CN113845631A - Preparation method and application of novel molecularly imprinted polymer with bio-based macromolecules - Google Patents
Preparation method and application of novel molecularly imprinted polymer with bio-based macromolecules Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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Abstract
The invention discloses a preparation method of a novel molecularly imprinted polymer with bio-based macromolecules, which selects modified Lignin as a cross-linking agent for preparing a novel molecularly imprinted polymer (Lignin-MIP) taking perfluorooctanoic acid as a template molecule, so that the selective adsorption capacity of the novel molecularly imprinted polymer on the template molecule perfluorochemical in a water body can be improved, the adsorption speed is high, the adsorption capacity is large, and a new thought is developed for the application of biomass materials in the aspect of water treatment.
Description
Technical Field
The invention relates to the technical field of organic matter synthesis, in particular to a preparation method and application of a novel molecularly imprinted polymer with bio-based macromolecules.
Background
The molecular imprinting technology is that template molecule is contacted with functional monomer under specific condition, the two are combined together to form polymer through covalent bond and non-covalent bond acting force between molecules, the template molecule is eluted by specific method, pore channels and combination sites corresponding to the template molecule are left in the polymer, and the pore channels and the combination sites correspond to the size, shape and chemical bond of the template molecule one by one, so that the template molecule can be identified highly selectively in a complex system, and the molecular imprinting technology can be used in the fields of separation, identification, detection and the like.
Perfluoro compounds have excellent chemical stability and are widely used in the fields of leather manufacture, surface antifouling, electroplating and the like. With its mass production and use, a large amount of the perfluoro compound is discharged into the environment, causing environmental pollution. The perfluor compound is an environmental pollutant with strong biological toxicity, and has biological accumulation, environmental persistence and difficult degradability in organisms and natural environment. How to remove the perfluorinated compounds in the water body quickly and efficiently is a problem to be solved by the technical personnel in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a novel molecularly imprinted polymer with a bio-based macromolecule, so as to solve the problem of how to quickly and efficiently remove perfluorinated compounds in a water body in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a novel molecularly imprinted polymer with bio-based macromolecules comprises the following steps:
step 1) dissolving a template agent and a functional monomer in an organic solvent, and mixing at room temperature to form a prepolymer solution; wherein the template agent is PFOA, the functional monomers are trifluoromethyl acrylic acid and 4-vinylpyridine, and the molar ratio of PFOA, trifluoromethyl acrylic acid and 4-vinylpyridine is 1 (1-3) to (3-1);
step 2) adding water and modified lignin into the prepolymer solution, introducing nitrogen for purging under the ultrasonic condition, adding an initiator, and reacting at 60-70 ℃ for 45-50h to form a tan precipitate; wherein the mol ratio of the modified lignin, the template agent and the functional monomer is (20-30) to 1:4, and the dosage of the initiator is 8-15% of the total mass of the reaction system;
and 3) filtering and washing the tan precipitate obtained in the step 2), washing the template agent with a mixed solution of acetic acid and methanol under an ultrasonic condition, repeatedly washing for multiple times, determining to elute the template agent, and freeze-drying the polymer without the template agent for 20-30h to obtain the novel molecularly imprinted polymer with the lignin group.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts perfluorinated compounds as template molecules, utilizes the polymer formed between the template molecules and functional monomers, and removes the template molecules from the polymer, so that cavities left in the polymer can remember the structure and the size of the template molecules, and can effectively and selectively adsorb the template molecules by virtue of non-covalent acting force, thereby effectively removing the perfluorinated compounds in the water body.
2. According to the invention, lignin is selected as a cross-linking agent, and through the research and the unexpected discovery, bio-based macromolecules are cross-linked on the polymer, so that the adsorption effect of the polymer on the perfluorinated compounds is remarkably improved, and the deep analysis discovers that active groups such as aromatic groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, sulfonic groups, carbon-based conjugated double bonds and the like exist in the molecular structure of the lignin, so that more adsorption sites are provided for the polymer, the ion exchange and adsorption capacities of the polymer are further improved, and the polymer can efficiently and selectively adsorb the perfluorinated compounds in a water body; meanwhile, the lignin has the characteristics of low cost, simple operation, convenient use and the like, and the discovery of the polymer improves the resource utilization of the lignin which is a renewable resource, expands the application range of the lignin, and has obvious social benefit and environmental benefit.
Detailed Description
The present invention will be further described with reference to the following examples.
Preparation method of novel molecularly imprinted polymer with bio-based macromolecules
Example 1
Step 1) dissolving 0.1mmol of template PFOA, 0.1mmol of trifluoromethyl acrylic acid and 0.3mmol of 4-vinylpyridine in 10mL of acetonitrile solution, and oscillating at constant temperature for 6h at room temperature to prepare a molecular imprinting prepolymer solution.
And 2) adding 1mL of deionized water into the prepolymer solution obtained in the step 1), adding 0.4g of modified lignin ALS, introducing nitrogen, performing ultrasonic treatment for 20min, placing in a water bath at 65 ℃, adding 0.06g of ammonium persulfate and 0.03g of sodium bisulfite as initiators, reacting for 48h, cooling to room temperature, and filtering, washing and drying to obtain a tan precipitate.
And 3) filtering and washing the tan precipitate obtained in the step 2), washing the template agent by using a mixed solution of acetic acid and methanol under an ultrasonic condition, repeatedly washing for 5 times, detecting the concentration of PFOA in the washing residual liquid by adopting liquid chromatography-mass spectrometry to determine the elution effect of the template agent, and freeze-drying the polymer from which the template agent is removed for 24 hours to obtain the novel molecularly imprinted polymer Lignin-MIP with Lignin groups.
Wherein, lignin is subjected to alkylation modification treatment, unsaturated bonds are introduced into an SLS molecular structure to obtain Alkylated Lignin (ALS), and the reactivity of the alkylated lignin is improved, wherein the specific reaction is as follows:
the modified lignin is prepared by the following method:
weighing 1.0g of lignin (SLS), dissolving in 20mL of NaOH aqueous solution with the concentration of 0.5mol/L at room temperature, adding 0.65g of bromoacetylene, stirring at 75 ℃ for reaction for 2h, cooling to room temperature, adjusting the pH to 2 with 2mol/L of HCl solution, precipitating, washing with deionized water for multiple times, and freeze-drying to obtain the Alkylated Lignin (ALS).
Example 2
The preparation method is completely the same as that of example 1, except that the preparation method of the modified lignin is different, unsaturated bonds are introduced into the SLS molecular structure through modification treatment to obtain methyl acrylate Modified Lignin (MLS), and the specific reaction is as follows:
the modified lignin is prepared by the following method:
dissolving 3.5g of lignin (SLS), 8.5g of methacrylic anhydride (MAA) and 0.1g of Triethylamine (TEA) in 60mL of deionized water at room temperature, heating to 70 ℃, stirring for reacting for 18h, cooling to room temperature, pouring the solution into an anhydrous ethanol solution, precipitating, washing for multiple times, and freeze-drying to obtain the methyl acrylate Modified Lignin (MLS).
By adopting the preparation method of the embodiment 1 and according to the raw material proportion in the table 1, the embodiments 3-6 are prepared.
TABLE 1
Meanwhile, a comparative example was prepared to compare the performance with the inventive example, wherein the preparation method of comparative example 1 was identical to that of inventive example 1 except that comparative example 1 used a common crosslinking agent ethylene glycol dimethacrylate (EDMA) in an amount of 25 times (molar ratio) that of the templating agent.
In the prior art, the molecular imprinting technology can prepare a specific adsorbent with selective adsorption performance on pollutants in a water body. A polymer is formed between the template molecules and the functional monomer, and then the template molecules are eluted from the polymer, and the structure and the size of the template molecules can be remembered by a cavity left in the polymer, so that the template molecule is used for selective adsorption of template pollutants in a water body. The adsorption capacity of the adsorbent is related to the number of adsorption sites left by the template agent, if the adsorption quantity of pollutants is increased, the use amounts of the template agent, the adsorption functional monomer and the cross-linking agent are increased to obtain more adsorption sites, and the problem of high production cost exists. In the research process of preparing the perfluorinated compound adsorbent by the molecular imprinting technology, the lignin is unexpectedly found to be incapable of being used as a cross-linking agent to be added into the molecular imprinting technology, but after the biomass macromolecular lignin is modified, the lignin can be used as the cross-linking agent to prepare the molecular imprinting adsorbent for removing the pollutant perfluorinated compound in the water body. Researches find that the adsorption effect of the adsorbent is remarkably improved due to the addition of the biomass-based lignin cross-linking agent. Deep analysis shows that active groups such as aromatic groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, sulfonic groups, carbon-based conjugated double bonds and the like exist in the molecular structure of lignin, and the modified lignin can be used as a cross-linking agent and also can provide more adsorption sites for polymers, so that the ion exchange and adsorption capacity of the molecularly imprinted polymer is improved, and the molecularly imprinted polymer can efficiently and selectively adsorb perfluorinated compounds in water. Meanwhile, the invention also finds that the molecularly imprinted polymer obtained after adding the modified lignin has good biocompatibility and small influence on the environment, the lignin has the characteristics of low cost, simple operation, convenient use and the like, the adsorbent prepared by adding the modified lignin has better adsorption effect under the condition of the same template molecule dosage, and the discovery of the polymer improves the resource utilization of the lignin which is a renewable resource, expands the application range thereof and has obvious social benefit and environmental benefit.
Second, performance verification
The adsorption effect was verified by taking examples 1 and 2 as examples.
Weighing 10mg of the molecularly imprinted polymer Lignin-MIP obtained by the method, putting the weighed 10mg into 50mL of a perfluorinated compound (PFCs) mixed solution, wherein the solution contains 5 perfluorinated compounds of perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPEA), perfluorodecanoic acid (PFDA), perfluorooctanesulfonic acid (PFOS) and perfluorohexanesulfonic acid (PFHxS), the concentration of the perfluorinated compounds is 20 mu g/L, adjusting the pH value of the solution to be 4.5, oscillating the solution in a constant temperature shaking table at 20 ℃ and 180rpm for 24h, filtering, collecting adsorption residual liquid, and measuring the selective adsorption performance of the Lignin-MIP by adopting liquid chromatography, wherein the result shows that the prepared Lignin-MIP has 94% of adsorption rate on the PFOA as a template agent and 6-62% of adsorption rate on a perfluorinated compound as a non-template agent, and the prepared Lignin-based molecularly imprinted adsorbent has obvious selective adsorption performance on the template agent.
Table 2 shows the adsorption rates of examples and comparative example 1 for various perfluorinated compounds in the mixed solution, wherein comparative example 2 is the adsorption of perfluorinated compounds in the solution by directly adding ordinary lignin SLS.
Table 2 (unit:%)
Through research, unmodified lignin can not be used as a cross-linking agent to prepare the molecular imprinting adsorbent, so that the adsorption rate of the conventional lignin added in comparative example 2 on the perfluorinated compounds is not ideal, even does not reach 40%, and thus, the lignin does not have the ideal adsorption effect on the perfluorinated compounds.
In comparative example 1, ethylene glycol dimethacrylate is selected as a cross-linking agent, although the adsorption rate of the prepared molecularly imprinted adsorbent to template molecules can reach 90%, if the adsorption rate is increased, the use amount of the template agent, the adsorption functional monomer and the cross-linking agent is increased, the use amount of the cross-linking agent in comparative example 1 is the same as that of the cross-linking agents in examples 1-2, and the adsorption effect is obviously lower than that of examples 1-2. Meanwhile, after the analysis of the embodiments 3 to 6, it is found that the higher the dosage of the modified lignin is, the better the dosage of the modified lignin is, when the dosage of the modified lignin is 20 mol ratio, the adsorption rate can also reach more than 80%, and when the dosage of the modified lignin reaches 30 mol ratio, the adsorption effect is not even as good as that of the embodiment with 20 mol ratio.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a novel molecularly imprinted polymer with bio-based macromolecules is characterized by comprising the following steps:
step 1) dissolving a template agent and a functional monomer in an organic solvent, and mixing at room temperature to form a prepolymer solution; wherein the template agent is PFOA, the functional monomers are trifluoromethyl acrylic acid and 4-vinylpyridine, and the molar ratio of PFOA, trifluoromethyl acrylic acid and 4-vinylpyridine is 1 (1-3) to (3-1);
step 2) adding water and modified lignin into the prepolymer solution, introducing nitrogen for purging under the ultrasonic condition, adding an initiator, and reacting at 60-70 ℃ for 45-50h to form a tan precipitate; wherein the mol ratio of the modified lignin, the template agent and the functional monomer is (20-30) to 1:4, and the dosage of the initiator is 8-15% of the total mass of the reaction system;
and 3) filtering and washing the tan precipitate obtained in the step 2), washing the template agent with a mixed solution of acetic acid and methanol under an ultrasonic condition, repeatedly washing for multiple times, determining to elute the template agent, and freeze-drying the polymer without the template agent for 20-30h to obtain the novel molecularly imprinted polymer with the lignin group.
2. The method of claim 1, wherein the modified lignin is prepared by alkylation reaction.
3. The method of preparing a novel molecularly imprinted polymer with a bio-based macromolecule according to claim 2, wherein the modified lignin is prepared by the following method:
dissolving lignin in a sodium hydroxide solution at room temperature, adding a modifier, stirring and reacting at 70-80 ℃ for 1-3h, cooling to room temperature, adjusting the pH value of a reaction system until precipitates, filtering, washing with water for multiple times, and freeze-drying to obtain modified lignin; wherein the molar ratio of the modifier to the lignin is (1-3) to 1.
4. The method of claim 3, wherein the modifier is one of bromoacetylene or bromopropyne.
5. The method of preparing a novel molecularly imprinted polymer with a bio-based macromolecule according to claim 2, wherein the modified lignin is prepared by the following method:
adding lignin, a modifier and triethylamine into deionized water at room temperature, stirring and reacting for 15-20h at 65-75 ℃, cooling to room temperature, pouring into absolute ethyl alcohol for precipitation, filtering, washing for multiple times, and freeze-drying to obtain modified lignin; wherein the molar ratio of the lignin to the modifier to the triethylamine is (8-10) to (40-50) to 1.
6. The method of claim 5, wherein the modifier is methacrylic anhydride.
7. The method of claim 1, wherein the initiator is (NH)4)2S2O8And NaHSO3The mass ratio of the two is (1-2) to 1.
8. The method of claim 1, wherein the volume ratio of acetic acid to methanol in the mixed solution of acetic acid and methanol is 1:4-1: 6.
9. The method for preparing a novel molecularly imprinted polymer having a bio-based macromolecule according to claim 1, wherein in step 1), the organic solvent is acetonitrile; in the step 2), the volume ratio of the prepolymer solution to water is (8-10) to 1.
10. The application of the novel molecularly imprinted polymer with the bio-based macromolecules is characterized in that the molecularly imprinted polymer prepared by the preparation method of any one of claims 1 to 9 is used for adsorbing template molecules in water.
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