internal standard solution: pyrene in ethyl acetate, pg / mL

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200 mg of polymer prepared in example 5a were packaged in 3 3mL SPE cartridges.

ml of the standard solution was loaded 6 times on each SPE column and 6 fractions were collected. 50 pL of internal standard was added to each collection glass tube and solvent was evaporated before collecting fractions in order to increase the concentration levels of the samples for analysis in GC-MS. The results are shown in Table 2.

Table 2.

% of unreacted pesticides from lemon Volume of loading (mL) Etion Malation Paration Load of polymer 1 0 23 1 Load 2 0 16 13 Load 3 0 12 15 Load 4 0 18 13 Load 5 0 14 12 Load 6 0 16 5

The results show that the polymeric separation material according to the invention, example 1, has a good ability to retain pesticides in essential oils represented in this experiment by commercially available lemon oil.

Example 9 - Citric Oil Loading Test,

Comparison between the resin of the invention and the Dowex polymer

Commercial material 1:

200 mg of DVB sulfonic acid polymer (commercial

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Dowex 50 W X 8-400 commercial; 38-75 pm), treated with silver ion, were packed in 3 ml SPE cartridges, example 2.

Material 2:

200 mg of polymer prepared in example 1, 20 to 90 pm, 5 treated with silver ion, as disclosed in example 5a, were packaged in 3 ml SPE cartridges.

ml of the standard solution in four different dilution systems was loaded five times and all fractions were collected separately.

50 pL of internal standard was added to each collector glass tube and solvent was evaporated before collecting the fractions in order to increase the concentration levels of the samples for analysis in GC-MS. The results are shown in table 3.

Table 3

% of pesticides not reacted Loading volume, mL Etion Malation Paration (citrus oil) 1 / material commercial 1 87 89 92 2 97 102 103 3 91 98 110 4 87 90 99 5 90 104 103 (citrus oil) 1 / Material 2 2 11 16 2 3 18 23 3 2 39 47 4 0 10 49 5 2 25 86

The results show that the separation material

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32/44 polymeric according to the invention, example 5a, (material 2) shows superior ability to retain pesticides, compared to material 1, in essential oils represented in this experiment by commercially available citric oil.

Example 10 - Extraction of other pesticides from limonene

Standard / Loading solution: bromopropylate, prochloraz, fention, methylparation and pyridapention in limonene, 10 pg / mL of internal standard solution: pyrene in ethyl acetate, 50 pg / mL

400 mg of polymer prepared in example 5a was packaged in a 3 ml SPE cartridge.

ml of standard solution was loaded 10 times on the SPE column and fractions were collected.

pL of internal standard was added to each collector glass tube and solvent was evaporated before collecting fractions in order to increase the concentration levels of the samples for analysis in GC-MS.

Table 4

% of pesticides that do not react they went Volume Methylparatio Pirimifosmeti Fentio Pyridapentium loaded n 1 n n , mL 1 0 0 0 0 2 0 0 0 0 3 0 0 0 0 4 0 0 0 0 5 0 0 0 0 6 0 0 0 0 7 0 0 0 0

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8 0 0 0 0 9 0 0 0 10 0 0 0

The results show that the polymeric separation material according to the invention, example 5a, shows good ability to retain structurally different pesticides, such as organothiophosphates (including, for example, heterocyclic derivatives).

Example 11 - Preparation of etiol-fortified grapefruit oil for the tea bag extraction and suspension extraction experiments. Tea bags: polypropylene, pore size 50 pm. Weigh 40.8 milligrams of ethion in a glass bottle. Transfer etion using grapefruit oil to 1 liter of grapefruit oil. Mix well using a magnetic stirrer for 15 minutes. The concentration of ethion in the oil is 4 0.8 mg / L. Take 0.5 L of fortified grapefruit oil for the tea bag extraction experiments and the other 0.5 L for suspension extraction experiments.

Extraction experiments

Take 0.5 L of etion-fortified grapefruit oil to a concentration of 40.8 mg / L and add a tea bag containing 1 gram of material from Example 5b. Continuously stir the oil on a magnetic stirrer. An oil aliquot was periodically collected and analyzed for the etion over a period of 24 hours. Details of the sampling times and the measured etion concentration are shown in table 2. The oil was transferred to another container at the end of the 24-hour period by discarding the tea bag.

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Table 5.

Start time Concentration % in etion of the experiment - etion measure - removed fur hours mg / L material O O 40.0 0.6 23, 0 44% 1.3 18.0 56% 1.8 14.2 65% 2.6 10.9 73% 3.4 8.7 79% 3.9 7.5 82% 4.4 6.3 84% 4.9 5.5 87% 5.5 5.3 87% 6, 0 4.2 90% 8.3 3.0 93% 24.0 Nd 100%

na = <1.0 ppm

Example 12 - Suspension mode extraction experiments

Take 0.5 L of etion-enriched grapefruit oil to a concentration of 40.8 mg / L and add 1 gram of material from Example 5b directly into the grapefruit oil. Continuously stir the oil on a magnetic stirrer. An aliquot of the oil was periodically collected and analyzed for the etion over a period of 24 hours. Details of the sampling times and the measured etion concentration are shown in table 3. At the end of the 24-hour period, the oil is filtered through Munktell # 3 filter paper.

Table 6

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Time to leave Concentration % in etion from the beginning of etion measure in removed fur experiment oil (mg / L) material - mode (hours) suspension O O 40.0 O O 39, 9 0.6 22.1 46% 1.3 17.4 57% 1.8 14.5 65% 2.6 10.3 75% 3.4 7.5 82% 3.9 6.7 83% 3.9 6.2 85% 4.4 5.1 88% 4.9 4.7 89% 5.5 5.1 88% 6, 0 4.3 89% 8.3 2.6 94% 24.0% Nd 100%

na = <1.0 ppm

Example 13 - Removing pesticides from grapefruit oil

400 mg of polymer prepared in example 5b were prepared in a 3 ml SPE cartridge.

1 mL of standard solution was loaded 10 times on each SPE column and 10 fractions were collected. 50 pL of internal standard was added to each collection glass tube and solvent was evaporated before collecting fractions in order to increase the concentration levels of samples for analysis in GC-MS. The results are shown in Table 7.

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Table

Fention O O O O O O O O O O Pirimiphos methyl O O O O O O O t — 1 t — 1 Cs] Bromopropylate 54 LO 64 co 87 65 85 co CO Methylparation 11 14 11 14 14 20 16 20 19 24 Prochloraz 12 57 co 60 60 81 62 81 66 co Chlorpyrifos O O O O O O O O t — 1 t — 1 Imazalil O O O O O O O O O O Standard solution grapefruit oil fortified with 2 5 ppm of pesticide respective t — 1 Cs] cn LO LO co cn 01

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Example 14 - removal of pesticides from orange oil. 400 mg of polymer prepared in example 5b prepared in order to obtain different particle sizes were packaged in 3 3 ml SPE cartridge.

1 mL of standard solution was loaded 10 times, containing ppm of each pesticide in each SPE column and 10 fractions were collected. 25 pL of internal standard, pyrene solution (50 ppm), was added to each collector glass tube and the solvent was evaporated before collecting the fractions in order to increase the concentration levels of the samples for analysis in GC-MS. The results are shown in Table 8. Checking the performance of batches with different particle sizes in column mode (SPE)

Table 8

Fraction of loading by material % of pesticides not retained Etion Malation Paration 1 (244 pm); 0 0 0 2 (244 pm); 0 0 0 3 (244 pm); 0 0 0 4 (244 pm); 0 0 2 5 (244 pm); 0 3 3 6 (244 pm); 0 0 1 (244 pm); 0 0 2

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7 1 (394 pm); 4 16 11 2 (394 pm); 1 6 4 3 (394 pm); 0 3 2 4 (394 pm); 0 2 3 5 (394 pm); 1 5 8 6 (394 pm); 0 3 4 7 (394 pm); 0 2 12 1 (108 pm); 0 0 0 2 (108 pm); 0 0 0 3 (108 pm); 0 0 0 4 (108 pm); 0 0 0 5 (108 pm); 0 0 0 6 (108 pm); 0 0 0 7 (108 pm); 0 0 0 (130 pm); 0 0 0

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1 2 (130 pm); 0 0 0 3 (130 pm); 0 0 0 4 (130 pm); 0 0 0 5 (130 pm); 0 0 0 6 (130 pm); 0 0 1 7 (130 pm); 0 0 1

Example 15 - Removing pesticides from lemon oil.

400 mg of polymer prepared in example 5b prepared to obtain different particle sizes were packaged in a 3 ml SPE cartridge.

1 mL of the standard solution was loaded 10 times containing ppm of each pesticide, in each SPE column and 10 fractions were collected. 25 pL of internal standard, pyrene solution (50 ppm), was added to each collector glass tube and solvent was evaporated before collecting fractions to increase sample concentration levels for analysis in GC-MS. The results are shown in Table 9. Checking the performance of batches with different particle sizes in column mode (SPE)

Table 9

Fraction of loading by material % of pesticides not retained Etion Malation Paration

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(244pm); 1 0 0 0 (2 4 4μπι); 2 0 0 0 (244pm); 3 0 0 0 (244pm); 4 0 0 0 (2 4 4μπι); 5 0 0 22 (2 4 4μπι); 6 0 2 30 (2 4 4μπι); 7 0 3 29 (394μπι); 1 2 20 37 (394μπι); 2 0 2 20 (394μπι); 3 4 21 42 (394μπι); 4 0 5 35 (394μπι); 5 3 16 55 (394μπι); 6 1 12 56 (394μπι); 7 0 9 54 (108μπι); 1 0 0 0 (108μπι); 2 0 0 0 (108μπι); 3 0 0 0 (108μπι); 4 0 0 0 (108μπι); 5 0 0 0 (108μπι); 6 0 0 0 (108μπι); 7 0 0 0 (130μπι); 1 0 0 0 (130μπι); 2 0 0 0 (130μπι); 3 0 0 0 (130μπι); 4 0 0 0 (130μπι); 5 0 0 0 (130μπι); 6 0 0 0 (130μιη); 7 0 0 0 (60 μπι); 1 0 0 0

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(60 pm); 2 0 0 0 (60 pm); 3 0 0 0 (60 pm); 4 0 0 0 (60 pm); 5 0 0 0 (60 pm); 6 0 0 0 (60 pm); 7 0 0 0

Example 16 - Lemon Oil Loading Test. 400 mg of polymer prepared in example 3 prepared to obtain different particle sizes were packaged in 3 ml SPE cartridges.

1 mL of standard solution was loaded 10 times, containing ppm of each pesticide in each SPE column and 10 fractions were collected. 25 pL of internal standard, pyrene solution (50 ppm), was added to each collector glass tube and the solvent was evaporated before collecting the fractions in order to increase the concentration levels of the samples for analysis in GC-MS. The results are disclosed in the Table

10.

Table 10

% of pesticides not retained Loading fraction by material Etion Malation Paration 1 0 0 28 2 0 0 29 3 0 0 27 4 0 0 81 5 0 0 93 6 0 0 79 7 0 0 78 8 0 0 91 9 0 0 95

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10 0 0 95

Example 17 - Loading Test for Oil

Lemon.

400 mg of polymer prepared in example 5e.

mL of the standard solution was loaded 10 times containing

25 ppm of each pesticide in each SPE column and 10 fractions were collected. 25 pL of internal standard, pyrene solution (50 ppm) was added to each collection glass tube and solvent was evaporated before collecting the fractions in order to increase the concentration levels of samples for analysis in GC-MS. The results are shown in Table 11.

Table 11

% of pesticides not retained Fraction of loading by material Etion Malation Paration 1 1 0 0 2 1 0 0 3 1 0 0 4 1 0 0 5 1 0 0 6 8 0 0 7 1 0 0

Example 18 - Lemon Oil Loading Test. 400 mg of polymer prepared in examples 5c, 5d and 5f prepared in order to obtain different particle sizes were packaged in a 3 ml SPE cartridge.

ml of standard solution was loaded 10 times containing 25 ppm of etion in each SPE column and 10 fractions were

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43/44 collected. 25 pL of internal standard, pyrene solution (50 ppm), was added to each collector glass tube and solvent was evaporated before collecting fractions in order to increase the concentration levels of samples for analysis in GC-MS. The results are shown in Table 12.

Table 12

Fraction in O. "O in etion Fraction in O. "O in etion loading not withheld loading not withheld Polymer Cu 1 2 Zn polymer 1 2 Polymer Cu 2 26 Zn polymer 2 48 Polymer Cu 3 55 Zn polymer 3 60 Polymer Cu 4 58 Zn polymer 4 61 Polymer Cu 5 52 Zn polymer 5 60 Polymer Cu 6 60 Zn polymer 6 61 Polymer Cu 7 55 Zn polymer 7 61 Polymer Ass 68 (I) 1 Polymer Ass 20 (I) 2 Polymer Ass 5 (I) 3 Polymer Ass 4 (I) 4 Polymer Ass 23 (I) 5 Polymer Ass 35 (I) 6 Polymer Ass 35 (I) 7

400 mg of polymer prepared in examples 5c, 5d and 5f

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44/44 prepared in order to obtain different particle sizes were packaged in 3 mL of SPE cartridge.

ml of the standard solution was loaded 10 times containing 25 ppm of ethion in each SPE column and 10 fractions were collected. 25 pL of internal standard, pyrene solution (50 ppm) was added to each collection glass tube and solvent was evaporated before collecting fractions in order to increase the concentration levels of samples for analysis in GC-MS. The results are shown in Table 13.

Table 13

Fraction in % of etion Fraction in % of etion not loading not withheld loading withheld Polymer Cu 1 2 Zn polymer 1 2 Polymer Cu 2 26 Zn polymer 2 48 Polymer Cu 3 55 Zn polymer 3 60 Polymer Cu 4 58 Zn polymer 4 61 Polymer Cu 5 52 Zn polymer 5 60 Polymer Cu 6 60 Zn polymer 6 61 Polymer Cu 7 55 Zn polymer 7 61 Polymer Cu (I) 1 68 Polymer Cu (I) 2 20 Polymer Cu (I) 3 5 Polymer Cu (I) 4 4 Polymer Cu (I) 5 23 Polymer Cu (I) 6 35 Polymer Cu (I) 7 35

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Claims (16)

1. Porous polymeric separation material, CHARACTERIZED by the fact that: contain pores in the mesoporous region; 2/4 according to any one of claims 1 to 5, CHARACTERIZED by the fact that the porous polymeric separation material is a copolymer of divinylbenzene and styrene substituted with one or more group (s) 2. Porous polymeric separation material, according to claim 1, CHARACTERIZED by the fact that the metal ion is selected from the group consisting of Ag ⁺ or Pd ²⁺ . 3/4 or salts thereof; and / or B. the crosslinking monomer is selected from divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or any combination 4/4 claims 12 to 14, CHARACTERIZED by the fact that said product is an essential oil or a combination of essential oils. 5 of these. 5 functional / functional selected (s) from the group consisting of sulfonic acid and carboxylic acid; or a copolymer of divinylbenzene and a polymerizable tertiary alkylamine. Porous polymeric separation material according to any one of claims 1 to 4, CHARACTERIZED by the fact that the material has a capacity between 0.2 and 1.0 mmol / g of material. 30 6. Porous polymeric separation material, of Petition 870180031293, of 04/18/2018, p. 52/56 5 have a total surface area> 50 m ² / g of material and a pore volume between 0.2 and 1.2 ml / g of material, as determined by the BET analysis and the material comprises one or more group (s) functional / functional bonded to one or more metal ion (s) selected from the Porous polymeric separation material according to any one of claims 4 to 6, 8. Method of preparing a polymeric separation material as defined in any one of the claims 9. Method, according to claim 8, 25 CHARACTERIZED by the fact that The. the functional monomer is selected from the group consisting of vinylbenzenesulfonic acid, such as 4-vinylbenzenesulfonic acid; vinylbenzyliminodiacetic acid, such as 4-vinylbenzyliminodiacetic acid; derived from Polymerizable tertiary alkylamines; or a combination Petition 870180031293, of 04/18/2018, p. 53/56 10 11. Method according to claim 10, CHARACTERIZED by the fact that the ammonium salt is tributylammonium salt or tetrabutylammonium salt. 10. Method according to claim 9, CHARACTERIZED by the fact that the functional monomer is an ammonium salt of vinylbenzenesulfonic acid or an ammonium salt of vinylbenzylinimodiacetic acid. 10 CHARACTERIZED by the fact that said (s) one or more functional / functional group (s) is / are selected from sulfonic acid. 10 group consisting of Cu ⁺ , Ag ⁺ , Pd ²⁺ , Cu ²⁺ or Zn ²⁺ . 12. Method of separating a pesticide from a food product or feed, CHARACTERIZED by the fact that it 13. Method, according to claim 12, CHARACTERIZED by understanding 20 forming a ternary complex between the porous polymeric separation material and the pesticide; collect the purified food or feed product; and eluting said pesticide. 14. Method according to claim 12 or 13, 25 CHARACTERIZED by the fact that said pesticide is selected from organophosphate pesticides, organothiophosphate pesticides or pesticides containing aryl groups containing heteroatoms selected from nitrogen and sulfur, or any combination thereof. 30 15. Method, according to any of the Petition 870180031293, of 04/18/2018, p. 54/56 Contacting the food product or feed with a porous polymeric separation material as defined in any one of claims 1 to 7. 15 1 to 7, CHARACTERIZED by the fact that it provides a functional monomer, a crosslinker monomer, optionally an initiator and a porogen; polymerize; obtaining a porous polymeric material; Contacting said porous polymeric material with one or more metal ions (s) selected from the group consisting of Cu ⁺ , Ag ⁺ , Pd ²⁺ , Cu ²⁺ or Zn ²⁺ ; and obtaining a porous polymeric separation material. 15 3. Porous polymeric separation material according to claim 1 or 2, CHARACTERIZED by the fact that the pores in the mesoporous region have a pore surface area> 50 m ² / g of material determined by BET analysis. 4. Porous polymeric separation material according to any one of claims 1 to 3, CHARACTERIZED by the fact that said one or more functional group (s) are selected from the group consisting of sulfonic acid, carboxylic acid and 25 tertiary alkylamine. 16. Method, according to claim 15, 5 CHARACTERIZED by the fact that said essential oils are made of citrus fruits, sweet orange, lemon, lime, bergamot, mandarin and mandarin and grapefruit, or any combination of these. Petition 870180031293, of 04/18/2018, p. 55/56