CN115141305B - Functional polymer, preparation method thereof and method for preparing ion imprinting polymer by using functional polymer - Google Patents
Functional polymer, preparation method thereof and method for preparing ion imprinting polymer by using functional polymer Download PDFInfo
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Abstract
The invention provides a functional polymer, a preparation method and a method for preparing an ion imprinting polymer by using the functional polymer, wherein the functional polymer has a structure shown as a formula I or a formula II. The preparation method of the ion imprinting polymer comprises the following steps: (1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to obtain coating material; (2) Coating the coating material in the step (1) on the surface of a substrate material, drying, irradiating with ultraviolet light, and performing post-treatment to obtain the ion imprinting polymer. The functional polymer comprises the photoreactive group and the functional group capable of coordinating with metal ions, when the photoreactive group is used for preparing the ion imprinted polymer, the photoreactive group can utilize ultraviolet light reaction to enable the substrate material and the functional polymer to realize chemical bonding, so that the bonding 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.
Description
Technical Field
The invention belongs to the technical field of adsorption and separation functional polymer materials, and relates to a functional polymer, a preparation method and a method for preparing an ion imprinting polymer by using the functional polymer.
Background
The ion imprinting technology is a novel technology for preparing the metal ion specific adsorption material by taking metal ions as templates, combining the metal ions with functional monomers by utilizing the actions of coordination bonds, covalent bonds and the like, and then performing cross-linking polymerization under the participation of an initiator and a cross-linking agent. The ion imprinting polymer has a binding site matched with the space configuration and the size of specific metal ions, so that the ion imprinting polymer has extremely strong selective recognition and separation enrichment capability.
The preparation method of the ion imprinting polymer mainly comprises bulk polymerization, sol-gel method, precipitation polymerization, surface imprinting method and the like. The surface imprinting method loads functional monomers on the surface of a substrate material in the modes of coating, cladding, self-assembly and the like, so that binding sites are distributed on the outer surface of the substrate material, and the problems of embedding depth and slow mass transfer rate of the binding sites are solved, thereby bringing great attention. However, the existing surface imprinting method is generally complex in preparation process, requires severe reaction conditions and long reaction time, and severely limits practical application.
CN105771701a discloses a preparation method of ion imprinted polymer, which comprises the steps of taking 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 cross-linking agent, irradiating for 4-10 hours by ultraviolet light for reaction, and eluting to remove template ions. The method has mild reaction conditions, greatly reduces the preparation difficulty of the ion imprinted polymer, and still has the problems of complex preparation process, long reaction time and the like.
Therefore, in the art, it is desired to develop a functional polymer, which can solve the problems of complicated preparation process, demanding reaction conditions, long reaction time, and the like of the existing surface imprinting method when it is 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 and a method for preparing an ion imprinting polymer by using the functional polymer, so as to solve the problems that the preparation process of the existing surface imprinting method is complex, harsh reaction conditions are needed, the reaction time is long, and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a functional polymer having a structure according to formula I or formula II:
wherein X is a photoreactive group;
y is a functional group capable of coordinating with metal ions;
R 1 and R is 2 Each independently selected from phenyl, hydrogen, or C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl);
R 3 is selected identically or differently on each occurrence from C1-C6 alkylene (e.g., methylene ethylene, propylene, etc.), -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 -, where R is 4 Selected from hydrogen or C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl);
m 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, 100, or the like, and the polymerization degree.
n is an integer of 1 to 300 in the polymerization degree, 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, 300 or the like.
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, for each occurrence from
Wherein-represents the ligation site.
Preferably, Y is selected, identically or differently, for each occurrence, from carboxyl, amide, ester, amino, sulfonate, pyridyl or imidazolyl groups.
Preferably, R 3 Is 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 -, where R is 4 Selected from hydrogen or C1-C6 alkyl.
Preferably, the functional polymer is selected from any one of the following polymers:
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 a functional polymer according to the first aspect, the method comprising the steps of:
mixing a compound containing photoreactive groups, a compound containing functional groups capable of coordinating with metal ions, other reagents and a solvent, reacting, and performing aftertreatment to obtain the functional polymer;
the molar ratio of the compound containing a functional group capable of coordinating with a metal ion, the compound containing a photoreactive group, and other reagents is 1 (0.05-0.5): (0.01-0.1), for example, 1:0.05:0.01, 1:0.05:0.05, 1:0.05:0.1, 1:0.1:0.01, 1:0.1:0.05, 1:0.1:0.1, 1:0.5:0.01, 1:0.5:0.05, or 1:0.5:0.1, etc.
Preferably, the photoreactive group-containing compound includes any one or a combination of at least two of 4-vinyl benzophenone, 4-vinyl-4 '-methoxybenzophenone, 4-propenoxy-2-hydroxybenzophenone, 4-propenoxy-benzophenone, 2-hydroxy-4- (methacryloxy) benzophenone, 3-isopentenyl-2, 4, 6-trihydroxybenzophenone, 4-diazepinyl-2, 2-disulfonate, alpha-arylalkenyl azide, vinyl azide, 4- (bromomethyl) benzophenone, 4-hydroxybenzophenone, 2, 4-dihydroxybenzophenone, 2' -dihydroxybenzophenone, 4 '-dihydroxybenzophenone, 4-chloro-4' -hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, or 2,3, 4-trihydroxybenzophenone.
Preferably, the compound containing a functional group capable of coordinating to a metal ion includes any one or a combination of at least two of acrylic acid, methacrylic acid, ethyl 2-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-propenolignan, polyacrylic acid, polymethacrylic acid, or polyethyleneimine.
Preferably, the other reagent comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, t-butyl benzoyl peroxide, methyl ethyl ketone peroxide, triethylamine, pyridine, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, or sodium hydroxide.
Preferably, the solvent comprises any one or a combination of at least two of trifluoroethanol, methanol, ethanol, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, dimethyl sulfoxide, water, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, hexamethylphosphoric triamide, or acetone.
Preferably, the temperature of the reaction is 10 to 120 ℃, e.g., 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or 120 ℃, and the like, and the reaction time is 0.1 to 24 hours, e.g., 0.1 hour, 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 24 hours, or the like.
Preferably, the reaction is carried out under inert gas.
Preferably, the inert gas comprises nitrogen or argon.
Preferably, the reaction comprises a 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 (3) dropwise adding the solution after the reaction is finished 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 a combination of at least two of diethyl ether, petroleum ether, acetone, n-hexane, n-pentane, n-heptane and carbon tetrachloride.
In a third aspect, the present invention provides a method of preparing an ion imprinted polymer, the method comprising the steps of:
(1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to obtain coating material;
(2) Coating the coating material in the step (1) on the surface of a substrate material, drying, irradiating with ultraviolet light, and performing post-treatment to obtain the ion imprinting polymer;
the functional polymer comprises the functional polymer of the first aspect.
The functional polymer comprises the photoreactive group and the functional group which can coordinate with metal ions, and the photoreactive group can utilize ultraviolet light reaction to enable the substrate material and the functional polymer to realize chemical bonding, so that the bonding 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.
In the process of preparing the ion imprinted polymer by utilizing the functional polymer, the photoreaction grafting method can be used for enabling the substrate material and the functional polymer to be quickly and chemically bonded, 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 the following.
Preferably, the cross-linking agent comprises any one or a combination of at least two of sodium 4, 4-diazastilbene-2, 2 disulfonate, epichlorohydrin, glutaraldehyde or ethylene glycol diglycidyl ether.
Preferably, the solvent of step (1) comprises any one or a combination of at least two of water, ethanol, methanol, n-hexane or n-heptane solutions.
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%, or 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%, or 20%, etc.), the crosslinker 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%, or 30%, etc.), and the remainder is solvent, based on 100% 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 of step (2) comprises a filter membrane, a filter cloth, a fiber or a microsphere.
Preferably, the material of the substrate material in the 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, polypropylene cyanide or nylon-6.
Preferably, the coating of step (2) is preceded by a step of washing and pre-treating the substrate material.
Preferably, the washing includes immersing the base material in ethanol and ultrasonic washing.
Preferably, the pretreatment mode comprises any one or a 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 of step (2) comprises any one or a combination of at least two of spraying, dipping, knife coating or surface printing.
Preferably, the drying in the step (2) includes any one of solvent evaporation, blow drying under nitrogen atmosphere or hot air drying.
Preferably, the light source for ultraviolet irradiation in the step (2) comprises a high-pressure mercury lamp, an ultraviolet curing device, an ultraviolet curing machine or an ultraviolet LED area light source.
Preferably, the time of the ultraviolet light irradiation in the 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 light irradiation is 50-1000 mW/cm 2 For example 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 Etc.
Preferably, the post-treatment of step (2) comprises washing and vacuum drying.
Preferably, the washing comprises immersing the material obtained after the ultraviolet irradiation in an eluent to wash out metal ions.
Preferably, the eluent comprises 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 solution.
As a preferred technical scheme of the invention, the preparation method of the ion imprinting polymer comprises the following steps:
(1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to obtain 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 rest is solvent;
(2) After the substrate material is cleaned and pretreated, the coating material in the step (1) is coated on the surface of the substrate material, dried and the strength is 50mW/cm to 1000mW/cm 2 Irradiating for 1-10 min under ultraviolet light, soaking the material obtained after ultraviolet light irradiation in an eluent to wash out metal ions, and vacuum drying 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 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 provided by the invention is used for preparing an ion imprinting polymer, the photoreactive group can be used for realizing chemical bonding between a substrate material and the functional polymer by utilizing ultraviolet light reaction, so that the bonding stability of the functional polymer and the substrate material is improved; the functional group which can coordinate 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 utilizing the functional polymer, the photoreaction grafting method can lead the substrate material and the functional polymer to be chemically bonded, 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 infrared spectrum of the functional polymer prepared in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of the functional polymer prepared in example 1;
FIG. 3 is a scanning electron microscope image of the ion-imprinted polymer prepared in example 1;
FIGS. 4a and 4b are graphs of contact angle test results for the ion-imprinted polymer prepared in example 1 and the non-ion-imprinted polymer, respectively;
FIG. 5 is an infrared spectrum of the functional polymer prepared in example 8;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the functional polymer prepared in example 8;
FIG. 7 is a scanning electron microscope image of the ion imprinted polymer prepared in example 8;
fig. 8a and 8b are graphs of contact angle test results of the ion-imprinted polymer prepared in example 8 and the contact angle test results of the non-ion-imprinted polymer, respectively.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
In this example, an ion imprinted polymer is provided, which is prepared by the following method:
(1) Preparation of functional polymers: adding 0.005mol of 4-propylene oxy-2-hydroxybenzophenone and 0.045mol of acrylic acid into a three-neck flask containing 50mL of absolute ethyl alcohol, vacuumizing and introducing nitrogen three times, adding 0.0005mol of azodiisobutyronitrile under the nitrogen atmosphere, vacuumizing and introducing nitrogen three times again, sealing, heating to 70 ℃ for reaction for 10 hours, and purifying to prepare a product to obtain the functional polymer, wherein the structural formula is shown as the following, the infrared spectrum is shown as the figure 1, and the nuclear magnetic resonance spectrum is shown as the figure 2;
(2) The functional polymer is prepared from Dy (NO) 3 ) 3 ·6H 2 Adding O and 4, 4-diazastilbene-2, 2 sodium disulfonate into water, and ultrasonic dispersing to obtain coating material (Dy (NO) based on 100% total weight of the coating material 3 ) 3 The content of the polymer is 3%, the content of the functional polymer is 10%, the content of the 4, 4-diazastilbene-2, 2 sodium disulfonate is 15%, the balance is water), the PVDF microporous filter membrane is cleaned, corona treatment is carried out for 30s, the coating material is coated on the surface of the PVDF microporous filter membrane, and after being dried, the strength is 500mW/cm 2 Irradiating for 5min under 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 (the test solvent is water) is shown in fig. 4 a.
Dy (NO) is not added in the step (2) 3 ) 3 ·6H 2 O, step (3) is not performed with the acid washing step, so that the nonionic imprinted polymer can be obtained, and the contact angle test result is shown in FIG. 4 b.
20.0mg Dy prepared in this example 3+ Ion imprinted polymer applied to Dy 3+ Adsorbing Dy in 50mg/L solution 3+ The adsorption capacity of the ion imprinting polymer of (2) 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 polymers: adding 0.015mol of 4-propenoxybenzophenone and 0.045mol of methacrylic acid into a three-neck flask containing 50mL of absolute ethyl alcohol, vacuumizing and introducing nitrogen three times, adding 0.0025mol of azodiisoheptanenitrile under the nitrogen atmosphere, vacuumizing and introducing nitrogen three times again, sealing, heating to 50 ℃ for reaction for 12 hours, and purifying to prepare a product to obtain the functional polymer, wherein the structural formula is shown as follows;
(2) The functional polymer and EuCl are mixed 3 ·6H 2 Adding O and 4, 4-diazastilbene-2, 2 sodium disulfonate into water, and ultrasonic dispersing to obtain coating material (EuCl based on 100% of the total weight of the coating material) 3 The content of the polymer is 0.5%, the content of the functional polymer is 5%, the content of the 4, 4-diazastilbene-2, 2 sodium disulfonate is 5%, and the balance is water), the PVDF microporous filter membrane is cleaned, corona treatment is carried out for 30s, the coating material is coated on the surface of the PVDF microporous filter membrane, and the intensity is 500mW/cm after the coating material is dried in the air 2 Irradiating for 5min under ultraviolet lamp;
step (3) is the same as in example 1.
20.0mg Eu prepared in this example 3+ Ion imprinted polymer applied to Eu 3+ Adsorbing Eu in 50mg/L solution 3+ The adsorption capacity of the ion imprinting polymer of (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 polymers: adding 0.02mol of 4-acryloyloxy-2-hydroxybenzophenone and 0.045mol of 3-propenolignan into a three-neck flask containing 50mL of absolute ethyl alcohol, vacuumizing and introducing nitrogen for three times, adding 0.004mol of azodiisobutyronitrile under the nitrogen atmosphere, vacuumizing and introducing nitrogen for three times again, sealing, then raising the temperature to 90 ℃ for reaction for 8 hours, and purifying to prepare a product to obtain the functional polymer, wherein the structural formula of the functional polymer is shown as follows;
(2) The functional polymer and CeCl are mixed 3 ·7H 2 Adding O and 4, 4-diazastilbene-2, 2 sodium disulfonate into water, and ultrasonic dispersing to obtain coating material (CeCl based on 100% of the total weight of the coating material) 3 The content of the polymer is 5%, the content of the functional polymer is 20%, the content of the 4, 4-diazastilbene-2, 2 sodium disulfonate is 30%, the balance is water), the PVDF microporous filter membrane is cleaned, corona treatment is carried out for 30s, the coating material is coated on the surface of the PVDF microporous filter membrane, and after being dried, the strength is 500mW/cm 2 Irradiating for 5min under ultraviolet lamp;
step (3) is the same as in example 1.
20.0mg Ce prepared in this example 3+ Ion imprinted polymer applied to Ce 3+ Adsorbing Ce in 50mg/L solution 3+ The adsorption capacity of the ion imprinting polymer of (2) was 11.7mg/g, and the imprinting factor was 1.44.
Example 4
This example differs from example 1 only in that the photoreactive group-containing compound used in the preparation of the functional polymer in step (1) is 4-acryloxybenzophenone, the compound containing a functional group capable of coordinating to a metal ion is acrylamide, the other reagent 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:
20.0mg of Ni prepared in this example 2+ Ion imprinted polymer applied to Ni 2+ Adsorbing in 50mg/L solution, ni 2+ The adsorption capacity of the ion imprinting polymer of (2) was 12.6mg/g, and the imprinting factor was 1.39.
Example 5
The present example differs from example 1 only in that the photoreactive group-containing compound used in the preparation of the functional polymer in step (1) is 2-hydroxy-4- (methacryloyloxy) benzophenone, the compound containing 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:
20.0mg of Cu prepared in this example 2+ Ion imprinted polymer applied to Cu 2+ Adsorbing Cu in 50mg/L solution 2+ The adsorption capacity of the ion imprinting polymer of (2) was 12.3mg/g, and the imprinting factor was 1.73.
Example 6
The present example differs from example 1 only in that the photoreactive group-containing compound used in the preparation of the functional polymer in step (1) is 2-hydroxy-4- (methacryloyloxy) benzophenone, the compound containing a functional group capable of coordinating to 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 structural formula of the functional polymer prepared in this example is shown below:
20.0mg of La prepared in this example 3+ Ion imprinted polymer applied to La 3+ Adsorbing in 50mg/L solution, la 3+ The adsorption capacity of the ion imprinting polymer of (2) was 9.5mg/g, and the imprinting factor was 1.43.
Example 7
This example differs from example 1 only in that work is produced in step (1)The photoreactive group-containing compound in the case of the energy-sensitive polymer is 4-acryloxybenzophenone, the functional group-containing compound capable of coordinating with metal ions is methyl methacrylate, and the metal salt in the coating material in the step (2) is Cu (NO 3 ) 2 ·3H 2 O。
The structural formula of the functional polymer prepared in this example is shown below:
20.0mg of Cu prepared in this example 2+ Ion imprinted polymer applied to Cu 2+ Adsorbing Cu in 50mg/L solution 2+ The adsorption capacity of the ion imprinting polymer of (2) was 15.3mg/g, and the imprinting factor was 1.78.
Example 8
(1) Preparation of functional polymers: 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 three times, adding 0.0005mol of potassium carbonate under the nitrogen atmosphere, vacuumizing and introducing nitrogen three times again, sealing, heating to 70 ℃ for reaction for 10 hours, and purifying to prepare a product to obtain the functional polymer, wherein the structural formula is shown as the following, the infrared spectrum is shown as the figure 5, and the nuclear magnetic hydrogen spectrum is shown as the figure 6;
(2) The functional polymer is prepared from Gd (NO 3 ) 3 ·6H 2 Adding O and 4, 4-diazastilbene-2, 2 sodium disulfonate into water, performing ultrasonic dispersion to obtain a coating material, cleaning a PVDF microporous filter membrane, performing corona treatment for 30s, coating the coating material on the surface of the PVDF microporous filter membrane, and air-drying the coating material, wherein the strength is 500mW/cm 2 Irradiating for 5min under ultraviolet lamp;
(3) Repeatedly washing the material prepared in the step (2) in 0.1mol/L hydrochloric acidWashing and removing 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 microscope image of the ion imprinted polymer is shown in fig. 7, and the contact angle test result is shown in fig. 8 a.
Gd (NO) is not added in the step (2) 3 ) 3 ·6H 2 O, step (3) is not performed with the acid washing step, so that the nonionic imprinted polymer can be obtained, and the contact angle test result is shown in FIG. 8 b.
20.0mg Gd prepared in this example 3+ Application of ion imprinting polymer in Gd 3+ Absorbing Gd in 50mg/L solution 3+ The adsorption capacity of the ion imprinting polymer of (2) 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 3 ) 3 3% of functional polymer, 3% of 4, 4-diphenylethylene-2, 2-disulfonate, 15% of water and the balance.
20.0mg Dy prepared in this example 3+ Ion imprinted polymer applied to Dy 3+ Adsorbing Dy in 50mg/L solution 3+ The adsorption capacity of the ion imprinting polymer of (2) 8mg/g and the imprinting factor of (1.39).
Comparative example 2
This comparative example differs from example 1 only in that Dy (NO 3 ) 3 3% of functional polymer, 25% of 4, 4-diphenylethene-2, 2-disulfonate, 15% of water and the balance.
20.0mg Dy prepared in this example 3+ Ion imprinted polymer applied to Dy 3+ Adsorbing Dy in 50mg/L solution 3+ The adsorption capacity of the ion imprinting polymer of (2) was 6.4mg/g, and the imprinting factor was 1.04.
The applicant states that the functional polymer and the method of preparation of the invention, and the method of preparation of the ion-imprinted polymer using the same, are described by the above examples, but the invention is not limited to the above examples, i.e. it is not meant that the invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (13)
1. A functional polymer, characterized in that the functional polymer is selected from any one of the following polymers:
wherein m is an integer of 1 to 100, and n is an integer of 1 to 300.
2. The method of producing a functional polymer according to claim 1, characterized in that the method of producing comprises the steps of:
mixing a compound containing photoreactive groups, a compound containing functional groups capable of coordinating with metal ions, other reagents and a solvent, reacting, and performing aftertreatment to obtain the functional polymer;
the molar ratio of the compound containing the functional group capable of coordinating with the metal ion, the compound containing the photoreactive group and other reagents is 1 (0.05-0.5): 0.01-0.1;
the photoreactive group-containing compound includes any one or a combination of at least two of 4-vinylbenzophenone, 4-vinyl-4 '-methoxybenzophenone, 4-propenoxy-2-hydroxybenzophenone, 4-propenoxy-benzophenone, 2-hydroxy-4- (methacryloxy) benzophenone, 3-isopentenyl-2, 4, 6-trihydroxybenzophenone, 4-diazidostilbene-2, 2-disulfonate, alpha-arylalkenyl azide, vinyl azide, 4- (bromomethyl) benzophenone, 4-hydroxybenzophenone, 2, 4-dihydroxybenzophenone, 2' -dihydroxybenzophenone, 4 '-dihydroxybenzophenone, 4-chloro-4' -hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, or 2,3, 4-trihydroxybenzophenone;
the compound containing a functional group capable of coordinating with a metal ion comprises any one or a combination of at least two 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-propenolonotannin, polyacrylic acid, polymethacrylic acid or polyethyleneimine;
the other reagent comprises any one or a combination of at least two of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, tertiary butyl benzoyl peroxide, methyl ethyl ketone peroxide, triethylamine, pyridine, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate or sodium hydroxide;
the reaction temperature is 50-90 ℃, and the reaction time is 8-12 h.
3. The method according to claim 2, wherein the solvent comprises any one or a combination of at least two of trifluoroethanol, methanol, ethanol, tetrahydrofuran, dichloromethane, chloroform, cyclohexanone, dimethyl sulfoxide, water, acetonitrile, N-dimethyl sulfoxide, N-dimethylformamide, hexamethylphosphoric triamide, and acetone.
4. The method according to claim 2, wherein the reaction is carried out under inert gas.
5. The method of claim 2, wherein the reaction comprises a radical polymerization reaction, an atom transfer radical polymerization reaction, or a substitution reaction.
6. The method of claim 2, wherein the post-treatment comprises purification, drying.
7. A method for preparing an ion imprinted polymer, which is characterized by comprising the following steps:
(1) Mixing and dispersing metal salt, functional polymer, cross-linking agent and solvent to obtain coating material;
(2) Coating the coating material in the step (1) on the surface of a substrate material, drying, irradiating with ultraviolet light, and performing post-treatment to obtain the ion imprinting polymer;
the functional polymer comprises the functional polymer of claim 1;
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+ 、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;
the cross-linking agent comprises any one or a combination of at least two of 4, 4-diazastilbene-2, 2-disulfonate, epichlorohydrin, glutaraldehyde or ethylene glycol diglycidyl ether;
the solvent in the step (1) comprises any one or a combination of at least two of water, ethanol, methanol, n-hexane or n-heptane solution;
the substrate material in the step (2) is made of any one or a combination of at least two of polyethylene, polystyrene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyurethane, polyimide, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile or nylon-6;
the time of the ultraviolet light irradiation in the step (2) is 5min, and the intensity of the ultraviolet light irradiation is 500mW/cm 2 。
8. The method according to claim 7, wherein the metal salt is contained in an amount of 0.5 to 10%, the functional polymer is contained in an amount of 5 to 20%, the crosslinking agent is contained in an amount of 5 to 30%, and the balance is a solvent, based on 100% by weight of the total coating material.
9. The method of claim 7, wherein the shape of the base material of step (2) comprises a filter membrane, a filter cloth, a fiber, or a microsphere.
10. The method of claim 7, wherein the coating of step (2) is preceded by the step of cleaning and pre-treating the substrate material.
11. The method according to claim 7, wherein the post-treatment in step (2) comprises washing and vacuum drying.
12. The method of claim 11, wherein the washing comprises immersing the material obtained after the ultraviolet irradiation in an eluent to wash out metal ions.
13. An ion imprinting polymer, which is prepared by the preparation method according to claim 7.
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