CN115141305A - Functional polymer, preparation method thereof and method for preparing ion imprinted polymer by using functional polymer - Google Patents

Functional polymer, preparation method thereof and method for preparing ion imprinted polymer by using functional polymer Download PDF

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CN115141305A
CN115141305A CN202210796614.XA CN202210796614A CN115141305A CN 115141305 A CN115141305 A CN 115141305A CN 202210796614 A CN202210796614 A CN 202210796614A CN 115141305 A CN115141305 A CN 115141305A
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polymer
functional polymer
functional
group
ion imprinted
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CN115141305B (en
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朱海艳
颜成虎
温树梅
丛威
翁瑶
满宇桐
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Institute of Process Engineering of CAS
Ganjiang Innovation Academy of CAS
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Ganjiang Innovation Academy of CAS
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    • C08J2479/02—Polyamines

Abstract

The invention provides a functional polymer, a preparation method thereof and a method for preparing an ion imprinted polymer by using the functional polymer. The preparation method of the ion imprinted polymer comprises the following steps: (1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to prepare coating material; (2) And (2) coating the coating material obtained in the step (1) on the surface of a substrate material, drying, irradiating by using ultraviolet light, and performing post-treatment to obtain the ion imprinted polymer. The functional polymer comprises a photoreactive group and a functional group capable of coordinating with metal ions, and when the functional polymer is used for preparing the ion imprinted polymer, the photoreactive group can realize chemical bonding between a substrate material and the functional polymer by utilizing ultraviolet light reaction, so that the combination stability of the functional polymer and the substrate material is improved; the functional group capable of coordinating with metal ions can adsorb the metal ions, so that the substrate material has adsorption performance.

Description

Functional polymer, preparation method thereof and method for preparing ion imprinted polymer by using functional polymer
Technical Field
The invention belongs to the technical field of high molecular materials with adsorption and separation functions, and relates to a functional polymer, a preparation method thereof and a method for preparing an ion imprinted polymer by using the functional polymer.
Background
The ion imprinting technology is a novel technology which takes metal ions as a template, combines the metal ions with functional monomers by utilizing the actions of coordinate bonds, covalent bonds and the like, and then prepares a metal ion specific adsorption material by cross-linking polymerization under the participation of an initiator and a cross-linking agent. The ion imprinted polymer has binding sites matched with the spatial configuration and size of specific metal ions, so that the ion imprinted polymer has extremely strong selective recognition and separation enrichment capacity.
The preparation method of the ion imprinted polymer mainly comprises bulk polymerization, a sol-gel method, precipitation polymerization, a surface imprinting method and the like. The surface imprinting method loads the functional monomer on the surface of the substrate material in the modes of coating, cladding, self-assembly and the like, so that the binding sites are distributed on the outer surface of the substrate material, the problems of deep embedding of the binding sites and low mass transfer rate are solved, and great attention is drawn. However, the existing surface imprinting method is generally complex in preparation process, requires harsh reaction conditions and long reaction time, and severely limits the practical application of the method.
CN105771701A discloses a preparation method of an ion imprinted polymer, which comprises the steps of taking a commercial microporous filter membrane as a substrate material, fixing a photoinitiator on the surface of the substrate material, placing the substrate material in a prepolymerization solution containing metal ions, functional monomers and a cross-linking agent, irradiating for 4-10 hours by using ultraviolet light for reaction, and then eluting to remove template ions. The method has mild reaction conditions, greatly reduces the preparation difficulty of the ion imprinted polymer, but still has the problems of more complex preparation process, longer reaction time and the like.
Therefore, in the art, it is desired to develop a functional polymer, which can solve the problems of the prior surface imprinting method, such as complicated preparation process, requirement of harsh reaction conditions and long reaction time, when used for preparing the ion imprinted polymer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a functional polymer, a preparation method thereof and a method for preparing an ion imprinted polymer by using the functional polymer, so as to solve the problems that the existing surface imprinting method is complex in preparation process, needs harsh reaction conditions and long reaction time and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a functional polymer having a structure represented by formula I or formula II:
Figure BDA0003732389140000021
wherein X is a photoreactive group;
y is a functional group capable of coordinating with metal ions;
R 1 and R 2 Each independently selected from phenyl, hydrogen or C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl);
R 3 each occurrence being the same or different and is selected from the group consisting of C1-C6 alkylene (e.g., methylene, ethylene, propylene, etc.), -O-, -CO-O-, -O-CO-O-, -NR 4 -、-NR 4 -CO-、-CO-NR 4 -、-NR 4 -CO-O-、-O-CO-NR 4 -or-NR 4 -CO-NR 4 -, in which R 4 Selected from hydrogen or C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl);
m is a polymerization degree and is an integer of 1 to 100, for example, 1, 2, 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100.
n is a polymerization degree and is an integer of 1 to 300, for example, 1, 2, 5, 8, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 130, 150, 180, 200, 220, 230, 250, 280, or 300.
The functional polymer of the invention comprises a photoreactive group (X) and a functional group (Y or-NH-) capable of coordinating with metal ions, and can be used for preparing ion imprinted polymers.
Preferably, X is selected, identically or differently on each occurrence, from
Figure BDA0003732389140000031
Figure BDA0003732389140000032
Figure BDA0003732389140000033
Wherein, -represents the attachment site.
Preferably, each occurrence of Y is selected, identically or differently, from a carboxyl group, an amide group, an ester group, an amino group, a sulfonic acid group, a pyridyl group or an imidazolyl group.
Preferably, R 3 Selected, identically or differently on each occurrence, from-CH 2 -、-CH 2 -CH 2 -、-O-、-CO-O-、-O-CO-、-O-CO-O-、-NR 4 -、-NR 4 -CO-、-CO-NR 4 -、-NR 4 -CO-O-、-O-CO-NR 4 -or-NR 4 -CO-NR 4 -, in which R 4 Selected from hydrogen or C1-C6 alkyl.
Preferably, the functional polymer is selected from any one of the following polymers:
Figure BDA0003732389140000041
wherein m is an integer of 1 to 100, and n is an integer of 1 to 300.
In a second aspect, the present invention provides a method for preparing the functional polymer of the first aspect, the method comprising the steps of:
mixing a compound containing a photoreactive group, a compound containing a functional group capable of coordinating with metal ions, other reagents and a solvent, reacting, and performing post-treatment to obtain the functional polymer;
the molar ratio of the functional group-containing compound capable of coordinating with a metal ion, the photoreactive group-containing compound, and the other agent is 1 (0.05-0.5) to (0.01-0.1), such as 1.
Preferably, the compound containing a photoreactive group comprises any one or a combination of at least two of 4-vinylbenzophenone, 4-vinyl-4 '-methoxybenzophenone, 4-acryloxy-2-hydroxybenzophenone, 4-acryloxy-benzophenone, 2-hydroxy-4- (methacryloxy) benzophenone, 3-isopentenyl-2,4,6-trihydroxybenzophenone, 4,4-diazidestilbene-2,2 disulfonic acid, α -arylalkenyl azide, vinyl azide, 4- (bromomethyl) benzophenone, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2' -dihydroxybenzophenone, 4,4 '-dihydroxybenzophenone, 4-chloro-4' -hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, or 3534-trihydroxy-3534.
Preferably, the compound having a functional group capable of coordinating to a metal ion includes any one of acrylic acid, methacrylic acid, 2-ethyl acrylate, methyl methacrylate, methyl 3- (2-amino-5-bromo-pyridin-3-yl) acrylate, methyl 3- (5-methoxypyridin-3-yl) acrylate, itaconic acid, monoethyl itaconate, acrylamide, methacrylamide, N-methyl-2-acrylamide, N-methylolacrylamide, N- [ tris (hydroxymethyl) methyl ] acrylamide, 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 3-acryloylrhodanine, polyacrylic acid, polymethacrylic acid or polyethyleneimine, or a combination of at least two thereof.
Preferably, the other reagent comprises any one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide t-butyl peroxide, methyl ethyl ketone peroxide, triethylamine, pyridine, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate or sodium hydroxide, or a combination of at least two thereof.
Preferably, the solvent comprises any one of trifluoroethanol, methanol, ethanol, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, dimethyl sulfoxide, water, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, hexamethylphosphoric triamide or acetone, or a combination of at least two thereof.
Preferably, the reaction temperature is 10 to 120 ℃, such as 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like, and the reaction time is 0.1 to 24h, such as 0.1h, 0.5h, 1h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h or 24h and the like.
Preferably, the reaction is carried out under an inert gas blanket.
Preferably, the inert gas comprises nitrogen or argon.
Preferably, the reaction comprises a free radical polymerization reaction, an atom transfer radical polymerization reaction, or a substitution reaction.
Preferably, the post-treatment comprises purification, drying.
Preferably, the specific steps of the purification include: and dropwise adding the solution after the reaction into a poor solvent to form a precipitate, filtering, and washing the precipitate obtained by filtering with an ethanol solution, wherein the poor solvent comprises any one or the combination of at least two of diethyl ether, petroleum ether, acetone, n-hexane, n-pentane, n-heptane or carbon tetrachloride.
In a third aspect, the present invention provides a method for preparing an ion imprinted polymer, the method comprising the following steps:
(1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to prepare coating material;
(2) Coating the coating material obtained in the step (1) on the surface of a substrate material, drying, irradiating by using ultraviolet light, and performing post-treatment to obtain the ion imprinted polymer;
the functional polymer comprises the functional polymer of the first aspect.
The functional polymer comprises a photoreactive group and a functional group capable of coordinating with metal ions, wherein the photoreactive group can realize chemical bonding between a substrate material and the functional polymer by utilizing ultraviolet light reaction, so that the stability of the combination of the functional polymer and the substrate material is improved; the functional group capable of coordinating with metal ions can adsorb the metal ions, so that the substrate material has adsorption performance.
In the process of preparing the ion imprinted polymer by using the functional polymer, the substrate material and the functional polymer can be quickly and chemically bonded by using a photoreaction grafting method, the reaction is quick, the reaction condition is mild, other reagents and equipment are not needed, the preparation steps are greatly simplified, and the cost is reduced.
Preferably, the metal ions in the metal salt comprise Sc 3+ 、Y 3+ 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Pm 3+ 、Sm 3+ 、Eu 3 + 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Sm 3+ 、Ho 3+ 、Er 3+ 、Tm 3+ 、Yb 3+ 、Lu 3+ 、Cr 3+ 、Fe 3+ 、Ni 2+ 、Cu 2+ 、Zn 2+ Or Pb 2+ Any one of them.
Preferably, the crosslinking agent comprises any one or a combination of at least two of 4,4-diazide stilbene-2,2 sodium disulfonate, epichlorohydrin, glutaraldehyde or ethylene glycol diglycidyl ether.
Preferably, the solvent in step (1) comprises any one of water, ethanol, methanol, n-hexane or n-heptane solution or a combination of at least two of them.
Preferably, the metal salt is present in an amount of 0.5 to 10% (e.g., 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.), the functional polymer is present in an amount of 5 to 20% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.), the crosslinking agent is present in an amount of 5 to 30% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.), and the balance is a solvent, based on 100% of the total weight of the coating material.
If the content of the functional polymer in the coating material is too high, the imprinting factor of the prepared ion imprinting polymer is reduced, and if the content of the functional polymer in the coating material is too low, the adsorption capacity of the prepared ion imprinting polymer is reduced.
Preferably, the dispersing of step (1) comprises ultrasonic dispersing or mechanical stirring.
Preferably, the shape of the base material in step (2) comprises a filter membrane, a filter cloth, a fiber or a microsphere.
Preferably, the material of the base material in step (2) includes any one of polyethylene, polystyrene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyurethane, polyimide, polyvinylidene fluoride, polyvinyl chloride, polysulfone, polyethersulfone, polyacrylonitrile, or nylon-6, or a combination of at least two of them.
Preferably, the step (2) of coating further comprises the step of cleaning and pretreating the substrate material.
Preferably, the cleaning comprises soaking the substrate material in ethanol and ultrasonically cleaning.
Preferably, the pretreatment mode comprises any one or combination of at least two of etching, ozone treatment, ultraviolet irradiation, corona treatment, plasma treatment, glow discharge or high-energy particle irradiation.
Preferably, the coating in step (2) comprises any one or a combination of at least two of spraying, dipping, knife coating and surface printing.
Preferably, the drying in the step (2) includes any one of solvent volatilization, blow drying in a nitrogen atmosphere, or hot air drying.
Preferably, the light source for ultraviolet light irradiation in step (2) comprises a high-pressure mercury lamp, an ultraviolet light curing device, an ultraviolet light curing machine or a UV LED area light source.
Preferably, the time of the ultraviolet irradiation in step (2) is 1-10 min, such as 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, and the intensity of the ultraviolet irradiation is 50-1000 mW/cm 2 E.g. 50mW/cm 2 、100mW/cm 2 、200mW/cm 2 、300mW/cm 2 、400mW/cm 2 、500mW/cm 2 、600mW/cm 2 、700mW/cm 2 、800mW/cm 2 、900mW/cm 2 Or 1000mW/cm 2 And the like.
Preferably, the post-treatment of step (2) comprises washing and vacuum drying.
Preferably, the washing comprises soaking the material obtained after the ultraviolet irradiation in an eluent to wash out metal ions.
Preferably, the eluent comprises a solution of 0.1 to 1mol/L (e.g., 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, or 1mol/L, etc.) of hydrochloric acid, sulfuric acid, nitric acid, or EDTA.
As a preferred technical scheme of the invention, the preparation method of the ion imprinted polymer comprises the following steps:
(1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to prepare coating material; wherein, the total weight of the coating material is 100 percent, the content of the metal salt is 0.5 to 10 percent, the content of the functional polymer is 5 to 20 percent, the content of the cross-linking agent is 5 to 30 percent, and the balance is solvent;
(2) Cleaning and pretreating a substrate material, coating the coating material obtained in the step (1) on the surface of the substrate material, drying, and keeping the strength at 50-1000 mW/cm 2 Irradiating for 1-10 min under ultraviolet light, soaking the material obtained after the ultraviolet light irradiation in an eluant to remove metal ions, and drying in vacuum to obtain the ion imprinted polymer;
the functional polymer comprises the functional polymer of the first aspect.
In a fourth aspect, the present invention provides an ion imprinted polymer, which is prepared by the preparation method according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) When the functional polymer is used for preparing the ion imprinted polymer, the photoreactive group can utilize ultraviolet light reaction to realize chemical bonding between a substrate material and the functional polymer, so that the combination stability of the functional polymer and the substrate material is improved; the functional group capable of coordinating with the metal ion can adsorb the metal ion, so that the substrate material has adsorption performance;
(2) In the process of preparing the ion imprinted polymer by using the functional polymer, the substrate material and the functional polymer can be chemically bonded by using a photoreaction grafting method, the reaction is rapid, the reaction condition is mild, other reagents and equipment are not needed, the preparation steps are greatly simplified, and the cost is reduced.
Drawings
FIG. 1 is an IR spectrum of a functional polymer prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the functional polymer prepared in example 1;
FIG. 3 is a scanning electron micrograph of an ion imprinted polymer prepared in example 1;
FIGS. 4a and 4b are a graph showing a contact angle test result of an ionic imprinted polymer and a contact angle test result of a non-ionic imprinted polymer, respectively, prepared in example 1;
FIG. 5 is an IR spectrum of a functional polymer prepared in example 8;
FIG. 6 is a nuclear magnetic hydrogen spectrum of the functional polymer prepared in example 8;
FIG. 7 is a scanning electron micrograph of an ion imprinted polymer prepared in example 8;
fig. 8a and 8b are a contact angle test result graph of an ionic imprinted polymer prepared in example 8 and a contact angle test result graph of a non-ionic imprinted polymer, respectively.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this example, an ion imprinted polymer is provided, which is prepared by the following method:
(1) Preparation of functional Polymer: adding 0.005mol of 4-propenyloxy-2-hydroxybenzophenone and 0.045mol of acrylic acid into a three-neck flask containing 50mL of absolute ethyl alcohol, vacuumizing and introducing nitrogen for three times, adding 0.0005mol of azobisisobutyronitrile under the nitrogen atmosphere, vacuumizing and introducing nitrogen for three times again, sealing, raising the temperature to 70 ℃ for reaction for 10 hours, and purifying to prepare a product, wherein the functional polymer is obtained, the structural formula of the functional polymer is shown as follows, the infrared spectrogram of the functional polymer is shown as figure 1, and the nuclear magnetic hydrogen spectrogram of the functional polymer is shown as figure 2;
Figure BDA0003732389140000111
(2) The functional polymer and Dy (NO) are mixed 3 ) 3 ·6H 2 O and 4,4-diazide stilbene-2,2 sodium disulfonate are added into water, and the coating material is prepared after ultrasonic dispersion (the total weight of the coating material is 100 percent, dy (NO) 3 ) 3 The content of 3 percent, the content of 10 percent of functional polymer, the content of 4,4-diazide stilbene-2,2 sodium disulfonate is 15 percent, and the balance is water), cleaning the PVDF microporous filter membrane, carrying out corona treatment for 30s, coating the coating material on the surface of the PVDF microporous filter membrane, airing, and then carrying out surface treatment on the PVDF microporous filter membrane with the strength of 500mW/cm 2 Irradiating for 5min under an ultraviolet lamp;
(3) Repeatedly washing the material prepared in the step (2) in 0.1mol/L hydrochloric acid to remove the template Dy 3+ Finally washing with a large amount of distilled water to remove residual hydrochloric acid, and vacuum drying to obtain Dy 3+ The scanning electron microscope image of the ion imprinted polymer is shown in fig. 3, and the contact angle test result image (the test solvent is water) is shown in fig. 4 a.
Dy (NO) is not added in the step (2) 3 ) 3 ·6H 2 And O, the step of acid washing is not carried out in the step (3), so that the nonionic imprinted polymer can be obtained, and the contact angle test result graph of the nonionic imprinted polymer is shown in FIG. 4 b.
20.0mg of Dy prepared in this example 3+ Application of ion imprinted polymer in Dy 3+ Adsorption in solution with the concentration of 50mg/L, dy 3+ The adsorption capacity of the ion imprinted polymer of (1) was 7.8mg/g, and the imprinting factor was 1.46.
Example 2
In this example, an ion imprinted polymer is provided, which is prepared by the following method:
(1) Preparation of functional Polymer: adding 0.015mol of 4-propylene oxygen benzophenone and 0.045mol of methacrylic acid into a three-neck flask containing 50mL of absolute ethyl alcohol, vacuumizing and introducing nitrogen for three times, adding 0.0025mol of azodiisoheptanonitrile under the nitrogen atmosphere, vacuumizing and introducing nitrogen for three times again, sealing, raising the temperature to 50 ℃, reacting for 12 hours, and purifying to prepare a product, wherein the structural formula of the functional polymer is shown as follows;
Figure BDA0003732389140000121
(2) Mixing the above functional polymer and EuCl 3 ·6H 2 O and 4,4-diazide stilbene-2,2 sodium disulfonate are added into water, and the coating material is prepared after ultrasonic dispersion (the total weight of the coating material is 100 percent, euCl 3 0.5 percent of the functional polymer, 5 percent of 4,4-diazide stilbene-2,2 sodium disulfonate and the balance of water), cleaning the PVDF microporous filter membrane, carrying out corona treatment for 30s, coating the coating material on the surface of the PVDF microporous filter membrane, airing, and carrying out the corona treatment on the PVDF microporous filter membrane at the strength of 500mW/cm 2 Irradiating for 5min under an ultraviolet lamp;
step (3) was the same as in example 1.
20.0mg Eu obtained by the preparation of this example 3+ Application of ion imprinted polymer to Eu 3+ Adsorption in a solution with a concentration of 50mg/L, eu 3+ The adsorption capacity of the ion imprinted polymer (2) was 15.3mg/g, and the imprinting factor was 1.53.
Example 3
In this example, an ion imprinted polymer is provided, which is prepared by the following method:
(1) Preparation of functional Polymer: adding 0.02mol of 4-acryloyloxy-2-hydroxybenzophenone and 0.045mol of 3-propenyllotannine into a three-neck flask containing 50mL of absolute ethyl alcohol, vacuumizing and introducing nitrogen for three times, adding 0.004mol of azobisisobutyronitrile in the nitrogen atmosphere, vacuumizing and introducing nitrogen for three times again, sealing, raising the temperature to 90 ℃, reacting for 8 hours, and purifying to prepare a product, wherein the structural formula of the functional polymer is shown as follows;
Figure BDA0003732389140000131
(2) Mixing the above functional polymer and CeCl 3 ·7H 2 O and 4,4-diazide stilbene-2,2 sodium disulfonate are added into water, and the coating material is prepared after ultrasonic dispersion (the total weight of the coating material is 100 percent, ceCl is used as the coating material) 3 5% of functional polymer, 20% of functional polymer, 30% of 4,4-diazide stilbene-2,2 sodium disulfonate and the balance of water), cleaning the PVDF microporous filter membrane, carrying out corona treatment for 30s, coating the coating material on the surface of the PVDF microporous filter membrane, airing, and carrying out surface treatment on the PVDF microporous filter membrane with the strength of 500mW/cm 2 Irradiating for 5min under an ultraviolet lamp;
step (3) was the same as in example 1.
20.0mg of Ce prepared in this example 3+ Application of ion imprinted polymer to Ce 3+ Adsorption in a solution with a concentration of 50mg/L, ce 3+ The adsorption capacity of the ion imprinted polymer of (1) was 11.7mg/g, and the imprinting factor was 1.44.
Example 4
This example differs from example 1 only in that the compound having a photoreactive group in the preparation of a functional polymer in step (1) is 4-acryloxybenzophenone, the compound having a functional group capable of coordinating with a metal ion is acrylamide, the other agent is dimethyl azodiisobutyrate, and the metal salt in the coating material in step (2) is NiCl 2 ·6H 2 O。
The structural formula of the functional polymer prepared in this example is shown below:
Figure BDA0003732389140000141
this example was preparedTo 20.0mg Ni 2+ Application of ion imprinted polymer in Ni 2+ Ni adsorption in 50mg/L solution 2+ The adsorption capacity of the ion imprinted polymer of (1) was 12.6mg/g, and the imprinting factor was 1.39.
Example 5
This example is different from example 1 only in that the compound having a photoreactive group in the preparation of the functional polymer in step (1) is 2-hydroxy-4- (methacryloyloxy) benzophenone, the compound having a functional group capable of coordinating to a metal ion is 2-vinylpyridine, and the metal salt in the coating material in step (2) is Cu (NO) 3 ) 2 ·3H 2 O。
The structural formula of the functional polymer prepared in this example is shown below:
Figure BDA0003732389140000142
20.0mg of Cu prepared in this example 2+ Application of ion imprinted polymer to Cu 2+ Adsorption in 50mg/L solution of Cu 2+ The adsorption capacity of the ion imprinted polymer of (2) was 12.3mg/g, and the imprinting factor was 1.73.
Example 6
This example is different from example 1 only in that the compound having a photoreactive group when the functional polymer is prepared in step (1) is 2-hydroxy-4- (methacryloyloxy) benzophenone, the compound having a functional group capable of coordinating with a metal ion is 1-vinylimidazole, and the metal salt in the coating material in step (2) is La (NO) 3 ) 3 ·7H 2 O。
The functional polymer prepared in this example has the following structural formula:
Figure BDA0003732389140000151
20.0mg of La prepared in this example 3+ Application of ion imprinted polymer to La 3+ At a concentration of 5Adsorbing in 0mg/L solution, la 3+ The adsorption capacity of the ion imprinted polymer of (1) was 9.5mg/g, and the imprinting factor was 1.43.
Example 7
This example is different from example 1 only in that the compound containing a photoreactive group when preparing a functional polymer in step (1) is 4-acryloxybenzophenone, the compound containing a functional group capable of coordinating with a metal ion is methyl methacrylate, and the metal salt in the coating material in step (2) is Cu (NO) 3 ) 2 ·3H 2 O。
The structural formula of the functional polymer prepared in this example is shown below:
Figure BDA0003732389140000161
20.0mg of Cu prepared in this example 2+ Application of ion imprinted polymer to Cu 2+ Adsorption in 50mg/L solution of Cu 2+ The adsorption capacity of the ion imprinted polymer of (1) was 15.3mg/g, and the imprinting factor was 1.78.
Example 8
(1) Preparation of functional Polymer: adding 0.005mol of 4- (bromomethyl) benzophenone and 0.045mol of polyethyleneimine with the molecular weight of 2.5 ten thousand into a three-neck flask containing 50mL of absolute ethyl alcohol, vacuumizing and introducing nitrogen for three times, adding 0.0005mol of potassium carbonate under the nitrogen atmosphere, vacuumizing and introducing nitrogen for three times again, sealing, raising the temperature to 70 ℃ for reaction for 10 hours, and purifying to prepare a product, wherein the functional polymer has a structural formula shown below, an infrared spectrogram shown in figure 5 and a nuclear magnetic hydrogen spectrogram shown in figure 6;
Figure BDA0003732389140000162
(2) Mixing the functional polymer and Gd (NO) 3 ) 3 ·6H 2 O and 4,4-diazide stilbene-2,2 sodium disulfonate are added into water, the coating material is prepared after ultrasonic dispersion,cleaning a PVDF (polyvinylidene fluoride) microporous filter membrane, carrying out corona treatment for 30s, coating a coating material on the surface of the PVDF microporous filter membrane, airing, and then carrying out corona treatment at the strength of 500mW/cm 2 Irradiating for 5min under an ultraviolet lamp;
(3) Repeatedly washing the material prepared in the step (2) in 0.1mol/L hydrochloric acid to remove the template Dy 3+ Finally washing with a large amount of distilled water to remove residual hydrochloric acid, and vacuum drying to obtain Gd 3+ The scanning electron micrograph of the ion imprinted polymer (D) is shown in FIG. 7, and the contact angle test result thereof is shown in FIG. 8 a.
No Gd (NO) was added in step (2) 3 ) 3 ·6H 2 And O, the step of acid washing is not carried out in the step (3), so that the nonionic imprinted polymer can be obtained, and the contact angle test result graph of the nonionic imprinted polymer is shown in FIG. 8 b.
20.0mg of Gd prepared in this example 3+ Application of ion imprinted polymer to Gd 3+ Adsorbing with 50mg/L solution of Gd 3+ The adsorption capacity of the ion imprinted polymer of (1) was 17.8mg/g, and the imprinting factor was 1.33.
Comparative example 1
This comparative example differs from example 1 only in that Dy (NO) was added in step (2) in an amount of 100% by total weight of the coating material 3 ) 3 The content of (A) is 3%, the content of the functional polymer is 3%, the content of 4,4-diazide stilbene-2,2 sodium disulfonate is 15%, and the balance is water.
20.0mg of Dy prepared in this example 3+ Application of ion imprinted polymer in Dy 3+ Adsorbing in 50mg/L solution to obtain Dy 3+ The adsorption capacity of the ion imprinted polymer of (2) was 2.8mg/g, and the imprinting factor was 1.39.
Comparative example 2
This comparative example differs from example 1 only in that Dy (NO) was added in step (2) in an amount of 100% by weight based on the total weight of the coating material 3 ) 3 The content of (A) is 3%, the content of the functional polymer is 25%, the content of 4,4-diazide stilbene-2,2 sodium disulfonate is 15%, and the balance is water.
20.0mg of Dy prepared in this example 3+ Application of ion imprinted polymer in Dy 3+ Adsorbing in 50mg/L solution to obtain Dy 3+ The adsorption capacity of the ion imprinted polymer (2) was 6.4mg/g, and the imprinting factor was 1.04.
The applicant states that the functional polymer and the preparation method of the present invention and the method for preparing the ion imprinted polymer using the same are illustrated by the above examples, but the present invention is not limited to the above examples, which does not mean that the present invention can be implemented only by relying on the above examples. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. A functional polymer having a structure according to formula I or formula II:
Figure FDA0003732389130000011
wherein X is a photoreactive group;
y is a functional group capable of coordinating with metal ions;
R 1 and R 2 Each independently selected from phenyl, hydrogen or C1-C6 alkyl;
R 3 selected, identically or differently on each occurrence, from C1-C6 alkylene-O-, -CO-O-, -O-CO-O-, -NR 4 -、-NR 4 -CO-、-CO-NR 4 -、-NR 4 -CO-O-、-O-CO-NR 4 -or-NR 4 -CO-NR 4 -, in which R 4 Selected from hydrogen or C1-C6 alkyl;
m is an integer of 1 to 100;
n is an integer of 1 to 300.
2. The functional polymer of claim 1, wherein X, identically or differently at each occurrence, is selected from
Figure FDA0003732389130000012
Figure FDA0003732389130000013
Figure FDA0003732389130000021
Figure FDA0003732389130000022
Wherein, -represents the attachment site;
preferably, Y is selected, identically or differently on each occurrence, from a carboxyl group, an amide group, an ester group, an amino group, a sulfonic acid group, a pyridyl group or an imidazolyl group;
preferably, R 3 Selected, identically or differently on each occurrence, from-CH 2 -、-CH 2 -CH 2 -、-O-、-CO-O-、-O-CO-、-O-CO-O-、-NR 4 -、-NR 4 -CO-、-CO-NR 4 -、-NR 4 -CO-O-、-O-CO-NR 4 -or-NR 4 -CO-NR 4 -, in which R 4 Selected from hydrogen or C1-C6 alkyl.
3. The functional polymer of claim 1 or 2, wherein the functional polymer is selected from any one of the following polymers:
Figure FDA0003732389130000023
Figure FDA0003732389130000031
wherein m is an integer of 1 to 100, and n is an integer of 1 to 300.
4. The method of any one of claims 1 to 3, wherein the method comprises the steps of:
mixing a compound containing a photoreactive group, a compound containing a functional group capable of coordinating with metal ions, other reagents and a solvent, reacting, and performing post-treatment to obtain the functional polymer;
the molar ratio of the compound containing the functional group capable of coordinating with the metal ions, the compound containing the photoreactive group and other reagents is 1 (0.05-0.5) to (0.01-0.1).
5. The method of claim 4, wherein the compound containing a photoreactive group comprises at least one or a combination of any two of 4-vinylbenzophenone, 4-vinyl-4 '-methoxybenzophenone, 4-acryloxy-2-hydroxybenzophenone, 4-acryloxybenzophenone, 2-hydroxy-4- (methacryloxy) benzophenone, 3-isopentenyl-2,4,6-trihydroxybenzophenone, 4,4-diazidestilbene-2,2 disulfonic acid, α -arylalkenyl azide, vinyl azide, 4- (bromomethyl) benzophenone, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2' -dihydroxybenzophenone, 4,4 '-dihydroxybenzophenone, 4-chloro-4' -hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, or 2,3,4;
preferably, the compound having a functional group capable of coordinating with a metal ion includes any one of acrylic acid, methacrylic acid, 2-ethyl acrylate, methyl methacrylate, methyl 3- (2-amino-5-bromo-pyridin-3-yl) acrylate, methyl 3- (5-methoxypyridin-3-yl) acrylate, itaconic acid, monoethyl itaconate, acrylamide, methacrylamide, N-methyl-2-acrylamide, N-methylolacrylamide, N- [ tris (hydroxymethyl) methyl ] acrylamide, 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 3-acryloylondannin, polyacrylic acid, polymethacrylic acid, or polyethyleneimine, or a combination of at least two thereof;
preferably, the other reagent comprises any one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide tert-butyl peroxide, methyl ethyl ketone peroxide, triethylamine, pyridine, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate or sodium hydroxide or a combination of at least two of the foregoing;
preferably, the solvent comprises any one of trifluoroethanol, methanol, ethanol, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, dimethyl sulfoxide, water, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, hexamethylphosphoric triamide or acetone, or a combination of at least two thereof.
6. The preparation method according to claim 4 or 5, characterized in that the reaction temperature is 10-120 ℃ and the reaction time is 0.1-24 h;
preferably, the reaction is carried out under the protection of inert gas;
preferably, the reaction comprises a free radical polymerization reaction, an atom transfer radical polymerization reaction, or a substitution reaction;
preferably, the post-treatment comprises purification, drying.
7. A preparation method of an ion imprinted polymer is characterized by comprising the following steps:
(1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to prepare coating material;
(2) Coating the coating material obtained in the step (1) on the surface of a substrate material, drying, irradiating by using ultraviolet light, and performing post-treatment to obtain the ion imprinted polymer;
the functional polymer comprises the functional polymer of any one of claims 1-3.
8. The method according to claim 7, wherein the metal ion in the metal salt includes Sc 3+ 、Y 3 + 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Pm 3+ 、Sm 3+ 、Eu 3+ 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Sm 3+ 、Ho 3+ 、Er 3+ 、Tm 3+ 、Yb 3+ 、Lu 3+ 、Cr 3+ 、Fe 3+ 、Ni 2+ 、Cu 2+ 、Zn 2+ Or Pb 2+ Any one of the above;
preferably, the cross-linking agent comprises any one of 4,4-diazide stilbene-2,2 sodium disulfonate, epichlorohydrin, glutaraldehyde or ethylene glycol diglycidyl ether or a combination of at least two of the two;
preferably, the solvent in step (1) comprises any one of water, ethanol, methanol, n-hexane or n-heptane solution or the combination of at least two of the two;
preferably, the content of the metal salt is 0.5 to 10%, the content of the functional polymer is 5 to 20%, the content of the cross-linking agent is 5 to 30%, and the balance is a solvent, based on 100% of the total weight of the coating material.
9. The method according to claim 7 or 8, wherein the base material of step (2) is preferably in a shape comprising a filter membrane, a filter cloth, a fiber or a microsphere;
preferably, the material of the base material in step (2) includes any one or a combination of at least two of polyethylene, polystyrene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyurethane, polyimide, polyvinylidene fluoride, polyvinyl chloride, polysulfone, polyethersulfone, polyacrylonitrile, or nylon-6;
preferably, the step (2) of coating further comprises the steps of cleaning and pretreating the substrate material;
preferably, the time of the ultraviolet irradiation in the step (2) is 1-10 min, and the intensity of the ultraviolet irradiation is 50-1000 mW/cm 2 ；
Preferably, the post-treatment of step (2) comprises washing, vacuum drying;
preferably, the washing includes soaking the material obtained after the ultraviolet irradiation in an eluent to wash out the metal ions.
10. An ion imprinted polymer, characterized in that the ion imprinted polymer is prepared by the preparation method of any one of claims 7 to 9.
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