CN102234355B - Synthetic method of molecule marking polymer particles or beads conducting selective detoxification on natural water polluted by endosulfans, analogs or derivatives, and product - Google Patents

Abstract

The invention relates to a synthetic method of molecule marking polymer particles or beads conducting selective detoxification on natural water polluted by endosulfans, analogs or derivatives, and a product. The invention more specifically relates to a crosslinking polymer composition through a molecule marking technology based on non-covalent strategy. The preparation of the crosslinking polymer particles and beads comprises the steps of adding functional monomers and additional monomers to chlorendicacid (template), and polymerizing with proper cross-linking agents and initiators. The invention also describes a method for completely removing endosulfans, analogs or derivatives from contaminated deionized water and polluted natural water, and for removing particles or beads of regeneration fake template markings by using methanol and ethanol.

Description

Synthesis method of molecularly imprinted polymer particles or microbeads for selective detoxification of natural water polluted by endosulfan, its analogs or derivatives and products thereof

technical field

The present invention relates to molecularly imprinted polymer particles or microbeads for selective detoxification of natural water polluted by endosulfan, its analogues or derivatives, and a method for its preparation. The present invention also relates to methods of using said polymer composition for the removal of endosulfan, its analogues or derivatives. More particularly, the present invention provides methods for the preparation of chlorendenic acid-imprinted polymer compositions which are useful for the selective removal of endosulfan, its analogues or derivatives from polluted natural waters. useful. the

Background technique

Detoxification of pesticide-contaminated samples has historically been performed by photocatalytic degradation (Evgenidou, E, Konstantinou, I., Fytianos, K., Poligs, I., Water research 41 (2007) 2015; Arques, A. Armat, A. M. Garcia Ripoli , A, Vicente, R., J. Hazard. Mater. 146 (2007) 447), biodegradable or carbon materials, metal nanoparticles/layered double hydroxides or microbial support materials or biodegradable polymers. the

Regarding the use of different microbial carrier materials to develop a biodegradation process for endosulfan, refer to Lee et al., J.Agric.Ford Chan 54(2006) 8824; HernandezRodrigeuz et al., World J.Microbiol.Biotechnol.22(2006) 753 Mersie et al. Agric. Ecosystems. Environ. 97 (2003) 215. Refer to Aslan & Turkman, on removal of endosulfan and nitrate by: Biological denitrification (Process Biochem.41(2006)882; 40(2005)935; 40(2005)417Environ.Int.30(2004)449), and the use of biodegradable polymers (Boley et al., Acta Hydrochim. Hydrobiol. 31 (2003) 195). the

References are made on the removal of endosulfan by: carbon materials (Mishra and Patel, J. Hazard. Mater. 152 (2008) 730; Gupta and Ali, Environ. Sci. Technol. 42 (2008) 766; Sudhakar and Dixit, J.Environ.Engg.134(2008) 102), metal nanoparticles (Nair et al., J.Environ.Monit.5(2003) 363), and layered double hydroxides (Park et al., J.Phys. & Chem.of solids, 65(2006)513). the

Imprinted materials are preferred over the above-cited materials because they are more environmentally friendly and have minimal disposal problems due to reduced poisoning due to the degree of macromolecular recognition and avoid frequent replacements in view of the high adsorption capacity . Thus, imprinted polymer materials are used for: removal of gasoline additive MTBE (Leone, U.S. Patent No. 6783,686; 2004), removal of caffeine (Leone, U.S. Patent No. 6,322834; 2001), removal of Impurities (Ersoz et al., Sep.Purif.Technol.38 (2004) 173), removal of clavulanic acid (Mosbach, U.S. Patent No. 7,084,748; 2006), removal of Cd (Denizli et al., J.Chromatogr.B 811 (2004 )119), and remove Al (Ind.Engg.Chem.Res.45(2006)178), remove Cu (Qi et al., Front.Chem.Engg.China 2(2008)109); For the removal of phosphate, nitrate and iron ions (Murray, US Patent No. 7,279,096, 2007; 6,780,323; 2004). A reference may be U.S. Patent No. 0,054,949; 2003 to Chang et al. Utilizing immobilized metal chelate complexes for the decontamination of organophosphorus pesticides and CWA's. the

The disadvantages of the above techniques are mainly that the templates used for the preparation of imprinted polymer materials intended for detoxification studies are highly toxic, persistent and still leave traces after thorough washing. A good solution to this problem is to use template analogs, ie "mimetemplates" or "pseudo-templates" of the original template, which are relatively non-toxic, cheaper and eliminate leakage of toxic templates into hazardous environmental samples after processing. For the following substances, regarding the use of trialkylamine, N-(4-isopropylphenyl)-N'-butylene urea, nickel(II) phthalocyanine tetrasulfonate, hyoscyamine and nickel(II) as pseudotemplates , the references are: atrazine (Matsui et al., Anal.Chem.72(2000) 1810), phenylurea herbicide (wang et al., 540(2005) 307), hemin (Jacob et al., J . Phys.chem.A 112 (2008) 3221), scopolamine (Theodoridis et al., J. Chromatogr. A, 987 (2003) 103) and uranium (Rao et al., manuscript in preparation). It is evident from the prior art that there has hitherto been no method for detoxifying natural water contaminated with pesticides. the

Purpose of the invention

The main purpose of the present invention is to provide molecularly imprinted polymer particles or microbeads for selective detoxification of natural water bodies polluted by endosulfan, its analogs or derivatives, and its preparation. the

Another object of the present invention is to provide a method for preparing molecularly imprinted polymer particles or microbeads. the

Another object of the present invention is to provide a method for removing endosulfan, its analogs or derivatives from aqueous solutions using molecularly imprinted polymer particles or microbeads. the

Another object of the present invention is to select non-toxic "pseudo-template" molecules of endosulfan and to provide a method for preparing said molecularly imprinted polymer particles or microbeads. the

Another object of the present invention is to provide an environmentally friendly and green technology for detoxification of water bodies polluted by endosulfan, its analogs or derivatives. the

Summary of the invention

The present invention relates to a method of synthesizing chlorendic acid-imprinted polymer particles or beads having accessible and uniform sites for Selective and complete reconjugation of endosulfan, its analogs or derivatives in natural water bodies. This enables the detoxification of pesticide-containing samples. The pseudo-templated polymer composition for the selective removal of endosulfan has the formula:

A _(x) B _(y) C _(z) D _(f)

where A is chlorendic acid (CA) (pseudo template), B is 4-vinylaniline (VA) (functional monomer), C is acrylamide (AA) (additional monomer), D is ethylene glycol di Methacrylate (EGDMA) or 1,1,1-tris(methylolpropane trimethacrylate (TRIM)) (crosslinking monomer) in a molar ratio of 1:2:1:15 to 1:5 :3:30, 2,2'-azobisisobutyronitrile (AIBN) was also added thereto. the

In this method, the polymerization proceeds thermally and washes with methanol to remove the pseudotemplate, resulting in leached molecularly imprinted polymer particles or beads that selectively collect endosulfan and are able to remove endosulfan. the

The following examples are given in order to illustrate how the invention works in practice and should therefore not be construed as limiting the scope of the invention in any way. the

Brief description of the drawings

Figure 1 shows the structural formulas of endosulfan and chlorendic acid. the

Figure 2 shows the relationship between the amount of MIP beads and endosulfan removal in the detoxification study of Example 7. the

Figure 3 shows the effect of pH on endosulfan removal in the detoxification study of Example 7. the

Fig. 4 schematically describes the process of the present invention. the

Figure 5 is an electron micrograph of pseudo-template imprinted polymer beads. the

Detailed description of the invention

While the present invention is susceptible to various changes and substitutions, specific aspects thereof have been shown by the examples and will be described in detail below. It should be understood, however, that there is no intent to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all changes, equivalents and alternatives falling within the spirit and scope of the invention as defined by the appended claims . the

The terms "comprises", "includes" or any other variation thereof are intended to cover a non-exclusive inclusion and not only those examples. the

In the following detailed description of aspects of the invention reference is made to embodiments which form a part hereof and in which are shown for purposes of illustration specific aspects in which the invention may be practiced. The aspects are described in detail to enable those skilled in the art to practice the invention. It is to be understood that other aspects may be utilized and changes may be made without departing from the scope of the present invention. The following description is therefore not limiting, and the scope of the invention is only defined by the appended claims. the

Therefore, the present invention provides a molecularly imprinted polymer particle or microbead for selective detoxification of natural water bodies polluted by endosulfan, its analogs or derivatives, and its preparation. The present invention also provides a method of preparing pseudotemplated polymer particles or microbeads, the method comprising:

a) select the false template chlorendic acid, which is a structural analog of endosulfan;

b) form a non-covalent complex between chlorendic acid and 4-vinylaniline;

c) dissolving the above complex and additional monomeric acrylamide in hexane or tetrahydrofuran (porogen);

d) the mixture of step c) is combined with crosslinking monomer and initiator;

e) adding an aqueous solution of polyvinyl alcohol in the case of preparing MIP microbeads;

f) thermally polymerizing the above-mentioned synthetic mixture;

g) in the case of polymer particles, grinding and sieving;

h) Washing away false templates from the aforementioned coarse MIP material particles or microbeads. the

In one embodiment of the present invention, the method for the synthesis of chlorendic acid molecularly imprinted polymer particles or microbeads for the selective detoxification of natural water bodies polluted by endosulfan, its analogs or derivatives comprises the following steps :

a. Linking templates with functional monomers via non-covalent interactions, and subsequent addition of additional monomers;

b. dissolving the monomer mixture obtained in step a) in an organic solvent by stirring;

c. adding crosslinking monomer and initiator to the mixture obtained in step b);

d. the mixture obtained in step c) is cooled to 0° C., purged with nitrogen for a period of 10-15 minutes, then sealed, and heated with stirring in an oil bath at about 80° C. for about 30 minutes;

e. washing the polymer material obtained in step d) with distilled water, then drying overnight;

f. Grinding and sieving the polymer material obtained from step e) to obtain molecularly imprinted polymer particles of chlorendic acid;

g. Add polyvinyl alcohol aqueous solution dropwise to the mixture obtained in step c), and follow the procedures of steps d) to f) to obtain chlorendic acid molecularly imprinted polymer (MIP) microbeads. the

In another embodiment of the invention, the template used is chlorendic acid. the

In yet another embodiment of the present invention, the functional monomer used is 4-vinylaniline. the

In another embodiment of the invention, the additional monomer used is acrylamide. the

In yet another embodiment of the present invention, the crosslinking monomer is selected from EGDMA (ethylene glycol dimethacrylate) and TRIM (1,1,1-tris(methylolpropane trimethacrylate).

In another embodiment of the invention, the initiator used is AIBN (2,2'-azobisisobutyronitrile). the

In yet another embodiment of the present invention, the organic solvent used in step b) is selected from hexane and tetrahydrofuran. the

In yet another embodiment of the present invention, the chlorendic acid molecularly imprinted polymer ( MIP) particles or microbeads have the following formula:

A _(x) B _(y) C _(z) D _(f)

where A is chlorendic acid (CA), B is 4-vinylaniline (VA), C is acrylamide (AA), and D is ethylene glycol dimethacrylate (EGDMA) or 1,1,1- Tris(methylolpropane trimethacrylate (TRIM)), the molar ratio is in the range of 1:2:1:15 to 1:5:3:30. the

In yet another embodiment of the present invention, the method of detoxifying deionized water doped with ethanol solutions of endosulfan, its analogs or derivatives using chlorendenic acid molecularly imprinted polymer (MIP) particles or microbeads comprises the following steps:

a. reflux the polymer particles or beads of chlorendic acid molecularly imprinted obtained in step f) and step g) of claim 1 together with methanol in a Soxhlet extractor to remove chlorendic acid, thereby obtain leached molecularly imprinted polymer particles or beads;

b. Stirring the leached molecularly imprinted polymer particles or beads obtained in step a) with the endosulfan-containing sample, and then filtering;

c. Determination of the endosulfan content in the filtrate by spectrometry. the

In yet another embodiment of the present invention, the concentration of the ethanol solution of endosulfan, its analogs or derivatives polluting deionized water and natural river water is in the range of 5 to 500 μg. the

In yet another embodiment of the present invention, the percentage removal of endosulfan, its analogues or derivatives from the polluted river water solution is determined by spectrometry using 4-(4-nitrobenzyl)pyridine reagent . the

In yet another embodiment of the present invention, >99% removal of endosulfan, analogs or derivatives thereof was observed using pseudo-template imprinted and non-imprinted polymer beads. the

In yet another embodiment of the present invention, the method of regenerating said chlorendenic acid-imprinted polymer particles or beads comprises equilibrating the used template-imprinted polymer particles or beads with alcohol. the

In yet another embodiment of the present invention, the alcohol is selected from methanol and ethanol. the

Example 1

Synthesis of chlorendic acid-imprinted and non-imprinted polymer particles using ethylene glycol dimethacrylate (EGDMA)

1.0mmol of chlorendic acid (CA) (0.39g), 2.0mmol of 4-vinylaniline (VA) (0.24g) and 1.0mmol of acrylamide (AA) (0.07g) were placed in a 50ml round bottom flask and dissolved in 10 ml of hexane with stirring and cooled to 0°C. 20 mmol of ethylene glycol dimethacrylate (EGDMA) (4 ml) and 50 mg of 2,2'-azobisisobutyronitrile (AIBN) were added thereto and stirred until a uniform solution was obtained. The monomer mixture was then cooled to 0 °C, purged with _N2 for 10 min, sealed and heated in an oil bath at 80 °C while stirring for about 30 min. The resulting material was washed with distilled water, dried overnight and ground to fine particles in a mortar and pestle. The chlorendic acid-imprinted polymer particles were refluxed with methanol for 4 hours in a Soxhlet extractor, filtered, washed with 500 ml of distilled water and left overnight to dry. Non-imprinted polymeric materials were similarly prepared without incorporation of chlorendic acid (dummy template) in the polymer mixture.

Example 2

Synthesis of chlorendic acid-imprinted and non-imprinted polymer particles using 1,1,1-tris-(hydroxymethyl)-propane trimethacrylate (TRIM)

1.0mmol of chlorendic acid (CA) (0.39G), 2.0mmol of 4-vinylaniline (VA) (0.24g) and 1.0mmol of acrylamide (AA) (0.07g) were placed in a 50ml round bottom flask and dissolved in 10 ml of hexane with stirring and cooled to 0°C. 20 mmol of 1,1,1-tris-(hydroxymethyl)-propane trimethacrylate (TRIM) (7 ml) and 50 mg of 2,2'-azobisisobutyronitrile (AIBN) were added thereto and stirred until a homogeneous solution is obtained. The monomer mixture was then cooled to 0 °C, purged with _N2 for 10 min, sealed and heated in an oil bath at 80 °C while stirring for about 30 min. The resulting material was washed with distilled water, dried overnight and ground to fine particles in a mortar and pestle. CA imprinted polymer particles (2 g) were refluxed with methanol for 4 hours in a Soxhlet extractor, filtered, washed with 500 ml of distilled water and kept overnight to dry. Non-imprinted polymer particles were similarly prepared without incorporation of the chlorendic acid pseudotemplate in the monomer mix.

Example 3

Synthesis of chlorendic acid-imprinted polymer microbeads

1.0mmol of CA (0.39g), 2.0mmol of VA (0.24g) and 1.0mmol of AA (0.07g) were placed in a 100ml round bottom flask and dissolved in 5ml of tetrahydrofuran (THF) by stirring, followed by It was cooled to 0 °C. 20 mmol of TRIM (7 ml) and 50 mg of AIBN were added thereto and stirred until a homogeneous solution was obtained. 50 ml of 0.5% (w/v) polyvinyl alcohol aqueous solution (prepared by heating to 60 °C) _was added dropwise to the monomer mixture during 30 min, and it was cooled to 0 °C, purged with N for 10 min, and sealed And heated in an oil bath of 80° C. while stirring for about 3 hours. The resulting microbeads were filtered, dried at 50° C. and then refluxed with methanol in a Soxhlet extractor for 4 hours. The resulting washed beads were filtered, washed again with 500 ml of water and dried at 50°C. This yielded 7.05 g of pseudo-template imprinted polymer beads (see Figure 5).

Example 4

Synthesis of non-imprinted polymer microbeads

2.0 mmol of VA (0.24 g) and 1.0 mmol of AA (0.07 g) were placed in a 100 ml round bottom flask and dissolved in 5 ml of THF by stirring, which was then cooled to 0°C. 20 mmol of TRIM (7 ml) and 50 mg of AIBN were added thereto and stirred until a homogeneous solution was obtained. 50 ml of 0.5% (w/v) aqueous polyvinyl alcohol solution (prepared by heating to 60 °C for 2 h) was added dropwise to this monomer mixture during 30 min, and it was cooled to 0 °C and purged with N for ₁₀ min , sealed and heated in an oil bath at 80° C. with stirring for 3 hours. The resulting microbeads were filtered, dried at 50° C. and then refluxed with methanol in a Soxhlet extractor for 4 hours. The resulting washed beads were filtered, washed again with 500 ml of distilled water and dried at 50°C. This yielded 7.78 g of non-imprinted polymer beads.

Example 5

Selective removal of endosulfan, its analogs or derivatives from deionized water by imprinted and non-imprinted polymeric materials prepared as described in Examples 1 and 2

20 mg of imprinted polymer and non-imprinted polymer particles prepared according to the procedure described in Examples 1 and 2 were transferred to a conical flask (250 ml) with a stopper. 100 ml of deionized water spiked with a freshly distilled ethanol solution of endosulfan, its analogs or derivatives (concentration: 1.0 ml of 500 ppm) was added thereto and stirred for 30 min. The polymer particles were filtered off and the collected endosulfan, its analogs or derivatives were obtained by spectrophotometrically measuring the concentration of the collected endosulfan, its analogs or derivatives in the filtrate using 4-(4-nitrobenzyl)pyridine. The amount of its analogs or derivatives. With molecularly imprinted polymer (MIP) and non-imprinted polymer (NIP) materials prepared according to the procedure described in Example 1 using EGDMA as the crosslinking monomer, removal rates of 61.7 and 28.0% were obtained . Similarly, imprinted polymeric materials prepared following the procedure described in Example 2 using TRIM as a crosslinker gave >98% removal of endosulfan, its analogs or derivatives (after accounting for its degradation). the

Example 6

Selective removal of endosulfan, its analogs or derivatives from deionized water by template-imprinted polymer and non-imprinted polymer beads as described in Examples 3 and 4

10 mg of template-imprinted polymer and non-imprinted polymer beads prepared as described in Examples 3 and 4 were transferred to a stoppered conical flask (250 ml). To this was added 100 ml of deionized water spiked with 1 ml of a freshly prepared ethanol solution of endosulfan, its analogs or derivatives (500 μg) and stirred for 30 min. The polymer beads were filtered off and the collected sulfur was obtained by measuring the concentration of collected endosulfan, its analogue or derivative in the filtrate spectrophotometrically using 4-(4-nitrobenzyl)pyridine reagent. The amount of Dan, its analogs or derivatives. >98% and 59.5% yield of endosulfan, its analogs or derivatives were obtained using pseudo-template-imprinted polymer and non-imprinted polymer beads prepared according to the procedure described in Examples 3 and 4, respectively. Extraction yield (after accounting for its degradation). the

Example 7

Selective removal of endosulfan, its analogs or derivatives from natural water samples using chlorendenic acid (pseudo-template)-imprinted polymer beads prepared as described in Example 3

10 mg of chlorendic acid (pseudo-template)-imprinted polymer beads prepared as described in Example 3 were transferred to a stoppered conical flask (250 ml) containing a mixture of dissolved 100 ml river water sample (collected at Karamana River, Trivandrum, India) of 500 μg endosulfan in 1 ml freshly distilled ethanol. The polymer beads were filtered off and the percent removal of endosulfan, endosulfan, its analogues or derivatives thereof from the aqueous solution doped with it was determined spectrophotometrically by using a 4-(4-nitrobenzyl)pyridine reagent. The detoxification rate of the substance. Complete removal of endosulfan, its analogues or derivatives was obtained at all concentrations with as little as 10 mg of chlorendic acid-imprinted beads. Additionally, the pseudo-template imprinted beads could be regenerated by equilibrating them with 10 ml of methanol without any loss in the uptake capacity of the beads for endosulfan. the

Salient features of the present invention include the following:

i) Selection of nontoxic pseudotemplates. the

ii) Synthesis of tailored MIP materials in the form of particles or microbeads by thermal polymerization. the

iii) Washing the polymeric material or microbeads to release the false template. the

iv) Detoxification of endosulfan-contaminated water. the

i) Selection of false templates

Because endosulfan is highly toxic (maximum permissible level = 20 ppb in drinking water) and persistently stable with an estimated half-life of 0.7-6 years. Chlorendenic acid, a structural analogue, was therefore chosen as a pseudotemplate (see Figure 1). the

ii) Synthesis of tailored pseudo-template MIP particles or microbeads

There are two main steps in the synthesis of pseudotemplated particles or microbeads: a) preparation of a polymer mixture containing chlorendic acid, vinylaniline, acrylamide and AIBN and b) thermal polymerization prepared as previously described mixture. the

iii) Washing MIP particles or beads

The MIP particles or microbeads synthesized in step II were washed by refluxing methanol in a Soxhlet extractor for ~4 hours to remove false templates, then they were scrubbed in water and dried, and they could be used to remove the false templates from deionized water. or natural water samples to remove endosulfan, its analogs or derivatives. the

iv) Detoxification research

The removal of endosulfan from deionized aqueous solutions has been performed using MIP beads and monitored spectrophotometrically. Various parameters responsible for achieving quantitative removal have been optimized. the

a. Amount of MIP beads

Optimization of the amount of MIP beads was performed with a fixed concentration of endosulfan (50 μg/mL in deionized water). The amount of MIP beads was varied within the range of 0.005-0.02 g. The results are shown in Figure 2, from which it was observed that quantitative removal could be achieved with a minimum of 10 mg of MIP beads. Under the same conditions, the meaningful detoxification efficiency of NIP is -50%. These observations can be attributed to imprinting effects. Therefore, MIP beads have been used for further studies. the

b.pH effect

The percent removal was quantitative when using 10 mg of MIP beads for 50 μg/mL of endosulfan in deionized water at a pH in the range of 6.0-7.5. At acidic (pH<2) and basic (pH>9) pH, there was no significant removal due to decomposition of endosulfan under these conditions (Figure 3). the

c. Effect of concentration and stirring time

A minimum of 5 min is sufficient for the quantitative removal of 5 μg/mL endosulfan from 100 mL of deionized water. An increase in removal was observed when the endosulfan concentration was increased from 0.05 μg/mL to 5 μg/mL with 10 mg beads. the

d. Influence of water phase volume

The solubility of endosulfan, its analogs or derivatives in aqueous solution is very low (ppb level). Therefore, the preconcentration ability of the material to remove endosulfan, its analogs or derivatives from deionized aqueous solutions has been tested by varying the volume of the aqueous phase from 25 mL to 100 mL. It was observed from this study that quantitative removal of endosulfan from 100 mL of aqueous solution is possible using as little as 10 mg of material. the

e. Detoxification rate of river water samples

The efficiency of endosulfan removal from collected river water samples has been studied by doping with known amounts of endosulfan, its analogues or derivatives. The results obtained are presented in Table 1, from which it can be seen that complete removal of endosulfan from pesticide-contaminated natural water is possible. The above studies clearly show the usefulness of MIP beads for the quantitative detoxification of endosulfan-doped natural water samples as described above. the

Table 1: Analysis of river water samples spiked with endosulfan

*Sampled from Karamana River, Trivandrum, Kerala

advantage

1. Therefore, the main advantage of the present invention is to provide a method for the synthesis of molecularly imprinted polymer particles or microbeads and products thereof, for the selective detoxification of natural water contaminated with endosulfan, its analogs or derivatives. the

2. Another advantage of the present invention is the selection of a non-toxic pseudotemplate molecule for detoxification of polluted water. the

3. Yet another advantage of the present invention is to provide an environmentally friendly and green technology for detoxifying water contaminated with endosulfan, its analogs or derivatives. the

Thus, the advantages of the disclosed invention are obtained in an economical, practical and accessible manner. Having shown and described preferred aspect and embodiment structures, it is to be understood that various further modifications and additional constructions will be apparent to those skilled in the art. The specific embodiments and configurations disclosed herein are intended to illustrate preferred properties and the best mode for carrying out the invention and should not be construed as limiting the scope of the invention. the

Claims (10)

1. a method for synthesizing the detoxification of endosulfan, its analog or derivative polluted water body, the polymer particles or microbeads of chlorendic acid molecular imprint, the method may further comprise the steps: a. Linking templates with functional monomers via non-covalent interactions, and subsequent addition of additional monomers; b. dissolving the monomer mixture obtained in step a) in an organic solvent by stirring; c. adding a crosslinking monomer and an initiator to the mixture obtained in step b); d. cooling the mixture obtained in step c) to 0° C., purging with nitrogen for a period of 10-15 minutes, then sealing and heating under stirring in an oil bath at about 80° C. for about 30 minutes; e. washing the polymer material obtained in step d) with distilled water and then drying overnight; f. Grinding and sieving the polymer material obtained from step e) to obtain chlorendic acid molecularly imprinted polymer particles; or g. adding polyvinyl alcohol aqueous solution dropwise to the mixture obtained in step c), and proceeding according to the procedure of steps d) to f) to obtain polymer microbeads imprinted with chlorendic acid molecules, Wherein the template used in step a) is chlorendic acid, wherein the functional monomer used in step a) is 4-vinylaniline, wherein the additional monomer used in step a) is acrylamide, wherein the crosslinking monomer used in step c) is ethylene glycol dimethacrylate or 1,1,1-tris(methylolpropane trimethacrylate), Wherein the molar ratio of the template, the functional monomer, the additional monomer and the crosslinking monomer is in the range of 1:2:1:15 to 1:5:3:30. 2. The method of claim 1, wherein the initiator is 2,2&apos;-azobisisobutyronitrile. 3. The method of claim 1, wherein the organic solvent used in step b) is selected from the group consisting of hexane and tetrahydrofuran. 4. Chlorendenic acid molecularly imprinted polymer particles or microbeads for detoxification of water bodies polluted by endosulfan, its analogs or derivatives, obtained using the method of claim 1 and having the following formula: A _(x) B _(y) C _(z) D _(f) where A is chlorendic acid, B is 4-vinylaniline, C is acrylamide, and D is ethylene glycol dimethacrylate or 1,1,1-tris(hydroxymethylpropane trimethacrylate) , the molar ratio is in the range of 1:2:1:15 to 1:5:3:30. 5. a method for detoxifying deionized water doped with endosulfan, its analogs or derivatives' ethanol solution using the polymer particles or microbeads of chlorendic acid molecularly imprinted according to claim 4, comprising the following steps: a. The chlorendic acid molecularly imprinted polymer particles or beads are refluxed together with methanol in a Soxhlet extractor to remove chlorendic acid, thereby obtaining leached molecularly imprinted polymer particles or beads grain; b. stirring said leached molecularly imprinted polymer particles or beads obtained in step a) with a sample containing endosulfan, followed by filtration; c. Determination of the endosulfan content in the filtrate by spectrometry. 6. The method of claim 5, wherein the concentration of the ethanol solution of endosulfan, its analogs or derivatives polluting deionized water and natural river water is in the range of 5 to 500 μg. 7. The method of claim 5, wherein the percentage of removal of endosulfan, its analogs or derivatives from the polluted river aqueous solution is determined by spectrometry using 4-(4-nitrobenzyl)pyridine reagent Sure. 8. The method of claim 5, wherein >99% removal of endosulfan, its analogs or derivatives is observed using chlorendic acid imprinted polymer beads. 9. A method for regenerating chlorendic acid-imprinted polymer particles or beads comprising equilibration of used chlorendic acid-imprinted polymer particles or beads with alcohol. 10. The method of claim 9, wherein the alcohol is selected from methanol and ethanol.