CN108976361A - A kind of preparation method and application of the affine imprinted polymer of the hollow boron of single hole - Google Patents
A kind of preparation method and application of the affine imprinted polymer of the hollow boron of single hole Download PDFInfo
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Abstract
The present invention relates to the methods that a kind of preparation method and application of the affine imprinted polymer of the hollow boron of single hole more particularly to distillation-precipitation polymerization prepare the hollow boron affinity molecule imprinted polymer of single hole, belong to biological medicine functional material preparation technical field；The invention patent passes through DPP first and causes the A Polystyrene Spheres Template surface that polymerization is coated on carboxy blocking using 4- vinylphenylboronic acid monomer；In addition, for the symmetrical volume contraction of adjoint microphase-separated effect and shell material induction of the generation of polymer shell mesoporous, etching polymer shell with holes by THF can be obtained the affine imprinted polymer of the hollow boron of single hole during DPP；Then the affine imprinted polymer of the hollow boron of single hole is sealed in bag filter and is used for Selective Separation purifying LTL；The affine imprinted polymer of the hollow boron of single hole prepared by the present invention overcomes the problems such as existing common molecular imprinting adsorbing agent is low to LTL adsorbing separation dynamics, saturated capacity is small and poor selectivity.
Description
Technical field
The present invention relates to a kind of preparation method and application of the affine imprinted polymer of the hollow boron of single hole, more particularly to distillation-
The method that precipitation polymerization prepares the hollow boron affinity molecule imprinted polymer of single hole belongs to biological medicine functional material technology of preparing neck
Domain.
Background technique
Luteolin (LTL) is a kind of natural chromocor compound, has stronger antioxidant activity, can inhibit tumour
The proliferation of cell, induction tumour cell failure are even dead.Natural reseda rich in peanut shell, composite family class Chinese herbal medicine
Element.Therefore, extracting from natural products has important science and economic significance with Selective Separation purifying luteolin.Mesh
Before, the extracting method of Luteolin from Peanut is more, mainly select a kind of solvent under the means such as ultrasound, microwave auxiliary into
Row extraction, common solvent have hot water, lye, methanol, ethyl alcohol, acetoneand ethyl acetate etc..The sweet-scented osmanthus obtained after extracting
Careless element crude extract ingredient is more, is the complex system that there is different chemical scales, form, multicomponent to coexist, need to further divide
The links such as health care product and clinical treatment could be applied to by removing impurity from purifying.
Common isolation and purification method mainly has the heavy method of acid, thin layer chromatography, column chromatography, gradient extraction and macropore tree
Rouge adsorption separation method etc..Although these methods respectively there are particular advantages, also respectively there is its limitation, wherein the defect of general character is method
Poor selectivity, obtained product purity be not high.Therefore, it establishes and improves Selective recognition and isolate and purify in peanut shell extracting solution
The new method of luteolin, to obtain higher degree while increase product yield be current project urgently to be solved.
Molecularly imprinted polymer (Molecularly Imprinted Polymers, MIPs) is a kind of with molecule knowledge
The novel high polymer material of other ability, also referred to as artificial antibody.Usually according to the structure of template molecule, selects or design is closed
At specific function monomer；Template molecule and function monomer assemble to form multiple action point, then by cross-linked polymeric process this
Kind effect " memory " is got off；After removing template molecule, it has been left in converging network and template molecule size, shape, functional group
Complementary hole recombines to the hole property of can choose template molecule, realizes the specific recognition to object.
Boron affine technolog is to carry out the new method of enrichment and separation, alkalinity to cis-form dihydroxy compound using substituted boracic acid
Hydroxide ion complexing under environment in boric acid base group in boron atom and environment, makes the hybridization state of boron atom by plane
sp2Hydridization is converted into the sp of tetrahedral3Hydridization, at this time the boric acid anion of tetrahedral can in cis-form dihydroxy molecule
O-dihydroxy covalent reaction occur generate five yuan or hexa-atomic of cyclic ester, when environment becomes acidic environment, cyclic ester compound
Reversible hydrolysis can occur for two covalent bonds that esterification is formed, and release cis-form dihydroxy compound.During boron is affine, play
In conjunction with cis-form dihydroxy structure be tetrahedral boric acid anion.Based on substituted boracic acid to the specificity of dihydroxy compounds
The releasability of identification and pH response, boron affine technolog have been used for isolating and purifying for the substances such as polysaccharide, glycoprotein.But it is single
The preparation of the affine imprinted polymer of the hollow boron in hole and the work isolated and purified applied to luteolin have not been reported.
Summary of the invention
It is an object of the invention to overcome, existing common molecular imprinting adsorbing agent is low to LTL adsorbing separation dynamics, is saturated
The problems such as capacity is small and poor selectivity, using distillation-precipitation polymerization (DPP) technology, using carboxy blocking polystyrene as hard template
Boron Coated is affine imprinted polymer, obtains the affine imprinted polymer of the hollow boron of single hole (H-PAVM) after removing removing template.The present invention
The Forming Mechanism in the hole based on microphase-separated and the symmetrical volume contraction of shell material is inquired into；It discloses and is selectively adsorbing and separating sweet-scented osmanthus
The performance of careless element.
The present invention passes through DPP technology first and is coated on the poly- of carboxy blocking using the initiation polymerization of 4- vinylphenylboronic acid monomer
Styrene ball template surface；In addition, during distillation-precipitation polymerization, pair of adjoint microphase-separated effect and shell material
Claim volume contraction induction of the generation of polymer shell mesoporous, etching polymer shell with holes by THF, to can be obtained single hole hollow
Boron is affine imprinted polymer.
To reach above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
Present invention firstly provides a kind of affine imprinted polymer of the hollow boron of single hole, 300 nm of polymer, have hydrophily and
Dispersibility.
The present invention also provides the affine imprinted polymer of the hollow boron of the single hole, i.e. the affine LTL polymer of the hollow boron of single hole is micro-
The synthetic method of ball (H-PAVM), specifically comprises the following steps:
(1) synthesis of polystyrene (CPS) bead of carboxy blocking:
It is synthesized using two step soap-free polymerizations: the acid water of 10 mL ammonium persulfates is added in the aqueous solution of 50 mL styrene first
Solution causes styrene polymerization, obtains monodisperse polystyrene (PS) bead that size is about 220 nm, polymerization reaction is in nitrogen
Carried out under atmosphere, first in 70 DEG C of polyase 13 hours, then 80 DEG C polymerase 10 .5 hours；Then, by acrylic acid, styrene, ammonium persulfate
It is added step-wise in above-mentioned colloidal solution, wherein the amount of acrylic acid is 0.3-1.5g, and is further polymerize under 50-90 DEG C of environment
3-8 hours；Finally, obtaining the carboxy blocking polystyrene that diameter is 400 nm by centrifuge separation and with water and ethanol washing
(CPS) bead.
Wherein, the acrylic acid, styrene, ammonium persulfate mass ratio be 20:200:1;
The molar ratio of the styrene, ammonium persulfate is 1:1.
(2) synthesis of the affine imprinted polymer microballoon (H-PAVM) of the hollow boron of single hole:
By the CPS bead of 7 mg/mL of 3-7 mL, 30-60 mg acrylamide (AA), 10-20 mg 4- vinyl benzene ylboronic acid
(VPBA), two isobutyl of 10-30 mg LTL, 170-210 mg ethylene glycol dimethacrylate (EGDMA) and 6-10 mg azo
Nitrile (AIBN) is dissolved in 30-70 mL acetonitrile, evenly dispersed in order to ensure CPS bead, with 500- in polymerization process
The magnetic stirring speed of 1000 rpm is stirred to react system.Slow prepolymerization 10- is carried out at 40-60 DEG C by free radical initiation
15 hours, then, polymerized/cross-linked reaction carried out 20-28 hours at 50-80 DEG C, and product is in 70-100 DEG C of further aging 4-8
Hour.Then, the core-shell structure microballoon PAVM with single hole is obtained by centrifugation and ethanol washing.Finally with tetrahydrofuran from
CPS karyolysis is removed in hole, and removes LTL template molecule with methanol/acetic acid (8:2, v/v) mixed solvent to prepare in single hole
The empty affine trace microballoon (H-PAVM) of boron.
As a comparison, the method for preparing the affine non-trace microballoon H-PAVN of the hollow boron of single hole is similar with H-PAVM, only not
Template molecule luteolin is added.
Compared with prior art, the beneficial effects of the present invention are embodied in following aspects:
Boron affine technolog is the special shape that reversible covalent combines, and the present invention utilizes the syn diol structure of boric acid and biomolecule
Cyclic ester is formed in alkaline aqueous medium, and reversible hydrolysis occurs in acid medium and releases syn diol structure.With other sweet-scented osmanthus
The adsorption and separation material of careless element is compared, and boric acid polymeric adsorbant has the advantage that selectivity is more preferable, adsorption effect is good；This material
Preparation is whole to use relatively mild method, and step is simple, and easy to operate, the material of synthesis is uniform and yield is high, has successfully been achieved
The effect of LTL is purified while separation and concentration LTL.
The present invention selects 4- vinylphenylboronic acid (VPBA) as function monomer, it only needs a step that can be added to CPS table
Face.The size of hollow sphere and the hole on surface can carry out a degree of adjustment according to reaction condition.It is prepared and is had by DPP
There is the hollow MIPs of the single hole of borate affinity, prepared H-PAVM is then used for Selective Separation purifying LTL.H-
PAVM has that large specific surface area, boron is affine imprinted sites affinity is high, is incorporated into that release dynamics are had excellent performance, capture ability goes out
The advantages that color.Therefore, H-PAVM is reversible Ideal adsorption material of the separation containing syn diol structure compound of selectivity.
Detailed description of the invention
Fig. 1 is the carboxy blocking polystyrene microsphere (a), the PAVM(b that prepare in embodiment 1), H-PAVM(c) TEM figure.
Fig. 2 is embodiment 1 PS and CPS(a that are prepared) and PAVM and H-PAVM(b) FT-IR spectrogram.
Fig. 3 is that CPS, PAVM, H-PAVM for being prepared in embodiment 1 pass through the fluid of dynamic light scattering (DLS) measurement
Aerodynamic diameter and size distribution plot.
Fig. 4 is the CPS(a that is prepared in embodiment 1) and EDS energy spectrum diagram H-PAVM(b), for H-PAVM's in illustration
B element peak.
Fig. 5 is the CPS(a that is prepared in embodiment 1) and XPS spectrum figure H-PAVM(b).
Fig. 6 is influence result figure of the pH condition to the adsorption capacity of H-PAVM, H-PAVN, PAVM.
Fig. 7 is H-PAVM, the curve of adsorption kinetics of H-PAVN, PAVM.
Fig. 8 is H-PAVM, the power of regeneration verification result of H-PAVN, PAVM.
Fig. 9 is H-PAVM, the adsorption capacity and absorption specificity verification result of H-PAVN.
Specific embodiment
Recognition performance evaluation carries out by the following method in the specific embodiment of the invention: complete using Staticadsorption experiment
At.H-PAVM, H-PAVN and PAVM of 10 mg are separately added into the LTL stock solution (35 mg/L) that initial pH is 5.5-8.5
In 12 hours, the content of LTL is measured with ultraviolet-uisible spectrophotometer after absorption, and calculates adsorption capacity according to result；It is full
After absorption, selecting other several has mutually isostructural substance with LTL, as competitive Adsorption object, participates in research H-PAVM, H-
The Selective recognition performance of PAVN and PAVM；By the adsorbance under several different pH value, H-PAVM, H-PAVN and PAVM are studied
Adsorption effect.The pH of LTL solution is adjusted with 0.1 M NaOH or HCl solution.
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1: the synthesis of the hollow LTL- imprinted polymer microballoon of single hole
Carboxy blocking polystyrene (CPS) bead is synthesized using two step soap-free polymerizations: being added first in the aqueous solution of 50 mL styrene
The acidic aqueous solution for entering 10 mL ammonium persulfates causes styrene polymerization, obtains the monodisperse PS bead that size is about 220 nm.It is poly-
Close reaction carries out under nitrogen atmosphere, first in 70 DEG C of polyase 13 hours, again 80 DEG C polymerase 10 .5 hours.Then, by 0.9 g propylene
Acid, 9.0 g styrene and 0.045 g ammonium persulfate are added step-wise in above-mentioned colloidal solution, and further small in 70 DEG C of polymerizations 5
When.Finally, separating carboxy blocking polystyrene (CPS) bead by centrifuge separation and with water and ethanol washing.
By the CPS microballoon (7 mg/mL) of 5 mL, 48 mg acrylamides (AA), 15 mg 4- vinyl benzene ylboronic acids
(VPBA), 20 mg LTL, 192 mg ethylene glycol dimethacrylates (EGDMA) and 8 mg azodiisobutyronitriles (AIBN) are molten
It is evenly dispersed in order to ensure CPS bead in 50 mL acetonitriles, with the magnetic agitation speed of 700 rpm in polymerization process
Degree is stirred to react system.In the first step, slow prepolymerization 12 hours is carried out at 43 DEG C by free radical initiation.Then, gather
Conjunction/cross-linking reaction carries out 24 hours at 60 DEG C, and product is aging 6 hours further at 85 DEG C.Finally, passing through centrifugation and ethyl alcohol
Washing is to obtain the PAVM microballoon with single hole.PS core is removed with tetrahydrofuran, and is mixed with methanol/acetic acid (8:2, v/v)
Solvent further removes LTL template molecule, to prepare the affine trace polymerization microballoon (H-PAVM) of the hollow boron of single hole.
As a comparison, the method for preparing the affine non-trace microballoon H-PAVN of the hollow boron of single hole is similar with H-PAVM, only not
Template molecule luteolin is added.
Fig. 1 a is to use the partial size of no soap copolymerization method synthesis micro- for the carboxy blocking polystyrene of 220 nm in the present embodiment
The TEM image of ball, the PS particle as template is uniform and height is monodispersed, casts in its aqueous dispersions on silicon wafer in room
Hexagoinal lattice is formed after drying under warm environment.
The TEM figure that Fig. 1 b is the PAVM of preparation, the core-shell structure copolymer microsphere sample have uniform thickness of the shell, and diameter is 300 nm,
The surface of high degrees of smoothness and spherical morphology confirm it is poly- (AA-co-VPBA) shell formed by the selective polymerisation of monomer, without
It is the irregular aggregation formation by polymer in PS bead surface.
After Fig. 1 c shows removing PS particle, the TEM image of the single hole H-PAVM microballoon of acquisition, the material of synthesis is uniform, and produces
Amount is high.
Fig. 2 is the embodiment PS and CPS(a that are prepared) and PAVM and H-PAVM(b) FT-IR spectrogram.From Fig. 2 a
In as can be seen that compared with unmodified PS, modified PS nanoparticle due to C=O key stretching vibration and in 1750 cm-1With
1710 cm-1Place has absorption band.Secondly, 3419 cm in PAVM and H-PAVM spectrogram in Fig. 2 b-1Neighbouring characteristic absorption peak
It is the stretching vibration of-OH He-NH-.In addition, 2948 cm in Fig. 2 b sample-1、2860 cm-1With 1465 cm-1Peak be attributed to C-
The stretching vibration and bending vibration of H.In 1731 cm-1Nearby there is a sharp peak, is the stretching vibration of C=O, belongs to
The ester bond of AA.In 1618 cm-1With 1454 cm-1Neighbouring characteristic peak is attributed to N-H in-plane bending vibration respectively and C-N is flexible
Vibration, this can be observed in PAVM and H-PAVM spectrogram.In addition, 1371 cm in PAVM and H-PAVM-1It observes newly at place
Absorption peak further confirms there is-B (OH) in polymer chain2Group illustrates to be successfully incorporated into boric acid base group.
Fig. 3 is the CPS(a that is prepared in the present embodiment), PAVM(b), H-PAVM(c) by dynamic light scattering (DLS)
The Hydrodynamic diameter and size distribution plot of measurement.The hydrodynamic diameter (Dh) of CPS is about 220 nm(Fig. 3 a), this is close
In the size measured by TEM.Fig. 3 b and Fig. 3 c show that the hydrodynamic diameter of PAVM and H-PAVM increases to 300 nm,
PAVM and H-PAVM is demonstrated with hydrophily and excellent dispersibility, is conducive to capture the LTL in water system sample.
Fig. 4 is the CPS(a that is prepared in the present embodiment) and EDS energy spectrum diagram H-PAVM(b) is H-PAVM in illustration
B element peak.As shown in fig. 4 a, in CPS there are C and O element, can be seen that in H-PAVM from Fig. 2 b there are C, O, N and
B, it was confirmed that the successful preparation for trace polymerization that boron is affine.
Fig. 5 is CPS(Fig. 5 a for being prepared in the present embodiment) and H-PAVM(Fig. 5 b) XPS spectrum figure.In fig 5 a,
There was only O1s(531.08 eV in CPS) and C1s(282.86 eV) two peaks.However, observing O1s (531.07 in H-PAVM
EV), N1s(397.72 eV), C1s(282.86 eV) and B1s(189.76 eV) exist, this show phenylboronic acid moiety success
Ground is introduced into converging network.These results are consistent with the discovery in FT-IR spectrum and EDS map.
Embodiment 2: the synthesis of the hollow LTL- imprinted polymer microballoon of single hole:
Carboxy blocking polystyrene (CPS) bead is synthesized using two step soap-free polymerizations: first in the aqueous solution of 50 mL styrene
The acidic aqueous solution that 10 mL ammonium persulfates are added causes styrene polymerization, obtains the monodisperse PS bead that size is about 220 nm.
Polymerization reaction carries out under nitrogen atmosphere, first in 70 DEG C of polyase 13 hours, again 80 DEG C polymerase 10 .5 hours.Then, by 1.5 g third
Olefin(e) acid, 15 g styrene and 0.075 g ammonium persulfate are added step-wise in above-mentioned colloidal solution, and further polymerize 8 at 90 DEG C
Hour.Finally, separating carboxy blocking polystyrene (CPS) bead by centrifuge separation and with water and ethanol washing.
By the CPS microballoon (7 mg/mL) of 7 mL, 60 mg acrylamides (AA), 20 mg 4- vinyl benzene ylboronic acids
(VPBA), 30 mg LTL, 210 mg ethylene glycol dimethacrylates (EGDMA) and 10 mg azodiisobutyronitriles (AIBN)
It is dissolved in 70 mL acetonitriles, it is evenly dispersed in order to ensure CPS bead, it is stirred in polymerization process with the magnetic force of 1000 rpm
It mixes speed and is stirred to react system.In the first step, slow prepolymerization 15 hours is carried out at 60 DEG C by free radical initiation.With
Afterwards, polymerized/cross-linked reaction carries out 28 hours at 80 DEG C, and product is aging 8 hours further at 100 DEG C.Finally, passing through centrifugation
The PAVM microballoon with single hole is obtained with ethanol washing.PS core is removed with tetrahydrofuran, and with methanol/acetic acid (8:2, v/
V) mixed solvent further removes LTL template molecule, to prepare the affine trace polymerization microballoon (H-PAVM) of the hollow boron of single hole.
As a comparison, the method for preparing the affine non-trace microballoon H-PAVN of the hollow boron of single hole is similar with H-PAVM, only not
Template molecule luteolin is added.
Embodiment 3: the synthesis of the hollow LTL- imprinted polymer microballoon of single hole:
Carboxy blocking polystyrene (CPS) bead is synthesized using two step soap-free polymerizations: first in the aqueous solution of 50 mL styrene
The acidic aqueous solution that 10 mL ammonium persulfates are added causes styrene polymerization, obtains the monodisperse PS bead that size is about 220 nm.
Polymerization reaction carries out under nitrogen atmosphere, first in 70 DEG C of polyase 13 hours, again 80 DEG C polymerase 10 .5 hours.Then, by 0.3 g third
Olefin(e) acid, 3 g styrene and 0.015 g ammonium persulfate are added step-wise in above-mentioned colloidal solution, and further small in 50 DEG C of polyase 13s
When.Finally, separating carboxy blocking polystyrene (CPS) bead by centrifuge separation and with water and ethanol washing.
By the CPS microballoon (7 mg/mL) of 3 mL, 30 mg acrylamides (AA), 10 mg 4- vinyl benzene ylboronic acids
(VPBA), 10 mg LTL, 170 mg ethylene glycol dimethacrylates (EGDMA) and 6 mg azodiisobutyronitriles (AIBN) are molten
It is evenly dispersed in order to ensure CPS bead in 30 mL acetonitriles, with the magnetic agitation speed of 500 rpm in polymerization process
Degree is stirred to react system.In the first step, slow prepolymerization 10 hours is carried out at 40 DEG C by free radical initiation.Then, gather
Conjunction/cross-linking reaction carries out 20 hours at 50 DEG C, and product is aging 4 hours further at 70 DEG C.Finally, passing through centrifugation and ethyl alcohol
Washing is to obtain the PAVM microballoon with single hole.PS core is removed with tetrahydrofuran, and is mixed with methanol/acetic acid (8:2, v/v)
Solvent further removes LTL template molecule, to prepare the affine trace polymerization microballoon (H-PAVM) of the hollow boron of single hole.
As a comparison, the method for preparing the affine non-trace microballoon H-PAVN of the hollow boron of single hole is similar with H-PAVM, only not
Template molecule luteolin is added.
Embodiment 4:
It is 5.5-8.5 that H-PAVM, H-PAVN, the PAVM prepared under the conditions of by 10 mg described in the embodiment 1, which is separately added into initial pH,
A series of LTL stock solutions (35 mg/L) in 24 hours.Final LTL concentration is by ultraviolet-uisible spectrophotometer 351
It is detected at nm.The pH of LTL solution is adjusted with 0.1 M NaOH or HCl solution.3 groups of experiment point synchronous progress.Then ethyl alcohol is used
With dual distilled water (5:5, V/V;PH=5.0) LTL captured on H-PAVM, H-PAVN, PAVM microballoon is eluted, pass through
0.1 M HCl and 0.1 M NaOH aqueous solution is added, eluent pH is adjusted to 8.5 from 5.5, and is divided light using UV, visible light
The residual concentration of degree meter research LTL.
The result shows that the adsorption capacity of H-PAVM, H-PAVN, PAVM from pH=5.5 to pH=7.5 increase, while pH is from 7.5
On a declining curve to 8.5, i.e., when the pH value of LTL solution is 7.5, the adsorbance of H-PAVM, H-PAVN, PAVM three reach peak
It is worth (result is as shown in Figure 6), it can be seen that it is optimal adsorption conditions that pH value, which is 7.5,.
Embodiment 5:
In order to measure H-PAVM microballoon to the absorption property of LTL, in the mixed solvent of ethyl alcohol and dual distilled water (5:5, V/V)
Middle research adsorption equilibrium experiment and the adsorption kinetic data.Optimal adsorption based on the experiment of pH obtained in embodiment 4 will be as a result, will
The pH value of LTL solution is adjusted to 7.5.In dynamic experiment, by the H-PAVM microsphere of 10 mg with the initial dense of 35 mg/L
Degree is added to the 35 mg ml of 10 mL-1In LTL solution, and in certain time interval (6.0min, 15 min, 30 min, 60
Min, 120 min, 180 min, 240 min, 360 min, 480 min, 720 min) measurement absorption after LTL solution concentration.
Mixture temperature is maintained at 25 DEG C by water bath with thermostatic control.
As a result, it has been found that the adsorption capacity of H-PAVM increases sharply in preceding 100 min, then keep being basically unchanged, this shows H-
The combination of PAVM and LTL reaches dynamic equilibrium (result is as shown in Figure 7).In order to determine power of regeneration, after selective absorption LTL
H-PAVM is regenerated with the identical mode of template is removed during trace particle synthesizes, and is then used further to the re-absorption of LTL.
In the present embodiment, adsorption and desorption cyclic process is repeated five times using H-PAVM, H-PAVN, PAVM.As a result
Display H-PAVM is average in five circulations only to lose its 3.3% adsorption capacity, and the adsorption capacity of H-PAVN reduces
The average adsorption ability of 3.7%, PAVM have dropped 7.9%, this is attributed to the fact that the hollow structure of H-PAVM.The reason of this result is
The regeneration condition of use is milder, and the excellent stability of absorption position, is also demonstrate,proved in the inner surface and the outer surface of H-PAVM microballoon
H-PAVM microballoon is illustrated and is able to maintain good power of regeneration in repetitive cycling (result is as shown in Figure 8).
Embodiment 6:
Selectivity test is carried out by comparing the molecular structure amount of recombining similar on MIP nanosphere, selects catechol
(CTC), trichlorophenol, 2,4,6,-T (TCP) and quinhydrones (HDQ) are used as competitive Adsorption substance.As a result, it has been found that H-PAVM is to LTL, TCP, CTC
Final adsorption capacity with the independent solution of QRT is respectively 22.01 mg/g, 2.31 mg/g, 2.33 mg/g and 2.71 mg/g.H-
PAVN is respectively 12.95 mg/g, 2.01 mg/g, 2.22 to the final adsorption capacity of the independent solution of LTL, TCP, CTC and QRT
Mg/g and 2.61 mg/g, this shows that H-PAVM is prominent to the selective adsorption capacity of LTL and H-PAVM inhales the selection of LTL
Attached ability specificity is very strong (result is as shown in Figure 9).
Claims (10)
1. a kind of preparation method of the affine imprinted polymer of hollow boron of single hole, which comprises the steps of:
(1) synthesis of polystyrene (CPS) bead of carboxy blocking:
Ammonium persulfate acidic aqueous solution is added first in styrene aqueous solution and causes styrene polymerization, obtains monodisperse polystyrene
Alkene bead；Then, acrylic acid, styrene, ammonium persulfate are gradually uniformly mixed with monodisperse polystyrene bead, and further
Polymerization obtains carboxy blocking polystyrene (CPS) bead；
(2) synthesis of the affine imprinted polymer microballoon (H-PAVM) of the hollow boron of single hole:
By CPS bead, acrylamide, 4- vinyl benzene ylboronic acid, two isobutyl of LTL, ethylene glycol dimethacrylate and azo
Nitrile is dissolved in acetonitrile, in order to ensure evenly dispersed, the magnetic agitation reaction system in polymerization process of CPS bead；Pass through
Free radical, which causes, carries out slow prepolymerization, then, polymerized/cross-linked reaction, the then further aging of product；Pass through centrifugation and ethyl alcohol
Washing is to obtain the core-shell structure microballoon PAVM with single hole；Finally CPS karyolysis is removed from hole with tetrahydrofuran, is used in combination
Methanol/acetic acid mixed solvent removes LTL template molecule to prepare the affine trace microballoon (H-PAVM) of the hollow boron of single hole.
2. a kind of preparation method of the affine imprinted polymer of the hollow boron of single hole according to claim 1, which is characterized in that step
Suddenly the volume ratio of the acidic aqueous solution of styrene aqueous solution described in (1) and ammonium persulfate is 5:1；The polymerization reaction is in nitrogen
Carried out under atmosphere, first in 70 DEG C of polyase 13 hours, then 80 DEG C polymerase 10 .5 hours.
3. a kind of preparation method of the affine imprinted polymer of the hollow boron of single hole according to claim 1, which is characterized in that step
Suddenly the mass ratio of acrylic acid described in (1), styrene, ammonium persulfate are as follows: 20:200:1；It is described to be further polymerized in 50-90
Further polyase 13-8 hours under DEG C environment.
4. a kind of preparation method of the affine imprinted polymer of the hollow boron of single hole according to claim 3, which is characterized in that step
Suddenly acrylic acid dosage described in (1) is 0.3-1.5g.
5. a kind of preparation method of the affine imprinted polymer of the hollow boron of single hole according to claim 1, which is characterized in that step
Suddenly by CPS bead, acrylamide, 4- vinyl benzene ylboronic acid, LTL, ethylene glycol dimethacrylate, azo described in (2)
The dosage of bis-isobutyronitrile and acetonitrile is respectively 3-7 mL, 30-60 mg, 10-20 mg, 10-30 mg, 170-210 mg, 6-10
Mg and 30-70 mL.
6. a kind of preparation method of the affine imprinted polymer of the hollow boron of single hole according to claim 1, which is characterized in that step
Suddenly pre-polymerization described in (2) is combined into carries out slow prepolymerization 10-15 hours at 40-60 DEG C.
7. a kind of preparation method of the affine imprinted polymer of the hollow boron of single hole according to claim 1, which is characterized in that step
Suddenly the reaction of polymerized/cross-linked described in (2) carries out 20-28 hours at 50-80 DEG C.
8. a kind of preparation method of the affine imprinted polymer of the hollow boron of single hole according to claim 1, which is characterized in that step
Suddenly product described in (2) 70-100 DEG C aging 4-8 hours.
9. the affine imprinted polymer of the hollow boron of a kind of single hole that any one of -8 preparation methods obtain according to claim 1,
It is characterized in that, 300 nm of polymer that there is hydrophily and dispersibility.
10. the affine imprinted polymer of the hollow boron of single hole as claimed in claim 9 is being selectively adsorbing and separating answering in luteolin
With.
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| CN112657475A (en) * | 2020-12-02 | 2021-04-16 | 常州大学 | Boron affinity functionalized microsphere adsorbent and preparation method and application thereof |
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